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  • 1995-1999  (10.093)
  • 1980-1984
  • 1997  (10.093)
  • Chemistry  (10.047)
  • Ultrastructure
  • Nuclear reactions
Materialart
Erscheinungszeitraum
  • 1995-1999  (10.093)
  • 1980-1984
Jahr
  • 1
    ISSN: 1432-2307
    Schlagwort(e): Key words Inflammation of the bronchi ; Bronchial biopsy ; Ultrastructure ; Vessels ; Laser therapy
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract  An ultrastructural and autoradiographic analysis of changes in 188 biopsy specimens of bronchial mucosa of the large bronchi from 76 patients with chronic inflammatory lung diseses was carried out. Fibrosis results in an apparent reduction of metabolic activity in endothelial cells, affecting the proliferation of basal cells with changes in cell differentiation. Endobronchial laser therapy with an helium-neon laser induces proliferative and metabolic processes in the lamina propria of the bronchial mucosa with hyperaemia, intensive diapedesis of leucocytes and formation of leucocytic infiltrations and granulation tissue. The proliferative and metabolic activity of endothelial and stromal cells increases, and delicate fibrous connective tissue is formed.
    Materialart: Digitale Medien
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  • 2
    Digitale Medien
    Digitale Medien
    Springer
    Urological research 25 (1997), S. 283-289 
    ISSN: 1434-0879
    Schlagwort(e): Detrusor ; Fixation ; Magnesium Osmolarity ; Smooth muscle cells ; Ultrastructure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract Magnesium ions added to fixatives for processing to Transmission Electron Microscopy (TEM) have been claimed to cause relaxation of detrusor smooth muscle cells [1]. This should facilitate the morphologic evaluation of the tissue. However, magnesium ions are osmotically active and their addition may cause the fixative to become hypertonic to the tissue. To ascertain whether the presence of magnesium ions causes significant changes compared to those found where the osmolarity is raised without the presence of magnesium, human detrusor specimens were fixed in glutaraldehyde to which increasing amounts of MgCl2 or NaCl were added in different concentrations. With the addition of increasing amounts of MgCl2 and NaCl, the osmolarity of the fixative increased, causing significant changes in the morphology and morphometry of the tissue. The intercellular distances increased, the cells shrank and the shape of the cells changed from smooth and rounded to spiky and angulated. With regard to its muscle-relaxing effect, it was not possible to distinguish the specimens fixed in magnesium-containing fixatives from those without. In this study it was not possible to prove any relaxing effect of magnesium ions added to the fixative. On the contrary the magnesium ions caused an increase in the osmolarity, with significant changes in both the morphometry and the morphology of the human detrusor smooth muscle cells.
    Materialart: Digitale Medien
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  • 3
    ISSN: 1432-0533
    Schlagwort(e): Key words Neuronal intranuclear inclusion ; Amyotrophic lateral sclerosis ; Ammon’s horn ; Ultrastructure ; Ubiquitin
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract We report the presence of round eosinophilic intranuclear inclusions in a patient with sporadic amyotrophic lateral sclerosis (ALS). The inclusions were limited to the hippocampal pyramidal neurons; they were frequently encountered in the CA1 and CA2 regions and much less frequently in the CA3 and CA4 regions and in the subiculum. Ultrastructurally, they consisted of randomly oriented straight filaments, each about 8–14 nm in diameter, some of which had a tubular appearance in cross-section. Electron-dense, granular material was intermingled with the filaments. Immunohistochemically, all the inclusions were positive for ubiquitin, but were negative for several kinds of cytoskeletal protein, including actin, glial fibrillary acidic protein, vimentin, neurofilament polypeptides, keratin, tubulin, tau protein and microtubule-associated protein 2. To our knowledge, this type of neuronal intranuclear inclusion has not so far been reported in ALS, and its distribution limited to the hippocampal formation is of great interest.
    Materialart: Digitale Medien
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  • 4
    Digitale Medien
    Digitale Medien
    Springer
    Acta neuropathologica 94 (1997), S. 240-246 
    ISSN: 1432-0533
    Schlagwort(e): Keywords Spectrin ; Dystrophin ; Ultrastructure ; Duchenne muscular dystrophy
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract Spectrin, a major component of the erythrocyte membrane skeleton, has previously been shown to form a two-dimensional lattice in erythrocytes, and in avian or chicken skeletal muscle. Those results were mainly obtained with antibodies against α-spectrin. Using immunofluorescence of semithin cryosections and single muscle fiber preparations, we show here that β-spectrin forms a costameric network which covers the plasma membrane of human skeletal muscle. These spectrin costameres are correlated with the Z-bands. They are longitudinally connected by fine strands and interrupted by myonuclear lacunae. Under mechanical stretching, the costameres retained their correlation to the Z-bands in normal and dystrophin-deficient muscle, up to the point at which the sarcolemma was disrupted. In stretched muscle, in some regions of the stretched fibers in which the costameres seemed to form double strands, the usually 1:1 correlation of spectrin to the Z-bands changed to a 2:1 relation. In dystrophin-deficient muscle, the costameric scaffold of spectrin in the well-preserved fibers appeared normal, indicating that spectrin can be correctly localized in the absence of dystrophin and that the subcellular spectrin organization does not primarily depend on dystrophin expression. The regular organization and the correlation of spectrin costameres to the Z-bands was notable even in stretched Duchenne muscular dystrophy (DMD) muscle. On the other hand, single teased muscle fibers of DMD muscle showed various degrees of morphological alterations of the costameric network, ranging from a focal disarray to complete loss of costameric organization. Because these findings indicate that the costameric spectrin scaffold undergoes secondary changes during the course of the dystrophic process in dystrophin-deficient muscle, spectrin staining of isolated muscle fibers may also serve as a tool to monitor the effect of gene therapy experiments at the single fiber level.
    Materialart: Digitale Medien
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  • 5
    Digitale Medien
    Digitale Medien
    Springer
    Acta neuropathologica 93 (1997), S. 285-293 
    ISSN: 1432-0533
    Schlagwort(e): Key words Pacinian corpuscles ; Reinnervation after ; axotomy ; Regenerated axon terminals ; Ultrastructure ; Cat
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract The reinnervation pattern of crural pacinian corpuscles was examined by light and electron microscopy in eight adult cats of both sexes 3–18 months after sciatic nerve crush. Normal pacinian corpuscles are each supplied with a single myelinated axon and a single cylindrical axon terminal which may branch in the distal part of the inner core. Reinnervation of these vibroreceptors was very satisfactory after sciatic nerve crush: in a sample of 68 corpuscles examined 3–18 months after the operation, 92.6% were found reinnervated, while only 7.4% remained denervated. At the nerve entry, 84.2% of the reinnervated corpuscles were supplied with a single myelinated axon, while 15.8% received two myelinated axons; some of the axons branched before or after entering the inner core. Near the mid-level of the inner core, 60.3% of 63 reinnervated corpuscles were innervated with a single axon terminal, 22.2% were biterminal, while 17.5% had three or more terminals. Regenerated axon terminals induced the formation of thin lamellar layers in the axial region of the original core and, exceptionally, also at the outer aspect of the original core. In monoterminal corpuscles, the shape and ultrastructure of regenerated endings resembled those of normal controls, whereas in multiterminal corpuscles their shape and profiles were variable. In contrast to previous reports, reinnervated corpuscles did not ultimately become monoterminal. On the contrary, the mean number of 1.3 terminals found in reinnervated crural corpuscles at 3–5 months increased to 1.9 terminals per corpuscle 6–18 months after axotomy.
    Materialart: Digitale Medien
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  • 6
    ISSN: 1432-0533
    Schlagwort(e): Key words Regeneration ; Diffuse axonal injury ; GAP43 ; Neurofilament ; Ultrastructure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract Traumatic brain injury in animals and humans is well known to cause axonal damage diffusely scattered throughout the brain without evidence of other brain parenchymal change. This observation has prompted some to posit that such damaged axons are well positioned to mount a regenerative attempt. The present study uses an immunocytochemical marker specific for regenerating neurites to explore this issue. Further, in an attempt to expedite and enhance any potential regenerative effort, this study evaluates the efficacy of intrathecally applied nerve growth factor. Three sets of experiments were performed in adult cats. One group of animals was subjected to moderate fluid percussion brain injury and followed for 7 or 14 days post injury, with the continuous intraventricular infusion of nerve growth factor delivered by implanted osmotic pumps. These animals were compared to a second group of time-matched, sham-operated animals receiving artificial cerebrospinal fluid infusion. To assess axonal damage immunohistochemical staining for the low molecular weight neurofilament subunit (NF-L) was carried out using an NR4 monoclonal antibody. To localize axons exhibiting a regenerative response immunohistochemical staining for the growth associated protein GAP43 was employed. In sham controls, at the light microscopic level NF-L-immunoreactive axonal swellings were numerous at 7 days, but by 14 days post injury their frequency declined markedly. In contrast, GAP43-immunoreactive, disconnected reactive axonal swellings were rarely observed at 7 days but were numerous at 14 days. Ultrastructural analysis at 14 days post injury of carefully matched sections revealed reactive axons demonstrating sprouting consistent with a regenerative effort. Analysis of tissue from animals of 14 days of survival indicated that supplementation with nerve growth factor did not appear to enhance the capacity of damaged brain axons to mount a regenerative attempt. Rather, it appears that regenerative efforts seen reflect a spontaneous response. A third group of adult cats, subjected to the same injury but not subjected to osmotic pump implantation, was allowed to survive for 22–28 days. Animals in this group also demonstrated GAP43 immunoreactivity in reactive axonal swellings in the brain stem. This study demonstrates that diffusely injured axons can mount a sustained regenerative attempt that is associated with a reorganization of their cytoskeleton and accompanied by an up-regulation of growth-associated proteins.
    Materialart: Digitale Medien
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  • 7
    Digitale Medien
    Digitale Medien
    Springer
    Anatomy and embryology 196 (1997), S. 215-226 
    ISSN: 1432-0568
    Schlagwort(e): Key words Natural killer cells ; Ultrastructure ; Parallel tubular arrays ; Perforin ; Granzyme B ; Chondroitin sulfate
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract  Human natural killer (NK) cells contain unique granules with parallel tubular arrays (PTA granules) of approximately 30 nm diameter that can be seen only by electron microscopy. In order to clarify the role of PTA granules in NK cell-mediated cytolysis we examined these structures with regard to frequency and expression of lytic proteins (perforin, granzymes). NK cells (CD3−, CD16+, CD56+) were obtained from heparinized blood of healthy donors and enriched by double-step negative selection using mAb coupled to magnetic beads. PTA granules were found in 31.3% of freshly separated NK cells. When NK cells were cultivated, even in the presence of various stimulating agents (rhIL-2, rhIL-4, rhIL-6, rhIL-12, GM-CSF, rhIFNα, anti-CD16 mAb, dexamethasone), PTA granules disappeared and transformed into conventional primary lysosomes. By immune electron microscopy using antibodies directed against perforin and granzyme B we observed distinct immuno-reactivity in the tubules and in the tubule-associated faintly electron-dense matrix of PTA granules. Immuno-labelling for perforin and granzyme B was also found in the fine granular matrix of primary lysosomes. Finally, we tested the distribution of chondroitin 4-sulfate which is suggested to inactivate lytic proteins. Immuno-reactivity for chondroitin 4-sulfate was detected only in the moderately electron-dense matrix but not in the tubules of PTA granules. These observations indicate that perforin and granzyme B are stored in an inactive form in PTA tubules due to highly ordered paracrystalline protein folding. As soon as the tubules decay the lytic proteins are kept in an environment of chondroitin 4-sulfate for inactivation.
    Materialart: Digitale Medien
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  • 8
    ISSN: 1432-0533
    Schlagwort(e): Key words Meningioma ; Inclusion body ; Vimentin ; Immunocytochemistry ; Ultrastructure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract Intracytoplasmic inclusion bodies are rarely found in meningiomas. A 74-year-old woman had an anaplastic meningioma with intracytoplasmic chromophobe inclusion bodies (CIB) histologically. These CIB were various shapes, e.g. round, teardrop-like, fusiform, horseshoe-like, crescentic and perinuclear. The size of CIB ranged from 7 to 14 μm and the nuclei of the tumor cells with CIB were often eccentric. Most CIB were immunopositive only for vimentin, staining more intensely than surrounding cytoplasm in a comparative study using adjacent sections stained with hematoxylin-eosin and vimentin. CIB showed loosely textured filamentous structures which were in parallel and entangled arrangements ultrastructurally. The diameter of the filaments was 13–14 nm and they were thicker than normal intermediate filaments. Moreover, these filaments appeared to be studded with granular and fuzzy substances. These findings suggest that CIB are mainly composed of abnormally synthesized and arranged vimentin filaments.
    Materialart: Digitale Medien
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  • 9
    Digitale Medien
    Digitale Medien
    Springer
    Acta neuropathologica 93 (1997), S. 579-584 
    ISSN: 1432-0533
    Schlagwort(e): Key words Hypobaric hypoxia ; Cerebral ; microvasculature ; Ultrastructure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract Prolonged hypoxia results in structural and functional adaptive responses to improve tissue oxygen delivery. Structural changes within the brain include vascular proliferation and elongation. The aim of the current study was to investigate whether ultrastructural changes in capillary walls also occur as part of the adaptive response. Adult rats were exposed to 2 or 3 weeks of moderate hypobaric hypoxia at 0.5 atmospheres and their cerebral microvasculature examined using quantitative ultrastructural methods. We found that hypoxic rats had an 18% increase in their brain capillary diameter but no change in endothelial wall thickness, basement membrane thickness, or coverage of the endothelial wall by pericytes. The increased diameter of cerebral capillaries may play an important role in decreasing the resistance to capillary perfusion which is brought about by the increased erythrocyte fraction in the blood of hypoxic rats. Ultrastructural features relevant to the blood-brain barrier were maintained in hypoxic rats. Pericytes, that are thought to form a second line of defense in the blood-brain barrier, maintained their numerical and size relationships to the endothelial cells. Endothelial junctions were unchanged and endothelial vesicles were somewhat lower in density than normal at 2 weeks of hypoxia, but had regained their normal density by 3 weeks. Mitochondria of the brain capillary endothelial cells maintained normal numerical and volume densities in hypoxia, but the mitochondria of the surrounding neuropil were decreased significantly by about 30%.
    Materialart: Digitale Medien
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  • 10
    Digitale Medien
    Digitale Medien
    Springer
    Acta neuropathologica 94 (1997), S. 425-435 
    ISSN: 1432-0533
    Schlagwort(e): Key words Cell culture ; Central neurocytoma ; Histogenesis ; Ultrastructure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract To clarify the histogenesis and differentiation potential of central neurocytoma, a pathological investigation of seven tumors from three patients was conducted using immunohistochemistry and ultrastructural analysis in addition to systematic in vitro studies. Six tumors were studied immunohistochemically and five were examined ultrastructurally. All cases that were immunostained were positive for synaptophysin in nuclear-free neuropil islands. In five tumors, a few tumor cells, in addition to reactive astrocytes, were positive for glial fibrillary acidic protein (GFAP). Vimentin staining was also positive in a few tumor cells of five specimens. Neurofilament staining was always negative. All cases for which ultrastructure was examined showed various synaptic abnormalities. Cultured cells were subdivided into three distinct tumor cell types: neuronal cells which stained for neurofilament proteins with neurosecretory granules; small flat undifferentiated cells with a high nuclear-cytoplasmic ratio and scant cytoplasmic organelles; and small round or multipolar astrocytic cells with 10-nm intermediate filaments which stained for GFAP. Our tissue culture studies disclosed that cultured neurocytoma cells form a cellular mosaic similar to subependymal plate layers that are composed of mitotically active cells, neurons and glia.
    Materialart: Digitale Medien
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  • 11
    ISSN: 1432-0533
    Schlagwort(e): Key words Mucopolysaccharidosis IIID ; Skin ; Ultrastructure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract Mucopolysaccharidosis IIID (MPS-IIID) is the rarest of the MPS-III syndromes. It is caused by deficient activity of lysosomal N-acetylglucosamine-6-sulfatase (G6S). To date, the clinical and biochemical features of seven patients with MPS-IIID have been reported, but no biopsy or autopsy findings have been described. The purpose of this report is to define the ultrastructure of affected cells seen in a skin biopsy from a 14-year-old boy. The child presented with progressive mental deterioration, hyperactivity and mild to moderate dysmorphism. The diagnosis of a mucopolysaccharidosis was suggested, but the initial urine analyses were negative for elevated mucopolysaccharides, and only the third analysis showed abnormal excretion of heparan sulfate. Because of the diagnostic difficulties posed by this case, a skin biopsy was performed for morphological and biochemical studies. Numerous vacuoles were noted in Schwann cells, fibroblasts, smooth muscle cells, eccrine gland and ductal epithelium in resin-embedded sections stained with toluidine blue. Ultrastructurally, many lysosomes were distended with abundant, fibrillar material. Occasionally, lamellated membranous structures were present within the same lysosomes. These findings are consistent with those seen in other forms of MPS, in which the lysosomal storage occurs predominantly, but not exclusively, in mesenchymal cells. Furthermore, deficient activity of G6S was confirmed in cultured skin fibroblasts. This study demonstrates that electron microscopy of skin biopsies is a useful method for identification of patients with clinical features of MPS-IIID whether or not heparan sulfaturia is present.
    Materialart: Digitale Medien
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  • 12
    Digitale Medien
    Digitale Medien
    Springer
    Acta neuropathologica 94 (1997), S. 499-503 
    ISSN: 1432-0533
    Schlagwort(e): Key words Meningioma ; Immunohistochemistry ; Glial fibrillary acidic protein ; Ultrastructure ; Intercellular lumina
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract We studied a recurrent meningioma located in the right frontal lobe. The tumor showed high cellularity and the cells had plump, hyalinous cytoplasm. Immunohistochemically, almost all the tumor cells were positive for epithelial membrane antigen and vimentin, and unexpectedly, glial fibrillary acidic protein (GFAP). Ultrastructural investigation revealed abundant 8- to 10-nm filaments in the cytoplasm. Conspicuous interdigitations with numerous desmosomes were present. Frequently, intracellular and intercellular lumina lined by microvilli were also found. We considered the present case to be an unusual variant of meningioma with GFAP expression. A few cases of meningioma with triple expression of GFAP, vimentin and cytokeratin have been reported previously. However, the present case showed obvious pathological differences from these, and had no immunoreactivity for cytokeratin.
    Materialart: Digitale Medien
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  • 13
    Digitale Medien
    Digitale Medien
    Springer
    Acta neuropathologica 94 (1997), S. 109-115 
    ISSN: 1432-0533
    Schlagwort(e): Key words Locus coeruleus ; Ultrastructure ; Dihydroetorphine ; Morphine ; Opioids
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract The locus coeruleus (LC) is a major noradrenergic nucleus in the brain. The activity of the LC neurons is chronically regulated by opioids. So far, very little is known about the morphological changes induced by chronic treatment with opioids. In the present study, the effects of chronic treatment with morphine and dihydroetorphine, a new narcotic analgesic with lower physical dependence potential than morphine, were investigated on the ultrastructure of the rat LC. Rats received saline or increasing doses of morphine or dihydroetorphine for 5 days by twice daily subcutaneous injections. Withdrawal was precipitated in half of the opioid-treated rats by a single intraperitoneal injection of naloxone 4 h after the last injections of opioids. The ultrastructure of the LC was examined by electron microscopy. Results showed that chronic morphine treatment induced a marked injury to the LC neurons. The primary changes in the cell body were the indentation of nuclei, the fragmentation and degranulation of rough endoplasmic reticulum, as well as the disaggregation of polyribosomes. Myelinoid bodies were seen in the processes. An accumulation of presynaptic vesicles was observed in some of the terminals which formed synaptic junctions with the LC neurons as compared to the normal controls. Naloxone-precipitated withdrawal from morphine did not stop the morphine-induced injury on the LC neurons except that less accumulation of presynaptic vesicles occurred. Chronic dihydroetorphine treatment only induced a slight change in the ultrastructure of the LC neurons. These results indicate that the LC neurons are more vulnerable to chronic treatment with morphine than to that with dihydroetorphine.
    Materialart: Digitale Medien
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  • 14
    Digitale Medien
    Digitale Medien
    Springer
    Acta neuropathologica 94 (1997), S. 338-344 
    ISSN: 1432-0533
    Schlagwort(e): Key words Amyotrophic lateral sclerosis ; Pericapillary rosette ; Immunocytochemistry ; Ultrastructure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract This report concerns a comparative immunocytochemical and ultrastructural investigation on pericapillary rosettes (PR) in the lumbar spinal cords of 21 patients with amyotrophic lateral sclerosis (ALS) and 18 age-matched neurologically normal individuals. The purpose of the study was to determine the alteration of PR in relation to the neuronal loss in ALS. The PR were almost always positively immunostained for phosphorylated neurofilament, and some PR immunoreacted with antibodies to synaptophysin and β-amyloid precursor protein. This finding suggests that axonal transport, whether fast or slow, is impaired in the terminal portion of the axon that reaches the capillaries. Some PR were also positively immunostained by the antibody against ubiquitin, anti-calbindin-D 28 K antibody, anti-parvalbumin antibody and the antibody to superoxide dismutase 1. Morphometrically, the number of PR in the anterior horns and lateral column was markedly diminished in ALS compared with controls. At the ultrastructural level, the PR consisted mostly of unmyelinated degenerated axons, and were frequently found outside the basal laminae of the endothelial cell and of the astrocytic foot processes on the opposite side of the capillary, and less often in the space between the two basal laminae. The data indicate that the fate of PR is intimately associated with the neuronal loss of the anterior horn cells and with degenerative change of nerve fibers extending from their mother neurons to the capillaries.
    Materialart: Digitale Medien
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  • 15
    ISSN: 1432-0568
    Schlagwort(e): Key words Mineralization ; Dentine ; Ultrastructure ; Elementanalysis ; Collagen fibrils
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract  The purpose of this study was to compare the biomineralization of circumpulpal dentine with that of mantle dentine by ultrastructural and element-analytical techniques. Forty upper second molar germs of 10-day-old albino rats were cryofixed in liquid nitrogen-cooled propane and embedded in resin after freeze drying. Semithin dry sections were cut for analyzing the calcium and phosphorus concentration in initial mantle dentine, at the mineralization front of circumpulpal dentine, in the middle region of circumpulpal dentine and in mantle dentine peripheral to circumpulpal dentine. For the morphological evaluation of mineral deposits we compared ultrathin and unstained sections of cryofixed molars with chemically fixed molars. For both dentine types it was found that they develop via identical steps of mineral formation at collagen fibrils and non-collagenous matrix molecules. In circumpulpal dentine no globular mineral protrusions along the mineralization front (i.e. calcospherites) and no indications of interglobular dentine at the transition from circumpulpal dentine to mantle dentine were present. The von Korff fibres were not only visible in mantle dentine but also in circumpulpal dentine. Matrix vesicles were present only during the formation of an initial coherent layer of mantle dentine and could not be observed during successive formation of mantle dentine and circumpulpal dentine. The element-analytical data did not demonstrate any difference in the mineral content between the two dentine types. Therefore, we conclude that mantle dentine and circumpulpal dentine in the rat molar possess a high degree of structural and chemical similarity and that only the extent of terminal branching of the odontoblast processes gives an approximate estimation of the thickness of mantle dentine.
    Materialart: Digitale Medien
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  • 16
    Digitale Medien
    Digitale Medien
    Springer
    Anatomy and embryology 196 (1997), S. 323-333 
    ISSN: 1432-0568
    Schlagwort(e): Key words Herbst mechanoreceptors ; Sensory axons ; White Leghorns ; Japanese quail ; Ultrastructure ; Quantitative study
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract  Herbst corpuscles were studied in the crural region of perinatal and adult chicken and quail in order to find out their number and dimensions and to learn more about their structure, especially in relation to size. Crural corpuscles are arrayed in an encapsulated string between tibia and fibula. They are closely packed together; a small number of corpuscles is found apart from the string, often attached to the periost. The strings of corpuscles are approximately 40 mm long in adult chicken and 20 mm long in the quail. The crural region of the chicken contains 382.8 ± 90.9 (mean ± SD) corpuscles, the numbers ranging from 301 to 582; in the quail, the mean number is 119.2 ± 27.9, with a range from 83 to 167 corpuscles. In the chicken, one axon supplies an average of 1.60 corpuscles; in the quail, the relation of axons to corpuscles is approximately 0.92. In both species, final numbers of crural corpuscles are already attained before hatching and no difference is found in the mean number and range of corpuscles between perinatal and adult birds. In both chicken and quail, individual strings contain corpuscles of various sizes, from large to very small. The chicken corpuscles are generally twice as large in diameter and often longer than those of the quail. The corpuscles are composed of an axon terminal that projects two rows of axonal spines into the clefts of the inner core and ends with an ultraterminal bulb; the terminal is surrounded with a bilaterally symmetrical inner core, amorphous inner space containing collagen fibrils of various thickness, and a capsule. Large chicken corpuscles contain inner cores composed of up to 100 lamellae, while quail inner cores have half that number at the most. The capsules are usually composed of 8 to 10 lamellar layers in both species, but they are thicker in the chicken than in the quail. The possible functional significance of individual structural components of Herbst corpuscles is discussed.
    Materialart: Digitale Medien
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  • 17
    ISSN: 1432-069X
    Schlagwort(e): Key words Diagnosis ; Mechanobullous disease ; Skin ; Ultrastructure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract Electron microscopy combined with morphometry was used to establish values for 24 parameters in normal skin. These results were compared with those similarly obtained from samples of epidermolysis bullosa with a view to facilitating classification of the disease. Six of the eight subtypes of epidermolysis bullosa investigated could be differentiated. Four subtypes showed values for structural components in intact skin which were outside the normal range: (1) epidermolysis bullosa simplex generalisata gravis (hemidesmosomes); (2) epidermolysis bullosa dystrophica Pasini and (3) Cockayne-Touraine (anchoring fibrils); and (4) epidermolysis bullosa acquisita (anchoring fibrils, hemidesmosomes, and lamina lucida and lamina densa aspects of the dermoepidermal junction). Two subtypes revealed specific features which could be assessed qualitatively: distinctive, circumscribed, clumped tonofilament bodies were present in basal keratinocytes from epidermolysis bullosa herpetiformis Dowling-Meara and thick (30 nm diameter) cross-striated anchoring fibrils were absent in epidermolysis bullosa dystrophica generalisata gravis. Epidermolysis bullosa simplex Köbner and Weber-Cockayne forms could not be distinguished.
    Materialart: Digitale Medien
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  • 18
    Digitale Medien
    Digitale Medien
    Springer
    Zeitschrift für Lebensmittel-Untersuchung und -Forschung 204 (1997), S. 121-128 
    ISSN: 1431-4630
    Schlagwort(e): Key words Surimi ; Sardine ; Starch ; Texture ; Water holding capacity ; Ultrastructure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Abstract  The effect of waxy corn starch (WCS) on the texture, water-holding capacity and microstructure of sardine (Sardina pilchardus) surimi gels in two different systems was studied. In the type A system, increasing amounts of WCS (2, 4, 6 or 8 g/100 g surimi) were added to surimi while maintaining the gel moisture constant at 78%; in the type B system, WCS was added without correcting the gel moisture. Gels were made using two different heat treatments [heat-induced setting (HS) and direct cooking (DC)]. When starch was replaced by surimi (type A) and a heat treatment was applied that favoured formation of a preliminary actomyosin (AM) network (i.e. HS), gel strength (GS) was lower than in the control and decreased as more starch was added, despite an increase in the amount of water held by the gel. Scanning electron microscopy (SEM) showed that the matrix network was fibrillar with a globular surface. Starch appeared to be totally gelatinized and surrounded by a continuous matrix. When the amount of dry matter in gels was increased (type B), in no case did starch have a reinforcing effect, despite an increasing water-holding capacity; SEM showed a denser continuous matrix surrounding the gelatinized starch. Both types of gel made using the heat treatment that allows simultaneous gelling of surimi and gelatinization of starch (i.e. DC) exhibited much poorer GS than did HS gels, while addition of starch made practically no difference to gel texture. The findings suggest that the effect of starch is related to the type of gel matrix that forms upon addition of ingredients. Although such gels contained more water or dry matter, their texture parameters were lower, possibly because of the type of network formed by sardine surimi. Nonetheless, gels of acceptable quality were successfully made with added starch by incorporating less surimi.
    Materialart: Digitale Medien
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  • 19
    ISSN: 1432-2145
    Schlagwort(e): Key words Asplenium trichomanes L. subsp. trichomanes ; Ferns ; Spermatozoids ; Flagella ; Ultrastructure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract  Asplenium trichomanes L. subsp. trichomanes spermatozoids are spirals of about five turns. Keels link the elements of the microtubular ribbon with the plates of the lamellar layer (LL) which are uninterrupted, parallel and curved with an inner angle of about 150°. Electron-opaque filaments connect the microtubules of the multilayered structure (MLS) and the osmiophilic crest, the LL and the MLS-associated mitochondrion and the latter and the plasmalemma. The nucleus occupies the 2.5–3 posterior turns and has an inner honeycomb-shaped chromatin mass and an outer highly condensed chromatin mass with randomly scattered electron-transparent areas. The basal bodies of the ca. 50 flagella are bounded by a reticulum of granular material which forms a plug inside their proximal region; the proximal region of the flagellum has a 9 + 0 pattern. The axoneme has a 9 + 2 pattern.
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  • 20
    Digitale Medien
    Digitale Medien
    Springer
    Sexual plant reproduction 10 (1997), S. 368-373 
    ISSN: 1432-2145
    Schlagwort(e): Key words Egg-cell isolation (angiosperm) ; Micromanipulation ; Plumbagozeylanica ; Viable egg ; Ultrastructure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract  A protocol for isolating viable eggs in Plumbago zeylanica by mechanical dissection is reported. The optimum solution for isolation was 0.8 M mannitol + 10 mM MOPS + 10 mM CaCl2, (pH 4.5–5.0) with an osmolality of 860–940 mmol/kg. Eggs retain their viability for at least 24 h. Isolated eggs were true protoplasts without cell walls and could tolerate osmolality of 437 mmol/kg to 965 mmol/kg. Observation of the isolated eggs using transmission electron microscopy indicated that they were well preserved and reflected the ultrastructure of physiologically active cells, displaying features similar to those of in vivo egg cells. Notable differences include the absence of a filiform apparatus and the accumulation of dense particles in the plastids, which was most conspicuous in egg cells that were damaged during isolation.
    Materialart: Digitale Medien
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  • 21
    ISSN: 1432-0738
    Schlagwort(e): Key words 2 ; 5-di(tert-butyl)-1 ; 4-Hydroquinone ; Ca2+ ATPase inhibitor ; Neurotoxicity ; Ultrastructure ; Motor endplate
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract Female Wistar rats were treated orally for 5 days with 80 mg/kg body weight of 2,5-di(tert-butyl)-1,4-hydroquinone (DTBHQ), a microsomal Ca2+ ATPase inhibitor. Motor endplates of the lumbrical muscles were examined by light and electron microscopy. There was a decrease in body weight in the treated rats from the first day after administration, and toxic signs appeared after the third day, such as adoption of a prone position, salivation, lacrymation, and an abnormal gait and/or muscle weakness. No remarkable macroscopic or light microscopic changes were noted in the lumbrical muscles as well as other peripheral nerves of hind legs of the treated rats killed 1 day after the last DTBHQ treatment. Ultrastructurally, neurotoxicity characterized by loss of synaptic vesicles and mitochondria in the motor endplates, and by destruction of the motor terminals was detected in the lumbrical muscles of the treated rats. These results strongly indicate that DTBHQ targets the motor endplates in the rat lumbrical muscles and suggest that the resultant damage is responsible for the appearance of neurological signs, such as an abnormal gait and loss of muscle control.
    Materialart: Digitale Medien
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  • 22
    Digitale Medien
    Digitale Medien
    Springer
    Boundary layer meteorology 85 (1997), S. 197-222 
    ISSN: 1573-1472
    Schlagwort(e): Turbulence ; Chemistry ; Closure ; Convective boundary layer
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Geologie und Paläontologie , Physik
    Notizen: Abstract We study the interactions of chemistry and turbulent mixing of tracersin the convective boundary layer with a second-order closure model,including higher order chemistry terms. In order to limit the number of predictive equations we prescribe the profiles for ¯w¯Θ, ¯w¯θ ¯θ and the lengthscale l. However, for model validation we treat temperature and humidity asinert tracers, and compare the results with profiles observed during theAir Mass Transformation Experiment, and with similarity expressions for thesurface layer. We find good agreement of the mean profiles, but the (co-)variances are slightly underpredicted. Furthermore, the model usesdiagnostic equations expressing third moments of concentration in terms ofsecond moments and their vertical derivatives. They are compared withlarge-eddy model results, showing good agreement and, therefore, thesimplifications are justified. The model is applied to the transport of two gases subject to one bimolecular reaction. The importance of concentration correlations on themean transformation rate is studied. For two gases diffusing in oppositedirections we find for moderate and fast chemistry a 50% and90% decreased transformation rate due to the negatively correlatedconcentrations. These values are similar to large-eddy results of Schumannand Sykes et al. For two bottom-up tracers we find that the covariance ofboth reactive species is either positive or negative, increasing or reducingthe effective transformation rate depending on the Damköhler number (the ratio of the turbulent and the chemistry timescale). A significantdirect influence of chemistry on the flux divergence is found in bothcases. According to the model the effective transport to mid-levels of theboundary layer is increased when two reactive tracers diffuse in oppositedirections, and decreased in the case of two bottom-up tracers.
    Materialart: Digitale Medien
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  • 23
    ISSN: 1432-2307
    Schlagwort(e): Key words HHV-7 ; Viral replication ; Virus morphology ; Ultrastructure ; Herpesviruses
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract  Human herpesvirus 7 (HHV-7) was grown in a CD4+ lymphoblastic cell line (SupT1) and in cord blood mononuclear cells (CBMC). Virus infection was demonstrated by immunohistology with positive control sera, with monoclonal antibodies and by in situ hybridization for viral DNA. Cytopathic effects following HHV-7 infection generally resemble those after HHV-6 infection but are less pronounced. The ultrastructural appearance of HHV-7 and the replicative stages were similar to those described by Kramarsky and Sander for HHV-6. There were some minor discrepancies, including quite an extensive and space-filling tegument, a slightly different structure of the nucleoid, the frequent finding of nucleocapsids without any visible core and apparently scarce or delicate spikes on the envelope. These differences may suggest HHV-7 rather than HHV-6, but this finding needs confirmation. Mature HHV-7 particles measured 170 nm in diameter, with nucleocapsids of 90–95 nm and a tegument of about 30 nm.
    Materialart: Digitale Medien
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  • 24
    Digitale Medien
    Digitale Medien
    Springer
    Cell & tissue research 291 (1997), S. 91-95 
    ISSN: 1432-0878
    Schlagwort(e): Key words ECL cells ; Omeprazole ; Granules/vesicles ; Ultrastructure ; Stomach ; Rat (Sprague Dawley)
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract  The ECL cells are histamine- and peptide hormone-producing endocrine cells in the rat oxyntic mucosa. They are rich in secretory vesicles and also contain microvesicles and electron-dense granules. They operate under the control of circulating gastrin. In the present study, we examined the ECL-cell ultrastructure after long term treatment with omeprazole, which is known to induce hypergastrinemia, and after withdrawal of the drug. Rats received omeprazole (400 µmol/kg per day, orally) for 16 days and were killed 1, 5, 20, or 40 days after the last dose of the drug. Oxyntic mucosal specimens were processed for electron microscopy. Electron micrographs of ECL-cell profiles were analyzed planimetrically. The ECL-cell profile area increased promptly in response to omeprazole, the secretory vesicles and granules were reduced in number and volume density, the microvesicles were unchanged in number but reduced in volume density, and vacuoles appeared. Within a week after stopping the omeprazole treatment, the numbers and volume densities of secretory vesicles and microvesicles returned to pre-stimulation values. Also, the vacuoles disappeared promptly. The ECL-cell profile area decreased below the pre-stimulation level within five days after stopping treatment, while, in contrast, the granules increased in number and volume density. Somewhat surprisingly, the cell size and the granule compartment did not return to normal until 40 days after stopping treatment.
    Materialart: Digitale Medien
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  • 25
    ISSN: 1432-0878
    Schlagwort(e): Key words: Exocytosis ; Endocytosis ; Gastrin cells ; Carbamylcholine ; Ultrastructure ; Pyloric antrum ; Guinea pig (Hartley) ; Mouse (ICR) ; Rat (Sprague Dawley)
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract. In order to capture the exocytotic figures of gastrin cells in the pyloric antrum of the stomach, we examined antral cells of the mouse, rat, and guinea pig by electron microscopy following stimulation with the cholinergic secretagogue carbamylcholine. Increased numbers of omega profiles indicative of exocytosis were seen in the basal or lateral cell membrane after stimulation with carbamylcholine. The number of exocytotic figures in stimulated gastrin cells was higher in the guinea pig than in the mouse and rat. Coated and non-coated omega profiles and coated pits in the plasma membrane were smaller than the secretory granules. Omega profiles with or without electron-dense contents were seen. Coated and non-coated vesicles were often visible near the plasma membrane of stimulated gastrin cells in all three species, large cytoplasmic vacuoles also being found in the guinea pig. In the mouse pretreated with horseradish peroxidase, reaction deposits were observed in the omega profiles and in microvesicles near the plasma membrane. These results suggest that, after exocytosis, membrane retrieval and endocytosis occur in the gastrin cells.
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  • 26
    Digitale Medien
    Digitale Medien
    Springer
    Cell & tissue research 290 (1997), S. 39-42 
    ISSN: 1432-0878
    Schlagwort(e): Key words: Ciliogenesis ; Striated rootlets ; Oviduct ; Ciliated cells ; Ultrastructure ; Human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract. Striated rootlets in ciliated cells are conical banded structures composed of longitudinally aligned filaments. The formation of striated rootlets during ciliognesis in the human oviduct epithelium was studied by electron microscopy. Primitive rootlets appeared at the proximal side of basal bodies before or at the same time as ciliary budding. After the formation of several striations, the tip of the rootlets extended deeply toward the interior of the cell and became differentiated into two distinct parts, viz., the proximal conical part connected to the basal body and the distal fibrillar part. The periodicity of the striations in the fibrillar part was 68.5±2.95 nm, about 5 nm longer than that of the conical part (63.9±2.25 nm). The dark band in the striation was thicker in the fibrillar part than in the conical part. Since the fibrillar part was not observed in the mature cilium, this part was considered as being either degraded or changed into the conical part during ciliogenesis.
    Materialart: Digitale Medien
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  • 27
    Digitale Medien
    Digitale Medien
    Springer
    Cell & tissue research 290 (1997), S. 623-631 
    ISSN: 1432-0878
    Schlagwort(e): Key words: PECAM-1 (platelet/endothelial cell adhesion molecule-1) ; Endothelium ; HUVEC (human umbilical vein endothelial cells) ; Myocardium ; Ultrastructure ; Human ; Rabbit
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract. The subcellular localization of PECAM-1 in endothelial cells was examined by using advanced morphological techniques, such as confocal scanning microscopy and immunolabeling procedures for electron microscopy. The localization of PECAM-1 was studied immunohistochemically with five specific monoclonal antibodies and one polyclonal antibody (all anti-human) in human and rabbit myocardium and in isolated endothelial cells. In vivo, PECAM-1 was localized uniformly on the plasma membrane of all vascular endothelial cells, predominantly on the luminal side of vessels. No specific increase in labeling was found at sites of cell-to-cell contact. In vitro, primary isolated cells (human umbilical vein endothelial cells) showed continuous labeling of the entire cell membrane. Cells of higher passages were labeled in a manner similar to freshly isolated cells. Our findings refute the commonly accepted hypothesis that PECAM-1 is localized only at cell-to-cell contacts. Further, we have not been able to confirm the hypothesis regarding the important mechanical role of PECAM-1 in stabilizing the endothelial monolayer. Since PECAM-1 is also expressed on platelets and is known to bind to itself, the way in which PECAM-1-positive endothelial cells are protected against binding of PECAM-1-positive platelets remains unclear. In view of these findings, the role of PECAM-1 in the leukocyte migration cascade needs to be re-evaluated.
    Materialart: Digitale Medien
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  • 28
    Digitale Medien
    Digitale Medien
    Springer
    Cell & tissue research 290 (1997), S. 655-664 
    ISSN: 1432-0878
    Schlagwort(e): Key words: Peroxisomes ; Ultrastructure ; Digestive gland ; Acanthochiton crinita ; Lepidochitona cinerea (Mollusca ; Polyplacophora)
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract . This paper presents the first description of peroxisomes in polyplacophorans. As in other molluscs, the hepatopancreas of chitons is composed of basophilic and digestive cells. In the basophilic cells, the endoplasmic reticulum is abundant and several Golgi stacks can be observed. These cells also possess secretion granules and vacuoles with spherites. The digestive cells are mainly characterized by the presence of many food vacuoles. Several peroxisomes were observed in the basophilic cells of Acanthochiton crinita, most of them almost spherical. The matrix is filled with tubular structures and a crystalline nucleoid is also present in these organelles. In the digestive cells of A. crinita, peroxisomes are also almost spherical and possess two kinds of nucleoids. One of them presents a diamond shape and a bundle of tubular structures forms a second kind of nucleoid, which shows an elongated form. In Lepidochitona cinerea, the peroxisomes of basophilic cells are spherical or oval. Within the matrix, a cluster of dense rods and a prismatic nucleoid were observed. In the digestive cells of this species, almost spherical or oval peroxisomes are common, but they are smaller than the peroxisomes of the preceding cells. Nucleoids were not detected, but a few dense rods could be observed in the matrix. In both cell types of the two species, catalase activity was detected in the peroxisomal matrix. In addition, the elongated nucleoid of A. crinita digestive-cell peroxisomes and the nucleoid of L. cinerea basophilic-cell peroxisomes also present catalase activity.
    Materialart: Digitale Medien
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  • 29
    Digitale Medien
    Digitale Medien
    Springer
    Cell & tissue research 290 (1997), S. 71-78 
    ISSN: 1432-0878
    Schlagwort(e): Key words: Development ; Mucosal surface area ; Ultrastructure ; Villus ; Microvillus ; Morphometric analysis ; Chicken
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract. The mucosal surface area of the chicken duodenum, jejunum, and ileum was determined during development (from 1-day to 12-week-old animals). The morphometric analysis was performed at three magnification levels. The nominal (serosal) surface area was determined at the macroscopic level, from intestinal length and perimeter. Villus and microvillus amplification factors were estimated at light-microscopic and transmission electron-microscopic levels, respectively. The results show, during the period considered: (1) a similar increase in nominal surface area for the three segments (6.5 to 7.2-fold), (2) a rise followed by a slight decrease in the villus amplification factor in the third week of age in the duodenum, a two-fold increase of this variable in the jejunum and no significant developmental variations in the ileum, (3) an increase in the microvillus amplification factor of 1.5-fold in the duodenum and jejunum and of 1.2-fold in the ileum, although a pronounced decrease in the first week of age was observed in the three segments. In conclusion, total mucosal surface area increased, from 1 day to 12 week, 12- to 13-fold in the duodenum and ileum and 20-fold in the jejunum.
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  • 30
    ISSN: 1432-0878
    Schlagwort(e): Key words: Kidney (proximal tubule) ; Apical tubule ; Endosome ; Ultrastructure ; Endocytosis ; Membrane recycling ; Rat (Wistar)
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract. The apical cytoplasm of several absorbing epithelia contains well-developed apical tubules (AT) which contribute to membrane recycling from endocytic vacuoles to the apical cell membrane. In this study, we examined three-dimensional structures of the AT in rat kidney proximal tubule cells by transmission and scanning electron microscopy. In thin sections, the AT appeared as straight tubules with a rather constant diameter (70–90 nm), but others were curved and, occasionally, branching. No AT were labeled with the marker for the external cell surface (ruthenium red) or exhibited histochemical enzyme activity for lysosomal hydrolase (acid phosphatase). After intravenous injection of horseradish peroxidase, it was absorbed in the kidney proximal tubule cells and the AT were labeled with HRP reaction products. Stereo-viewing of the labeled AT in thick sections revealed that they formed an interconnected tubular network. Scanning electron microscopy allowed a three-dimensional view of the AT, in which a network of branching and anastomosing tubules was revealed. These observations indicate that the AT are intracellular endosomal compartments which form an extensive tubular network in the apical cytoplasm. The possibility that this apical tubular network serves as a large membrane store for membrane recycling is discussed.
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  • 31
    ISSN: 1615-6102
    Schlagwort(e): Cell differentiation ; Immunolocalisation ; Nitrogenase ; Non-heterocystous cyanobacteria ; Trichodesmium ; Ultrastructure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Summary Trichodesmium is the first described example of a filamentous cyanobacterium without heterocysts that contains cells specialised for nitrogen fixation. The ultrastructure of cells with and without nitrogenase were compared using primarilyTrichodesmium tenue Wille, but alsoT. thiebautii Gomont andT. erythraeum Ehrenberg et Gomont. Immunohistochemistry demonstrated that the cytoplasm of certain cells was densely labelled with antibodies against Fe-protein (dinitrogenase reductase). Comparative TEM-image analysis revealed that these cells were also distinguished by a denser thylakoid network, dividing the vacuole-like space into smaller units. The nitrogenase-containing cells also exhibited less extensive gas vacuoles as well as fewer and smaller cyanophycin granules compared to cells which lacked nitrogenase. Carboxysomes were present in both cell types in equal proportion. Longitudinal sections showed that cells with nitrogenase were arranged adjacent to each other, and that groups of cells with and without nitrogenase may coexist in the same trichome. The correlation between modifications in ultrastructure and the presence of nitrogenase suggests a new type of cyanobacterial cell specialisation related to nitrogen fixation. The results obtained also question the systematic affiliation of the genusTrichodesmium.
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  • 32
    Digitale Medien
    Digitale Medien
    Springer
    Protoplasma 200 (1997), S. 31-34 
    ISSN: 1615-6102
    Schlagwort(e): Blastocystis hominis ; Central vacuole ; Accumulation ; Basic proteins ; Ultrastructure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Summary Basic proteins ofBlastocystis hominis were detected by the ammoniacal silver and ethanolic phosphotungstic acid techniques using electron microscopy. The central vacuole showed many silver grains when treated with ammoniacal silver and an increased electron density when treated with phosphotungstic acid. The intensity of positive reactions correlated with the electron density of the central vacuole, because cells having an electron-lucent central vacuole showed no silver grain deposits. Since it is known that the concentration of electron-dense materials in the central vacuole increases during log phase of growth, and then decreases in stationary phase, this organelle must accumulate basic proteins during cell growth.
    Materialart: Digitale Medien
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  • 33
    ISSN: 1573-5052
    Schlagwort(e): Algae ; Chloroplast ; Micrasterias ; Photosynthesis ; Ultrastructure ; UV-B
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract Exposure of postmitotic growing and non-growing cells of the unicellular green alga Micrasterias denticulata to different UV-B cut-off wavelengths together with simulated sunlight in a sun simulator has revealed a marked resistence of the algae against strong irradiation. While down to a cut-off wavelength of 284 nm irradiated during the most sensitive stage of cell development chloroplast ultrastructure remains unaffected, severe changes in arrangement and structure of stroma and grana thylakoids occur only at the lowest cut-off wavelengths of 280 and 275 nm. The structural alterations end up in a more or less complete desintegration of grana and stroma thylakoids with the remaining membraneous structures appearing in negative staining thus indicating drastic changes in membrane composition. Photosynthetic activity determined by chlorophyll fluorescence (ratio of variable to maximal fluorescence) and oxygen evolution responded more sensitively to UV-B irradiation. With decreasing UV cut-off wavelengths and prolonged incubation a decrease of photochemistry of PS II occured reaching its lowest values after 60 min at 275 and 280 nm. Oxygen production was even maintained under strong UV irradiation with a cut-off wavelenght of 275 nm up to 15 min. With prolonged UV-B treatment any activity was lost. HPLC separations of pigments exhibited the appearance of break-down products (mainly derivatives of chl b and chl a) with decreasing cut-off wavelength and increasing exposure time. The xanthophyll cycle pigments seemed to be unaffected at least for an irradiation period of 60 to 90 min at low UV cut-offs. Possible mechanisms of UV stress avoidance or protection are discussed with regard to the varying altitudes of the natural habitats of the algae.
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  • 34
    ISSN: 1573-5117
    Schlagwort(e): Riseriellus occultus ; Heteronemertea ; Proboscis ; Ultrastructure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract We have examined with transmission electron microscopythe epithelial layer exposed to the rhynchocoel fluidof the proboscis in the heteronemertine Riseriellus occultus. This epithelium is organized asa monociliated, pseudostratified myoepitheliumconsisting of two cell types: apically situatedmonociliated supportive cells and subapical myocyteslacking cilia. The low supportive cells form acontinuous adluminal sheet and reach with numerouscytoplasmic processes into the extracellular matrix;these cells are characterized by numerous, irregularlyshaped, apical folds projecting into the rhynchocoelfluid, delimiting broad extracellular spaces. Theauthors suppose that both apical and basal folds couldaccommodate stretching of the endothelium when theproboscis is everted. The apical folds of thesupportive cells increase the interface of these withthe rhynchocoel fluid; this feature, together with thepresence of pinocytotic vesicles in such cells,suggest that they could be involved in the exchange ofsubstances between the rhynchocoel fluid and theproboscis. The myocytes are scattered singly withinthe monociliated pseudostratified myoepithelium. Theyare situated between the supportive cells and thesubjacent extracellular matrix. Basement membraneseparating both cells types is lacking. Myofibrillarparts protrude basally from the myocyte somata. Themyofibrillar parts lie in direct apposition to theextracellular matrix, and are oriented circular to thelongitudinal axis of the proboscis. We consider themyocytes to be intra-epithelial, myoepithelial cells.
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  • 35
    Digitale Medien
    Digitale Medien
    Springer
    European archives of oto-rhino-laryngology and head & neck 254 (1997), S. 196-199 
    ISSN: 1434-4726
    Schlagwort(e): Nasopharyngeal angiofibroma ; Ultrastructure ; Myofibroblast ; Immunohistochemistry ; Electron microscopy
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract Twenty-eight cases of nasopharyngeal angiofibroma were studied immunohistochemically for cytoskeletal phenotyping of stromal cells. Electron microscopy was also used to study the ultrastructure of five of the tumors. All typical stromal cells showed intensive immunostaining for vimentin, but were negative for smooth muscle actin and desmin. Ultrastructurally, most of these cells appeared to be exclusively fibroblasts. However, in some areas stromal cells were seen that morphologically resembled myofibroblasts by their shapes and arrangement, and were characterized by the coexpression of vimentin and smooth muscle actin. Electron microscopy confirmed their myofibroblastic nature. The present study showed that the typical stromal cells in nasopharyngeal angiofibromas were fibroblasts and not myofibroblasts. In these tumors myofibroblasts occurred only focally, in connection with fibrotic areas and exclusively as a vimentin+/actin+ cytoskeletal phenotype. This indicates that myofibroblasts are not primary stromal tumor cells in nasopharyngeal angiofibromas, but occur due to regressive changes.
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  • 36
    Digitale Medien
    Digitale Medien
    Springer
    European archives of oto-rhino-laryngology and head & neck 254 (1997), S. 73-77 
    ISSN: 1434-4726
    Schlagwort(e): Development ; Stria vascularis ; Spiral ligament ; Ultrastructure ; Rat cochlea
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract The ultrastructural morphology of the interface region between the stria vascularis (SV) and spiral ligament (SL) was examined in the neonatal rat cochlea via transmission electron microscopy. At postnatal day (PND) 3, morphology of both basal cells and fibrocytes was simple and immature. Only a small number of fibrocytes was observed in the SL. Intercellular junctions between basal cells and fibrocytes, and between adjacent fibrocytes, were few. At PND 7, the number of fibrocytes increased, and more organelles appeared within their cytoplasm. From PND 11 to 14, nuclei of the basal cells appeared to be more spindle-shaped and contained more heterochromatin. The cytoplasm of the fibrocytes was pale, and a greater number of cytoplasmic vesicles and mitochondria emerged. More intercellular junctions were observed between basal cells and fibrocytes at the interface region and between fibrocytes in the SL. By PND 21, the morphology of basal cells and fibrocytes and their intercellular junctionsappeared to be adult-like. These morphological observations correlate with previous reports on the functional maturation of the developing rat cochlea.
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  • 37
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 244 (1997), S. 43-66 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The market development of bisphenol-A-polycarbonate has shown higher growth than any other engineering thermoplastic. The reasons can be found in the permanent improvement of the cost/performance-relationship and in the technical use of the variability of the basic structure. Incorporation of specific monomer units leads to tailor-made properties for a wide range of applications, as for example medical devices, electronic parts and glazing.This process has not yet slowed down, rather it is accelerated by new results from research and development. The improvement of flaw behavior and pit replication for new grades of materials for the next generation of compact discs, new grades that can be sterilized by γ-radiation without degradation and the microstructuring by low-energy laser systems are examples for the ongoing expansion of polycarbonate applications. Surface modification by hardcoatings with nanosized particles will allow to enter the fast growing market of glazing.
    Zusätzliches Material: 27 Ill.
    Materialart: Digitale Medien
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  • 38
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 244 (1997), S. 67-92 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: Polyamide, Polyester und Polyoxymethylen sind mit einem weltweiten Verbrauch von derzeit 2,4 Mio t pro Jahr wichtige technische Kunststoffe. Sie werden aufgrund ihrer besonderen Eigenschaftsprofile überwiegend im Fahrzeugbau und in der Elektroindustrie für hochbelastete Funktionsbauteile eingesetzt. Der vorliegende Beitrag behandelt Polymerisationswege, Eigenschaften und ausgewählte neue Entwicklungen dieser Polymerklassen.Teilaromatische Polyamide stoßen durch ihre Dimensionsstabilität und thermische Belastbarkeit in Anwendungen vor, die bisher Duromeren oder Metallen vorbehalten waren. Glasfaserverstärkte Polyamide mit besonders hoher Dauerwärmebeständigkeit übemehmen wichtige Funktionen im Motorbereich von Fahrzeugen. Polyamid-Blends sind als Karosseriewerkstoffe ein Schlüssel zu leichten Autos mit niedrigem Treibstoffverbrauch. Halogenfrei flammgeschützte Polyamide erhöhen Sicherheit und Umweltverträglichkeit in brandgefährdeten Anwendungsbereichen.Polybutylenterephthalat als technisch wichtigster Polyester eröffnet in Mischung mit amorphen Polymeren neue Perspektiven durch geringerenVerzug und bessere Oberfläche bei glasfaserverstärkten Teilen. Polybutylennaphthalat erweitert den Anwendungsbereich zu höheren Temperaturen. Von Polybutylenterephthalat abgeleitete Copolyester sind biologisch abbaubar und daher vielversprechend für kompostierbare Folien.Polyoxymethylen-Copolymere haben ihre Stärke in der günstigen Kombination aus Steifigkeit, Dimensionsstabilität, Gleit/Reibe-Verhalten und Beständigkeit gegen heißes Wasser und Kraftstoff.Aufgrund ihres hohen und noch weiter steigerungsfähigen Leistungsvermögens werden Polyamide, Polyester und Polyoxymethylen das in den letzten Jahren gezeigte Wachstum in Zukunft weiter ausbauen können.
    Notizen: Polyamide, polyester and polyoxymethylene having presently a worldwide sales volume of 2,4 million tons a year are important engineering thermoplastics. Based on their special property profiles they are mainly used in the automotive and electronic industry for high performance functional parts. This contribution presents polymerisation processes, properties, and selected new developments for these polymer classes.Semiaromatic polyamides due to their dimensional stability and thermal resistance lend themselves to applications which were so far reserved for thermosets or metals. Glass fiber reinforce polyamides designed to have the highest possible heat ageing resistance can take important functions under the hood. A polyamide blend used as a material for exterior body parts is key to light weight cars with strongly reduced fuel consumption. Halogene free flame retardant polyamide increases fire safety and environmental safety in flame sensitive applications.Polybutyleneterephthalate as the technically most important polyester offers new perspectives in blends with amorphous polymers leading to lower distortion and better surface quality in glass fiber reinforced parts. Polybutylenenaphthalate is widening the range of application of polyesters towards higher temperatures. Copolyesters derived from polybutyleneterephthalate are biologically degradable and are therefore promising materials for fermentable foils.Polyoxymethylene copolymers show an outstanding combination of stiffness, dimensional stability, friction and wear as well as resistance against hot water and fuel.As a result of their excellent properties and the existing potential for further improvements polyamide, polyester and polyoxymethylene will continue to grow above average in the future.
    Zusätzliches Material: 18 Ill.
    Materialart: Digitale Medien
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  • 39
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 244 (1997), S. 121-133 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The world-wide production of polyurethanes has exceeded 6 mio. metric tons in 1994. Compared with the produced amounts of large-scale thermoplastics such as PE, PVC, PP and PS, polyurethanes keep the 5th place.Polyurethanes (PUR) are segmented polymers, which can be synthesized from preformed building blocks in a modular unit construction system. The chemical modules and the various possibilities of combination will be discussed here.Tailor-made polyurethane materials can be divided into two main-fields of application: foams and compact PUR.The main constituents of polyurethane materials are diisocyanates and polyols. These key- chemicals are well characterised with respect to their technological, economical and ecological properties. Taking into account the availability, the masses of production and the experiences that have been collected with the PUR main constituents, these PUR precursors seem to be very mature already.In contrast to this, the PUR-materials made from these building blocks still offer numerous novel problem-solutions, resulting from the variability of the diisocyanate-poly-addition reaction: PUR materials are most commonly segmented into several phases. The formation of hard- and softsegments can be easily demonstrated by looking at thermoplastic polyurethanes (TPU). A deeper understanding of this phase separation and the molecular organisation within these materials promises to realize prospectic polymeric architectures with new and improved properties. PUR materials will still be able to offer new answers to future requirements in balancing economical and ecological needs. By looking at the life-cycles of soft and hard-foams, polyurethane-coatings and thermoplastic PUR-elastomers, this contribution will adress the question: “Is PUR-chemsitry still a challenging field?”
    Materialart: Digitale Medien
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  • 40
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 245 (1997), S. 23-35 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: Die Zugabe von 10-20 Gew.-% Kaliumnitrat (KN03) zu Polyamid 6 (PA 6) vermindert die Brennbarkeit des Polymeren. Das thermische Verhalten der KN03/PA 6-Mischung wurde mittels Thermogravimetrie, Differentialkalorimetrie und Analyse der fluchtigen Anteile untersucht. Feste Zersetzungsprodukte der Mischung wurden mittels Infrarotspektroskopie, Rontgendiffraktometrie und Elektronenresonanzspek-'troskopie analysiert. Es wurde gefunden, daß KNO3 dem Flielßen und Tropfen der Schmelze vorbeugt und die Karbonisierung auf der Oberflache des Polymeren fordert. Das verringert die Brandgefahr und verbessert die Feuerbestandigkeit. Andererseits geht KNO3 mit PA 6 in der kondensierten Phase eine exotherme Reaktion ein und setzt Sauerstoff frei, der wiederum die Brennbarkeit von PA 6 begiinstigt. Der Mechanismus der chemischen Wechselwirkung van KNO3 mit PA 6 wird diskutiert.
    Notizen: The addition of 10-20 wt.-% of potassium nitrate (KNO3) to polyamide 6 (PA 6) improves the fire retardance of the polymer. The thermal decomposition behaviour of the PA 6/KN03-mixture was studied using thermogravimetry, differential scanning calorimetry and thermal volatilisation analysis. Solid products of the thermal decomposition of the mixture were analysed by infrared spectroscopy, X-ray diffraction and electron paramagnetic resonance. It was found that KNO, prevents flowing and dripping of the melt and promotes charring on the surface of the polymer which decreases its fire hazard and improves its fire retardance. On the other hand, KNO3 exothermally reacts with PA 6 in the condensed phase and supplies oxygen to the gas phase which increases the combustibility of PA 6. The mechanism of the chemical interaction of KN03 with PA 6 is discussed.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 41
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 245 (1997), S. 49-62 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: Der Einfluß einer Beimischung von Tricalciumphosphat (TCP), Hydroxyethylmethacrylat (HEMA) und Ethylenglycoldimethacrylat (EGDMA) auf die Eigenschaften eines chirurgischen Knochenzements wurde untersucht. Die in Zugversuchen entstandenen Bruchflächen wurden mittels Rasterelektronenmikroskopie charakterisiert. Der Einfluß der Additive auf den Temperaturanstieg während der Polymerisation wurde geprüft. Zug-, Biege- und Druckfestigkeit des ausgehärteten Zements nahmen mit zunehmendem TCP-Gehalt ab, der Elastizitätsmodul stieg dagegen an. Die Zugfestigkeit nahm mit steigendem HEMA-Gehalt geringfügig zu und blieb oberhalb 15 Gew.-% HEMA konstant. Zug-, Biege- und Druckfestigkeit zeigten bei einem EGDMA-Gehalt von 2 Gew.-% (in HEMA) ein Maximum. HEMA und EGDMA beschleunigten die Polymerisation, wogegen TCP retardierend wirkte.
    Notizen: The effects of the addition of tricalcium phosphate (TCP), hydroxyethyl methacrylate (HEMA), and ethylene glycol dimethacrylate (EGDMA) on the properties of standard surgical Simplex-P radiopaque bone cement have been investigated. The fracture surface after tensile test was studied by scanning electron microscopy. The influence of these components on the temperature rise during polymerization was investigated. It was found that the tensile strength, the bending strength, and the compressive strength decreased with increasing TCP content, whereas the inverse was observed for the Young's modulus. The tensile strength slightly increased with increasing HEMA content and then it levelled off when the HEMA content was higher than 15 wt.-%. It seemed that there were maximum tensile, bending and compressive strengths when 2 wt.-% EGDMA (in HEMA) was added. Polymerization occurred more rapidly when HEMA and EGDMA were added, whereas the inverse result was found with TCP.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 42
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 245 (1997), S. 89-104 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: Polyurethanelastomere wurden in Gegenwart von zwei Dihydroxynaphthalin(DHN)-Verbindungen und deren bromierter Derivate als Kettenverlängerer hergestellt. Als Polyole wurden Polycaprolactondiol und Polytetramethylenglykol und als Diisocyanat-Komponenten Diphenylmethandiisocyanat (MDI) und Dicyclohexylmethan-4,4′-diisocyanat (HMDI) eingesetzt. Der Einfluß der Struktur der Kettenverlängerer auf die physikalischen und thermischen Eigenschaften der Polyurethane wurde untersucht. Wegen der besseren Phasenmischungswirkung der 1,5-DHN-Segmente haben die damit hergestellten Polyurethane höhere Glasübergangstemperaturen und bessere dynamische Eigenschaften als die Polyurethane auf 2,7-DHN-Basis. Der Einbau von bromierten DHN-Einheiten erschwert die Entflammbarkeit. Durch das große freie Volumen der Bromatome wird jedoch die Rotation der DHN-Einheiten eingeschränkt, was zu Polyurethanen mit verringerten Phasenmischungs- und Kristallisationsgraden führt. Die bromhaltigen Polyurethane zeigen zudem eine Verschlechterung der mechanischen und physikalischen Eigenschaften und eine erhöhte Löslichkeit.
    Notizen: Polyurethane elastomers were synthesized based on polyols such as poly(caprolactonediol) and poly(tetramethylene glycol), diisocyanates such as diphenylmethane-4,4′-diisocyanate (MDI) and dicyclohexylmethane-4,4′-diisocyanate (HMDI), and two dihydroxynaphthalenes (DHNs) and their brominated derivatives used as chain extenders. The effects of the chemical structures of the chain extenders on the physical and thermal properties of the polyurethanes were investigated. Because of the higher degree of phase mixing of the 1,5-DHN unit, the 1,5-DHN-based polyurethanes have higher Tg values and higher dynamic properties than 2,7-DHN-based polyurethanes. Introduction of bromine atoms increased the flame retardance. However, the large free volume of bromine atoms restricted the rotation of DHNs, thus, directly decreasing the degree of phase-mixing and crystallinity of the polyurethanes. Introducing bromine atoms also decreased the mechanical and dynamic properties and increased the solubility of the polyurethanes.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 43
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 245 (1997), S. 139-147 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: Aus Poly(oxytetramethylen), 4,4′-Bibenzyldiisocyanat, N-Methyldiethanolamin als Kettenverlängerer und Acrylsäure/Polyacrylsäure als Quaternisierungsagens wurden Poly(etherurethan)-Kationomere hergestellt. In aus diesen Kationomeren hergestellten Filmen wurde Pyrrol (15 Gew.-%) in Gegenwart von CuCl2 polymerisiert. Die Filme wurden mittels dynamisch-mechanischer Analyse, Thermogravimetrie und Differentialthermoanalyse charakterisiert. Die elektrische Leitfähigkeit beträgt für den Film ohne Polypyrrol 7.5 · 10-12 Ω-1 cm-1 und mit Polypyrrol 4.5 · 10-6 Ω-1 cm-1.
    Notizen: Poly(ether urethane) cationomers based on poly(oxytetramethylene), 4,4′-bibenzyldiisocyanate, N-methyldiethanolamine as chain extender, and acrylic acid/poly(acrylic acid) as quaternization agent were synthesized. Pyrrole (15 wt.%%) was polymerized in films of the ionomer containing CuCl2. The films were characterized by dynamic mechanical analysis, thermogravimetry and differential scanning calorimetry. The electric conductivity of the film without polypyrrole is 7.5 · 10-12 Ω-1 cm-1, while incorporation of polypyrrole increases the conductivity to 4.5 · 10-6 Ω-1 cm-1.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 44
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 245 (1997), S. 155-164 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: Wachsartige Monomere und Vernetzer wurden aus kommerziellen Wachsen durch Veresterung mit 2-Hydroxyethylmethacrylat, Glycerindimethacrylat oder Glycidylmethacrylat oder durch Funktionalisierung mit 2-Isocyanatoethylmethacrylat synthetisiert. Die erhaltenen opaken Methacrylate mit Schmelzpunkten zwischen 45 und 80°C wurden in Substanz bzw. Toluollösung in Gegenwart von Radikalinitiatoren polymerisiert. Die Polymeren zeichnen sich durch eine breite Molmassenverteilung aus. Im Gegensatz zur Substanzpolymerisation ist der Doppelbindungsumsatz nach der Lösungspolymerisation nahezu vollständig. Aufgrund der hohen Molmasse der Monomeren ist der beobachtete Polymerisationsschrumpf sehr gering. Polymerisate mit Vernetzermonomeren zeigen eine verbesserte mechanische Stabilität.
    Notizen: Waxy monomers and crosslinkers, respectively, were synthesized from commercially available waxes by esterification with 2-hydroxyethyl methacrylate, glycerol dimethacrylate, or glycidyl methacrylate or by functionalization with 2-isocyanatoethyl methacrylate. The resulting opaque methacrylates with melting points between 45 and 80°C were polymerized in bulk and in toluene solution in presence of free radical initiators. The obtained polymers were characterized by a broad molecular weight distribution. Opposite to the bulk polymerization, the double bond conversion in solution polymerization is nearly quantitative. The observed volume shrinkage during polymerization is very low due to the high molecular weight of the monomers. Polymerizates containing crosslinking comonomers exhibit improved mechanical stability.
    Zusätzliches Material: 5 Tab.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 45
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 245 (1997), S. 165-181 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: The stabilized free-radical precipitation polymerization of the cationic monomer N-(2-methacryloyloxyethyl)-N,N-dimethylbenzylammonium chloride (MADAMBQ) in aqueous solutions of sodium chloride was studied by reaction calorimetry. Poly(ethylene oxide) was used as stabilizer. The rate of polymerization reaches its maximum immediately after initiation and remains nearly constant up to 50 % conversion followed by a decrease that could be described by a first order kinetics. The particles formed are approximately 1 to 30 μm in diameter and are stable over a period of several months.A model based on the theory of homogeneous particle nucleation is suggested to describe the kinetic course of polymerization, taking into account the rate of polymerization in both phases. With the assumption that the concentration of monomer in the phases is determined by a Nernst distribution law, the kinetics of the early stage of polymerization can be modelled reasonably well.The solution polymerization and the unstabilized precipitation polymerization of MADAMBQ was also studied.
    Notizen: Die Kinetik der stabilisierten Fällungspolymerisation des kationischen Monomeren N-(2-Methacryloyloxyethyl)-N,N-dimethylbenzylammoniumchlorid (MADAMBQ) in wäßrigen Natriumchlorid-Lösungen wurde mittels Reaktionskalorimetrie untersucht. Polyethylenoxid höherer Molmasse wurde als Stabilisator eingesetzt. Die Reaktionsgeschwindigkeit ist über einen größeren Umsatzbereich nahezu konstant und fällt anschließend mit dem Umsatz annähernd linear ab. Die Teilchengrößenverteilung der gebildeten Dispersion ist bimodal mit Teilchen von etwa 1 bis 30 μm Durchmesser.Zur Beschreibung des Geschwindigkeitsverlaufs der Fällungspolymerisation wird ein Modell vorgeschlagen, das die Polymerisation in der Wasser- sowie in der Polymerphase berücksichtigt. Die Teilchenbildung soll durch homogene Nukleierung erfolgen. Es wird angenommen, daß die Konzentration des Monomeren in den Phasen durch ein Nernstsches Verteilungsgleichgewicht bestimmt wird. Zu Vergleichszwecken wurde auch die Polymerisation von MADAMBQ in Lösung und als nicht stabilisierte Fällungspolymerisation durchgeführt.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 46
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 246 (1997), S. 1-9 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: Cellulosepulver, hergestellt durch Nitrierung von Eichen-Furfural-Lignocellulose, wurde mit Acrylamid radikalisch gepfropft. Die Pfropfreaktion wurde sowohl in Gegenwart eines äußeren Magnetfeldes (0,15-0,35 T) als auch ohne Magnetfeld durchgeführt. Der Einfluß von Monomerkonzentration, Initiatorkonzentration, Polymerisationszeit und temperatur sowie der magnetischen Feldstärke auf den Polymerisationsverlauf wurde untersucht. Es wurde festgestellt, daß der Pfropfumsatz mit zunehmender Feldstärke signifikant ansteigt.
    Notizen: Cellulose powder obtained from oak furfural lignocellulose by nitration reaction was grafted with acrylamide using a radical initiation. The grafting reactions were carried out and compared both in presence and in absence of a continuous external magnetic field with the intensity extended between 0.15-0.35 T. The effect of monomer and initiator concentration, time and temperature of reaction and magnetic field intensity onto the grafting process were examined. It was observed that the presence of a magnetic field leads to a significant increase of the graft conversion.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 47
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: Poly(L-milchsäure) ist ein biokompatibler, semikristalliner, thermoplastischer Polyester mit ungünstigen mechanischen Eigenschaften. Daher wurde in einem “reactive blending”-Prozeß ein Acrylkautschuk, n-Butylacrylat, mittels einer Suspensionspolymerisation in Wasser auf in einem organischen Lösungsmittel gelöste Poly(L-milchsäure) gepfropft. Die gebildeten Copolymeren konnten isoliert und durch NMR-Spektroskopie und DSC-Messungen charakterisiert werden. Die Untersuchung der mechanischen Eigenschaften ergab keine befriedigenden Ergebnisse, weil die Kautschukphase wahrscheinlich aus viskosen linearen Makromolekülen besteht und daher keine elastischen Eigenschaften besitzt. In weiteren Arbeiten soll der Syntheseweg so modifiziert werden, daß durch den Einbau von Diacrylaten eine zumindest partielle Vernetzung der Kautschukphase erreicht wird.
    Notizen: Poly(L-lactic acid) is a biocompatible polyester, semicrystalline, thermoplastic, with low versatility in mechanical properties. To overcome this problem, a reactive blending procedure was performed by grafting an acrylic rubber, n-butyl acrylate, via water suspension polymerization onto poly(L-lactic acid) dissolved in an organic solvent. It was possible to isolate the copolymeric phase formed from the two polymers and characterize it by using NMR and DSC techniques. Mechanical tests on blends gave no satisfactory response, probably because the rubbery phase is composed essentially of viscous linear macromolecules, not able to perform elastic properties. Work is in progress to modify the synthetic pathway to incorporate diacrylates in order to realize a rubbery phase at least partially cross-linked.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 48
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: Zur Entwicklung von neuen Styrol-Butadien-Kautschuken (SBRs) für Reifenanwendungen sind mehrere Arten von Zinn-Polymer-Bindungen (Styryl-, Butadienyl-, Isoprenyl- and α-Methylstyryl-Zinn) sowohl in linearen als auch in verzweigten Ketten untersucht worden. Die dynamisch-mechanischen Eigenschaften von Vulkanisaten mit Ruß wurden analysiert, um eine Beziehung zwischen den Strukturparametern der Polymeren und den Materialeigenschaften herzustellen. Der Polymer-Füll-stoff-Wechselwirkungsparameter, der durch das Verhältnis von mechanischen und dynamischen Termen definiert ist, wurde zur Charakterisierung der Verbindungen herangezogen. Der Einbau von verschiedenen Zinn-Polymer-Bindungen in lineare und in verzweigte SBR-Ketten bewirkte eine Verbesserung der Hystereseeigenschaf-ten der Vulkanisate und eine Veranderung des Wechselwirkungsparameters.
    Notizen: Following the development of new SBRs for tyre applications, several kinds of tin-polymer bonds (styryl-, butadienyl-, isoprenyl- and α-methylstyryltin) have been studied, in both branched and linear chains.Dynamic-mechanical properties of the carbon black vulcanizates have been analyzed to establish a relationship between structural parameters of polymers and compound properties. The filler-polymer interaction parameter, defined by a ratio of mechanical and dynamic terms, has been used for the evaluation of the compounds. The introduction of different types of tin-polymer bonds, in branched and linear chains of the SBRs, implies an improvement in the hysteresis properties of the vulcanizates as well as a modification of the interaction parameter.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 49
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: Copoly (amid-ether) rnit zwei unteschiedlichen Aminfunktionalitäten wurden als antistatische Modifikatoren für Polyethylenterephthalatfasern (PET) eingesetzt. Die tertiären Aminogruppen schmelzegesponnener Copolymerfilamente wurden rnit drei Alkylierungsmitteln umgesetzt, wobei ein Sulfobetain, ein Carbobetain bzw. Ammoniumionen gebildet wurden. Dadurch wurde der scheinbare spezifische Widerstand der Filamente auf größfienordnungsmäßfiig 106 bis 108 Ω/cm verringert. Da sich die quaternisierten Copolymeren beim Blend-Spinnen rnit PET zersetzen, wurden Blendfasern von PET mit einem Copolymeren nach dem Schmelzespinnen einer Quaternisierung oder Vernetzung rnit Alkylierungsmitteln bzw. Epoxyvernetzern unterzogen, was die antistatischen Eigenschaften der Fasern im Vergleich rnit der unbehandelten Faser verbesserte. Insbesondere die mit Epoxiden vernetzten Fasern wiesen antistatische Eigenschaften auf, wie sie mit dieser Modifizierungsmethode bislang nicht erreicht wurden. Die antistatischen Eigenschaften blieben nach dem Fkben erhalten, da sowohl die hydrophilen als auch die ionischen Gruppen auf der Faseroberflache immobilisiert waren. Da Quaternisierung bzw. Vernetzung in einem Arbeitsgang rnit dem Verspinnen und Verstrecken der Fasern innerhalb einer kurzen Reaktionszeit erfolgen, sollte diese “spin-finishing„ genannte Methode konventio- nellen Verfahren bezuglich Kosten und Produktivitat uberlegen sein.
    Notizen: Copoly(amide-ethers) containing two types of tertiary amine units were made as antistatic modifiers for poly(ethylene terephthalate) (PET) fibers. The filaments of the copolymers were melt-spun and reacted with three alkylating agents in order to quaternize the tertiary amine into a sulfo-betaine, a carbobetaine, and an ammonium ion. The apparent electric resistivity of the filaments was greatly reduced by this reaction, being in the range of 106 to 108 Ω/cm. However, because these quaternized copolymers incurred decomposition during blend spinning with PET, a blend PET fiber containing one type of copoly(amide-ether) was melt-spun and subjected to quaternization of the amino groups as well as to surface crosslinking with various alkylating and epoxy agents. The quaternized blend fibers obtained showed improved antistatic properties compared with the original blend fiber. Particularly, the fibers crosslinked with epoxy compounds were found to have the best antistatic properties that had ever been attained with this type of modification. The antistatic properties were retained even after dyeing, because both hydrophilic and ionic groups had been effectively immobilized on the surface. Since this quaternization and crosslinking could be conducted on-line with spinning and drawing within a short reaction time, this modification technique is called “spin-finishing method”, which should be superior to the conventional methods in terms of cost performance and productivity.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 50
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 249 (1997), S. 33-46 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: Filme aus Polyethylen niedriger Dichte (LDPE) wurden mit rauchender Salpetersäure behandelt. Die Oberflächeneigenschaften sowie die Bildung polarer Gruppen wie auf der geätzten Filmoberfläche wurden mit SEM-, IR- und XPS-Methoden analysiert. Die mechanische Festigkeit eines aus dem geätzten LDPE-Film und einem Epoxidharz hergestellten Laminats sowie die Bedruckbarkeit der geätzten Oberflächen wurden untersucht und mit einer unbehandelten Probe verglichen. Die Oberflächenrauhigkeit und die Gegenwart polarer Gruppen erhöhen die mechanische Festigkeit des Laminats aus dem geätzten Film durch mechanische Verankerung und chemischer Wechselwirkungen. Die Oberfläche des behandelten LDPE-Films ist besser bedruckbar als die des unbehandelten Films.
    Notizen: Low-density polyethylene (LDPE) films were treated with fuming nitric acid (FNA). The surface characteristics and also the insertion of polar groups like on the etched LDPE film surface were measured by SEM, IR and XPS analyses, respectively. The mechanical performance of a laminate of the etched film with epoxy resin and also the printability of the etched film surface were tested and compared with the unetched sample. The surface roughening and the presence of polar groups enhance the mechanical strength of the laminate of FNA-treated film due to mechanical interlocking and chemical interaction. The printability of the treated film surface is also superior to that of the untreated LDPE film surface.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
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  • 51
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 249 (1997), S. 11-32 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: This paper reports on polymer membranes characterized by a surface layer of hydroxyalkyl derivatives of cellulose. Water compatible polymers like hydroxyalkyl derivatives of cellulose are preferably those exhibiting good chemical stability and desired membrane characteristics. Normally, water-compatible polymers used in the coating solutions must be rendered water-insoluble after coating. By adapting crosslinking conditions on separation problems, the membranes are useful for many processes in the fields of biotechnology, food and chemical industry.The membranes presented here possess the advantage of being highly resistant to chemical and biological degradation and, hence, have long lifetimes under many process conditions.
    Notizen: Es wird die Entwicklung hydrophiler Polymermembranen diskutiert, die nach Beschichtung mit Celluloseethern und anschließender Vernetzung auf den asymmetrischen Trägermembranen interessante Permeations- und Trenneigenschaften bei hervorragenden chemischen Stabilitäten, vor allem beim Membrantrennverfahren der Nanofiltration, aufzeigen. Weiterhin werden Aussagen zu den Gastrenneigenschaften der Celluloseetherkompositmembranen getroffen.Erläutert werden die Permeations- und Trenndaten der Kompositmembranen in Korrelation zur Vernetzung der Celluloseether anhand verschiedener Einflußgrößen, was qualitative und gegebenenfalls quantitative Aussagen zum Vernetzungsmechanismus der Celluloseetherderivate erlaubt. Dabei stehen die Vernetzungstemperatur, der Einfluß der katalysierenden Wasserstoffionen und bedingt die Vernetzungszeit im Vordergrund. Abgerundet werden die Arbeiten durch Ermittlungen rheologischer Daten, die in Zusammenhang zu den Vernetzungsreaktionen und damit zu membranspezifischen Größen stehen.Infolge der hervorragenden chemischen Stabilität der Celluloseether werden Einsatzmöglichkeiten der Kompositmembranen zur Nanofiltration niedermolekularer Verbindungen aus organisch hochbelasteten Systemen beschrieben.
    Zusätzliches Material: 30 Ill.
    Materialart: Digitale Medien
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  • 52
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 251 (1997), S. 13-21 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: Polysulfide wurden mit hoher Ausbeute durch Hochtemperatur-Lösungspolykondensation von 4,4′-Dimercaptobiphenyl mit ausgewählten aliphatischen und aromatisch-aliphatischen Dihalogenkohlenwasserstoffen hergestellt. Um die optimalen Polykondensationsbedingungen zu bestimmen, wurde der Einfluß folgender Faktoren auf die reduzierte Viskosität und die Ausbeute der Polysulfide ermittelt: Art des organischen Lösungsmittels, Art des Halogenwasserstoff-Akzeptors, Konzentration der organischen Reagenzien, Reaktionstemperatur und -zeit. Die Polykondensation des Dithiols mit Bis(4-chlormethylphenyl)methan wurde als Modellsystem eingehender untersucht. Die Polysulfidstrukturen wurden mittels Elementaranalyse, IR-Spektroskopie und Röntgenstrukturanalyse bestätigt. Aus der thermogravimetrischen Analyse wurden die Zersetzungstemperatur, der Gewichtsverlust bei dieser Temperatur und das Maximum der Zersetzungsgeschwindigkeit erhalten. Weiterhin wurden einige physikalisch-chemische, mechanische und dielektrische Eigenschaften ermittelt. Die beste thermische und chemische Bestandigkeit zeigt das aus dem Dithiol und 4,4′-Bis(chlormethyl)biphenyl hergestellte Polysulfid, was auf dessen vorwiegend aromatische Struktur zuriickgefuhrt werden kann.
    Notizen: Polysulfides were synthesized with high yield by high-temperature solution polycondensation of 4,4′-biphenyldithiol with selected aliphatic and aromatic-aliphatic hydrocarbon dihalides. To determine the optimum polycondensation conditions, the influence of the following factors on reduced viscosity and yield was studied: type of organic solvent, type of hydrogen halide acceptor, concentration of reagents, reaction temperature, and reaction time. A thorough examination was carried out only for the polycondensation of dithiol with bis(4-chloromethylphenyl)methane chosen as model system. The structures of the polysulfides were confirmed by elemental analysis, X-ray analysis, and infrared spectroscopy. The temperature of initial decomposition, the percentage of mass loss, and the temperature of the fastest decomposition, process were determined from curves of differential thermal and thermogravimetric analysis. Some physicochemical, mechanical and electrical properties were determined. The highest thermal and chemical resistance has been found for the polysulfide obtained from 4,4′-biphenyldithiol and 4,4′-bis(chloromethyl)biphenyl, probably because of the predominantly aromatic structure.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 53
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 251 (1997), S. 61-72 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: Drie organisch-anorganische Hybridmaterialien wurden nach dem Sol-Gel-Verfahren durch kovalenten Einbau von Poly(styrol-co-methylmethacrylat)(Poly(St-co-MMA))-, Polymethylmethacrylat(PMMA)- und Polystyrol(PS)-Struktureinheiten in ein SiO2-Netzwerk hergestellt und als Füllstoffe (bis zu 60 Gew.-%) in Dentalharzen verwendet. Der Einfluß der Füllstoffe auf einige mechanische Eigenschaften der Harze wurde untersucht. Die Härte der gefüllten Dentalharze nahm mit steigendem Füllstoffgehalt zu, wogegen die Biegefestigkeit abnahm. Die Druckfestigkeit der gefüllten Harze war besser als die des ungefüllten Harzes, nahm jedoch mit steigendem Füllstoffgehalt ab.
    Notizen: By incorporating poly(methyl methacrylate) (PMMA), polystyrene (PS), and poly(styrene-co-methyl methacrylate) (poly(St-co-MMA)) structure units covalently into the SiO2 glass network via a sol-gel approach, three organic-inorganic hybrid materials (PMMA-SiO2, PS - SiO2, and poly(St-co-MMA) - SiO2) have been prepared. The three hybrid sol-gel materials were used as filler (up to 60 wt.-%) for dental composite resins. The effect of the three filler materials on several mechanical properties of the dental composite resins was investigated. The hardness of the filled dental composites increased with increasing filler content, whereas the bending strength decreased. The compressive strength of the composites was improved, compared with the unfilled resin, but decreased with inreasing filler content.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 54
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 251 (1997), S. 107-116 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: Die Adsorption von Benzol, Toluol und p-Xylol (BTX) aus wäßrigen Lösungen mittels hochvernetzter kationischer Stärke mit tertiären Amingruppen wurde untersucht. Der endotherme Adsorptionsvorgang ist vom Anfangs-pH-Wert und der Anfangskonzentration abhängig und kann mit einer Langmuir-Isotherme beschrieben werden.Die Adsorptionswärme (Δ) bei pH 4 beträgt für Benzol, Toluol und Xylol 29,45 kJ mol-1, 34,41 kJ mol-1 bzw. 35,58 kJ mol-1, bei pH 10 30,17 kJ mol-1, 35.56 kJ mol-1 bzw. 39,39 kJ mol-1. Die adsorbierte Menge nimmt in der Reihenfolge Benzol 〉 Toluol 〉 Xylol ab.
    Notizen: The removal of benzene, toluene and p-xylene (BTX) compounds from aqueous solutions with highly crosslinked cationic starch containing tertiary amine groups was investigated. The adsorption process has found to be initial pH- and initial concentration-dependent, endothermic, and follows the Langmuir isothermal adsorption.The heats of adsorption (ΔH) at initial pH = 4 of benzene, toluene and p-xylene compounds are 29.45 kJ mol-1, 34.41 kJ mol-1, and 35.58 kJ mol-1, respectively, those at initial pH = 10 are 30.17 kJ mol-1, 35.56 kJ mol-1, and 39.39 kJ mol-1, respectively. The order of the amount of adsorbed BTX compounds on the adsorbent is benzene 〉 toluene 〉 p-xylene.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 55
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 251 (1997), S. 157-170 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: Bi-Sr-Ca-Cu-Komplexverbindungen von Polymethacrylsäure (PMAA) und Kresolnovolaken, die als Precursoren für Hochtemperatursupraleiter (HTSL) eingesetzt werden, sowie deren Cu-Komplexsalze wurden ESR-spektroskopisch und thermogravimetrisch untersucht. In den PMAA-Proben wurden drei verschiedene Cu2+-Spezies nachgewiesen: i) Cu2+-Paare, ii) isolierte Cu2+-Ionen und iii) Cu2+-Cluster. Bei niedrigem Cu-Gehalt der Proben bilden die Cu2+-Paar-Bindungen den Hauptanteil, bei hohem Cu-Gehalt überwiegen die Clusterbindungen. In den Novolakproben wurden nur isolierte Cu2+-Ionen und Cu2+-Cluster nachgewiesen. Die Einführung der Cu-Ionen erniedrigt die thermische Stabilität der Polymeren, der thermische Abbau erfolgt stufenweise. In den PMAA-Proben wird die erste Abbaustufe bei ≈ 220°C durch die Cu2+-Paar-Komplexe verursacht.
    Notizen: Bi-Sr-Ca-Cu complexes of poly(methacrylic acid) (PMAA) and cresol novolac, which are precursors for high-temperature superconductors (HTSC) and Cu complexes of those polymers were investigated by ESR spectroscopy and thermogravimetry. In the PMAA samples three different kinds of Cu2+ species were detected: i) Cu2+ pairs, ii) isolated Cu2+ ions and iii) Cu2+ clusters. While Cu2+ pairs are the main species at low Cu concentrations, clusters become dominant at high Cu contents. In the novolac samples Cu2+ was only detected in isolated sites and clusters. The introduction of Cu ions lowered the thermal stability of the polymers and led to a stepwise decomposition. In the PMAA samples the first decomposition step at ≈ 220°C is caused by the Cu2+ pair complexes.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 56
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 251 (1997), S. 193-205 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: Neodymchlorid-2-ethylhexanolate mit der allgemeinen Formel NdCl3 · nL wurden durch eine Liganden-Austauschreaktion zwischen Neodymchloridisopropanolat (I) und 2-Ethylhexanol (EH) hergestellt. Die Hexanolate NdCl3 · 1,5 EH (II) und NdCl3 · 2,5 EH (III) wurden durch Elementaranalyse und Gravimetrie charakterisiert. Die katalytische Aktivität der Hexanolate bei der Homopolymerisation von 1,3-Butadien in Gegenwart von Triethylaluminium wurde untersucht. Die Verbindung III zeigte eine höhere Aktivität als die Verbindung II. Höhere Katalysator- und Cokatalysatorkonzentrationen sowie eine höhere Temperatur steigerten den Umsatz, wogegen die Viskosität der Produkte abnahm. Mit zunehmender Reaktionszeit erhöhten sich sowohl der Umsatz als auch die Viskosität. Die cis-1,4-Konformation wurde durch die Variation von Temperatur und Cokatalysatorkonzentration beeinflußt. Der gesamte Anteil der cis-1,4-Stuktur lag jedoch in allen Fällen über 99%, während die Produkte nur einen sehr geringen Vinyl-Anteil von 〈1% enthielten. Die Zugabe einer elektronenspendenden Verbindung verringerte den cis- 1,4-Gehalt aber auf 87%.
    Notizen: Neodymium chloride 2-ethylhexanolates of the general formula NdCl3 · nL were prepared by ligand exchange reaction between neodymium chloride ispropanolate (I) and 2-ethylhexanol (EH). These hexanolates, NdCl3 · 1.5 EH (II) and NdCl3 · 2.5 EH (III), were characterized by elemental analysis and gravimetry. The catalytic activity of these hexanolates in combination with triethyl aluminium in the homopolymerization of 1,3-butadiene was studied, and the activity was found to be higher with III than II. The conversions increased with increasing the catalyst and co-catalyst concentrations and the temperature, whereas the intrinsic viscosity decreased. The conversions and the intrinsic viscosity decreased. The conversions and the intrinsic viscosity increased with reaction time. The cis-1,4 structure was influenced by variation in temperature and co-catalyst concentration, however, the total cis-1,4 structure was always more than 99% with very low vinyl content (〉1%). Addition of an external electron donor decreased the cis-1,4 content to 87%.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 57
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: MgCl2-Träger für einen Ethylenpolymerisationskatalysator wurden mit Hilfe der Rekristallationsmethode hergestellt, wobei Methanol als Lösungsmittel diente. Der Einfluß verschiedener Lösungsmethoden des rekristallisierten MgCl2-Alkohol-Adduktes auf die morphologischen Charakteristika der Katalysatoren wurde untersucht. Die Lösungsmethode beeinflußt die Eigenschaften der Katalysatoren beträchtlich. Die dargestellten Katalysatoren wiesen unterschiedliche Ti/Mg-Verhältnisse auf, sowohl was die Oberfläche als auch die gesamten Katalysator-Partikel betrifft. Betrachtet man die Ti-Verteilung und Aktivitätsprofile, dann erweisen sich nicht nur die Polymerisationsbedingungen, sondern auch die Ti-Verteilung auf dem Katalysator als wichtige Faktoren, welche die Dichte der Polymeren beeinflussen.
    Notizen: The MgCl2 supports for an ethylene polymerization catalyst were prepared by the recrystallization method using methanol as a solvent. The effects of different desolvation methods of the recrystallized MgCl2-alcohol adduct on the morphological characteristics of the catalysts were examined. The desolvation method greatly affects the characteristics of the catalyst. The prepared catalysts had different Ti/Mg ratios with respect to both surface content and entire catalyst particles. Considering Ti distribution and activity profiles, not only the polymerization conditions but also the Ti distribution on the catalyst appear to be an important factor which affects the bulk density of the polymers.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 58
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 253 (1997), S. 89-97 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: Aromatische Poly(etherketon)e mit Ferrocen-Einheiten in der Hauptkette wurden durch direkte Polykondensation von 1,1′-Ferrocendicarbonsäure mit Diphenylether oder 1,4-Diphenoxybenzol hergestellt. Als Katalysatoren wurden Trifluormethansulfonsäure, Methansulfonsäure/P2O5 (Eatons Reagens) oder Trifluormethansulfonsäure/P2O5 verwendet. Polykondensationen bei Raumtemperatur für 24 h ergaben Poly(arylenetherketon)e mit Grenzviskositäten bis zu 40 mL g-1. Die Monoacylierung von Diphenylether mit Ferrocencarbonsäure wurde im Hinblick auf die Effektivität von Eatons Reagens als Katalysator und Lösungsmittel eingehender untersucht.
    Notizen: Aromatic poly(ether ketone)s with ferrocene units in the main chain were prepared by direct polycondensation of 1,1′-ferrocenedicarboxylic acid with diphenyl ether or 1,4-diphenoxybenzene using various catalysts such as trifluoromethanesulfonic acid (triflic acid), a combination of methanesulfonic acid/P2O5 (Eaton's reagent) or a combination of triflic acid/P2O5. Polycondensations at room temperature for 24 h gave poly(arylene ether ketone)s with inherent viscosities up to 40 mL g-1. Monoacylation of diphenyl ether with ferrocenecarboxylic acid was studied in detail in order to show the efficiency of polymer formation employing Eaton's reagent as catalyst and solvent.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 59
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 251 (1997), S. 73-80 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: Die mechanischen und strukturellen Eigenschaften von Blends aus Phenolphthalein-Polyethersulfon und ultrahochmolekularem Polyethylen (UHMWPE) wurden anhand von Zug- und Biegeversuchen, Raster- und Transmissionselektronenmikroskopie untersucht. Die Zugabe einer geringen Menge UHMWPE (2 Gew.-%) führt zu einer Verstärkung der PES-C-Matrix. Höhere UHMWPE-Konzentrationen verschlechtern die mechanischen Eigenschaften. Die Strukturuntersuchungen zeigen, daß die Blends im gesamten Zusammensetzungsbereich mehrphasig sind. Bei geringen UHMWPE-Konzentrationen ist die UHMWPE-Phase gleichmäßig verteilt und entlang der Fließrichtung orientiert, was mit der starken Grenzflächenadhäsion zur Verbesserung des mechanischen Verhaltens beiträgt. Mit steigender UHMWPE-Konzentration nimmt die Domänengröß der UHMWPE-Phase zu.
    Notizen: Mechanical and structural properties of blends of phenolphthalein poly(ether sulfone) (PES-C) with ultra-high molecular weight polyethylene (UHMWPE) were investigated using tensile and bending testing, scanning electron microscopy and transition electron microscopy. The incorporation of minor amounts of UHMWPE (2 wt.-%) into PES-C has a reinforcement effect. With higher concentrations of UHMWPE, the mechanical properties decrease gradually. Structural studies demonstrated that the blends are multiphasic in the whole composition range. The minor UHMWPE, dispersed uniformly and oriented along the flow direction, as well as the strong interfacial adhesion contribute to the increase of the mechanical performance of the blends. The domain size of the UHMWPE phase was found to increase with the increase of its concentration.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 60
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 251 (1997), S. 117-130 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: Ein Redoxcopolymeres, ein makroporöses Poly(Styrol-co-Divinylbenzol) (S/DVB)-Harz mit N-Bromsulfonamidgruppen, wurde angewandt, um Cyanide aus wäßrigen Lösungen zu entfernen. Dieses Harz enthält aktives Brom in den funktionellen Gruppen (1.86 mmol g-1, 3.72 meq g-1) und weist Oxidationseigenschaften auf. Es wurde sowohl in statischen als auch in dynamischen Systemen für die Oxidation von Cyanidionen zu nichttoxischen Verbindungen angewandt. Die Reaktionen wurden in wäßrigen Lösungen mit 26-2600 mg L-1 CN- bei unterschiedlichen pH-Werten durchgeführt. Die Ergebnisse zeigten, daß dieses Harz die Cyanide leicht zu Cyanaten oxidiert, die ca. 1000 mal weniger toxisch sind. Bei Kontakt mit dem Harz fiel die Cyanidkonzentration in den Lösungen unter 0.05 mg L-1 CN-. Die —SO2NBrNa-Gruppen gingen dabei in —SO2NH2-Gruppen über. Diese konnten wiederum mit Natriumhypochlorit- und Natriumbromid-Lösungen reaktiviert werden. Es wurde auch eine Alternative zu der Cyanidionenoxidation mit N-Bromsulfonamid-Harz untersucht, indem ein analoges N-Chlorsulfonamid-Harz in Gengenwart von katalytischen Mengen von Bromiden angewandt wurde.
    Notizen: A redox copolymer, macroporous poly(styrene-co-divinylbenzene) (S/DVB) resin having N-bromosulfonamide groups, was used for removal of cyanide ions from aqueous solutions. This resin contains active bromine in functional groups (1.86 mmol g-1, i. e. 3.72 meq g-1) and shows oxidative properties. It was employed in static and flow system for oxidation of cyanide ions to non-toxic compounds. The reactions were carried out in aqueous media containing 26-2600 mg L-1 CN- at different pH values. The data showed that the resin having active bromine easily oxidized cyanides, forming cyanates being 1000-times less toxic than cyanides. In contact with the resin the concentration of cyanides in tested solutions dropped below 0.05 mg L-1 CN-. During the oxidation processes the —SO2NBrNa groups transform to —SO2NH2 groups. They can be reactivated by use of sodium hypochlorite and bromide solutions. As an alternative to oxidation of cyanides by N-bromosulfonamide resin, the oxidation of these ions by N-chlorosulfonamide resin with addition of a small amount of bromides was examined.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 61
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 251 (1997), S. 207-208 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: No Abstract
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 62
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 252 (1997), S. 33-43 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Novel Polyester glycols with alkyl side groups were used for the improvement of thermal stability and hydrolytic stability of polyester urethane elastomers. The novel polyester glycols used are poly( β -methyl- δ -valerolactone)glycol (PMVL), poly(3-methyl pentamethylene adipate) glycol (PMPA), poly(nonamethylene-co-2-methyl octamcthylene carbonate) gycol (PNCO). A mixture of PNCO and poly(dimethyl siloxane)gycol (PNCO/PDMS) was also used. Polyurethane network elastomers were prepared from 4,4′-diphenylmethane diisocyanate (or 2,4-tolylene diisocyanate), and a mixture of 1,4-butane diol and trimethylol propane by a prepolymer method. Mechanical properties, Tg, thermal stability, and hydrolytic stability were measured. Morphology were also measured by means of polarizing microscopy, dynamic viscoelastometer, and ESR. The properties of novel polyurethane elastomers have good mechanical properties comparable to those of the general purpose polyester urethanes, and better thermal and hydrolytic stability than PTMG-based polyurethane. These polyurethane elastomers were exposed in out door during 2 year in Nagasaki, JAPAN. The novel polyurethane clastomers held alomost constant values for gel fraction, swelling ratio, relative modulus during 12 months, while poly(oxytetramethylene oxide)-based polyurethane as a control decreased the these values. Relationship of degradation behaviors with chemical structure and morphology were discussed.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 63
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 252 (1997), S. 139-151 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: In the chain oxidation of N-alkylamides with molecular oxygen, propagation is the ratedetermining step under conditions when the oxidation rate is independent of oxygen pressure. The oxidizability of lactams and lactam-based polyamides correlates with the energy of the formation of N-alkylamide radical by abstraction of hydrogen from the methylene group adjacent to nitrogen. While for lactams this energy depends on the number of carbons in the lactam ring, for N-alkylamides and polylactams such dependence is not observed.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 64
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 252 (1997), S. 179-193 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: An X-band EPR-Imaging apparatus which allowed us to determine the distribution of nitroxyl radicals within solid samples of polymeric materials containing hindered amine stabilizers, is described. It is shown that EPR Imaging represents a powerful tool for investigating the growth and decay of nitroxyls formed in polymers irradiated under air for long periods. Since the variations of the radical concentration can be monitored both in time and in the space, this technique provides valuable information not easily attainable by means of other methods.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 65
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 252 (1997), S. 237-256 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: A re-examination of the photo-oxidation mechanism of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) at both long and short irradiation wavelengths under accelerated conditions is reported. The formation rate of poly-2,6-dimethylphenoxy (PDMP) radicals, have been observed by esr spectroscopy, while benzylic-type radicals have been detected by spin trapping experiments using nitrosodurene under UV irradiation conditions. The changes of FTIR spectra obtained under accelerated photo-oxidative conditions show the formation of primary oxidation products such as aromatic aldehydes and quinones. The direct formation of radical cations and superoxide anions by a photo-induced electron-transfer reaction is suggested under our conditions. In addition, some results on the of photo-oxidation PPO/PS blends as a function of polystyrene tacticity are also reported. In the case of syndiotactic polystyrene the blend photostability shows some differences in comparison with the blend containing atactic polystyrene. This effect has been ascribed to the absence of excimers in syndiotactic polystyrene which are not revealed by fluorescence measurements. Finally, the chemical modification of PPO with bromine gave a bromomethylated PPO with different amounts of CH2 Br groups, which has been used for further substitution reactions with alkoxy sodium salts of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and 4-hydroxy-1,2,2,6,6-pentamethylpiperidine (PMPP). The accelerated photo-oxidation of a modified copolymer PPO-PMPP containing a 60% PMPP moieties as side groups and its blends with pure PPO has been followed by FTIR and esr spectroscopies. Some comparisons with a commercially available hindered amine light stabilizers (HALS) and a modified copolymer PPO-PMPP are also reported under the same photo-oxidative conditions.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 66
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 253 (1997), S. 27-49 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: For innovative applications of plastics, which take advantage of special properties of polymeric materials, comprehensive understanding on strengthening and toughening mechanisms is required. The temperature-dependent mechanical behaviour of PMMA, PS and PC under dynamic loading conditions were investigated by means of an instrumented Charpy impact tester. The elastic-plastic fracture mechanics parameters, the energy-determined J-integral, and the deformation-determined crack opening displacement, δ, enable to do structure-related quantification of micromechanical processes. The J-integral values showed a maximum, resulting from an energy-dissipative process. The maximum values for PMMA occurred at 50°C and for PC at 40°C , which is related to the secondary(β) relaxation as evaluated from the frequency dependence of the mechanical loss factor. The 0-relaxation initiated shear deformation mechanisms, which led to a local increase of toughness. In polycarbonate, toughness is strongly increased due to a stress-induced shear flow process at temperatures higher than -25°C. Correlations between morphology and toughness can be derived with the help of optical investigations of stable crack propagation on fracture surfaces.
    Notizen: Innovative Kunststoffanwendungen, die die speziellen Eigenschaften polymerer Werkstoffe gezielt ausnutzen, erfordern vertiefte Kenntnisse über festigkeits- und zähigkeitsbestimmende Mechanismen. Das sich in Abhängigkeit von der Temperatur ändernde Werkstoffverhalten von PMMA, PS und PC wurde bei dynamischer Beanspruchung mittels instrumentierter Kerbschlagbiegeprüfung bestimmt. Mit der verformungsbestimmten Rißöffnungsverschiebung δ und dem energiebestimmten J-Integral stehen Kenngrößen der Fließbruchmechanik zur Verfügung, die eine strukturbezogene Quantifizierung der temperaturabhängigen mikromechanischen Prozesse erlauben. Die J-Integralwerte zeigen für PMMA bei 50°C und für PC bei -60°C ein durch einen energiedissipativen Prozeß verursachtes Maximum. Dieses Maximum steht, wie sich aus der Interpretation der Frequenzabhängigkeit des mechanischen Verlustfaktors ergibt, mit der Neben(β)-Relaxation in Beziehung. Dabei initiiert die β-Relaxation Scherdeformationsmechanismen, die ihrerseits die lokale Zähigkeitserhöhung bewirken. Ab -25°C führt für PC ein spannungsinduzierter Scherfließprozeß zu einer erheblichen Zähigkeitssteigerung. Durch die Einbeziehung lichtmikroskopischer Untersuchungen des stabilen Rißfortschritts auf der Bruchfläche können Morphologie-Zähigkeits-Korrelationen abgeleitet werden.
    Zusätzliches Material: 16 Ill.
    Materialart: Digitale Medien
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  • 67
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 253 (1997), S. 71-88 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: Eine Reihe von Polyamidimid-Polyimid-Blockcopolymeren (PAI-PI-BCPs) wurde durch Polykondensation von PAI-Blöcken mit Amino-Endgruppen und PI-Blöcken mit Anhydrid-Endgruppen hergestellt. Zur Synthese der Blöcke mit Molekulargewichten im Bereich von ca. 2000 bis 15000 wurden nur technisch leicht zugängliche Monomere, wie Trimellitsäureanhydridchlorid, Benzophenontetracarbonsäuredianhydrid, 4,4′-Diaminodiphenylmethan, 2,4-Toluylendiamin und 4,4′-Diaminodiphenylsulfon eingesetzt. Dabei zeigte sich, daß durch den blockartigen Aufbau die Löslichkeit-und damit die Verarbeitbarkeit-im Vergleich zu den reinen, unlöslichen Polyimiden wesentlich verbessert werden konnte, bei nahezu gleichbleibender Thermostabilität. So wurden BCPs mit guten mechanischen Eigenschaften, Thermostabilitäten bis ca. 480°C (Thermogravimetrie, 5% Gewichtsverlust) und guten Löslichkeiten in Dimethylacetamid und anderen polaren aprotischen Lösungsmitteln erhalten.
    Notizen: New poly(amide-imide)-poly(imide) block copolymers (PAI-PI-BCPs) were prepared by polycondensation of amino-terminated PAI-blocks with anhydride-terminated PI-blocks. For the syntheses of the blocks with molecular weights from 2000 to 15000 only commercially available monomers were used, e.g. trimellitic acid anhydride chloride, benzophenone tetracarboxylic acid dianhydride, 4,4′-diaminodiphenylmethane, 2,4-toluenediamine and 4,4′-diaminodiphenylsulfone. The BCPs were shown to have better solubility compared to the pure, insoluble PIs with only minor decrease of the thermostability. Thus, BCPs with good mechanical properties, thermostabilities up to 480°C (thermogravimetric analysis, 5% weight loss) and good solubility in dimethylacetamide and other polar aprotic solvents were obtained.
    Zusätzliches Material: 4 Tab.
    Materialart: Digitale Medien
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  • 68
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 253 (1997), S. 139-149 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: Eine Reihe von Polysiloxan/Poly(N-acetyliminoethylen)-(PSiO/PNAI)-Block- und -Pfropfcopolymeren wurde durch Polymerisation von 2-Methyl-2-oxazolin (MeOZO) mit funktionellen Polysiloxan-Prepolymeren als Initiatoren synthetisiert. Die Copolymeren wurden mit IR- und 1H NMR-Spektroskopie sowie Elementaranalyse, Differentialkalorimetrie und Thermogravimetrie charakterisiert. Der Einbau sowohl von hydrophoben als auch von hydrophilen Sequenzen verleiht den Polymeren amphiphile Eigenschaften. Ihre Eigenschaften in Lösung und als Feststoffe lassen die Produkte für Anwendungen als nichtionische Emulgatoren, Oberflächenmodifikatoren, Gele, usw. geeignet erscheinen.
    Notizen: A series of polysiloxane/poly(N-acetyliminoethylene) (PSiO/PNAI) block and graft copolymers were synthesized by the initiation of 2-methyl-2-oxazoline (Me-OZO) polymerization with functional polysiloxane prepolymers. The copolymerization products were characterized by IR- and 1H NMR spectroscopy, elemental analysis, DSC and thermogravimetry. The insertion of both hydrophobic and hydrophilic sequences in the macromolecular structure induces a behavior characteristic of amphiphilic compounds. Their solution and solid state behavior evidenced peculiarities which make them able to act as nonionic emulsifiers, surface modifiers, gels, etc.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 69
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: Der Zustand von Wasser in Protonenaustausch-Membranen, hergestellt durch Pfropfen von Styrol auf Polyvinylidenfluorid-Filme (PVDF-g-PS) mittels Elektronenstrahlen und anschließendes Sulfonieren (PVDF-g-PSSA), wurde mittels Differentialkalorimetrie (DSC), Raman-Spektroskopie und Rontgen-Diffraktion (SAXS) ermittelt. Die Raman-Untersuchungen zeigten, daß einzelne Wassermolekule durch hydrophobe Wechselwirkungen an die Polymerketten gebunden sind. Die DSC-Untersuchungen zeigten, daß Wasser in den Membranen in drei verschiedenen Umgebungen vorliegt: nicht gefrierendes ionisch gebundenes Wasser, gefrierendes freies Wasser und gefrierendes gebundenes Wasser. Die Menge an nicht gefrierendem Wasser betragt unabhangig vom Pfropfungsgrad etwa 10 H2O/SO3H (mol/mol). Die Menge an gefrierendem Wasser ist stark vom Pfropfungsgrad abhangig. Oberhalb eines Pfropfungsgrades von 50% werden Werte von 40 H20/S03H (mol/mol) erreicht. Die Leitfahigkeit von nur nicht gefrierendes Wasser enthaltenden Membranen ist gering, d. h., das ionisch gebundene Wasser kann nicht allein die fur den Transport von Protonen und Wasser notwendigen Kanale bilden. Die SAXS Untersuchungen zeigten, daß Wasser/Sulfonsaure-Cluster in Membranen aus hydratisiertem PVDF-g-PSSA mit einem Bragg-Abstand von 25 Å gebildet werden. Diese Cluster formen die Kanale fur den Ionentransport und die Leitfähigkeit.
    Notizen: The state of water in proton exchange membranes prepared by pre-irradiation (electron beam, 100 kGy) grafting of styrene onto poly(vinylidene fluoride) films (PVDF-g-PS), followed by sulfonation (PVDF-g-PSSA), has been studied with thermal analysis, Raman spectroscopy and small angle X-ray diffraction (SAXS). Raman spectra show that, in addition to free liquid water in the membranes, single water molecules are weakly bound to the polymer backbone. Thermal analysis shows that there are three types of water molecules in the membrane; non-freezable water associated with the ionic sites, freezable free water, and freezable bound water. The amount of non-freezable water is around 10 H2O/SO3H (mol/mol), and is independent of the degree of grafting (d.o.g.). The amount of freezable water is strongly dependent on the d.o.g. as long as the grafting has not penetrated the whole of the film, and reaches a value of around 40 H2O/SO3H (mol/mol) above a d.o.g. of 50%. The conductivity of membranes containing only the non-freezable water is low, i. e. the ionically bound water alone does not form the domains necessary for proton and water transport. SAXS measurements show that water/sulfonic acid clusters in hydrated PVDF-g-PSSA membranes with a Bragg distance of 25 Å are formed; these form the ion conducting channels in the membrane.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 70
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 253 (1997), S. 211-211 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 71
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 253 (1997), S. 201-210 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: Die Zug- und Biegemoduli von preßgeformten Polypropen-Probekörpern mit unterschiedlichen Oberflächenkristallinitäten wurden basierend auf der Annahme eines Schicht-Verbund-Modells untersucht. Es zeigte sich, daß die Spannungs-Dehnungs-Kurven der Zugversuche und die Werte der Biegeablenkung im wesentlichen von der Oberfächenkristallinität abhängen, jedoch erwiesen sich die Bruchspannungen als von der Oberflächenkristallinität unabhängig. Es wird angenommen, daß das beobachtete Zug- und Biegeverhalten der Proben auf der Grundlage eines Schicht-Verbund-Modells, bei dem eine massive, starre Platte zwischen zwei weichen Schichten eingebettet ist, charakterisiert werden kann.
    Notizen: The tensile and flexural moduli of the compression-molded sheets of polypropene with different surface layer crystallinity were investigated based on a layered composite model. It was found that the tensile stress-strain curve and flexural deflection depended largely on the surface layer crystallinity, but the ultimate strain-at-break values were independent of the surface layer crystallinity. It is suggested that the tensile and flexural behavior can be characterized using a layered composite model in which a bulk plate was sandwiched between two surface layers.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 72
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 252 (1997), S. 45-54 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Addition of HALS-stabilisers, the cut-off wavelength of the light source, the temperature and the oxygen pressure have an influence on the UV-degradation mechanism of polyolefins. All these parameters influences the conversion of oxygen into polymeric carbonyls. The results are explained assuming that the initiation of the UV-degradation of pololefins is due to substrate-oxygen charge transfer complexes (CTCs).
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 73
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 252 (1997), S. 69-88 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The applicability of fracture mechanics was studied on UV-exposed HDPE Charpy specimens. The failure distribution of the stress at failure measured in three-points bending tests showed a bifurcation in failure processes. At high stresses yielding occurs, resulting in large strain at failures. At lower stresses crack propagation causes low strain at failures. Due to the bifurcation in failure processes the ductile-brittle transition temperature of exposed specimens is hard to determine.Specimens notched after exposure showed a decrease in the critical stress intensity values. The effective notch depth of exposed specimens was found to be larger than the thickness of the oxidized layer measured by FT-IR and density measurements.
    Zusätzliches Material: 21 Ill.
    Materialart: Digitale Medien
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  • 74
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 252 (1997), S. 119-138 
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: In the 2-hydroxyphenyl-1,3,5-triazines, the intramolecular hydrogen bond is stronger than in the corresponding 2-hydroxyphenylbenzotriazoles. Compounds with only one aryl group in the 2-hydroxyphenyl-1,3,5-triazine series show proton-transferred fluorescence with large Stokes shift and high quantum yield. No such fluorescence is observed, in contrast, for compunds with three aryi groups bearing no electrondonating groups on the aryl moieties. When the hydrogen atom of the intramolecular hydrogen bond is replaced by CH3, the respective derivative shows fluorescence with a normal Stokes shift.Various copolymers of MA-TIN 1 (2-[2-hydroxy-3-tert.-butyl-5-(O-[2-hydroxy-3-(2-methylpropenoyloxy)propyl]-2-carbonyloxyethyl)phenyl]benzotriazole), and MA-TZ 1 (2,4-Bis(2,4-dimethyl-phenyl)-6-[2-hydroxy-4-(2-hydroxy-3-[2-methylpropenoyloxy])propoxyphenyl]-1,3,5-triazine) with styrene, methyl methacrylate, and methacrylic acid have been synthesized by radical polymerization. The absorption spectra in the longwavelength UV region appear unchanged compared to those of the monomeric UV absorbers indicating that the stabilizer chromophores are conserved intact in the polymer. Both the monomeric and the polymeric stabilizers exhibit a strongly Stokesshifted, temperature-dependent, low-quantum-yield, proton-transferred fluorescence. This may be taken as evidence that the intramolecular hydrogen bond, which is essential for the photostability of this type of UV absorber, remains intact also in the copolymers. Activation energies of the radiationless deactivation process can be evaluated from the temperature dependence of this fluorescence. These energies lie between 4 and 5 kJ/mol for most of the benzotriazole and triazine stabilizers investigated.Fluorescence-decay measurements with crystalline MA-TIN 1 at different temperatures reveal a close correspondence of the temperature dependence between decay times and relative quantum yields. The radiationless process is thence concluded to originate from the proton-transferred level S1'. The decay time at room temperature is estimated at 70 ps, close to the value for crystalline TIN P (2-(2-hydroxy-5-methylphenyl)benzotriazole). The proton-transferred fluorescence of MA-TIN 1 exhibits a biexponential decay profile whereas solid TIN P, in contrast, displays only one single lifetime.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 75
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Biopolymers 41 (1997), S. 5-25 
    ISSN: 0006-3525
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Buckling transitions in superhelical DNA are sudden changes in shape that accompany a smooth variation in a key parameter, such as superhelical density. Here we explore the dependence of these transitions on the elastic constants for bending and twisting, A and C, important characteristics to DNA's bending and twisting persistence lengths. The large range we explore extends to other elastic materials with self-contact interactions, modeled here by a Debye-Hückel electrostatic potential.Our collective description of DNA shapes and energies over a wide range of ρ = A/C reveals a dramatic dependence of DNA shape and associated configurational transitions on ρ: transitions are sharp for large ρ but masked for small ρ. In particular, at small ρ, a nonplanar circular family emerges, in agreement with Jülicher's recent analytical predictions; a continuum of forms (and associated writhing numbers) is also observed.The relevance of these buckling transitions to DNA in solution is examined through studies of size dependence and thermal effects. Buckling transitions smooth considerably as size increases, and this can be explained in part by the lower curvature in larger plasmids. This trend suggests that buckling transitions should not be detectable for isolated (i.e., unbound) DNA plasmids of biological interest, except possibly for very large ρ. Buckling phenomena would nonetheless be relevant for small DNA loops, particularly for higher values of ρ, and might have a role in regulatory mechanisms: a small change in superhelical stress could lead to a large configurational change.Writhe distributions as a function of ρ, generated by Langevin dynamics simulations, reveal the importance of thermal fluctuations. Each distribution range (and multipeaked shape) can be interpreted by our buckling profiles. Significantly, the distributions for moderate to high superhelical densities are most sensitive to ρ, isolating different distribution patterns. If this effect could be captured experimentally for small plasmids by currently available imaging techniques, such results suggest a slightly different experimental procedure for estimating the torsional stiffness of supercoiled DNA than considered to date. © 1997 John Wiley & Sons, Inc.
    Zusätzliches Material: 13 Ill.
    Materialart: Digitale Medien
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  • 76
    ISSN: 0006-3525
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Molecular mechanics and dynamics calculations were carried out on the disaccharides α-L-Rhap-(1 → 2)-α-L-Rhap-(1 → OMe) (1) and α-L-Rhap-(1 → 3)-α-L-Rhap-(1 OMe) (2), and the trisaccharide α-L-Rhap-(1 → 2)-α-L-Rhap-(1 → 3)-α-L-Rhap-(1 → OMe) (3). The semiflexible conformational behavior of these molecules was characterized by the occupation of a combination of different glycosidic linkage and side-chain conformational positions whose relative occupations were sensitive to dielectric screening. Molecular dynamics simulations of the trisaccharide 3 showed little difference between the linkage conformations in the trisaccharide and the component disaccharides 1 and 2.Experimental optical rotation data of 1 and 2 were obtained as a function of temperature in varying solvents. The molecular models were combined with the semiempirical theory of Stevens and Sathyanarayana to yield calculated optical rotations. Interpretation of the data of both 1 and 2 implied that a combination of conformations, both in glycosidic and side-chain positions, could explain the experimental data. Solvents effects were important in influencing the conformational mix and averaged optical rotation.Three-bond heteronuclear coupling constants 3JC, H were obtained for the glycosidic linkages of 1 and 2 in D2O and DMSO. Analysis of the coupling constants with a Karplus curve showed that small reductions in the glycosidic torsion angles of the conformations of the models used here of ca. 10°-15° in φ and 5°-10° in ψ were required to give better agreement with experiment; a combination of conformations for both 1 and 2 was consistent with the data. There was a negligible influence on the coupling constants of 1 on changing the solvent from D2O to DMSO. © 1997 John Wiley & Sons, Inc.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 77
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Biopolymers 41 (1997), S. 165-180 
    ISSN: 0006-3525
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: For a minimalist model of protein folding, which we introduced recently, we investigate various methods to obtain folding sequences. A detailed study of random sequences shows that, for this model, such sequences usually do not fold to their ground states during simulations. Straightforward techniques for the construction of folding sequences, based solely on the target structure, fail. We describe in detail an optimization algorithm, based on genetic algorithms, for the “simulated breeding” of folding sequences in this model. We find that, for any target structure studied, there is not only a single folding sequence but a patch of sequences in sequence space that fold to this structure. In addition, we show that, much as in real proteins, nonhomologous sequences may fold to the same target structure. © 1997 John Wiley & Sons, Inc.
    Zusätzliches Material: 13 Ill.
    Materialart: Digitale Medien
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  • 78
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Biopolymers 41 (1997), S. 205-212 
    ISSN: 0006-3525
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The self-association of several N-urethanyl-L-amino acids (N-t-Boc-glycine, N-t-Boc-L-alanine, N-t-Boc-L-methionine, and N-t-Boc-O-Bz-L-tyrosine has been investigated in carbon tetrachloride by Fourier transform (FTIR) spectrometry. The fractions of nonbonded OH and NH groups have been determined from the intensities of the free OH and NH-stretching vibrations. The FTIR spectra have been examined in the carbonyl stretching regions by using Fourier self-deconvolution techniques. The results show that intermolecular hydrogen bonds are formed between the carboxylic acid group of one molecule and the urethane group of another molecule, suggesting that the leading factor for the self-association of N-t-Boc amino acids is the acidity of the OH groups. In N-t-Boc glycine, more heterodimers are formed than in the other amino acids. In N-t-Boc-O-Bz-L-tyrosine where the steric hindrance of the substituent implanted on the Cα atom is higher, the concentration of homodimers and heterodimers is lower than in N-t-Boc-L-alanine or N-t-Boc-L methionine. © 1997 John Wiley & Sons, Inc.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 79
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Biopolymers 41 (1997), S. 239-250 
    ISSN: 0006-3525
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A heteropolymer model of randomly self-interacting chains in two dimensions is studied with numerical simulations in order to elucidate the folding mechanism of protein. We find that the model occasionally shows folding propensity depending on the sequence of random numbers given to the chain. We study the thermodynamic and kinematic roles in the folding mechanism by grouping the local energy minima found in the simulations into clusters according to the similarity of their conformations. It is suggested that the local minima to which some heteropolymers show a folding tendency are always the lowest energy states of the energy spectrum within a cluster, though which cluster is selected depends on the sequence. For the eight random sequences we study, we find that the energy gap between the ground state and excited states is little correlated with folding or nonfolding. We rather find that folding propensities are correlated with the global structure of the average energy surface, implying a dominant kinetic role in the folding mechanism, although thermal factors cannot be ignored as the mechanism of choosing the ground state within a cluster of states connected by small deformations. We suggest that a hierarchical cluster structure plays an important role in selecting a unique folded state out of the huge number of local minima of heteropolymers. © 1997 John Wiley & Sons, Inc.
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
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  • 80
    ISSN: 0006-3525
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The nucleocapsid protein NCp7, which is the major genomic RNA binding protein of human immunodeficiency virus type 1, plays an important role in several key steps of the viral life cycle. Many of the NCp7 activities, notably the nucleic acid annealing and the genomic RNA wrapping ones, are thought to be linked to a nonspecific binding of NCp7 to its nucleic acid targets. The mechanism of these activities is still debated but several clues are in favor of an intermediate aggregation of nucleic acids by NCp7. To check and characterize the nucleic acid aggregating properties of NCp7, we investigated the interaction of NCp7 with the model RNA homopolymer, polyA, by quasielastic light scattering and optical density measurements. The ordered growth of monodisperse large particles independently of the nucleic acid size and the almost complete covering of polyA by NCp7 strongly suggested an ordered aggregation mechanism. The aggregate kinetics of growth in the optimum protein concentration range (≥2 μM) were governed by a so-called Ostwald ripening mechanism limited by transfer of NCp7-covered polyA complexes from small to large aggregates. The aggregation process was strongly dependent on both Na+ and Mg2+ concentrations, the optimum concentrations being in the physiological range. Similar conclusions held true when polyA was replaced by 16S + 23S ribosomal RNA, suggesting that the NCp7 aggregating properties were only poorly dependent on the nucleic acid sequence and structure. Finally, as in the NCp7 annealing activities, the basic regions of NCp7, but not the zinc fingers, were found critical in nucleic acid aggregation. Taken together, our data indicate that NCp7 is a highly efficient nucleic acid aggregating agent and strengthen the hypothesis that aggregation may constitute a transient step in various NCp7 functions. © 1997 John Wiley & Sons, Inc.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 81
    ISSN: 0006-3525
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The nmr solution conformation of cyclotheonamide A (CtA) was determined in aqueous media. The data produced 15 distance and 10 torsional constraints which were used to generate conformations using restrained simulated annealing (SA) and distance geometry/simulated annealing (DG/SA) calculations. Two different calculation protocols were performed to ensure proper sampling of conformational space and even though the torsional restraints were input differently, both calculation methods yielded the same conformation of CtA. In the structure calculations, all solutions of the Karplus equation were sampled simultaneously using the restrained SA protocol and large ranges were used for the dihedral restraints in the DG/SA protocol because all solutions to the Karplus equation could not be sampled simultaneously. The solution conformation was also compared to the solid state x-ray conformations of CtA bound to thrombin and trypsin. The conformation of the residues important for active site binding (d-Phe, h-Arg, and Pro) are nearly identical in aqueous solution and solid state with largest differences at the a-Ala and v-Tyr residues. CtA appears to be preordered in structure and does not undergo a significant conformational change upon binding to the enzyme active site. © 1997 John Wiley & Sons, Inc.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 82
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Biopolymers 41 (1997), S. 381-389 
    ISSN: 0006-3525
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A Monte Carlo Protein Building method to construct the backbone and Cβ atomic coordinates from known Cα coordinates is reported. The method selects values of dihedral angles from ranges established from a statistical analysis of the relationship between dihedral angles of the backbone and Cα coordinates for a protein data base. The averaged coordinates from ten backbone models of a protein were used to define a mean structure that was refined by energy minimization using the AMBER force field (GB/SA). By the latter method the average atomic deviation and rmsd of the backbone and Cβ atoms for 24 proteins is between 0.14 and 0.32 Å (average 0.22 Å) and 0.22 and 0.61 Å (average 0.43 Å), respectively. A comparison with other methods is made. © 1997 John Wiley & Sons, Inc.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 83
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Biopolymers 41 (1997), S. 391-405 
    ISSN: 0006-3525
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A model of nine proteins including side-chain atoms have been built from the known Cα coordinates and amino acid sequences using a Monte Carlo Protein Building Annealing method. The Cartesian coordinates for the side-chain atoms were established with bond lengths and angles selected randomly from within previously determined ranges. A simulated annealing technique is used to generate some 300 structures with differing side-chain conformations. The atomic coordinates of the backbone atoms are fixed during the simulated annealing process. The coordinates of the side-chain atoms of 300 low energy conformations are averaged to obtain a mean structure that is minimized with the Cα atoms constrained to their position in the x-ray structure using the OPLS/AMBER force field with the GB/SA water model. The rms deviation of the main-chain atoms (without Cβ) compared with the corresponding crystal structures is in the range 0.20-0.64 Å. The rms deviation of the side-chain atoms is between 1.72 and 2.71 Å and for all atoms is between 1.19 and 1.99 Å. The method is insensitive to random errors in the Cα positions and the computational requirement is modest. © 1997 John Wiley & Sons, Inc.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 84
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Biopolymers 41 (1997), S. 443-450 
    ISSN: 0006-3525
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We analyze the electrostatic and hydrodynamic properties of a nuclease from the pathogenic gram-negative bacterium Serratia marcescens using finite-difference Poisson-Boltzmann methods for electrostatic calculations and a bead-model approach for diffusion coefficient calculations.Electrostatic properties are analyzed for the enzyme in monomeric and dimeric forms and also in the context of DNA binding by the nuclease. Our preliminary results show that binding of a double-stranded DNA dodecamer by nuclease causes an overall shift in the charge of the protein by approximately three units of elementary charge per monomer, resulting in a positively charged protein at physiologic pH. In these calculations, the free enzyme was found to have a negative (-1 e) charge per monomer at pH 7. The most dramatic shift in pKa involves His 89 whose pKa increases by three pH units upon DNA binding. This shift leads to a protonated residue at pH 7, in contrast to the unprotonated form in the free enzyme. DNA binding also leads to a decrease in the energetic distances between the most stable protonation states of the enzyme. Dimerization has no significant effect on the electrostatic properties of each of the monomers for both free enzyme and that bound to DNA.Results of hydrodynamic calculations are consistent with the dimeric form of the enzyme in solution. The computed translational diffusion coefficient for the dimer model of the enzyme is in very good agreement with measurements from light scattering experiments. Preliminary electrooptical calculations indicate that the dimer should possess a large dipole moment (approximately 600 Debye units) as well as substantial optical anisotropy (limiting reduced linear electric dichroism of about 0.3). Therefore, this system may serve as a good model for investigation of electric and hydrodynamic properties by relaxation electrooptical experiments. © 1997 John Wiley & Sons, Inc.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 85
    ISSN: 0006-3525
    Schlagwort(e): biovector ; light scattering ; lipid ; microgel ; polysaccharide ; soft sphere ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The structure of a new supramolecular drug carrier (named Biovectors - BV) was studied using light scattering and scanning electronic microscopy techniques. This system consists of a polysaccharide core of chemically cross-linked maltodextrins to which phospholipids (and, in some cases, cholesterol) are added. Both polysaccharide cores and BV cross-linked with phosphate (negatively charged) and epichlorhydrin (no net charge) are spherical particles. The increase in the ionic strength of the medium increases the density of the charged polysaccharide cores. The lipid strongly interacts with neutral and negatively charged cores, decreasing both intra- and interparticle interactions. The results (mainly, ρ = Rg/Rh 〈 0.775 in some cases) suggest that BV are gel-like particles of variable density, referred to as microgels or soft spheres. Neutral polysaccharides have a strong tendency to self-aggregate. This self-aggregation of polysaccharide neutral cores is prevented by the addition of lipid or dimethylsulfoxide. © 1997 John Wiley & Sons, Inc. Biopoly 41: 511-520, 1997
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 86
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Biopolymers 41 (1997), S. 533-544 
    ISSN: 0006-3525
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A dynamical model of interdomain “hinge bending” of T4 lysozyme in aqueous solution has been developed on the basis of molecular dynamics (MD) simulation. The MD model study provides a description of the conformational reorganization expected to occur for the protein in aqueous solution as compared to the crystalline environment. Three different 500 ps molecular dynamics simulations were calculated, each using a distinctly different crystal conformation of T4 lysozyme as the starting points of the MD simulations. Crystal structures of wild-type lysozyme and “open” and “closed” forms of M6I variant structures were analyzed in this study. Large-scale, molecular-conformational rearrangements were observed in all three simulations, and the largest structural change was found for the open form of the M6I allomorph. All three simulated proteins had closed relative to the wild-type crystal structure, and the closure of the “jaws” of the active site cleft occurred gradually over the time course of the trajectories. The time average MD structures, calculated over the final 50 ps of each trajectory, had all adapted to conformations more similar to each other than to their incipient crystal forms. Using a similar MD protocol on cytochrome P450BM-3 [M. D. Paulsen and R. L. Ornstein (1995) Proteins: Structure Function and Genetics, Vol. 27, pp. 237-243] we have found that the opposite type of motion relative to the starting crystal structure, that is, the open form of the crystal structure, had opened to a greater degree relative to the incipient crystal structure form. Therefore we do not believe that either result is merely a simulation artifact, but rather the protein dynamics are due to protein relaxation in the absence of crystal packing forces in the simulated solution environments. © 1997 John Wiley & Sons, Inc. Biopoly 41: 533-544, 1997
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 87
    ISSN: 0006-3525
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Antibodies induced against intact foot-and-mouth disease Virus (FMDV) particles bind to the retro-inverso analogue of fragment 141-159 of the viral coat protein VP1 of FMDV, variant A, equally well as to the parent peptide. A conformational investigation of this retro-inverso peptide was carried out by nmr spectroscopy and restrained molecular modeling in order to identify the structural basis for the antigenic mimicry between these retro-inverso and parent peptides. In 100% trifluoroethanol a well-defined left-handed α-helical region exists from residue 150 to residue 159, which is consistently present in all conformational families obtained from restrained modelling. A less-defined left-handed helical region is present in the tract 144-148, which is also consistent for all structures. Conformational flexibility exists about Gly149, which leads to two types of structures, either bent or linear. In the bent structures, a three-residue inverse tight turn is found, which can be classified as an inverse γ-turn centered at Gly149. The overall structural features of the retro-inverso peptide are shown to be similar to those of the parent L-peptide. The two molecules, however, are roughly mirror images because they share inherently chiral secondary structure elements. By comparing these conformational conclusions with the x-ray structure of the Fab complex of a corresponding VP1 antigenic fragment, a rationale is proposed to account for the topological requirements of specific recognition that are implied by the equivalent antigenic activity of the natural and retro-inverso compounds. © 1997 John Wiley & Sons, Inc. Biopoly 41: 569-590, 1997.
    Zusätzliches Material: 12 Ill.
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  • 88
    ISSN: 0006-3525
    Schlagwort(e): Leu-enkephalin ; [13C, 15N]-backbone-labeled ; reverse micelles ; conformation ; CD ; FTIR ; nmr ; distance geometry ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Enkephalin represents one of the bioactive peptide molecules most extensively investigated both in solution and in the crystal state. Depending upon the environment chosen for such studies, three main conformational states were identified for this flexible, linear pentapeptide - i.e., an extended conformation, a single-bend, and a double-bend structure. Since CD and Fourier transform ir (FTIR) spectra of Leu-enkephalin solubilized in negatively charged reverse micelles of bis (2-ethylhexyl)sulfosuccinate sodium salt/isooctane/water were supportive of a restricted conformational space of the aromatic side chains and of a bended type fold, we have analyzed by nmr the conformational preferences of Leu-enkephalin in reverse micelles using a synthetic [13C, 15N]-backbone-labeled sample. The overall conformation derived from nuclear Overhauser effect spectroscopy (NOESY) and 15N-filtered rotating frame NOESY (ROESY) spectra and by distance geometry calculations is a double-bend fold of the backbone that is comparable to one of the known x-ray structures. Thereby the tyrosine side chain is inserted into the hydrophobic core of the reverse micelles in a restrained conformational space as well evidenced by NOEs between the aromatic ring protons and the surfactant. The proximity of the aromatic rings of tyrosine and phenylalanine indicate a preferred structure consistent with the postulated conformation of the opioid peptide in the δ-receptor-bound state. These results confirm the interesting and promising properties of reverse micelles as membrane mimetica. © 1997 John Wiley & Sons, Inc. Biopoly 41: 591-606, 1997
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
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  • 89
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Biopolymers 41 (1997), S. 673-702 
    ISSN: 0006-3525
    Schlagwort(e): protein folding ; coupling effect ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A 1-4 and 2-3 residue-correlation model is proposed to predict the β-turns in proteins. The average rate of correct prediction for the 455 β-turn tetrapeptides and 4018 non-β-turn tetrapeptides in the training data base is 80.1%, and that for the 223 β-turn tetrapeptides and 12562 non-β-turn tetrapeptides in the testing data base is 80.9%. Compared with the rates of correct prediction based on the residue-independent model reported previously, the quality of prediction is significantly improved by the new model, implying that the correlation effect between the 1st and the 4th residues and that between the 2nd and 3rd residues along a tetrapeptide are important for forming a β-turn in a protein during the process of its folding. © 1997 John Wiley & Sons, Inc. Biopoly 41: 673-702, 1997
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  • 90
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Biopolymers 41 (1997), S. 721-729 
    ISSN: 0006-3525
    Schlagwort(e): Poly(β-L-aspartate)s ; helical conformations ; quantum mechanical calculations ; cooperative energy effects ; helix stability ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The conformational preferences of the monomeric units of a series of poly(α-alkyl-β-L-aspartate)s were examined by quantum mechanical calculations. α-Alkyl-β-aspartamyl m-oligopeptides with a number of residues m ranging from 1 to 7 and arranged in the conformations experimentally observed for their corresponding polymers were computed. Both their total relative energies and their cooperative energy differences were compared as a function of the length of the oligopeptide and the nature of the alkyl side group. Results revealed that the 13/4 helical arrangement is the most stable structure for the isolated polymer chain for any side group, although a 17/4 helix becomes favored in the case of methyl and ethyl groups due to the packing effects. On the other hand, the stability of the 4/1 helix appears to be the preferred conformation for side groups with a branched constitution. © 1997 John Wiley & Sons, Inc. Biopoly 41: 721-729, 1997
    Zusätzliches Material: 5 Ill.
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  • 91
    ISSN: 0006-3525
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: No abstract.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 92
    ISSN: 0006-3525
    Schlagwort(e): gastrin ; lipo-gastrin derivatives ; cholecystokinin-B/gastrin receptor ; molecular modeling ; ligand binding sites ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Double-tailed lipo-tetragastrin derivatives of increasing fatty acid chain length were used to identify the minimum size of the fatty acid moieties (≥C10) that restricts the access to the CCK-B/gastrin (CCK: cholecystokinin) receptor via a membrane-bound pathway. Then dimyristoyl-mercaptoglycerol/maleoyl-gastrin adducts of increasing peptide chain length were synthesized to define the minimal peptide size required for receptor binding affinities comparable to those of underivatized gastrin peptides despite anchorage of the lipid tails in the membrane bilayer. The experimental results indicated that most of the little-gastrin sequence, i.e., 2-17, is needed for optimal interaction of the molecule with the binding cleft of the receptor. From these data experimentally based restraints could be derived for docking of lipo-gastrin onto a CCK-B/gastrin receptor model applying molecular dynamics simulations and energy minimizations. In the receptor-bound state some of the secondary structure elements of gastrin as determined by nmr analysis of gastrin-peptides in low dielectric constant media are retained. The N-terminal gastrin portion interacts in a more or less extended conformation with the receptor surface, and upon a sharp kink at the Ala-Tyr dipeptide portion the C-terminal pentapeptide amide part inserts deeply into the helix bundle. Besides Arg-57 on top of helix 1 of the receptor, for which no potential interaction with the ligand could be detected, the other amino acid residues identified by mutagenesis studies as involved in gastrin recognition were found to interact with the C-terminal portion of gastrin. Even taking into account the strong limitations of such a model system, it represents an interesting tool for rationalizing the experimental results of the extensive structure-function studies performed previously on gastrin and to delineate more precisely the putative ligand binding site on the extracellular face of the receptor. © 1997 John Wiley & Sons, Inc. Biopoly 41: 799-817, 1997
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
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  • 93
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Biopolymers 42 (1997), S. 49-60 
    ISSN: 0006-3525
    Schlagwort(e): micellar catalysis ; cis/trans isomerization ; peptidyl-prolyl cis/trans isomerase ; proline ; FKBP12 ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Under physiological conditions, peptidyl-prolyl cis/trans isomerases catalyze powerfully the cis/trans isomerization of the -Xaa-Pro- bond (Xaa: natural amino acids) in oligopeptides and proteins (PPIases; EC 5.2.1.8). However, incorporation of proline containing tetrapeptide-4-nitroanilides in micelles and phospholipid vesicles also leads to increased rates of this unimolecular conformational interconversion. The isomerization rate was dependent on the detergent and vesicle concentration, respectively. The observed rate constants fit the pseudophase model of micellar catalysis allowing the calculation of micellar turnover numbers (kcismic) and dissociation constants (KCmic). Comparing kcismic values to the rate constants of the uncatalyzed cis to trans isomerization, an acceleration factor of about 20-fold was obtained for Suc-Ala-Phe-Pro-Phe-4-nitroanilide (Suc: succinyl) bound to zwitterionic SB12 (N-dodecyl-N,N-dimethylammonium-3-propanesulfonate) micelles. In addition, a marked increase in the population of the trans conformer relative to cis was noted for all investigated combinations of peptides and detergents. In a series of tetrapeptides, Suc-Ala-Xaa-Pro-Phe-4-nitroanilide kcismic/KCmic as well as kcismic values are linearly correlated with the high performance liquid chromatography capacity factor R′ describing the hydrophobicity of the amino acid Xaa. The same correlation can describe quantitatively the dependency of kcar/Km on substrate hydrophobicity for the FKBP12-catalyzed isomerization. Despite the great differences in catalytic power, these results confirm the suspicion that micelles and FKBP12 may share a common component in the catalytic mechanism of peptidyl-prolyl bond isomerization. © 1997 John Wiley & Sons, Inc. Biopoly 42: 49-60, 1997
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 94
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Biopolymers 42 (1997), S. 89-100 
    ISSN: 0006-3525
    Schlagwort(e): tapping mode atomic force microscopy ; scleroglucan networks ; denaturation-renaturation ; fractal dimension ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Tapping mode Atomic Force Microscopy (TmAFM) has been used to study the fungal polysaccharide scleroglucan deposited from aqueous solution and dimethyl sulfoxide (DMSO) onto a mica surface. The solutions from which the microscope samples were produced were prepared by first dissolving the solid scleroglucan in 0.1M NaOH, then neutralizing the solution with HCl, followed by dilution to the required concentration in either water or DMSO. It was found that from the aqueous solution described above, scleroglucan forms networks. Based on a comparison of the denatured-renatured and aqueous solution samples, network formation is due to the imperfect registration between the chains forming the triple helices. The relatively large stiffness of the scleroglucan triple helix is also assumed to contribute to the formation of the extended networks. The triple helix diameter was measured to be 0.92 ± 0.27 nm, which is in the same range as that obtained by other researchers using similar techniques. Denatured scleroglucan, deposited from DMSO onto mica, forms a web-like layer on top of which there are sphere-like structures. These morphologies are believed to be due to triple helix denaturation yielding highly flexible single chains in DMSO, which results in coiling and web-like dense packing of scleroglucan upon deposition onto mica. Most interestingly after addition of water to the samples deposited from DMSO, some of the chains can be renatured into short, stiff rod-like structures which are similar to the structures observed by other researchers. The imaging data for aqueous solution deposition can be analyzed by plotting maximum end-to-end distance versus the perimeter of the networks deposited onto mica. This yields a Flory-like exponent of 0.67, which is almost similar in value to that obtained by other researchers for linear structures of scleroglucan but less than that expected for a polymer chain following a self-avoiding walk (v = 0.75) model on a two-dimensional surface. The fractal dimension that can be used to characterize the networks was determined graphically to be 1.22 ± 0.06. © 1997 John Wiley & Sons, Inc. Biopoly 42: 89-100, 1997
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
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  • 95
    ISSN: 0006-3525
    Schlagwort(e): triple helix stabilization ; intercalation ; DNA ligands ; benzo[4,3-b]indole ; polynucleotides ; linear dichroism ; CD ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The binding modes of three benzopyrido [4,3-b]indole derivatives (and one benzo[-f]pyrido [4-3b] quinoxaline derivative) with respect to double helical poly(dA) · poly(dT) and poly[d(A-T)]2 and triple-helical poly(dA) · 2poly(dT) have been investigated using linear dichroism (LD) and CD: (I) 3-methoxy-11-amino-BePI where BePI = (7H-8-methyl-benzo[e]pyrido [4,3-b]indole), (II) 3-methoxy-11-[(3′-amino) propylamino]-BePI, (III) 3-methoxy-7-[(3′-diethylamino)propylamino] BgPI where BgPI = (benzo[g]pyrido[4,3-b]indole), and (IV) 3-methoxy-11-[(3′-amino)propylamino] B f P Q where B f P Q = {benzo[-f]pyrido[4-3b]quinoxaline}. The magnitudes of the reduced LD of the electronic transitions of the polynucleotide bases and of the bound ligands are generally very similar, suggesting an orientation of the plane of the ligands' fused-ring systems preferentially perpendicular to the helix axis. The LD results suggest that all of the ligands are intercalated for all three polynucleotides. The induced CD spectrum of the BePI chromophore in the (II-BePI)-poly[d(A-T)]2 complex is almost a mirror image of that for the (I-BePI)-poly(dA) · poly(dT) and (I-BePI)-poly(dA) · 2poly(dT) complexes, suggesting an antisymmetric orientation of the BePI moiety upon intercalation in poly[d(A-T)]2 compared to the other polynucleotides. The induced CD of I-BePI bound to poly(dA) · 2poly(dT) suggests a geometry that is intermediate between that of its other two complexes. The concluded intercalative binding as well as the conformational variations between the different BePI complexes are of interest in relation to the fact that BePI derivatives are triplex stabilizers. © 1997 John Wiley & Sons, Inc. Biopoly 42: 101-111, 1997
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 96
    ISSN: 0006-3525
    Schlagwort(e): molecular modeling ; c-erbB2 receptor ; dimerization ; coiled-coil structure ; wild transmembrane helices ; oncogenic transmembrane helices ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Dimerization models of c-erbB2 transmembrane domains (Leu651-Ile675) are studied by molecular mechanics and molecular dynamics simulations. Both wild and Glu mutated transmembrane helices exhibit the same relative orientation for favorable associations and dimerize preferentially in left-handed coiled-coil structures. The mutation point 659 belongs to the interfacing residues, and in the transforming domain, symmetric hydrogen bonds between Glu carboxylic groups stabilize the dimeric structure. The same helix packing found for the wild dimers, except side-chain - side-chain hydrogen bonds, suggests that the transmembrane domains dimerize according to similar process. Structural and energetical characterization of the models are presented. © 1997 John Wiley & Sons, Inc. Biopoly 42: 157-168, 1997
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 97
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Biopolymers 42 (1997), S. 183-189 
    ISSN: 0006-3525
    Schlagwort(e): electrophoresis ; retardation ; native proteins ; semidilute polymer solution ; scaling theory ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The retardation of proteins in the Mt range of 15-500 kDa in capillary electrophoresis conducted in semidilute solutions of the polymer polyethylene glycol (Mt range 0.2-8.0 × 106), was measured. The purpose was to test the predictions of the scaling theory with regard to the relation of retardation to (a) the Mt of the polymer, (b) the concentration of the polymer, and (c) the radius of the protein particles. These predictions derive from a mechanism that relates retardation to the screening length of the polymer solution, viewed as the average distance between the entanglement points of polymer chains.For the molecular weight range from 60 to 500 kDa of (near) spherical proteins, the retardation was found to be related to polymer concentration c asμ/μo = exp(-Ac0.69)where μ/μ0 is the retardation expressed as the ratio between the mobility in polymer solution and that in free solution. The value of the exponent of 0.69 is in close agreement with the value of 0.75 predicted by the scaling theory. Parameter A was found (a) to scale as the 0.04th power of Mt (polymer), approximating the predicted value of 0; and (b) to be proportional to particle radius as predicted. All measured values of retardation were independent of electric field strength in the range of 37-370 V/cm. Thus, experimental findings are consistent with the mechanism relating electrophoretic retardation to the screening length of the polymer network in the specified molecular weight range of proteins.Under the same conditions, log(μ/μ0) of proteins with Mt's less than 60 kDa (a) scales as the -0.06th power of Mt (polymer), and (b) is proportional to polymer concentration, suggesting a retardation mechanism that is not related to the screening length. © 1997 John Wiley & Sons, Inc. Biopoly 42: 183-189, 1997
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 98
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Biopolymers 42 (1997), S. 191-202 
    ISSN: 0006-3525
    Schlagwort(e): molecular volume ; van der Waals radius ; molecular orbital calculation ; accessible surface area ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Molecular volumes for hydrocarbons, amino acids, peptides, and 14 globular proteins were calculated by techniques using van der Waals radii and by semiempirical molecular orbital methods. The resulting values were compared to experimentally determined volumes. The values obtained by methods employing van der Waals radii were found to be up to three times smaller than the experimentally determined values in the case of proteins, 25% smaller than the experimental values for peptides, and up to 50% greater than experimental values for simple hydrocarbons. For the semiempirical calculations, neither the type nor precision of the calculation altered the percentage of the electron density required to reproduce the experimentally observed volumes for any of the different types of molecules tested. For molecules en vacuo, the amount of electron density included was approximately 98.5% of the total calculated value. For solvated molecules, the percentage was closer to 99.5%. From the results of our studies, we conclude that semiempirical techniques are more reliable, less arbitrary, and hence are more accurate for the determination of molecular volumes. The methods by which we employ semiempirical techniques for determination of molecular volume will be described in detail. © 1997 John Wiley & Sons, Inc. Biopoly 42: 191-202, 1997
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 99
    ISSN: 0006-3525
    Schlagwort(e): fourier transform ir spectroscopy ; protein conformations ; cytochrome C ; Langmuir-Blodgett film ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A qualitative and quantitative analysis of the conformation of Langmuir-Blodgett (LB) dried films of cytochrome C on silicon wafers was performed by Fourier transform ir (FTIR) spectroscopy. A deconvolution procedure was applied to the amide I band analysis, in order to determine the percentage of the different secondary structures. Qualitative analysis was performed by examining difference spectra.Films obtained by spreading protein solutions at pH 7.4 and 1, dried at 25 and 100°C, on silicon wafers were also examined in order to detect spectral components associated with denatured protein domains, and to compare them with cytochrome C LB films.FTIR spectroscopy showed that the following important changes characterise LB film spectra: (a) the α-helix component is higher (its percentage is 57 and 54%) than the one estimated in dried film obtained by spreading the solutions at pH 7.4 on a silicon substrate (43%), (b) there is an increase in the intensity of bands attributed to protonated carboxy group bands, involved and not involved in the formation of hydrogen bonds, and a decrease in those attributed to deprotonated carboxy groups, (c) the intensity of several bands attributed to aromatic amino acids and aliphatic chains increases, and (d) bands due to O(SINGLEBOND)H stretching vibrations of crystallization water are present.These conformational changes could be induced by protein-protein interaction caused by the close packing of molecules that occurs during LB film formation; it cannot be excluded that they may be accompanied by partial changes in the tertiary structure of the protein. A preferential orientation of protein molecules in LB films is also a possibility. © 1997 John Wiley & Sons, Inc. Biopoly 42: 227-237, 1997
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 100
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Biopolymers 41 (1997), S. 407-418 
    ISSN: 0006-3525
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Zinc fingers, 30-residue peptides anchored on Zn(II) coordinated to pairs of cysteines and histidines, recognize DNA triplets and, as tandem modules, effect sequence read out. The focus of zinc finger-DNA interaction studies thus far has been to probe the nature of the binding of the 12-residue recognition element of the finger with DNA code bases. To understand the possible role of the Zn(II) ligand and to assess its own DNA interaction profile, [(CH)2Zn] (C: cysteine; H: histidine; Figure 1) was constructed from bis-t Boc-cystinyl-di-His-OMe via thiol-disulfide exchange, Zn(II) complexation, and deprotection. [(CH)2Zn] binds with polyd- (G·C)·polyd(G·C) with association constants - 1.8 × 107 M-1 (specific DNA-phosphate) and 3.3 × 103 M-1 (nonspecific DNA-phosphate); perturbs its B-DNA profile; and enhances the Tm from 62.5 to 70.15°C in a concentration-independent manner, with an ideal reversal profile on cooling, not observed in the DNA alone; releases polyd(G·C)·polyd(G·C)-bound ethidium bromide; enhances the fluorescence of polyd(G·C)·polyd(G·C)-bound ethidium bromide at low concentrations; and quenches it at higher ranges. [(CH)2Zn] also binds to d(ACGCTGGGCGT), the sequence associated with Zif-268, 3-finger binding site. Such interactions were not seen in parallel studies with (a) polyd(A·T)·polyd(A·T) and [(CH)2Zn] and (b) {[C′H2] (C′: cystine; H: histidine; the direct metal-free precursor of [(CH)2Zn]}, ionic zinc nitrate, and covalent zinc acetyl acetonate Zn(AcAc)2, with poly[d(G·C)·polyd(G·C)].The results are rationalized on the basis of two types of association between [(CH)2Zn] and polyd(G·C)·polyd(G·C), a nonspecific recognition of the sugar phosphate backbone, by an imidazole of [(CH)2Zn] and a specific one involving the amino group of [(CH)2Zn] and the guanine base of DNA. Control experiments show that the latter greatly promotes DNA recognition. The possibility for such specific interactions with relatively small structures of the type [(CH)2Zn] would be of use in the design of DNA recognition elements and also provide an explanation for the experimentally found variation in the placement of the zinc finger docking unit around the major groove of DNA. © 1997 John Wiley & Sons, Inc.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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