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  • 1985-1989  (734)
  • 1980-1984
  • 1986  (734)
  • Inorganic Chemistry  (668)
  • Ultrastructure
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    European archives of oto-rhino-laryngology and head & neck 243 (1986), S. 121-125 
    ISSN: 1434-4726
    Keywords: Bacterial labyrinthitis ; Ultrastructure ; Mycobacterium ; Mouse
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary We used electron microscopy to investigate Mycobacterium fortuitum -induced changes in the inner ears of mice. We found that the inner and outer hair cells had degenerated and disappeared in the organ of Corti. Changes in the lower turn of the cochlea were more severe than those of the upper turn while the changes of the outer hair cells were more severe than those of the inner hair cells. Disappearance, fusion and ballooning of the sensory hairs were observed in the vestibular organs. The bacterial extract also induced inner ear damage which was similar to that caused by live M. fortuitum.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    European archives of oto-rhino-laryngology and head & neck 243 (1986), S. 260-264 
    ISSN: 1434-4726
    Keywords: Argyria ; Chemosensory function ; Oral Mucosa ; Ultrastructure ; X-ray microanalysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Generalized argyrosis can produce a number of abnormalities, including skin discoloration, liver and kidney dysfunction. We describe a patient with generalized argyrosis following long-term self-treatment with oral silver intake, in whom skin discoloration, progressive taste and smell disorders, vertigo and hypesthesia were observed. These findings were confirmed by chemosensory tests and electrophysiological investigations. The development of hypogeusia was assessed by subjective tests, while the progression of hyposmia was followed by recording olfactory evoked cortical potentials. Light and electron microscopy of tissue samplings demonstrated electron-dense mineral deposits in basal membranes, in macrophages, in the perineurium of peripheral nerves, along elastic and collagenous fibers, and in necrotic cells of the oral submucosa. Silver and sulfur deposits in affected tissues could be defined by X-ray microanalysis. The quantitative ratio between silver and sulfur in involved tissues was similar to that of an inorganic silver-sulfide (Ag2S) standard. The minute increase in the sulfur content when compared to the inorganic standard suggested a sulfur containing organic matrix of the tissue precipitates. Our findings indicate that the affinity of silver for membrane and neuronal structures and the deposition of silver as an insoluble compound (Ag2S) induce the progression of clinical disease.
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  • 3
    ISSN: 1432-0584
    Keywords: Karyotype ; Bladder carcinoma ; Ultrastructure ; CSF ; Cell line
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The cell line 5637 which originated from a human urinary bladder carcinoma is known to produce GM-CSF and Multi-CSF ectopically. Determination of cell surface antigens defined by monoclonal antibodies was recently reported [6]. Here we report on the ultrastructure and karyology of this CSF secreting cell line. At the ultrastructural level the monolayer in vitro culture and the solid tumors formed in nude mice showed all characteristics consistent with a well-differentiated transitional cell carcinoma (TCC). A subclone was found to grow in suspension and did not secrete any CSF activity. High resolution chromsome analysis revealed chromosomal abnormalities which agreed only in few particulars with nonrandom chromosomal aberrations usually found in TCC. Analysis of the cytogenetic results showed that nearly all structural abnormalities present are known to be associated with acute or chronic human leukemia. The possibility that the ectopic production of CSF in this cell line may be correlated to one or more of the described chromosomal aberrations is discussed.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Archives of dermatological research 278 (1986), S. 398-406 
    ISSN: 1432-069X
    Keywords: Nevocytic nevi ; Congenital ; Ultrastructure ; Nevus cells ; Nerve contacts
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary As only few previous investigations considered size-dependent differences in the histology of congenital nevocytic nevi (CNN) or focused on their ultrastructure, a light- and electron-microscopic study of six giant and six medium-sized CNN was performed. Histologically, giant CNN showed minimal junctional nevus elements and a pandermal, diffuse nevus cell extension including the subcutaneous tissue, while medium-sized CNN exhibited more abundant junctional nests and a rather focal pattern of nevus cell extension into the reticular dermis. Ultrastructurally, giant CNN often showed nevus cells with irregular and indented nuclei and also nevus cells with highly complicated dendrites. Nuclear inclusions, multiple cilia and centrioles, and collagen phagocytosis in nevus cells were found in both groups of CNN. Direct contacts between nevus cells and nerve fibers were observed in mediumsized CNN only. The findings provided no clear morphological indication why giant CNN have a higher risk for malignant degeneration than medium-sized CNN or acquired nevocytic nevi (ANN). On the other hand, the histological differences speak in favor of a different ontogenesis of the various size classes of CNN and ANN.
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  • 5
    ISSN: 1432-2307
    Keywords: Epithelioid haemangioendothelioma ; IVBAT ; Immunohistochemistry ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Three patients with epithelioid haemangioendothelioma (EHE) are described. Two patients presented with pulmonary infiltrates and one with a hepatic tumour. All had a metastatic disease ending fatally, and all were autopsied. The diagnosis was confirmed either by immunohistological or ultrastructural analysis. All three tumours were cytokeratin-negative and vimentin-positive, while only two contained cells reacting with the antibody of factor VIII-related antigen. Electron microscopy of the third tumour revealed features indicating endothelial differentation. A short literature review is also presented demonstrating that the outlook of EHE is worse than previously thought.
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  • 6
    ISSN: 1432-2307
    Keywords: Mesothelioma ; Serous membrane ; Localized tumour ; Histogenesis ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary It is uncertain whether localized lesions of serosal membranes have a kinship to mesotheliomas or are truly fibromatous in nature. Ultrastructural and immunohistochemical investigations were carried out on 12 localized benign and malignant pleural and peritoneal tumours from 10 patients. Electron microscopic findings, including the consistent and non-fibroblastic cellular organization of localized neoplasms, the presence of some form of intercellular junctions in 7 of 10 cases, basal lamina deposition in 3 cases, and polarized microvilli in one case indicated a form of mesothelial differentiation. Using monoclonal and polyclonal antibodies, positive immunostaining of tumour cells for cytokeratin peptides was detected in one case, while antibody to vimentin stained four cases. Light microscopic, ultrastructural and immunohistochemical features of one benign localized serosal tumour, with a unique blend of epithelial and spindle cells, provided further evidence for a histogenic link between localized serosal tumours and diffuse epithelial mesotheliomas. On the basis of the current findings and reports in the literature, it would appear that the majority of localized tumours of serosal membranes are a subset of mesothelioma, while a minority are fibromas.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Virchows Archiv 410 (1986), S. 43-48 
    ISSN: 1432-2307
    Keywords: Endocarditis ; Staphylococcus ; Colonisation ; Morphology ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The initial colonization, byStaphylococcus aureus, of the catheter damaged aortic valve and aorta of the rabbit, was examined by light and electron microscopy at 15 min, 3 h and 24 h post inoculation (PI). At 15 min PI, the majority of bacteria (80%) were located on the lateral surfaces of the thrombic vegetations while 20% were attached directly to the connective tissue of the aortic valve and aorta in areas where the endothelial lining was disrupted. By 3 h the bacteria on the thrombic vegetations were covered by fibrin. At this time, the bacteria both within the vegetations and on the surface of the vasculature were undergoing multiplication to form small groups. The precipitation of thrombus around the bacteria attached to the surface of the aorta to form microscopic infected vegetations had occurred by 24 h PI. The colonizing bacteria did not elicit any phagocytic response. The colonization of the cardiovasculature byStaph. aureus did not necessarily require pre-existing vegetations.
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  • 8
    ISSN: 1432-2307
    Keywords: Human acute pancreatitis ; Enzyme immunocytochemistry ; Ultrastructure ; Acinar cell degranulation ; Fat necrosis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Human acute pancreatitis results from an autodigestive process frequently associated with alcohol abuse, gall stone disease and shock. Peripancreatic fat necrosis was identified as one of the earliest visible lesions, whereas acinar cell necrosis and haemorrhage were regarded as secondary changes. To examine the alterations in acinar cells in more detail, their enzyme content and fine structural features were studied immunocytochemically using antisera against α-amylase, lipase, trypsin, chymotrypsin and pancreatic stone protein, and electronmicroscopically in pancreatic tissues from patients with severe acute pancreatitis. Peripheral acinar cells in the immediate vicinity of fat necrosis were found to be heavily degranulated, while acinar cells at some distance of necrosis fully retained their enzyme content. Other frequent changes of the acinar cells included cuboidal transformation, loss of microvilli, increased occurrence of autophagosomes, and formation of enlarged acinar lumina. As there was no apparent cell membrane leakage or rupture of duct lumina, it is concluded that the acinar cells adjacent to fat necrosis release their granules by undirected basolateral extrusion. The findings thus suggest that one of the basic defects in acute pancreatitis is the uncontrolled release of enzymes from peripheral acinar cells into the interstitial space which, in turn, presumably by the action of lipase, leads to autodigestive fat necrosis.
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  • 9
    ISSN: 1434-0879
    Keywords: Monkey spermatozoa ; Gossypol effect ; In vivo examination ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The present study examines the ultrastructure of ejaculated spermatoza from bonnet monkey, Macaca radiata under noraml conditions, with gossypol treatment and during recovery from such treatment. Monkeys were fed orally with gossypol acetic acid (GAA) for 3 months (4 mg/monkey/5 days a weak). Semen samples collected by electroejaculation, and the spermatozoa were examined using both light and electron microscopy. The degree of motility was also noted by Kalla et al. [12]. Ejaculated spermatoza were immotile 90 days after GAA treatment, but little evidence for any abnormality in the spermatozoa could be seen by light microscopy. Some ultrastructural changes were observed, but not to the extent previously reported in spermatozoa of Macaca fascicularis [23]. After termination of treatment, semen samples were obtained every 5th day until sperm count and motility recovered to the normal level. After 90 days only a small proportion of spermatozoa showed abnormal structure. We conclude that in a subhuman animal model gossypol induced effects on sperm motility and morphology are reversible.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 173 (1986), S. 295-298 
    ISSN: 1432-0568
    Keywords: Cardiodilatin ; Peptide Hormone ; Heart ; Human ; Immunohistochemistry ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The immunogold technique was applied to detect cardiodilatin-immunoreactivity (CDD-IR) in human heart. Using antibodies directed against C-terminal regions of CDD, we could identify colloidal gold label in specific atrial granules of human heart. The granules in all areas of the myoendocrine cells were homogeneously labelled and all right atrial biopsy specimen of patients with different heart diseases reacted positively and had the same distribution of label. The Golgi-apparatus and ergastoplasma exhibited and extremely weak CDD-IR. The results indicate a predominant storage of CDD in specific granules.
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 173 (1986), S. 361-370 
    ISSN: 1432-0568
    Keywords: Electrical synapses ; Chemical synapses ; Ultrastructure ; Morphometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Thin sectioning and freeze-fracturing have revealed the distribution of gap junctions and chemical synapses in the synaptic interface of the large myelinated club endings on the lateral dendrite of the goldfish Mauthner cell. In 12 samples of club endings fractured completely or nearly completely, the apposed synaptic membrane area averaged 39.090 μm2, of which 16.6% was occupied by gap junctions and about 4 to 5% by the active zones of chemical synapses. The numerical profile density (number per unit area of the synaptic membrane) of gap junctions varied greatly, from 1.78 to 6.30, and was mostly in inverse proportion to their size. The chemical synapses were located mainly in two places: in the circumferential rim of the synaptic membrane next to the widened extracellular space, and in the margins of intraterminal invaginations of the synaptic cleft. The axoplasm of the preterminal axon, just after losing its myelin sheath, was filled with microtubules, among which neurofilaments gathered into many small bundles. The correlation between the areas of gap junctions and the chemical synapses and the amplitude of the excitatory postsynaptic potentials (EPSP) is discussed.
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 173 (1986), S. 385-391 
    ISSN: 1432-0568
    Keywords: Elastic cartilage ; Chondrogenesis ; External ear ; Rat ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Selected ultrastructural features of chondrocytes and the extracellular matrix in the developing elastic cartilage of the external ear were studied in rat fetuses and young animals. The cytoplasmic lipid droplets were first observed in the 19-day fetus. They increase in number and size during the first post-natal week. The elastogenesis proceeds in the sequence: oxytalan fibers (17-day fetus), elaunin fibers (1-day rat), elastic fibers (5-day rat). Intermediary stages between the randomly oriented individual microfibrils and bundles of microfibrils (oxytalan fibers) were also observed.
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 174 (1986), S. 27-33 
    ISSN: 1432-0568
    Keywords: Cerebral cortex ; Antisera ; Biopsy ; Postmortem Alzheimer's type dementia ; Ultrastructure ; Epilepsy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary NPY-containing neuronal structures in the cereoral cortex of surgical tissue samples were compared to those in postmortem material by immunocytochemical methods. However, the quality of preservation of individual neurons and axonal and dendritic plexuses in the neuropil is unusually fine in the surgical specimens. This result is most likely attributable to the excellent fixation that can be regularly achieved by rapid and careful handling of tissue during and after surgical removal. The tissue is suitable for both light and electron microscopy, and the superior preservation also leads to intense, reliable antibody reactions. Postmortem tissue samples can provide good specimens for immunocytochemistry when properly handled as previously described. However the postmortem delays prior to fixation disrupt neuronal integrity in the immunostained structures. Nevertheless, postmortem material from carefully studied subjects of neurological diseases compared with age matched controls can provide valuable information.
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  • 14
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 173 (1986), S. 317-322 
    ISSN: 1432-0568
    Keywords: Paneth cell ; Ultrastructure ; Morphometry ; Germfree rats ; Ex-germfree rats
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Ultrastructural changes of Paneth cells of germfree (Gf) rats which had been inoculated with bacteria-containing feces from conventionally-reared (SPF) rats were quantitatively examined. 12 and 24 h after inoculation, the Paneth cells showed a striking decrease in the number of secretory granules and the occurrence of large vacuoles. Phagosomes containing bacteria were not seen. After 4 days, the secretory granules reaccumulated and smooth-surfaced apical vesicles increased in number. It is discussed that the large vacuoles may be related to membrane-retrieval events following the massive extrusion of secretory granules whereas the apical vesicles appear to serve this function when exocytosis is not pronounced. In addition to the large secretory granules ca. 10% of Paneth cell profiles contained a few dense-cored vesicles measuring about 150 nm in diameter which resemble peptidergic neurosecretory granules.
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  • 15
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 71 (1986), S. 83-87 
    ISSN: 1432-0533
    Keywords: Astrocytes ; Brain neoplasms ; Oligodendroglioma ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Ultrastructural concentric laminations have previously been thought to be specific to oligodendroglioma. However, these structures were also recognized in fibrillary astrocytomas, a mixed glioma and a glioblastoma. These laminations continued or closely related to attenuated processes or cytoplasm of astrocytic tumor cells. In addition, some lamellae contained glial filaments. It is considered that the concentric laminations are derived from attenuated astrocytic processes and have no relationship with myelin.
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  • 16
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 70 (1986), S. 44-52 
    ISSN: 1432-0533
    Keywords: Gliosarcoma ; Myxoid tumor ; Extracranial metastasis ; Ultrastructure ; Immunohistochemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The case of a 22-year-old female suffering from glioblastoma with sarcomatous component (WHO; gliosarcoma) is presented. The tumor consisted of glioblastomatous and sarcomatouos components, and in part of the pleomorphic astrocytomatous region of the glioblastoma there was a prominent production of myxoid matrix. On the basis of its histochemical and immunohistochemical characteristics, the present case strongly suggested that glial cells of neuroectodermal origin assume part of the responsibility for production of myxoid material.
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  • 17
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 72 (1986), S. 134-141 
    ISSN: 1432-0533
    Keywords: Cerebral embolism ; Fungal vasculitis ; Paecilomyces javanicus ; Prosthetic valve endocarditis ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary A 41-year-old diabetic woman developed Paecilomyces javanicus endocarditis and subsequent cerebral fungal embolism and vasculitis with massive infarction and hemorrhage 6 years after a mitral valve replacement with porcine heterograft. The organism was identified by the culture from the infected brain tissue and aortic valve. Cerebral infection due to fungus Paecilomyces is rare. This report documents the cerebral manifestations of fungus Paecilomyces javanicus and describes for the first time the ultrastructure of such an organism obtained from the infected tissue. Their ultrastructural findings, similar to those described in Paecilomyces farinosus derived from culture, include a double-layered cell wall, a triple unit plasma membrane, abundant cytoplasmic lipid droplets, vacuoles, membranous profiles and septal formation. This report further demonstrates hyphae with packed 50A filaments and granulofibrillary material and features suggestive of intrahyphal hyphae, not previously described in fungus Paecilomyces.
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  • 18
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 70 (1986), S. 127-134 
    ISSN: 1432-0533
    Keywords: Avian muscle spindle ; Denervation ; Intrafusal fiber ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The role of the nerve in maintaining the ultrastructural integrity of avian muscle spindles was investigated by denervating the pigcon's extensor digitorum communis for periods of 10, 19, and 28 days. The equatorial region of control intrafusal fibers had a reduced density of myofilaments. Sensory endings contained mitochondria and structures resembling synaptic vesicles, and were associated with satellite cells. In the polar region, fibers had a high concentration of myofilaments; small motor endings, unlike sensory endings, lay outside of the fiber's basal lamina. The outer capsule consisted of thin, tightly layered cells which gradually became reduced in number distal to the equatorial region. In both equatorial and polar regions the capsule became more disrupted with longer denervation periods, and lysosomes and phagocytes became more abundant. The equatorial region of denervated fibers contained many myofibrils and some had peripherally-located nuclei, unlike the controls; sensory terminals were absent. The polar region of some fibers had disorganized myofilaments and others had a reduced myofilament density. Fiber diameters increased significantly in both regions. Thus, denervated intrafusal fibers lost some characteristics which distinguish them from extrafusal fibers.
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  • 19
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 70 (1986), S. 71-74 
    ISSN: 1432-0533
    Keywords: 6-Aminonicotinamide ; Ependymal cell ; Mitosis ; Suckling mice ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Mitotic ependymal cells were encountered in 10-day-old mice treated with 6-aminonicotinamide, an antagonist of niacin. These occurred along the medial surface of the lateral ventricle and the ventral portion of the aqueduct. Electron microscopy revealed that both mitotic ependymal cells had eccentrically placed chromosomes without a nuclear membrane and well-formed gap junctions in contact with adjacent ependymal cells. Microtubules from a centriole radiated to the chromosomes. These data show that cell division occurs in morphologically matured ependymal cells in the postnatal brain under pathological conditions. We believe this to be the first ultrastructural demonstration of this phenomenon.
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  • 20
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 174 (1986), S. 379-389 
    ISSN: 1432-0568
    Keywords: Lungs ; Amphibia ; Ultrastructure ; Morphometry ; Surfactant
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Lungs ofHyla arborea L. were examined by scanning and transmission electron microscopy and morphometric methods. The lungs contain several interconnected folds in a netlike reticular arrangement of first, second and third order, mainly covered with pneumocytes. On the septa of first and second order, irregularly distributed small patches of ciliated epithelium devoid of goblet cells are located. Dome-shaped neuroepithelial bodies can be seen in the vicinity of ciliated epithelium. The pulmonary epithelium consists of one type of pneumocyte, which contain in their cytoplasm three kinds of bodies: lamellar, dense and multivesicular. The dense bodies are precursors of lamellar bodies (LBs), while the multivesicular bodies are incorporated into the LBs, being later secreted to the air space. The lining layer covering the internal lung surface contains numerous transformed LBs but tubular myelin figures are scarce. The surface of the lining layer is coated by a thin film. The air-blood barrier, consisting of three layers: epithelium, interstitial space and endothelium, is 0.6 μm thick.
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  • 21
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 69 (1986), S. 81-90 
    ISSN: 1432-0533
    Keywords: Creutzfeldt-Jacob disease ; Slow virus infection ; Subacute spongiform encephalopathy ; Ultrastructure ; Synapse
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Guinea pigs inoculated with brain homogenate from serially passaged Creutzfeldt-Jakob disease (CJD) were killed biweekly starting at week 2 until terminal illness (about 200 days following inoculation). A mild swelling of postsynaptic dendrites and an increase in the number of glial filaments in astrocytic processes was seen at week 4, followed by increased swelling and lucency of axons and dendrites by week 6 post inoculation (p.i.). Severe undulation and focal interruptions of synaptic membranes were also observed both at weeks 4 and 6. By week 8, one could see cystically dilated cellular processes. These sometimes showed continuity with adjacent swollen processes through focally disrupted plasma membranes, and most likely represent a progressive enlargement of vacuoles through fusion and subsequent addition of adjoining processes. The spongiform changes increased mildly between week 8 and week 10 and remained essentially the same in subsequent weeks. After week 24 there was a sharp increase in both the number and size of vacuoles. At week 24 severe structural alterations were present both in the neurons and astrocytes, and numerous intranuclear inclusions were demonstrated in many neuronal nuclei. This study shows that morphological changes in the brain occur considerably earlier than the clinical manifestations of the disease. In the early phase of the disease, there were significant alterations on the dendrites and synapses.
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  • 22
    ISSN: 1432-0533
    Keywords: Streptozotocin-diabetic rat ; Myenteric plexus ; VIP-ergic nerves ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Enteric nerves in the ileum of rats 8 weeks after streptozotocin-induction of diabetes were examined under the electron microscope before and after immunolabeling for vasoactive intestinal polypeptide (VIP). These studies have provided evidence of degenerative changes in the myenteric nerve fibres of diabetic rats, many of which were shown to contain VIP. It is suggested that VIP-ergic nerves in the gut may play a role in the developent of gastrointestinal dysfunction in diabetes.
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  • 23
    ISSN: 1432-0533
    Keywords: Brain tumor ; Rhabdomyosarcoma ; Immunohistochemistry ; Ultrastructure ; Cerebral paragonimiasis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary A necropsy case of a primary rhabdomyosarcoma with chronic paragonimiasis in the cerebrum of a 68-year-old man is reported. The clinical data showed a right hemiplegia and dysarthria which became lethal in 6 months even though operation and radiation therapy were performed. Computed tomography revealed a large low-density area associated with the peripheral enhancement in the left basal ganglia, and multiple conglomerated calcified masses in the left temporal and occipital lobes. Biopsied and necropsied materials of the tumor in the basal ganglia was reddish brown in color and histologically was composed of purely mesenchymal derivatives with both embryonal and mature striated muscle cells but neither neuronal nor glial elements. Some of the tumor cells with extending slender cytoplasms showed obvious cross striations at the light and electron microscope levels and immunohistochemical reactivity for myoglobin. All tumor cells were also positive for vimentin, but not for glial fibrillary acidic protein. The clinical and necropsy findings revealed no primary lesion anywhere but in the brain. In addition, numerous dead oval eggs ofParagonimus westermani were found in many cystoid lesions encapsulated by thick connective tissues with calcification and/or ossification. Clinicopathological features of 24 cases of primary rhabdomyosarcoma of the central nervous system reported in the literature are reviewed briefly. The histogenesis of this tumor are discussed together with comments on cerebral paragonimiasis.
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  • 24
    Electronic Resource
    Electronic Resource
    Springer
    Archives of dermatological research 279 (1986), S. 77-82 
    ISSN: 1432-069X
    Keywords: Lichen nitidus ; Lichen plahus ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Lichen nitidus (LN) and lichen planus (LP) are considered by some investigators to be two variants of the same disease, and by others to be two distinct dermatoses. In order to obtain further information about the relationship between LN and LP we examined the ultrastructure of lesions from two LN patients. In the central part of the lesion, the basement membrane was absent, or was interrupted by migrating phagocytes or lymphocytes. The basal cells and the lower cells of the stratum spinosum exhibited karyolysis and appeared to be compressed and often necrotic. In the upper dermis irregular cell debris full of clumps of tonofilaments and colloid-body-like structures was observed. A dense dermal infiltrate of macrophages, lymphocytes, fibrocytes, and Sezary-like cells was present. Signs of cooperation between lymphocytes and macrophages were also evident. The periphery of the lesion showed no pathological features except for enlargement of the intercellular spaces and the presence of mononuclear cells scattered through the epidermis. Several normal Langerhans cells were noticed. These ultrastructural findings were quite similar to those reported for LP.
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  • 25
    Electronic Resource
    Electronic Resource
    Springer
    Cellular and molecular life sciences 42 (1986), S. 144-147 
    ISSN: 1420-9071
    Keywords: Ultrastructure ; catalase ; D-amino acid oxidase ; fetal mouse liver ; hepatocytes ; peroxisomes ; muscular dysgenesis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary In the hepatocytes of ‘normal’ fetal mice from mothers which were carriers of muscular dysgenesis, catalase and D-amino acid oxidase (DAAO) positive as well as negative peroxisomes were observed. DAAO reaction product was occasionally localized in patches around cell membranes and DAAO-positive peroxisomes were frequently observed near mitochondria.
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  • 26
    ISSN: 1432-1106
    Keywords: Optic tectum ; Neurotransmitters ; Cholinergic markers ; Ultrastructure ; Goldfish
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Neurochemical parameters associated with cholinergic and excitatory amino acid transmission, were measured in synaptosomes of the goldfish optic tectum at different times after unilateral eye ablation. Significant decreases in choline acetyltransferase and acetylcholinesterase were measured 12 and 30 days after enucleation. The high affinity choline uptake did not parallel the decrease in cholinergic enzymes. Instead there was a significant increase of the uptake per unit of protein (though not relative to the total number of tectal synaptosomes). No decrease of the high affinity D-3H aspartate uptake was measured in the deafferentated optic tectum. Electron microscopic observations showed a correspondence between the time course of cholinergic enzyme decrease and the degeneration of retinal afferents to the tectum. The present results support the notion that acetylcholine is a better candidate than the excitatory amino acids for a neurotransmitter role in the fish optic tectum.
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  • 27
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    European journal of pediatrics 144 (1986), S. 557-562 
    ISSN: 1432-1076
    Keywords: Rimmed vacuoles ; Childhood ; Myopathy ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract A 5-year-old boy suffered from a slowly progressive non-familial neuromuscular disease, clinically marked by generalised muscle weakness, atrophy and hypotonia, a “myopathic” EMG and mildly elevated CK values. His gastrocnemius muscle showed marked myopathy, type I fibre predominance, and numerous “rimmed” vacuoles. This boy's condition is regarded as a childhood neuromuscular disease with rimmed vacuoles.
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  • 28
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    Child's nervous system 2 (1986), S. 297-300 
    ISSN: 1433-0350
    Keywords: Pineocytoma ; Magnetic resonance imaging ; Computed tomography ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The radiological and pathological findings in three children with pineocytomas are described. The patients presented with symptoms and signs of increased intracranial pressure. CT scans demonstrated obstructive hydrocephalus, but failed to visualize pineal masses that were subsequently seen on MR scans. A suboccipital, supracerebellar approach was used to obtain tissue for histological diagnosis and, in one case, achieve a total removal. Light microscopy demonstrated typical pineocytomatous rosettes without evidence of gangliocytic or astrocytic differentiation. Electron microscopy revealed numerous dense core vesicles with synaptic ribbons, suggesting neurosecretory capability. These three cases demonstrate the diagnostic advantage of MR imaging for tumors in the pineal region as well as the relatively well-differentiated histopathological characteristics of pineocytomas.
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  • 29
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    Virchows Archiv 409 (1986), S. 163-169 
    ISSN: 1432-2307
    Keywords: Thymoma ; Thymic carcinoma ; Ultrastructure ; Immunohistochemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary A case of thymic carcinoma arising within a lymphocyte rich thymoma is reported. The undifferentiated carcinoma contained cellular elements resembling choriocarcinoma but could be differentiated there-from by positive staining for prekeratin antigen and an absence of staining for B-HCG antigen utilizing immunohistochemical techniques.
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  • 30
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    Theoretical and applied genetics 72 (1986), S. 840-844 
    ISSN: 1432-2242
    Keywords: Chlorophytum comosum ; First pollen mitosis ; Male plastid inheritance ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary The behaviour of plastids and mitochondria during the formation and development of the male gametophyte of Chlorophytum comosum has been investigated using electron microscopy. During first pollen mitosis an intracellular polarization of plastids occurs in that the plastids are clustered in the centre of the microspore. The originating generative cell normally lacks plastids. Only in a small number of microspores have plastids been observed near the dividing nucleus of the microspore and later on in the generative cell. These observations agree with the genetic investigations of Collins (1922) on the mode of plastid inheritance which demonstrated a small amount of biparental plastid inheritance in Chlorophytum. The cytological mechanisms underlying plastid polarization during the first pollen mitosis are discussed.
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  • 31
    ISSN: 1432-0878
    Keywords: Glucocorticoids ; Cartilage ; Growth ; Histochemistry ; Ultrastructure ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The effects of different doses of various steroids on growth, and on costal and epiphyseal chondrocytes, have been studied in prenatal, immature, and adult Long-Evans rats using histochemical techniques, and both light and electron microscopy. Both prenatal and postnatal treatments have been employed. The steroids used were cortisone (CA), betamethasome (BM), and, in the prenatal group only, dexamethasone (DM). Body weight is reduced in all treated rats (except the low dose of CA) by day 17 of gestation, with greater weight reductions occurring in rats receiving the higher dose level of each steroid. In rats treated prenatally or neonatally, and sacrificed postnatally on days 39–43 or days 116–127, body weights, and tibial and tail lengths, are less than in correspondingly aged controls, thus showing a persistence of the effects of treatment. Costal and epiphyseal cartilages in prenatal rats show cellular, synthetic, and ultrastructural alterations induced by treatment with glucocorticoids but the responses are not necessarily comparable. Except for the low dose of DM, the higher doses of each steroid are more effective in inhibiting, or altering, growth and cellular differentiation in the developing fetuses. Surprisingly, a low dose of DM has a more devastating effect on the cells and extracellular matrix of both costal and epiphyseal cartilage, than do higher dose-levels of the various steroids. Low doses of CA and BM are also effective in inhibiting or altering growth and cellular differentiation, but their effectiveness is largely limited to 17 days of gestation. The order of effect of the various doses of the different steroids on fetal cartilage, listed in decreasing order of severity, is as follows: 0.12 DM, 0.24 DM, 0.42 BM, 50 CA, with 25 CA and 0.18 BM being approximately equal and only slightly different from control cartilages. The effect of prenatal or neonatal glucocorticoid treatment on chondrocytes is minimal in the 30–43 day, or 116–127 day, postnatal groups. In immature and adult rats, cortisone affects the chondrocytes more deleteriously than does betamethasone, and a 5.0 mg dose of CA seems to affect chondrocytes, body weight, and tibial and tail lengths more than 0.2 or 7.5 mg doses.
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  • 32
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    Cell & tissue research 244 (1986), S. 457-466 
    ISSN: 1432-0878
    Keywords: Microthrix ; Microvillus ; Ultrastructure ; Fixation ; Tapeworm ; Hymenolepis diminuta
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The ultrastructure of microtriches of the rat tapeworm, Hymenolepis diminuta, was examined with a number of electron-microscopic techniques. Fixatives containing different buffers, non-ionic detergents, chelators, tannic acid and various concentrations of aldehydes were tested for ability to stabilize cytoskeletal components while extracting background material. These methods revealed features unique to these specialized microvilli, and permitted construction of a detailed model of microthrix architecture. The microtriches of H. diminuta are comprised of a microfilament-containing base, a dense cap and a complex junctional region between the base and cap. The microfilaments of the base are contiguous distally with a tubular structure (the junctional tubule) within the junctional region; proximally, the microfilaments end abruptly: a terminal web appears to be absent. A beveled bilayered cylinder of dense material (the core tunic) encircles the microfilamentous core. The core tunics and junctional tubules of the microtriches are specifically and uniformly aligned along the strobila. Microtriches therefore can be distinguished from other microvilli (e.g., those of enterocyte brush borders) by their complex ultrastructure and precise orientation upon the cytoplasmic surface.
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  • 33
    ISSN: 1432-0878
    Keywords: Duodenum ; Cholecystokinin ; Gastrin ; Immunocytochemistry ; Ultrastructure ; Man
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Human duodenal endocrine cells reactive with antibodies to cholecystokinin (CCK) 33 (10–20) and/or gastrin 34 (1–15) were studied by a combination of immunohistochemical and electron-microscopic methods. By immunohistochemistry, three types of endocrine cells were distinguished in human duodenal mucosa, i.e., those only positive for only CCK, those positive for both CCK and gastrin and those only positive for only gastrin. Ultrastructurally, the first cell type is characterized by many secretory granules with an eccentric dense core (mean diameter; 271+-74 nm). The second cell type, which was less frequent than the other two, has ultrastructural features that resemble type-I cells. The last cell type was composed of two types of cells containing small secretory granules identical to those of IG cells (mean diameter; 171+-31 nm) or large secretory granules indistinguishable from those of I cells (mean diameter; 286+-50 nm).
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  • 34
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    Cell & tissue research 246 (1986), S. 39-44 
    ISSN: 1432-0878
    Keywords: Ultimobranchial glands ; Cysts ; C-cells ; Ultrastructure ; Chicken (Gallus gallus)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The ultimobranchial glands of the chicken were examined by electron microscopy and immunocytochemistry using a calcitonin antiserum. Electron microscopy confirmed the presence of C-cells, containing numerous secretory granules storing calcitonin, in the luminal lining of cyst-like structures found in these glands. These cells were furnished with prominent microvillar projections at their luminal surface, and the cytoplasm of the apical region was filled with fibril material. Furthermore, the cells contained prominent junctional complexes and desmosomes at their apico-lateral surfaces. In these C-cells, secretory granules were concentrated near the lumen and some were attached to the apical cell membrane. The luminal content of the cysts had a colloid-like and flocculent appearance, and was frequently seen attached to the cytoplasmic projections or apical cell membrane of the C-cells. Since the cysts progressively increase in volume and number with age, it is suggested that they may partly play a role in the storage of excess or unneeded hormonal products.
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  • 35
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    Cell & tissue research 245 (1986), S. 91-100 
    ISSN: 1432-0878
    Keywords: Testis ; Leydig cells ; Crystalloids ; Ultrastructure ; Rat, Rattus fusdpes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The ultrastructure of Leydig cells in a seasonally breeding rodent, Rattus fuscipes, was studied in the breeding and non-breeding season and compared with Leydig cell morphology after suppression of gonadotrophin secretion induced by hypophysectomy or chronic administration of testosterone. Serum luteinizing hormone (LH) and testosterone (T) were measured and in-vitro T production by testes was assessed by stimulation with human chorionic gonadotrophin (hCG). In non-breeding wild-trapped rats and rats with experimental suppression of gonadotrophins, the Leydig cells were atrophied and exhibited variable amounts of cytoplasmic lipid and crystalloid inclusions, the latter commonly dominating the cytoplasmic area. Compared with fertile rats, serum LH and hCG-stimulated T production of experimentally regressed rats was significantly reduced, confirming structural features indicative of Leydig cell inactivity. Atrophy of Leydig cell nuclei was accompanied by the formation of unusual intranuclear vesicles sometimes containing small crystalloids. Ultrastructural analysis suggested transfer of the vesicles to the cytoplasm where their unification gave rise to much larger crystalloid bodies. Crystalloids occurred when serum LH was depressed and with either full (T treatment) or arrested spermatogenesis (hypophysectomy) suggesting that their formation is governed by pituitary function and is not dependent upon the degree of spermatogenic activity.
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  • 36
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    Cell & tissue research 246 (1986), S. 607-621 
    ISSN: 1432-0878
    Keywords: Rod photoreceptor ; Light damage ; Albino rat ; Ultrastructure ; Reversible change
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The temporal sequence of ultrastructural changes induced in the rat rod photoreceptor by 80 lux light-stress has been studied. The changes seen were compared with those produced by a much dimmer (3 lux) illumination. Some of the early signs of abnormality were (1) degradation of some disk membranes at the tips of outer segments, (2) disaggregation and detachment of ribosomes, (3) lighter matrices in swollen mitochondria, (4) disappearance of the Golgi apparatus, (5) proliferation of autophagic bodies in the inner segments, and (6) appearance of perimitochondrial membrane whorls in the synaptic terminals. No single change could be identified that would inexorably lead to cell death. The overall picture, however, suggested that an inability of the cell to maintain its anabolic balance is responsible for the pyknosis that occurs when the 80 lux exposure exceeds 12–15 h. All changes were reversible when exposure duration did not exceed 12 h, the normal length of the light cycle for these rats.
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  • 37
    ISSN: 1432-0878
    Keywords: Smooth-muscle cell ; Cell culture ; Ultrastructure ; Optical measurement ; Cell contraction ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary In numerous investigations using cultured smooth-muscle cells, investigators have consistently added 10–20% fetal calf serum (FCS) to the medium to maintain viable cells. In the present study we utilized an optical technique to investigate whether smooth-muscle cells, cultured with or without FCS, maintain their contractile activity in vitro. With such optical measurement, we were able to detect signals due to spontaneous contractions, in muscle cells cultured in FCS-free medium for up to 8 days, and, for the first time, were also able to observe the conduction of these cell contractions. The ultrastructural characteristics of cultured smooth-muscle cells during contractile activity, were also examined by electron microscopy. The cells were mature and well-differentiated, and were packed with numerous myofilaments. They had developed long cell processes, and were linked to one another by gap junctions. These observations indicated that the smooth-muscle cells, cultured without FCS for 7 to 8 days, were morphologically mature and maintained their contractile activity, whereas the cells cultured in FCS-containing medium showed no detectable signs of contractile activity.
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  • 38
    ISSN: 1432-0878
    Keywords: Chemoreceptor ; Ultrastructure ; Parasitic copepod crustacean ; Pachypygus gibber
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The topography, external structure and ultrastructure of a cephalic sense organ, described for the first time, were studied by light and electron microscopy in the parasitic copepod Pachypygus gibber. This species is unusual in that it has three reproductive sexual forms (two males, one female).The cephalic organ, present only in the atypical male, is made up of numerous functional units, each composed of 4 cells: two sensory cells, one basal enveloping cell and one apical canal-forming cell opening outside via a pore. Many hundred pores are situated within the cuticle of the ventral pleural borders. Through each pore protrude two ciliary endings. An interesting feature is that the ciliary ends are without cuticular cover and thus, directly exposed to the surroundings, a situation unique in arthropods. The structural characteristics of this sense organ and the particular mode of life of the atypical male (with an additional free planktonic phase), lead to the hypothesis that its function is linked to chemical reception in the complex behavioural patterns such as host and sex recognition, during the free life.
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  • 39
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    Cell & tissue research 245 (1986), S. 457-460 
    ISSN: 1432-0878
    Keywords: Anterior pituitary ; Somatotroph ; Lactotroph ; Ultrastructure ; Immunocytochemistry ; Fetal and neonatal rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The ultrastructure of immunoreactive somatotrophs and lactotrophs in pituitaries of fetal rats at 19, 20 and 21 days of gestation and on the day of birth was studied. Somatotrophs, first detectable at 19 days of gestation, undergo only minor modifications before reaching the structure described for adults. In particular there is an increase in the endoplasmic reticulum and Golgi apparatus. Lactotrophs, first identifiable in newborn rats, are very different in ultrastructure from adult cells, because the secretory granules are generally small, but variable in shape and size, and the Golgi complex is prominent.
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  • 40
    ISSN: 1432-0878
    Keywords: Organ culture ; Amelogenesis ; Dentinogenesis ; Ultrastructure ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Molar tooth germs from three-day-old rats were cultured successfully for fourteen days, permitting the study of the development in vitro of both extracellular matrix and cellular elements such as odontoblasts and ameloblasts. The ultrastructure of the cultured tooth germs was compared with the ultrastructure of tooth germs in vivo at a comparable developmental stage. Progenitor cells of odontoblasts and ameloblasts were found to differentiate in vitro. Odontoblasts seemed to contain more lysosome-like bodies and fewer secretory granules than in vivo. They formed normally mineralizing dentine or a thick layer of dense, unmineralized predentine with incidentally some amorphous, extracellular material. Enamel was exclusively present opposite well developed dentine. It was often hyperor hypomineralized and enamel rods were not as regularly shaped as in vivo. In places where no enamel formation had taken place, large amounts of amorphous extracellular material were sometimes seen. From these observations it can be concluded that cellular development in cultured tooth germs appeared more or less normal, but extracellular matrix formation and mineralization were sometimes disturbed.
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  • 41
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    Cell & tissue research 244 (1986), S. 165-171 
    ISSN: 1432-0878
    Keywords: Iridophores ; Motility ; Innervation ; Ultrastructure ; Teleost (Odontobutis obscura)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Reflecting chromatophores in the dermis of the skin of a freshwater goby, Odontobutis obscura, are of an iridophore type. These chromatophores contain numerous reflecting platelets, which are similar to those in iridophores of other fish and amphibian species. It was found that these iridophores are motile, i.e., these cells respond to certain stimuli with translocation of the platelets within the cells. K+ ions induced dispersion of the platelets in excised scale preparations, but not in excised scales from chemically denervated fish. Norepinephrine and melatonin also induced dispersion of the platelets. Alpha-MSH was effective in aggregating these organelles into the centrospheres of the cells. The conclusions reached are: (1) iridophores of O. obscura are motile; (2) the movement of the iridophores is under nervous and hormonal control.
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  • 42
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    Cell & tissue research 243 (1986), S. 405-414 
    ISSN: 1432-0878
    Keywords: Leydig cells ; Ethane dimethanesulphonate ; Ultrastructure ; Destruction ; Gonadotrophins ; Testosterone ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The cytotoxic effects of ethane dimethanesulphonate upon rat Leydig cells were examined ultrastructurally up to 3 days after treatment and related to changes in serum levels of gonadotrophins and testosterone. Six hours after administration of ethane dimethanesulphonate the usual tubulo-vesicular morphology of Leydig-cell smooth endoplasmic reticulum was converted to small vesicles and the Golgi apparatus showed focal hypertrophy into anastomosing tubules. These changes became more marked by 12 h with many Leydig cells exhibiting karyopyknosis and hyperchromatism. Necrotic Leydig cells were often engulfed by macrophages, the latter containing pyknotic fragments of Leydig cells within their cytoplasm. One day after administration, advanced necrosis of Leydig cells occurred, many of which were phagocytosed by macrophages, and on day 3, destruction of Leydig cells was complete resulting in their elimination from the interstitial tissue, which contained only loose connective tissue and macrophages. Structural alterations to the Leydig cells from 6–24 h was reflected by a significant reduction in serum testosterone levels which further declined to the limits of detection accompanying the abolition of Leydig cells on day 3. These changes were paralleled by a significant elevation of serum LH and FSH levels suggesting diminished feedback regulation of pituitary gonadotrophin secretion. The results indicate that ethane dimethanesulphonate is a rapidly acting Leydig cell toxin which may be a useful experimental tool in further studies of spermatogenic function mediated via Sertoli cell-Leydig cell interaction.
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  • 43
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    Cell & tissue research 244 (1986), S. 493-499 
    ISSN: 1432-0878
    Keywords: Endothelium ; Capillaries ; Kidney ; Ultrastructure ; Mouse
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary A new endothelial cell structure, named the endothelial pocket, has been found by combined transmission and scanning electron microscopic studies of renal peritubular capillaries. Transmission EM observations made on these and other fenestrated capillaries demonstrated that each pocket consists of an attenuated fold of fenestrated endothelium that projects 200 nm into the lumen above the rest of the endothelial surface. Beneath this luminal fold, there is a space and then another layer of fenestrated endothelium which abuts the basal lamina. The linear density of endothelial pockets was measured in the capillaries of the kidney cortex, intestinal mucosa and exocrine pancreas in mice and determined to be 0.067, 0.017 and 0.007 pockets·μm-1 respectively. Cationic ferritin decoration of the anionic sites on the luminal surface of the endothelium in these capillary beds revealed that both unlabelled and labelled diaphragms are clustered. In such specimens, the majority of the luminal diaphragms on endothelial pockets did not have cationic ferritin binding sites detectable by either scanning or transmission EM. On this account as well as on account of their general morphology, endothelial pockets appear to be multifold versions of the simple transendothelial channel.
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  • 44
    ISSN: 1432-0878
    Keywords: Capillary ; Epithelium ; Retina ; Retinal pigment epithelium ; Ultrastructure ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Light- and urethane-induced retinopathies in rats are characterized by loss of photoreceptors. Retinal capillaries subsequently become incorporated into the normally avascular retinal pigment epithelium. These models provided an opportunity to study the response of epithelial cells to closely apposed capillaries, in order to determine if capillaries contribute to the polar organization of epithelial cells. Pigment epithelial cells reorganized their lateral plasma membrane where the latter faced intraepithelial capillaries. This normally flat, undifferentiated membrane developed attachment sites, folds and intracytoplasmic tubules, and exhibited endocytosis and putative basal lamina secretion. These structural and functional specializations are normally restricted to the basal plasma membrane — the normal vascular front of the cell facing the dense meshwork of capillaries constituting the choriocapillaris. We conclude that RPE cells, and perhaps epithelia in general, polarize in response to an adjacent capillary bed.
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  • 45
    ISSN: 1432-0878
    Keywords: VIP ; Nerve fibers ; Ganglion cells ; Chromaffin cells ; Ultrastructure ; Adrenal gland ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary VIP-like immunoreactivity was revealed in a few chromaffin cells, medullary ganglion cells and a plexus of varicose nerve fibers in the superficial cortex and single varicose fibers in the juxtamedullary cortex and the medulla of the rat adrenal gland. VIP-like immunoreactive chromaffin cells were polygonal in shape without any distinct cytoplasmic processes and they appeared solitarily. Their cytoplasm contained abundant granular vesicles having a round core and the immunoreactive material was localized to the granular core. VIP-immunoreactive ganglion cells were multipolar and had large intracytoplasmic vacuoles. The immunoreactive material was localized not only in a few granular vesicles but also diffusely throughout the axoplasm. VIP-immunoreactive varicose nerve fibers in the superficial cortex were characterized by abundant small clear vesicles and some large granular vesicles, while those in the juxtamedullary cortex and medulla and the ganglionic processes were characterized by abundant large clear vesicles, as well as the same vesicular elements as contained in the nerves in the superficial cortex. The immunoreactive material was localized on the granular cores and diffusely in the axoplasm in both nerves. Based on the similarity and difference in the composition of the vesicles contained in individual nerves, it is likely that the VIP-immunoreactive nerve fibers in the medulla and the juxtamedullary cortex are derived from the medullary VIP-ganglion cells, while those in the superficial cortex are of extrinsic origin. The immunoreactive nerve fibers in both the cortex and the medulla were often in direct contact with cortical cells and chromaffin cells, where no membrane specializations were formed. The immunoreactive nerve fibers were sometimes associated with the smooth muscle cells and pericytes of small blood vessels in the superficial cortex. In addition they were often seen in close apposition to the fenestrated endothelial cells in the cortex and the medulla, only a common basal lamina intervening. Several possible mechanisms by which VIP may exert its effect in the adrenal gland are discussed.
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  • 46
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    Cell & tissue research 243 (1986), S. 137-144 
    ISSN: 1432-0878
    Keywords: Lung ; Blood-air barrier ; Surfactant ; Ultrastructure ; Freeze fracture ; Birds ; Penguin (Aptenodytes forsten)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Of all avian species the emperor penguin is the best adapted bird to attain the greatest diving depths and diving durations. Therefore the lung of this bird was investigated with electron-microscopic, i.e., freeze-fracture and thin-section methods. The parabronchi are surrounded by bundles of smooth muscle cells innervated by varicosities of autonomic nerves. The parabronchial epithelium is flat, bears a few microvilli and does not show any conspicuous ultrastructural specializations; only individual cells contain secretory granules. The atrial epithelial cells bear apical microvilli and are interconnected by adhering and tight junctions (5–10 sealing strands), the latter presumably forming an effective barrier against paracellular fluid movements. The cells contain lamellar inclusions of two types: (i) round membrane-bounded granules, the lamellar content of which is fixation-labile, and (ii) large polymorphic compact deposits of well-preserved lamellae. In both types of inclusions the individual lamellae can be of trilaminar appearance, whereas their fracture faces are smooth. Lamellar material also covers the epithelium of atria, infundibula and air capillaries. In thin areas the diameter of the morphological blood-air barrier measures 220–330 nm. Usually the endothelium of the blood capillaries is thicker (40–180 nm) than the air capillary epithelium (25–150 nm). Both epithelium and endothelium are interconnected by tight junctions, which seem to be more extensive and presumably tighter in the epithelium than in the endothelium. Frequently the common basal lamina is the thickest individual component of the blood-air barrier, measuring between 170–230 nm. Often collagen fibrils occur in this area of the barrier. In comparison with that of other birds the entire blood-air barrier of the emperor penguin is relatively thick, probably owing to an adaptation of the lung tissue which must resist high hydrostatic pressure during diving excursions.
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  • 47
    ISSN: 1432-0878
    Keywords: Parathyroid gland ; Protein A-gold technique ; Ultrastructure ; Storage granules ; Mammals
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Electron-microscopic immunocytochemistry for the demonstration of parathormone in parathyroid chief cells was performed in adult male rats, gerbils, mice, and dogs, using the protein A-gold technique. Protein A-gold particles were detected over both large and small secretory granules in all the animals examined. In the former, they were concentrated not only over type-I granules with a large core, but also over type-II granules with a small core. They were also located over atypical granules, including heterogeneously dense granules, granules having vesicles in a finely particulate core, and distorted granules. All labelled secretory granules were characterized by the presence of a clear halo of varying width around the core. Occasionally, Golgi cisternae as well as Golgi vacuoles with a finely particular content were also labelled. The labelling of the secretory granules was strong in dogs, moderate in rats and gerbils, and weak in mice. In addition, it was more intense in the non-osmicated preparations than in the osmicated preparations. The frequency of both types of large granules showed species differences. The possible factors involved in these differences are discussed.
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  • 48
    ISSN: 1432-0878
    Keywords: Peripolar cells ; Juxtaglomerular apparatus ; Kallikrein ; Ultrastructure ; Mammals
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Peripolar cells are granulated glomerular epithelial cells that form a cuff around the vascular pole of the glomerulus. Quantitation of these cells in 17 species of mammals (including man, several laboratory animals and a variety of other species) indicated that they were detectable by light microscopy in all but one of the mammals that were examined (the Australian hopping mouse). In adult mammals with detectable peripolar cells, the “peripolar cell index” (the percentage of randomly sectioned glomeruli that displayed peripolar cells in histological sections of kidney) ranged from 0.15 (for echidna) to 11.86 (for sheep). Newborn lambs and rats showed strikingly high values (23.30 and 10.76, respectively) compared with their adult counterparts. Using electron microscopy, peripolar cells were observed in all species that were examined, including the Australian hopping mouse. Morphologically, peripolar cells were similar in all species although their size and granule population varied. They showed a predominantly outer cortical glomerular distribution and a close anatomical relationship with the renin-containing myoepithelioid cells. These findings indicate that peripolar cells are present in a wide variety of species and support the view that such cells may play a significant role in the regulation of normal renal function.
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  • 49
    ISSN: 1432-0878
    Keywords: Uterus ; Epithelium ; Ultrastructure ; Pig
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The ultrastructure of the endometrial epithelium of the pig was studied during the estrous cycle and early pregnancy up to implantation. Special attention was given to the luminal epithelium and morphological indications of protein synthesis. Although the general morphology of the luminal and glandular epithelia is similar (both tissues consist of secretory cells and ciliated cells at all the stages studied), it appears that the two epithelia should be considered as two functionally different units in the pre-implantation period. Morphological evidence suggests the presence of at least three different secretory products within luminal epithelial cells; they are released at different times, i.e. at estrus, between day 8 and 10 and after day 11. The glandular epithelium shows release of secretory products from day 10–11. Increasing amounts of glycogen were found within epithelial cells, especially in pregnant gilts from day 12. The possible significance of secretory activity of the epithelium is discussed in relation to the development of the embryos.
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  • 50
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    Plant systematics and evolution 153 (1986), S. 259-264 
    ISSN: 1615-6110
    Keywords: Gymnosperms ; Angiosperms ; Pteridosperms ; Caytoniales ; Caytonanthus ; Ultrastructure ; pollen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The pollen grain wall structure ofCaytonanthus arberi was studied with SEM and TEM. The monosulcate, bisaccate pollen grain of this taxon has an alveolar wall structure that is more like that found in saccate Conifers than primitive Angiosperms. Pollen grain morphology does not support a Caytonialean ancestry for the Angiosperms.
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  • 51
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    Plant systematics and evolution 154 (1986), S. 31-39 
    ISSN: 1615-6110
    Keywords: Angiosperms ; Lactoridaceae ; Ultrastructure ; pollen ; fossil pollen (Cretaceous)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The pollen wall ultrastructure of the primitive AngiospermLactoris fernandeziana Phil. (Lactoridaceae) is described. The monosulcate aperture, granular wall structure and sacci (all primitive features) suggest placement of this family in theMagnoliales. Pollen ofLactoris is compared to fossil dispersed pollen from the Lower and lower-Upper Cretaceous. The fossil pollen shares characteristics which are restricted to theLactoridaceae suggesting that this family was present during the early Cretaceous.
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  • 52
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    Protoplasma 131 (1986), S. 1-10 
    ISSN: 1615-6102
    Keywords: Cell division ; Lomentaria ; mitosis ; Red algae ; Rhodophyta ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Mitosis in the marine red algaLomentaria baileyana (Rhodymeniales, Rhodophyta) was studied with the electron microscope. Nucleus associated organelles known as polar rings (PRs) migrate to establish the division poles at prophase. At prometaphase, shallow invaginations in the nuclear envelope (NE) form on two sides of each PR and soon rupture. The gaps that are consequently formed contain several small fragments of NE. A larger region of NE remains intact between the two gaps. By metaphase several cisternae of perinuclear endoplasmic reticulum (PER) have enclosed most of the nucleus but remain absent from the polar regions. The nucleolus disperses partially and a typical metaphase plate of chromosomes is formed. Each PR has disjoined into separate proximal and distal portions. MTs converge widely on all regions of the polar area, but do not extend into the cytoplasm. Some MTs end near or at the chromosomes while others extend slightly farther past the chromosomes or diagonally to the NE. As chromosomes move to opposite poles at anaphase, they are accompanied by nucleolar material. An interzonal midpiece (IZM) is created as the pole to pole distance increases and the NE remains intact except for the polar gaps. Following detachment from the IZM, the daughter nuclei are separated by a large central vacuole as a cleavage furrow develops and eventually constricts to form two cells following pit connection formation. It is suggested that mitosis inLomentaria represents an evolutionary intermediate between that seen in the higher and lower groups of red algae. This conclusion is in agreement with conventional morphological and light microscopic criteria used to placeLomentaria in theRhodymeniales, which is considered to be the next to most advanced order in theRhodophyta.
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  • 53
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    Protoplasma 134 (1986), S. 154-162 
    ISSN: 1615-6102
    Keywords: Cell division ; Leishmania ; Mitosis ; Ultrastructure ; Kinetoplastida
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary The interphase nucleus ofLeishmania adleri has clumps of chromatin associated with the nuclear envelope and a large centrally located nucleolus. Prior to mitosis the basal bodies replicate at the cell anterior. Subsequently, dense plaques appear in the equatorial region of the nucleus at the time of spindle development. Microtubules appear in the nucleus adjacent to the nuclear envelope and embedded in the matrix of the plaques. A central spindle composed of a single bundle of microtubules develops and spans the nucleus. Plaques and nucleolar components laterally associate with the spindle and migrate towards the poles. The central spindle elongates to three to four times its original length separating the forming daughter nuclei and producing an interzonal spindle. A remnant of the interzonal spindle remains attached to each of the daughter nuclei until late into cytokinesis. The kinetoplast does not divide until after the completion of mitosis.
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  • 54
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    Protoplasma 131 (1986), S. 166-173 
    ISSN: 1615-6102
    Keywords: Chloroplast development ; Pisum sativum ; Prolamellar body ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary We analyzed transformation, recrystallization, splitting and dispersion of prolamellar bodies during chloroplast development in pea seedlings illuminated by white, red and blue light of low intensity. With the help of a stereometric method we determined that there was a significant increase of prolamellar body number and a sharp decrease of their volume in differentiating chloroplast even in the first 2 hours of illumination. Decrease of prolamellar body dimensions was due both to gradual dispersion of its elements into primary thylakoids (indicated by the decrease of total volume of prolamellar bodies in plastid) and to splitting of prolamellar bodies (indicated by the increase of number of promellar bodies in plastid). Red light was more effective in transformation, splitting and dispersion of prolamellar bodies than blue light during the first 8–12 hours. Longer treatment with blue light had a stronger influence on these processes and on complete recrystallization than other light treatments.
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  • 55
    ISSN: 1615-6102
    Keywords: Chlamydomonas ; Endoplasmic reticulum ; Golgi apparatus ; Wall mutants ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Ultrastructural observations on the principal endomembranes (endoplasmic reticulum, Golgi apparatus) of synchronously growing of wild type and mutant (CW 2, CW 15) strains ofChlamydomonas reinhardii have been carried out. The dictyosomes of the Golgi apparatus in all three cases are highly polar in morphology but lack intercisternal filaments. A clear spatial relationship between dictyosomes and endoplasmic reticulum is seen and a transfer of vesicles from the latter to the former is easily visualized. Coated vesicles invariably appear to be restricted to the trans-pole of the dictyosomes. The endoplasmic reticulum adjacent to the cis pole of dictyosomes is considerably hypertrophied in the case of the wild type, only partially so in the mutant CW 2 but not at all in the mutant CW 15. In the wild type this swelling is most extreme during the period of wall deposition and for several hours afterwards. The results are discussed in relation to the biosynthesis and intracellular transport of, particularly O-glycosidically linked, glycoproteins.
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  • 56
    ISSN: 1615-6102
    Keywords: Chloroplast development ; Grana formation ; Pisum sativum ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary We analyzed the formation of thylakoids and grana during the development of pea chloroplasts, illuminated by white, red and blue low intensity light. The total length of granal and intergranal thylakoids, and the length of granal thylakoids per unit area of plastid section were measured. Initially the greatest increase in length of granal thylakoids and the highest incidence of grana with large thylakoid content occurred in red light. On the other hand, with illumination times of over 12 hours blue light appeared to be more efficient in stimulating grana formation and thylakoid growth.
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  • 57
    ISSN: 1615-6102
    Keywords: Diapensia lapponica ; Mitochondria ; Morphometry ; Seasonal variation ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Seasonal changes in the mitochondrial ultrastructure were examined in palisade parenchyma cells of a tuft-formingDiapensia lapponica L. collected at monthly intervals in Northern Finland. Quantitative analyses to measure volume and surface densities were conducted during different periods of growth (stages of growth, acclimation, winter period and deacclimation) in the annual cycle. The volume density was highest in the summer and lowest in the spring; the difference was significant with both fixatives used GA and GA/FA. The largest membrane area (the mitochondrial outer membrane and the cristal membranes together) was observed in the summer and autumn, and was significantly less in the winter and spring. This correlated with fewer mitochondria in the spring and a smaller number of cristae in the winter and spring. In the material fixed in GA/FA the distribution of length/width ratios of mitochondria was relatively uniform in all seasons. However, the mitochondrial ultrastructure had the most varied appearance during the winter. Hypertonie GA/FA solution did not cause significant differences either in the ultrastructure or the volume and surface densities of the mitochondria.
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  • 58
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    Protoplasma 135 (1986), S. 102-111 
    ISSN: 1615-6102
    Keywords: Ultrastructure ; Haptoglossa mirabilis ; Differentiation ; Gun cell
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary The most prominent ultrastructural characteristics of the cyst ofHaptoglossa mirabilis are a large centrally-placed nucleus which is partially ringed by three or four parallel cisternae of rough endoplasmic reticulum (r-ER), a centriole pair and single large Golgi complex which occupy the anterior end of the cell, and a population of provacuoles which occupies the posterior. During germination these organelles migrate into a narrow germ tube which subsequently expands to form the gun cell initial. The extracellular components of the attack apparatus (i.e. missile and injection tube) are formed entirely in the developing gun cell; indirect evidence suggests that both the Golgi complex and r-ER are involved in their synthesis. The intra-cellular component of the attack apparatus comprises the posterior, anterior and apical vacuoles. The posterior vacuole forms by fusion and expansion of the original cyst provacuoles; the formation of the anterior and apical vacuoles occurs late in gun cell differentiation and involves fusion of Golgi-derived vesicles.
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  • 59
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    Protoplasma 134 (1986), S. 102-110 
    ISSN: 1615-6102
    Keywords: Isoelectric focusing ; Isolation ; Potato tuber cell walls ; Purification ; Salt extraction ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary A preparative procedure for cell wall isolation and purification was developed. The purity of the isolated cell walls was judged biochemically by the lack of activity of cytoplasmic marker enzymes and morphologically by examination at both the light and electron microscope levels. The purified cell walls were extracted with various salt treatments and the molecular weight range of most of the extracted proteins was between 14 and 31 kDa. The salt extracted hydrolytic enzymes were basic in nature (pI〉7.0) compared to their cytosolic counterparts (pI〈7.0). Some enzymes were readily extracted from cell walls (β-glucosidase and β-NAcglucosaminidase) with high salt treatment while most of the α-mannosidase activity associated with purified cell walls could not be removed even with sequential high salt treatments.
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  • 60
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    Protoplasma 135 (1986), S. 119-129 
    ISSN: 1615-6102
    Keywords: Differentiation ; Pectin ; Phytophthora ; Surface ; Ultrastructure ; Zoospore
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Populations ofPhytophthora palmivora zoospores induced to undergo synchronous differentiation by the addition of pectin showed an ordered sequence of surface changes. Within 10 seconds “blebs” and “microvilli” appeared on the cell and flagellar surfaces. These projections gave the zoospore a highly irregular and even convoluted surface for up to 30 seconds poststimulation. Between 30 and 40 seconds, pits appeared on the surface, which began to assume a smoother texture. Zoospores then rounded up and by 4 minutes had assumed an almost spherical form. At this time the surface became wrinkled as though shrinkage had occurred. Germ tubes could be seen emerging from almost all cells by 40 minutes, and as germ tubes enlarged, the cell surface became smooth again but with a fibrous texture. Many zoospores retained their flagella through to the germling stage. When cells were stimulated in iso-osmotic rather than hypo-osmotic media, germ tubes in most cases emerged at or very near the site of flagellar attachment. Differentiation in iso-osmotic media showed the same sequence except that the cells did not assume the spherical shape normally characteristic of cysts and germlings differentiating under hypo-osmotic conditions. Strontium-induced differentiation again followed the same general sequence as desribed above, although the cell surface was noticeably more convoluted and irregular prior to the stage of the formation of pits, and flagella were always shed between 40 seconds and 1 minute. Calcium addition up to 20 seconds after the initiation of differentiation with pectin prevented a high proportion of zoospores from encysting, the cells remained motile, and although the frequency of surface blebs and microvilli increased, pits did not appear. These surface changes are consistent with those expected during stimulus-mediated secretion, and it appears that calcium is able to inhibit differentiation only before the secretory step (pit formation).
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  • 61
    ISSN: 1615-6102
    Keywords: Dark-stress ; Recovery ; Root-nodules ; Soybean ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Root-nodules of soybean plants dark-stressed for 8 days and then allowed to recover for up to 17 days were examined by transmission electron microscopy. Control nodules possessed all the ultrastructural features characteristic of infected and uninfected nodule cells. Minimal changes in the appearance of host cells and bacteroids occurred during the first four days of dark stress. After 8 days of dark stress, damage was observed in the cellular and organelle membranes; however, very few changes were observed in the bacteroids. Nodule structure continued to degrade during the first two days of recovery after which time nodules either recovered or completely degraded. In the former case, structural integrity returned to all nodule cells. In the latter case all structural integrity of the host cell disappeared; however, bacteroids appeared intact suggesting that they remained viable.
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  • 62
    ISSN: 1615-6102
    Keywords: Root meristems ; Cell plate ; Ultrastructure ; 2,6-dichlorobenzonitrile
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary The effect of 2,6-dichlorobenzonitrile on cytokinesis of meristematic cells of onion root during both treatment and recovery has been studied by electron microscopic techniques. 2,6-dichlorobenzonitrile interferes with cell plate formation in such a way that Golgi apparatus vesicles of treated cells appear to be different than controls and seem to coalesce as anomalous partial cell plates. During recovery, an apparently normal progression of cytokinesis is observed and abnormal portions of the cell plate are retained. Nuclear constrictions are observed frequently during recovery as a result of temporal alterations in cytokinesis. Our results show that 2,6-dichlorobenzo-nitrile induces anomalous and/or incomplete cell plates, which might be caused by an altered function of Golgi apparatus.
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    European journal of plastic surgery 9 (1986), S. 122-129 
    ISSN: 1435-0130
    Keywords: Congenital lymphoedema in dogs ; Ultrastructure ; Chronic lymphoedema ; Chronic inflammation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary In two congenitally lymphoedematous dogs, a quantitative fine structural study was made of the subcutaneous tissue. It was found that the blood vessels, inital lymphatics and tissue channels all increased considerably, as did the small vesicles and vacuoles in the endothelium of both blood and lymph vessels. Collagen, fibroblasts, macrophages, and fat containing macrophages “fat cells” all increased greatly, while the small and medium lymphocytes increased to a moderate extent. These results are similar to those found in chronic experimental lymphoedema in dogs, in chronic high-protein oedema and in chronic inflammation. The underlying similarity of all these conditions is emphasised.
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    European archives of oto-rhino-laryngology and head & neck 243 (1986), S. 265-268 
    ISSN: 1434-4726
    Keywords: Respiratory cilia ; Measurement of ciliary orientation ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary We have created a method for measuring the orientation of cilia in the respiratory epithelium. Ciliary orientation is the direction perpendicular to the plane defined by the central tubules of the cilia and is an estimate of ciliary beat direction. Ciliary orientation can be estimated by measuring the angle between the plane defined by the central tubules and a reference line. The standard deviation of these measurements describes the variation present in the beat directions of the cilia. The reference line must be so chosen that the majority of measurements falls at about the middle of the 0°–180° range. We tested measurements by using both a glass angle measure and a semiautomatic image analyzer (IBAS I). The latter approach was faster and more reproducible. We made our measurements of normal tissues on samples obtained from two healthy adult non-smokers. Measurements were made in four areas of each sample, with 59–110 cilia in each. The differences between the maximum and minimum angles of the ciliary orientation in the same area varied from 167.9° to 85.4° from the reference line. The standard deviation varied from 18.0° to 35.4° and we consider this to be a normal variation in ciliary orientation. Of the cilia, 57% were within a standard deviation of 20°.
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  • 65
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Main Group Element Transition Metal Multiple Bonds, IV. Catalytic Assistance by [Cp(CO)3Mo]2 in the Aggregation of Metallo-arsanes via Arsenic Metal Double Bond Complexes2)The metallo-arsanes Cp(CO)3M—AsMe2 (1a, b) (M = Mo, W) are converted to the double arsenido-bridged dinuclear complexes [(μ-AsMe2)Mo(CO)2Cp]2 (3a, b) in the presence of [Cp(CO)3Mo]2. Due to the unusual mild conditions of aggregation the intermediate formation of the double bonded species Cp(CO)2M=AsMe2 (2a, b) is postulated. The crystal structure of 3a is reported, which shows mutual trans arrangement of the cyclopentadienyl and CO ligands.
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    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 387-400 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Aliphatic Liquid Crystals, 7. Some Mesogenic Tercyclohexyl DerivativesStarting from bicyclohexyl-4-one 1 the tercyclohexyl-3-one 6 is synthesized via the acetyl derivatives 3a,b. Methoxycarbonylation of 6 gives the keto ester 12 which on the one hand is tranformed to the esters 15a,b and 17 - 20 and the nitriles 21a,b, on the other hand to the methylated keto esters 23a,b and 24a,b. From 23a the ester 26 with an axial 1-methyl group is obtained. Nearly all the products are mesogenic.
    Notes: Aus dem Bicyclohexyl-4-on 1 wird über die Acetylderivate 3a,b das Tercyclohexyl-3-on 6 aufgebaut, daraus durch Methoxycarbonylierung der Ketoester 12, der einerseits zu den Estern 15a,b und 17 - 20 und den Nitrilen 21a,b, andererseits zu den methylierten Ketoestern 23a,b und 24a,b umgesetzt wird. Aus 23a erhält man den Ester 26 mit axialer 1-Methylgruppe. Fast alle Produkte sind mesogen.
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    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 1361-1373 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, 169. Sterically Demanding N-Lithioaminoboranes: Reagents for the Synthesis of Symmetrically and Unsymmetrically Substituted DiborylaminesN-Metalation of R2BNH2 or R2BNMeH yields lithium amides R2BNR′Li with sterically demanding R groups (R = tBu, iPr). These compounds are synthons for symmetrically or unsymmetrically substituted diborylamines as well as for B-functional diborylamines. NMR data reveal the conformation of these diborylamines. Compounds of the type tBu2B—NMe—BR2 contain tBu2B groups whose BC2 plane stands nearly orthogonal to the B2NC skeleton. In contrast, the BRX group in diborylamines of the type tBu2B—NH—BRX is strongly twisted with respect to the B2NH plane.
    Notes: Durch N-Metallierung erhältliche Lithiumamide R2BNR′Li mit sperrigen Substituenten R = tBu, iPr eignen sich sowohl zur Darstellung symmetrisch und unsymmetrisch substituierter Diborylamine als auch zur Gewinnung B-funktioneller Diborylamine. Kernresonanzspektroskopische Untersuchungen zeigen, daß Diborylamine tBu2B—NMe—BR2 eine tBu2B-Gruppe enthalten, deren BC2-Ebene weitgehend orthogonal zur B2NC-Gerüstebene steht. In Diborylaminen tBu2B—NH—BRX ist hingegen die BRX-Gruppe gegen die B2NH-Ebene verdrillt.
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    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 1437-1440 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Multiple Bonds Between Main Group Elements and Transition Metals, XXV. Synthesis and Reactivity of Se1- and Se2-Bridges in Organochromium CompoundsReaction of the ionic complex K[(η5-C5Me5)Cr(CO)3] (1) with selenium(I) with selenium(I) chloride, Se2Cl2, yields the diselenium compounds 2 of composition (η5-C5Me5)Cr(CO)5Se2 which is converted to the Se1 derivative (μ-Se)[η5-C5Me5)Cr2(CO)2]2 (3) with triphenylphosphane. 3 exhibits a linear, multiple bonded CrSeCr core structure. Reaction of 2 with diazomethane gives the novel mononuclear, paramagnetic selenoformaldehyde complex (η5-C5Me5)-Cr(CO)2(SeCH2) (4).
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    Berichte der deutschen chemischen Gesellschaft 119 (1986) 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 1441-1444 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-tert-Butylpivalohydroxamic Acid: s-trans-Conformation and H-Bonding in the CrystalIt is shown by an X-ray crystal structure analysis that, in the crystal, teh title compound has the s-trans-conformation and the molecules are linked by strong intermolecular H-bonds to linear chains.
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    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 1445-1454 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses of 2,6,7-Triazabicyclo[2.2.2]oct-2-ene-5,8-diones and 4(3H)-Pyrimidinones via 1,4-Dipolar Cycloaddition Reactions of Pyrimidinium-4-olates to NitrilesThe 3,6-dihydro-6-oxo-1-pyrimidinium-4-olate 1a, which carry no substituent in the 2 position, undergoes 1,4-dipolar cycloaddition reactions with ethyl cyanoformate (2a) and benzoyl cyanide (2b) to produce novel bicyclic primary adducts 3a, b, respectively, which at higher temperature fragment into 4(3H)-pyrimidinones 4a, b with elimination of phenyl isocyanate. However, pyrimidinium-4-olates 1b - h or 5, which are substituted in the 2 position, react directly with nitriles 2a - c to form high yields of 4(3H)-pyrimidinone derivatives of type 4 or 7, respectively. Furthermore, the reactions of 1a with isocyanic acid as well as with cyan amide are described.
    Notes: Das in 2-Position unsubstituierte 3,6-Dihydro-6-oxo-1-pyrimidinium-4-olat 1a geht mit Cyanameisensäure-ethylester (2a) und Benzoylcyanid (2b) 1,4-Dipolare Cycloadditionen zu neuen bicyclischen Primäraddukten 3a bzw. b ein, die bei höherer Temperatur unter Phenylisocyanat-Abgabe in 4(3H)-Pyrimidinone 4a, b fragmentieren. Dagegen reagieren die in 2-Stellung substituierten Pyrimidinium-4-olate 1b - h oder 5 mit Nitrilen 2a - c in hohen Ausbeuten direkt zu den 4(3H)-Pyrimidinon-Derivaten vom Typ 4 bzw. 7. Weiterhin werden die Reaktionen von 1a mit Isocyansäure sowie mit Cyanamid beschrieben.
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  • 72
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Sterically Hindered Free Radicals, XV. The First Unsymmetrical Dimer from Two Different Stable Radicals: 3-(tert-Butylphenylmethylene)-6-(triphenylmethyl)-1,4-cyclohexadiene from tert-Butyldiphenylmethyl and TriphenylmethylThe quinonoid title compound 6 is formed in an equilibrium to 95% and can be isolated, when the two title radicals 1 and 3 are generated in solution. The reason for this is the sterically less strained position of the bulky tBu group at the sp2-C atom of the methylene group. The structure of 6 is proved by 1,5-H migration giving 8 and autoxidation of the latter at -10°C giving tBuOH and 4-tritylbenzophenone (12). The synthesis of several analogous compounds are described.
    Notes: Die chinoide Titelverbindung 6 entsteht im Gleichgewicht zu 〉95% und kann isoliert werden, wenn die beiden Titelradikale 1 und 3 in Lösung erzeugt werden. Ursache hierfür ist die räumlich günstigere Unterbringung der sperrigen tBu-Gruppe am sp2-C-Atom der Methylengruppe. Die Struktur von 6 wird durch 1,5-H-Verschiebung zu 8 sowie dessen Autoxidation bei -10°C zu tBuOH und 4-Tritylbenzophenon (12) bewiesen. Synthesen analoger Verbindungen werden beschrieben.
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2025-2049 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Effect of Phenyl Groups on the Homoconjugation in the Bicyclo[3.2.1]octa-3,6-dien-2-yl Anion. A 13C NMR StudyThe effects of deuterium atoms in the positions 2 and 4 of exo-6-bromo- (11) and endo-6-methoxytricyclo[3.2.1.02,7]oct-3-ene (12) as well as exo-4-methoxybicyclo[3.2.1]octa-2,6-diene (13) on their 13C chemical shifts are in line with the previous interpretation of the effects in correspondingly deuterated bicyclo[3.2.1]octa-3,6-dien-2-yl anions 1, and thus provide evidence for the homoconjugative interaction in 1. 3-Phenylbicyclo[3.2.1]octa-2,6-diene (16) and endo- (19a) as well as exo-4-phenylbicyclo[3.2.1]octa-2,6-diene (19b) have been prepared from bicyclo[3.2.1]oct-6-en-3-one (14) and bicyclo[3.1.0]hex-2-ene-endo-6-carbaldehyde (17), respectively. 2,4-Diphenylbicyclo[3.2.1]octa-2,6-diene (6) and 19a, b were deprotonated by methyllithium and n-butyllithium, respectively, whereas the proton abstraction from tricyclo[6.3.1.02,7]dodeca-2,4,6,9-triene (4) and from 16 required potassium tert-butoxide/n-butyllithium. As products the corresponding bicyclo[3.2.1]octa-3,6-dien-2-yl anion derivatives have been identified. By means of potassium tert-butoxide/n-butyllithium 19a, b were converted into 21K, i.e. the anion with K+ as counterion. The NMR spectra of 21Li turned out to depend upon the temperature in the range between +45 and -30°C in contrast to those of 21K. The 13C NMR spectra of the anions and of the corresponding hydrocarbons are discussed in detail in relation to the spectra of the unsubstituted species 1 and 2. In particular, the wide variations of the chemical shifts of C-6,7 depending upon the substituents of the allylic moiety of the bicyclo[3.2.1]octa-3,6-dien-2-yl anion system give strong support for the bishomoaromatic nature of these anions.
    Notes: Die Effekte von Deuteriumatomen in den Positionen 1 und 4 von exo-6-Brom- (11) und endo-6-Methoxytricyclo[3.2.1.02,7]oct-3-en (12) sowie exo-4-Methoxybicyclo[3.2.1]octa-2,6-dien (13) auf deren 13C-chemische Verschiebungen stützen die frühere Interpretation der Effekte bei entsprechend deuterierten Bicyclo[3.2.1]octa-3,6-dien-2-yl-Anionen 1 und belegen so die homokonjugative Wechselwirkung in 1.  -  Ausgehend von Bicyclo[3.2.1]oct-6-en-3-on (14) und Bicyclo[3.1.0]hex-2-en-endo-6-carbaldehyd (17) stellte man 3-Phenyl- (16) bzw. endo-4-Phenyl-(19a) und exo-4-Phenylbicyclo[3.2.1]octa-2,6-dien (19b) dar. 2,4-Diphenylbicyclo[3.2.1]octa-2,6-dien (6) und 19a, b wurden mit Methyllithium bzw. n-Butyllithium, Tricyclo[6.3.1.02,7]dodeca-2,4,6,9-tetraen (4) sowie 16 mit Kalium-tert-butoxid/n-Butyllithium deprotoniert, wobei die entsprechenden Bicyclo[3.2.1]octa-3,6-dien-2-yl-Anionderivate 7, 21Li, 5 und 22 entstanden. Aus 19a, b wurde mit Kalium-tert-butoxid/n-Butyllithium auch 21K, d. h. das zugehörige Anion mit K+ als Gegenion erhalten. Die NMR-Spektren von 21Li erwiesen sich im Gegensatz zu jenen von 21K im Bereich von +45 bis -30°C als temperaturabhängig. Die 13C-NMR-Spektren der Anionen und der zugehörigen Kohlenwasserstoffe werden im Vergleich mit den Spektren der unsubstituierten Verbindungen 1 und 2 ausführlich diskutiert. Insbesondere die starken Variationen der chemischen Verschiebungen von C-6,7 in Abhängigkeit von den Substitutenten am Allylteil des Bicyclo[3.2.1]octa-3,6-dien-2-yl-Anionsystems bieten ein starkes Argument für die bishomoaromatische Natur dieser Anionen.
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  • 74
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2094-2103 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Physical Properties of Novel 1,3-Dithiolylium-4-methanides and 1,3-Thiazolium-5-methanidesThe synthesis and physical properties of the novel title compounds of type 9 from carboxylic acid derivatives 3 and CH acidic compounds 4 are described.
    Notes: Die Synthese und physikalischen Eigenschaften der neuen Titelverbindungen vom Typ 9 aus Carbonsäure-Derivaten 3 und CH-aciden Verbindungen 4 werden beschrieben.
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  • 75
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2080-2093 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Metallaheterocumulenes, IV. 2-Azaallylidene Complexes  -  Novel Compounds with a Bent CNCR2 Fragment as Complex Ligand(2-Azoniaallenylidene)pentacarbonyltungsten tetrabromoaluminate complexes [(CO)5W(CNCR2)]+AlBr4- (2-AlBr4) (CR2=C(C6H4Br-4)2 (a), CPh2 (b), C(C6H4OMe-4)2 (c), C(C6H4)2O (d), C(2,4,6-C6H2Me3)2 (e)) Which are synthesized by the reaction of (CO)5W[C(OEt)N=CR2] (1) with AlBr3, react with freshly distilled tetrahydrofuran to give neural trans-bromo(2-azaallylidene) complexes trans-Br(CO)4W(CNCR2) (3) and small amounts of (CO)5W—C≡N—[CR2]2—N≡C—W(CO)5 (4). The compounds 4 correspond to the product of a reductive dimerization of two cations 2. If 1b (or the corresponding methoxy compound 5) reacts with BBr3 instead of AlBr3/THF 4b is the main product. The spectroscopic data of 3 and the results of an X-ray analysis of 3b show that the replacement of a CO ligand in the cations 2 by Br- with formation of 3 results in a drastic change of the bonding situation within the CNCR2 ligand. 3a-e are the first compounds in which a strongly bent CNCR2 fragment functions as a complex ligand. The aminocarbyne complex trans-Br(CO)4W≡CNPh2 (7) was synthesized by BBr3-induced fragmentation of (CO)5W[C(NPh2)N=C(Ph)OMe] (6).
    Notes: (2-Azoniaallenyliden)pentacarbonylwolfram-tetrabromoaluminat-Komplexe [(CO)5W(CNCR2)]+AlBr4- (2-AlBr4) (CR2=C(C6H4Br-4)2 (a), CPh2 (b), C(C6H4OMe-4)2 (c), C(C6H4)2O (d), C(2,4,6-C6H2Me3)2 (e))  -  darstellbar durch Umsetzung von (CO)5W[C(OEt)N=CR2] (1) mit Albr3  -  reagieren mit frisch destillierten Tetrahydrofuran zu neutralen trans-Bromo(2-azaallyliden)-Komplexen trans-Br(CO)4W(CNCR2) (3) und wenig (CO)5W—C≡N—[CR2]2—N≡C—W(CO)5 (4). Die Verbindungen 4. entsprechen dem Produkt einer reduktiven Dimerisierung zweier Kationen 2. 4b wird zum Hauptprodukt der Umsetzung, wenn 1b (oder der entsprechende Methoxy-Komplex 5) mit BBr3 anstatt AlBr3/THF umgesetzt wird. Wie die spektroskopischen Daten von 3 sowie die Ergebnisse der an 3b durchgeführten Röntgenstrukturanalyse zeigen, führt der Austausch eines CO-Liganden in den Kationen 2 gegen Br- unter Bildung von 3 zu einer drastischen Veränderung der Bindungsverhältnisse im CNCR2-Liganden. 3a-e sind die ersten Verbindungen, in denen ein stark gewinkeltes CNCR2-Fragment als Komplexligand fungiert. Durch BBr3-induzierte Fragmentierung von (CO)5W[C(NPh2)N=C(Ph)OMe] (6) wurde der Aminocarbin-Komplex trans-Br(CO)4W≡CNPh2 (7) dargestellt.
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  • 76
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterocyclic β-Enamino Esters, 41. Vinylogeous Principle on 6,7-Dihydro-1H-azepines; Cycloaddition and Novel Rearrangement to 2,3,3a,7a-Tetrahydroindoles.  -  Thermal [2 + 2]-Cycloadditions with 4-R-TADThe conjugated π-Systems of 6,7-dihydrooxepines, -thiepines, and -azepines (1-5) show a remarkable alternance of their 13C NMR shifts. In a cycloaddition-ring enlargement sequence the 6,7-dihydroazepine 3 reacts with acetylenedicarboxylates at the 4,5-double bond to afford first the intermediary 8,9-dihydro-1H-azonines 6B. These give in turn the indoles 7a,b via thermal 6π-electron cyclization. Under subsequent rearrangement 2,3,3a,7a-tetrahydroindoles 8a,b are formed. The structure of 8a is established by X-ray diffraction. In a polar [2 + 2]-cycloaddition 4-R-1,2,4-triazoline-3,5-dione (4-R-TAD) gives with 3 and 5 the [1,2,4]triazolo[1′,2′:1,2]diazet-[3,4-d]azepines 10a-d and 11a,b resp., and with the bis-TAD 12 the 2:1-adduct 13. Treatment of 10a with phenyl isocyanate originates the carbodiimide 14 which is converted with basic ring closure into the pyrimido[4,5-b]azepine 15.
    Notes: 6,7-Dihydrooxepine, -thiepine und -azepine (1-5) zeigen eine ausgeprägte Alternanz ihrer 13C-NMR-Verschiebungen im konjugierten π-System. Das 6,7-Dihydroazepin 3 reagiert mit Acetylendicarbonsäureestern zunächst unter Cycloaddition-Ringerweiterung an der 4,5-Doppelbindung zu den intermediären 8,9-Dihydro-1H-azoninen 6b. Diese ergeben sogleich unter thermischem 6π-Elektronenringschluß die Indole 7a,b. Nach erneuter Umlagerung entstehen 2,3,3a,7a-Tetrahydroindole 8a,b; die Konstitution von 8a wird durch Röntgenstrukturanalyse ermittelt. Mit 4-R-1,2,4-Triazolin-3,5-dionen (4-R-TAD) entstehen aus 3 und 5 in polarer [2 + 2]-Cycloaddition die [1,2,4]Triazolo[1′,2′:1,2]diazet[3,4-d]azepine 10a-d und 11a,b mit dem Bis-TAD 12 das 2:1-Addukt 13. 10a ergibt mit Phenylisocyanat das Carbodiimid 14 und beim basischen Ringschluß das Pyrimido[4,5-b]azepin 15.
    Additional Material: 5 Tab.
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  • 77
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2135-2142 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: New Reagents, XXXVII. (α-Lithioalkyl)diphenylarsane Oxides: Synthesis and Application for the Indirect Nucleophilic HaloalkylationDue to ready accessibility and high nucleophilicity (α-lithioalkyl)diphenylarsane oxides (2) are favorable reagents for the synthesis of many organoarsenic compounds. In organic synthesis they are recommendable as reagents for indirect nucleophilic haloalkylation reactions (Hal=Cl, Br, I).
    Notes: (α-Lithioalkyl)diphenylarsanoxide (2) sind wegen ihrer bequemen Zugänglichkeit und hohen Nucleophilie günstige Reagenzien zur Darstellung zahlreicher Organoarsenverbindungen. In der organischen Synthese sind sie als Reagenzien für indirekte nucleophile Haloalkylierungen (Hal=Cl, Br, I) empfehlenswert.
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  • 78
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2159-2172 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthese with Cyclobutadienes, 13. Azapentafulvenes from 2,3,4-Tri-tert-butylcyclobutadiene-1-carboxylic Esters and IsonitrilesFrom kinetically stabilized cyclobutadienes 6a and b and isonitriles 7a-c the azapentafulvenes 9a-d are obtained. In contrast, 6a reacts with 7d exclusively to form the constitution isomeric azapentafulvene 11e. Both isomers (9f and 11f) are realized in the reaction of 6a with 7e. The structural assignment of the isomers 9 and 11 is based on 13C NMR investigations as well as on an X-ray analysis performed for 9a. Hydrolysis of 9 and 11 yields the tri-tert-butyl substituted cyclopentadienones 20a,b and 21. By photochemical means 21 is transformed into the isomer 20a, which can also be obtained directly from the cyclobutadiene 6a and carbon monoxide.
    Notes: Aus den kinetisch stabilisierten Cyclobutadienen 6a bzw. b und den Isonitrilen 7a-c erhält man die Azapentafulvene 9a-d. Im Gegensatz dazu reagiert 6a mit 7d ausschließlich unter Bildung des konstitutionsisomeren Azapentafulvens 11e. Beide Möglichkeiten (9f und 11f) werden bei der Umsetzung von 6a mit 7e wahrgenommen. Die Strukturzuordnung der Isomeren 9 und 11 beruht auf 13C-NMR-Untersuchungen sowie auf der Röntgenstrukturanalyse für 9a. Hydrolyse von 9 und 11 macht die tri-tert-butylsubstituierten Cyclopentadienone 20a,b und 21 zugänglich. Photochemisch läßt sich 21 in das Isomere 20a umwandeln, das auch unmittelbar aus dem Cyclobutadien 6a und Kohlenmonoxid erhalten werden kann.
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  • 79
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2178-2190 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Enantioselektive diastereospezifische Synthese von anti-α-Alkyl-β-hydroxycarbonsäureestern durch Cuprat-Ringöffnung von GlycidesternEine über die Zwischenglieder 4-7 ablaufende diastereospezifische Kettenverlängerung von Aldehyden 1 zu anti-α-Alkyl-β-hydroxyestern 2 wird beschrieben. Durch Verwendung der Sharpless-Epoxidierung kann 2 mit Enantiomerenüberschüssen von 〉90% in Form beider Antipoden erhalten werden.
    Notes: A diastereospecific chain elongation of the aldehydes 1 of anti-α-alkyl-β-hydroxy esters 2 via the intermediates 4-7 is described. By means of the Sharpless epoxidation, 2 may be obtained with 〉90% ee in either enantiomer.
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  • 80
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2191-2207 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Stereoselective Aldol Reaction with Chiral Secondary AcetamidesThe deprotonated acetamides 4a-c und 5a-c are added to prochiral carbonyl compounds. The influence of the solvent, of the reaction temperature, and of the enolate gegenion on the ratio of the isomeric products 8/9, 18/19, and 26/27, respectively, are studied. The highest degrees of diastereoselectivity are observed, when the titanium enolate of the acetamide 4a or the threefold deprotonated N-acetyl-α-phenylglycinol (5a) is used. The diastereomers 18a-d, formed in excess in the addition of 5a to aldehydes, are isolated in a pure form by a single recrystallization, and afford the enantiomerically pure β-hydroxy carboxylic acids 3a-d. Thereby, the chiral auxiliary, α-phenylglycinol (14), is recovered.
    Notes: Die deprotonierten Acetamide 4a-c und 5a-c werden an prochirale Carbonylverbindungen addiert. Dabei wird der Einfluß von Lösungsmittel, Temperatur und Enolat-Gegenion auf das jeweilige Verhältnis der isomeren Produkte 8/9, 18/19 und 26/27 untersucht. Die höchsten Diastereoselektivitäten lassen sich mit dem Titan-enolat des Amids 4a und dem dreifach deprotonierten N-Acetyl-α-phenylglycinol (5a) erzielen. Die bei der Addition von 5a an Aldehyde im Überschuß gebildeten Diastereomeren 18a-d können durch einmaliges Umkristallisieren rein erhalten werden und liefern nach alkalischer Hydrolyse die enantiomerenreinen β-Hydroxycarbonsäuren 3a-d. Dabei wird der chirale Hilfsstoff, α-Phenylglycinol (14), zurückgewonnen.
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  • 81
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthese von Ketenaminalen mit Imidazolidinring durch Kondensation von 4,5-Dihydro-2-(methylthio)-1H-imidazolen mit CH-aciden Methylenverbindungen und einige Additions-und Cyclokondensations-Reaktionen4,5-Dihydro-2-(methylthio)-1H-imidazole 1a, b reagieren mit aktiven Methylenverbindungen 2a-f unter Eliminierung von Methanthiol zu den entsprechend substituierten Methylenimidazolidinen 3a-f und 4c-f. Die Verbindungen 2g-j, die eine aktivere Carbonylgruppe enthalten, ergeben mit 1a unter Eliminierung einer Methylthio- und Acylgruppe 3g-i. 3a, g-i reagieren mit Estern ungesättigter Säuren in einer Additions- und Cyclokondensations-Sequenz zu den entsprechenden Imidazo[1,2-a]pyridinen 5,6 und 7, ergeben aber mit Azodicarbonsäure-diethylester nur die Additionsprodukte 8.
    Notes: The 4,5-dihydro-2-(methylthio)-1H-imidazoles 1a,b react with active methylene compounds 2a-f to afford the corresponding substituted methyleneimidazolidines 3a-f and 4c-f by elimination of methanethiol. The reaction of compounds 2g-j, which contain a more active carbonyl group, with 1a gives 3g-i by elimination of a methylthio group as well as an acyl group, too. 3a,g-i react with esters of α,β-unsaturated acids to afford the corresponding imidazo[1,2-a]pyridines 5,6, and 7 in an addition and cyclocondensation reaction sequence, but with diethyl azodicarboxylate only to give the addition product 8.
    Additional Material: 2 Tab.
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  • 82
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2233-2248 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Deamination Reactions, 43. The Effect of Trifluoromethyl Groups on the Reactivity of Aliphatic Diazonium Ions and CarbocationsVarious trifluoroalkanamines (9, 26, 35, 38, 45, 56, and 67) have been prepared and diazotized (water, pH 3.5) to probe the effect of trifluoromethyl groups on the reactivity of aliphatic diazonium ions. The product distributions reveal that α-CF3 groups enhance inverting displacement and enforce rearrangements (hydride shifts) separating the positive charge from CF3. Migrations of the positive charge from the β- to the γ-position are less strongly promoted than those from α to β. Enhancement factors of ca. 15 (α → β) and 4 (β → γ) may be derived by comparison with analogous alkanediazonium ions. The positive charge does not migrate in the reverse direction (β → α) except for minor amounts of a pinacolic rearrangement (68 → 7). A migration of the positive charge from γ to β has been detected with 36 but a tenfold decrease as compared to the analogous butanediazonium ion 37 is indicated. All observations are reasonably explained in terms of the relative stabilites of the intermediate trifluoroalkyl cations.
    Notes: Eine Reihe von Trifluoralkanaminen (9, 26, 35, 38, 45, 56 und 67) wurde dargestellt und diazotiert (Wasser, pH 3.5), um den Einfluß von Trifluormethylgruppen auf die Reaktionsweise aliphatischer Diazonium-Ionen zu untersuchen. Die Produktverteilungen zeigen, daß α-CF3-Gruppen die invertierende Substitution verstärken und Umlagerungen (Wasserstoffverschiebungen) fördern, welche die positive Ladung von der CF3-Gruppe trennen. Die Wanderung der positiven Ladung von der β- zur γ-Position wird weniger stark gefördert als die von α nach β. Aus dem Vergleich mit analogen Alkandiazonium-Ionen lassen sich Beschleunigungsfaktoren von ca. 15 (α → β) und 4 (β → γ) ableiten. In umgekehrter Richtung (β → α) wandert die positive Ladung nicht, abgesehen von einem kleinen Anteil Pinakol-Umlagerung (68 → 7). Eine Ladungsverschiebung von der γ- zur β-Position wurde bei 36 gefunden; im Vergleich zum analogen Butandiazonium-Ion 37 ist sie um den Faktor 10 verringert. Alle Beobachtungen sind im Einklang mit der relativen Stabilität der intermediären Trifluoralkyl-Kationen.
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  • 83
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2272-2288 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Novel 2,6-Disubstituted AzulenesMethods are described to introduce varying residues into 2- and 6-positions of azulene, starting from diethyl 6-bromo-2-methoxy-1,3-azulenedicarboxylate (1). 2-Substitution is achieved by Grignard reaction or exchange of the alkoxy group and by aldol condensation of 2-methyl compounds whereas 6-substitution is conducted by nucleophilic displacement and by homo- and hetero-aromatic coupling. Consecutive dealkoxycarbonylation yields azulenes 20 with free 1,3-positions. Biazulenes 9a-c and 201, 20m, styryl- and bis(styryl)-azulenes 15-18 and 20i-k, and finally the azulenedialdehyde 19 are novel compounds which were difficult to prepare or were inaccessible so far.
    Notes: Ausgehend von 6-Brom-2-methoxy-1,3-azulendicarbonsäure-diethylester (1) werden Methoden zur Einführung unterschiedlicher Reste in 2- und 6-Position entwickelt. 2-Substitution gelingt durch Grignard-Reaktion oder Austausch der Alkoxygruppe sowie durch Aldol-Kondensation von 2-Methylverbindungen, während 6-Substitution durch nucleophilen Austausch und durch Homo- und Kreuz-Aromaten-Kupplungen erfolgt. Anschließende Dealkoxycarbonylierung erbringt Azulene 20 mit freien 1,3-Stellungen. Die Biazulene 9a-c und 201, 20m, die Styryl- und Bis(styryl)azulene 15-18 und 20i-k sowie der Azulendialdehyd 19 sind Verbindungen, die bisher schwierig oder nicht zugänglich waren.
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  • 84
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2339-2349 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Concerning the Question of Positional Isomerism in Disubstituted BullvalenesWe report about 15 new disubstituted bullvalenes (2, 4, 5, 11, 12, 14-20, 22-24) and discuss their substitution pattern together with 9 known species (1, 3, 6-10, 13, 21). The results which are partly unexpected are put together phenomenologically. We have no reasonable explanation for some results, i.e. only a few substituents with „complementary“ properties like the pair CH2OH/Br or CH3/CN in compounds 16 and 18, respectively, prefer a vicinal arrangement at a double bond.
    Notes: Wir berichten über 15 neue disubstituierte Bullvalene (2, 4, 5, 11, 12, 14-20, 22-24) und diskutieren ihr Substitutionsmuster gemeinsam mit dem von 9 bekannten Vertretern (1, 3, 6-10, 13, 21). Die teilweise unerwarteten Ergebnisse werden phänomenologisch geordnet. Für einige Befunde fehlen befriedigende Erklärungen. So bevorzugen z. B. nur manche Substituenten mit „komplementären“ Eigenschaften wie das Paar CH2OH/Br oder CH3/CN in den Verbindungen 16 bzw. 18 eine vicinale Anordnung an der Doppelbindung.
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  • 85
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2317-2338 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Regio- and Stereoselectivity of Novel Thermal [3 + 2] Cycloaddition Reactions of Mesonionic 1,3-Oxathiol-4-ones to Alkynes and AlkenesAs potential carbonyl ylides, the 1,3-oxathiolyium-4-olates 1c or 1d combine with dibenzoylacetylene or 1-(diethylamino)-1-propyne via nonisolable [3 + 2] primary adducts of type 2, which release COS to give the furan derivatives 3a or b, respectively. On the other hand, some representative of 1 reacts with symmetrically and unsymmetrically substituted olefinic substrates with regio- and/or stereoselective formation of the isolable [3 + 2] primary adducts 4-16. In the example of the reactions of 1c with trans- and cis-cyclooctene, the stereospecificities and the competition constant are determined. Furthermore, the thermolyses of the cycloadducts 4b,5,6, and 7a,b are investigated. The addition directions, derived from the FMO and PMO theory, are compared with the experimentally realized regiochemistry.
    Notes: Als potentielle Carbonyl-ylide vereinigen sich die 1,3-Oxathiolylium-4-olate 1c oder 1d mit Dibenzoylacetylen oder 1-(Diethylamino)-1-propin über nicht isolierbare [3 + 2]-Primäraddukte vom Typ 2 unter COS-Abspaltung zu Furan-Derivaten 3a bzw. b. Demgegenüber reagieren einige Vertreter von 1 mit symmetrisch und unsymmetrisch substituierten olefinischen Substraten regio- und/oder stereoselektiv zu isolierbaren [3 + 2]-Primäraddukten 4-16. Am Beispiel der Umsetzung von 1c mit trans- und cis-Cycloocten werden die Stereospezifitäten und die Konkurrenzkonstante ermittelt. Weiterhin werden die Thermolysen der Cycloaddukte 4b, 5, 6 und 7a,b untersucht. Die aus der FMO- und PMO-Theorie abgeleiteten Additionsrichtungen werden mit der experimentell realisierten Regiochemie verglichen.
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  • 86
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2397-2413 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Reaction of α-(Dimethylamino)alkanal DimethylhydrazonesSeveral α-(dimethylamino)aldehyde hydrazones of the general structure 11 have been obtained by alkylation of the lithium salt of 9 or by addition of Grignard reagents to 15 or 17. The compounds react with acyl chlorides to give hydrazones of unsaturated aldehydes. The same products 27 are obtained by thermal degradation of the ammonium salts 26. In the hydrazonoammonium salts 26a, g the trimethylammonium group can be substituted by a variety of nucleophiles (→ 34-39).
    Notes: Verschieden substituierte α-(Dimethylamino)aldehyd-hydrazone der allgemeinen Struktur 11 lassen sich aus dem Lithium-Salz des (Dimethylamino)acetaldehyd-dimethylhydrazons durch Alkylierung sowie durch Addition von Grignard-Verbindungen an das Ammoniumsalz 15 oder das N,O-Acetal 17 darstellen. Die Verbindungen 11 enthalten eine leicht eliminierbare Dimethylaminogruppe und gehen mit Säurechloriden oder nach Methylierung thermisch in Hydrazone 27 α,β-ungesättigter Aldehyde über. In den Salzen 26a, g läßt sich die Trimethylammoniumgruppe durch verschiedene Nucleophile verdrängen (→ 34-39).
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  • 87
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2414-2429 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Intramolecular Interactions in Radical Cations of Di- and Tetra(α-methoxy)-9,10-dihydro-9,10-ethanoanthracenes[4 + 2]-Cycloaddition of maleic anhydride, 2-chloropropenoyl chloride and (E)-dichloroethene to 1,4-di- (3a) and 1,4,5,8-tetramethoxyanthracene (3b) yields the dihydroethanoanthracenes 4, 5, and 8, respectively. The predominant maleic anhydride adduct 4a is assigned the exo-configuration on the basis of the ESR spectrum of the radical cations 4a+·. The cycloadducts 5 and 8 are converted to the dihydroethanoanthracenes 10 via the ketones 6 or the dihydroethenoanthracenes 9, respectively. Aluminium chloride in nitromethane oxidizes the α-methoxydihydroethanoanthracenes 4, 6a, 8, and 10 to radical cations the ESR spectra of which are analyzed. Besides the expected proton hyperfine splittings of the 1,4-dimethoxybenzene moiety, one observes long-range transfer of spin density to the unsubstituted benzene ring [a(4H) = 0.008-0.010 mT] as well as to the syn-[10a+·: a(2H) = 0.013 mT] and anti-protons [a(2H) = 0.059-0.069 mT] of the ethano bridge. Of the radical cations possessing two 1,4-dimethoxybenzene rings, 4b and 10b do not exhibit dynamic ESR spectroscopic phenomena. On the other hand, the unpaired electron is exchanged rapidly (with respect to the hyperfine splitting time scala) between the 1,4-dimethoxybenzene rings of the radical cation 8b+·. The dependence of the exchange frequency on the temperature and the aluminium chloride concentration is indicative of ion-pair effects.
    Notes: Durch [4 + 2]-Cycloaddition von Maleinsäureanhydrid, 2-Chlorpropenoylchlorid bzw. (E)-Dichlorethen an 1,4-Di- (3a) und 1,4,5,8-Tetramethoxyanthracen (3b) entstehen die Dihydroethanoanthracene 4, 5 bzw. 8. Dem überwiegenden der Maleinsäureanhydrid-Addukte 4a wird aufgrund des ESR-Spektrums der Radikalkationen 4a+· die exo-Konfiguration zugeordnet. Die Cycloaddukte 5 und 8 werden über die Ketone 6 bzw. Dihydroethenoanthracene 9 in die Dihydroethanoanthracene 10 übergeführt. Aluminiumchlorid in Nitromethan oxidiert die α-Methoxydihydroethanoanthracene 4, 6a, 8 und 10 zu Radikalkationen, deren ESR-Spektren analysiert werden. Neben den erwarteten Protonen-Hyperfeinaufspaltungen des 1,4-Dimethoxybenzolrings beobachtet man weitreichenden Transfer von Spindichte zum unsubstituierten Benzolring [a(4H) = 0.008-0.010 mT] sowie zu den syn-[10a+·: a(2H) = 0.013 mT] und anti-Protonen [a(2H) = 0.059-0.069 mT] der Ethanobrücke. Von den Radikalkationen mit zwei 1,4-Dimethoxybenzolringen zeigen die aus 4b und 10b erhaltenen keine dynamischen ESR-spektroskopischen Phänomene. Dagegen wird in 8b+· das ungepaarte Elektron rasch bezüglich der Hyperfeinaufspaltungs-Zeitskala zwischen den 1,4-Dimethoxybenzolringen ausgetauscht. Die Abhängigkeit der Austauschfrequenz von der Temperatur und der Aluminiumchlorid-Konzentration weist auf Ionenpaar-Effekte hin.
    Additional Material: 4 Ill.
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  • 88
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2444-2457 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses, Structures, and Properties of N-(Alkoxymethylene)carbamatesN-(Alkoxymethylene)carbamates 1 are synthesized from the imidate hydrochlorides 7 or from the imidates 8 and formates 9 in the presence of amine bases in mostly satisfactory yields (two optimized procedures, 10 examples).—An X-ray analysis of the derivative 1dbc shows an almost planar EtO—RC=N—C skeleton with an exo-s-cis-ethoxy function; the carboxylic group is nearly perpendicular to that plane.  - Quantum mechanical ab initio optimizations (3-21 G//3-21 G) were performed for nine conformations of the model substances 11; the calculated rotational barrier around the amide type bond is estimated to be ca. 5 kcal/mol. The ground state energy of the conformers of 11 is ca. 20 kcal/mol higher than that of the model for 10, N-formylcarbamic acid (12). —IR, 1H, and 13C NMR data for solutions of 1 are discussed.
    Notes: N-(Alkoxymethylen)carbamidsäureester 1 können durch Umsetzung der Imidsäureester-hydrochloride 7 oder der Imidsäureester 8 mit Chlorameisensäureestern 9 in Gegenwart von Aminbasen in meist guten bis sehr guten Ausbeuten hergestellt werden (zwei optimierte Syntheseverfahren, 10 Beispiele). Schonende Hydrolyse der Verbindungen 1 ergibt die N-Acylcarbamidsäureester 10.  - Die Röntgenstrukturanalyse des Derivates 1dbc zeigt ein planares RO—RC=N—C-Molekülgerüst mit exo-ständiger s-cis-orientierter Ethoxygruppe; die Carboxylgruppe steht annähernd senkrecht auf dieser Ebene.  - Mit Hilfe quantenmechanischer ab-initio-Berechnungen (3-21G//3-21 G) wurden Strukturen und Energien der Modellverbindungen 11 bestimmt und deren Rotationsbarriere um die amidische -Bindung abgeschätzt (ca. 5 kcal/mol). Im Vergleich mit N-Formylcarbamidsäure (12) (Modell für 10) besitzen die Verbindungen 11 eine um ca. 20 kcal/mol höhere Grundzustandsenergie. —IR-, 1H- und 13C-NMR-Daten von Lösungen von 1 werden diskutiert.
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  • 89
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2473-2496 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Relative Reactivities of Alkyl-Substituted Alkenes and Cycloalkenes towards Diarylcarbenium IonsThe relative reactivities of alkyl-substituted alkenes 4 towards diarylmethyl cations 2 generated in situ from diarylmethyl chlorides 1 and Lewis acids were determined by competition experiments. The relative reactivities were almost independent of the nature of the Lewis acid. Eventual differences of the solvation free enthalpies of various activated complexes are, therefore, independent of the nature of the gegen ions. The rate acceleration by methyl groups - 6-50 by CH3 at the attacked vinylic position and approximately 104 at the developing carbenium centre - indicates a scarcely bridged transition state.
    Notes: Nach der Konkurrenzmethode wurden die relativen Reaktivitäten Alkyl-substituierter Alkene 4 gegenüber Diarylmethyl-Kationen 2 bestimmt, die in Gegenwart von Alken-Gemischen aus Diarylmethylchloriden 1 und Lewis-Säuren erzeugt wurden. Die Konkurrenz-konstanten werden durch die Art der Lewis-Säure nur wenig beeinflußt, so daß eine eventuelle Differenz der freien Solvatationsenthalpie verschiedener aktivierter Komplexe von der Natur des Gegenions unabhängig sein muß. Aus der 6-50fachen Reaktionsbeschleunigung durch Methylgruppen, die sich am angegriffenen Alken-Kohlenstoff befinden und der 104fachen Reaktivitätssteigerung durch Methylgruppen am neuen Carbeniumzentrum wird auf einen wenig verbrückten Übergangszustand geschlossen.
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  • 90
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 844-849 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses of 2,5-Diazido-3,6-dicyano- and 2,6-Diazido-3,5-dicyano-1,4-benzoquinone for the Preparation of DicyanoketeneTwo short syntheses of 2,5-diazido-3,6-dicyano- (1) and 2,6-diazido-3,5-dicyano-1,4-benzo-quinone (3) as starting materials for the preparation of dicyanoketene in situ are reported; beyond that the compounds 14, 15, and 16a, b are synthesized.
    Notes: Es wird über zwei wenigstufige Synthesen von 2,5-Diazido-3,6-dicyan- (1) und 2,6-Diazido-3,5-dicyan-1,4-benzochinon (3) als Ausgangssubstanzen zur Darstellung von Dicyanketen in situ berichtet; darüber hinaus werden die Verbindungen 14, 15 und 16a, b dargestellt.
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  • 91
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 850-856 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Esters of Ferrocenedithiocarboxylic AcidTwo methods were used to prepare esters of ferrocenedithiocarboxylic acid: 1. Alkylation of the ferrocenedithiocarboxylate anion in the piperidinium salt [C5H10NH2]+[Fc—CS2]- (1) by CH3I, C2H5I, and ethylene oxide gave mononuclear esters Fc—C(S)SR (R = CH3 (2), C2H5 (3), CH2CH2OH (4)), whereas the dinuclear methylene diester [Fc—C(S)S]2CH2 (9a) was formed using either CH2Cl2 or CH2I2. 2. The reaction of ferrocenecarbonyl chloride, Fc—C(O)Cl, with methanethiol, CH3SH, to give Fc—C(O)SCH3 (7) and subsequent sulfuration by P4S10 furnished Fc—C(S)SCH3 (2). The analogous reactions with dithiols, HS[CH2]nSH (n = 2 - 4), led to the dinuclear compounds [Fc—C(S)S]2[CH2]n (n = 2 (9b), 3 (9c), 4 (9d)). All the intermediates of the composition Fc—C(O)S[CH2]nSH (11b - d), [Fc—C(O)S]2[CH2]n (12b - d), and Fc—C(S)S[CH2]nSC(O) - Fc (13b - d) could be isolated. The new compounds were characterized on the basis of their 1H and 13C NMR spectra.
    Notes: Zwei Methoden wurden zur Darstellung von Estern der Ferrocendithiocarbonsäure angewandt: 1. Die Alkylierung des Ferrocendithiocarboxylat-Anions im Piperidinium-Salz [C5H10NH2]+ [Fc—CS2]- (1) mit CH3I, C2H5I und Ethylenoxid ergab einkernige Ester, Fc—C(S)SR (R = CH3 (2), C2H5 (3), CH2CH2OH (4)), während mit CH2Cl2 oder CH2I2 der zweikernige Methylendiester [Fc—C(S)S]2CH2 (9a) entstand. 2. Die Umsetzung von Ferrocencarbonsäurechlorid, Fc—C(O)Cl, mit Methanthiol, CH3SH, zu Fc—C(O)SCH3 (7) und anschließende Sulfurierung mit P4S10 lieferte Fc—C(S)SCH3 (2). Die analoge Reaktion mit Dithiolen HS[CH2]nSH (n = 2 - 4) führte zu den Zweikernverbindungen [Fc—C(S)S]2[CH2]n (n = 2 (9b), 3 (9c), 4 (9d)); alle Zwischenstufen der Zusammensetzung Fc—C(O)S[CH2]nSH (11b - d), [Fc—C(O)S]2[CH2]n (12b - d) und Fc—C(S)S-[CH2]nSC(O) - Fc (13b - d) konnten isoliert werden. Die neuen Verbindungen wurden anhand der 1H- und 13C-NMR-Spektren charakterisiert.
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  • 92
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 857-871 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Properties of Substituted 1-Alkoxy-2-azaallenium Salts12 novel substituted 1-alkoxy-2-azaallenium salts 1 have been prepared by reaction of the N-methyleneamides 3 with trialkyloxonium salts 4. During the alkylation reaction of the N-benzylideneamides 3m, n a formal disproportionation takes place to yield higher and lower oxidized 2-azaallenium salts (13, 14 from 3n) as the major products. The salts 1n, r, which are therefore not easily accessible by the alkylation route, can be prepared successfully by an acylation cleavage reaction of the N-(alkoxymethyl)imidates 8. The protonation of the substances 3 takes place exclusively at the nitrogen atom to give the N-acyliminium salts 19. Detailed spectroscopic data (IR, 1H, 13C NMR, MS) are included.
    Notes: Durch Umsetzung der N-Methylencarbonsäureamide 3 mit den Trialkyloxonium-Salzen 4 wurden 12 bislang nicht beschriebene substituierte 1-Alkoxy-2-azaallenium-Salze 1 hergestellt. Bei der Alkylierung der N-Benzylidencarbonsäureamide 3m, n tritt eine formale Disproportionierung zu höher und niedriger oxidierten 2-Azaallenium-Salzen (13, 14 bei 3n) als Hauptreaktion ein, deren Mechanismus untersucht wurde. Die durch Alkylierung nur schlecht zugänglichen Salze 1n, r können besser durch eine Acylspaltung von N-(Alkoxy-methyl)imidsäureestern 8 hergestellt werden. Die Protonierung der Verbindungen 3 erfolgt am Stickstoffatom unter Bildung der N-Acyliminium-Salze 19. Ausführliche spektroskopische Daten (IR, 1H- und 13C-NMR, MS) werden mitgeteilt.
    Additional Material: 1 Tab.
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  • 93
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 872-877 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Seven- (N2O2Si3) and Eight-membered (N2O2Si4) Rings from a (Hydroxysilyl)hydrazine and 1-Amino-3-fluorosiloxanesHalogeno-functional siloxanes [(Me3C)2SiCl—O—SiHalR2, Hal = F, R = CMe3 (2), Hal = Cl, R = Ph (3)] are obtained in the reaction of dihalogenosilanes with (Me3C)2Si(Cl)OLi (1a). (Me3C)2Si(Cl)OH reacts smoothly with ammonia to form the aminosilanol (Me3C)2Si(NH2)OH (4). With fluorosilanes its lithium salt 4a yields the amino- and fluoro-functional siloxanes 5 - 8 [(Me3C)2Si(NH2) —O—SiFRR′, R = R′ = Me (5), R = R′ = CMe3 (6), R = F, R′ = CMe3 (7), R = F, R′ = N(SiMe3)2 (8)]. Primary amines react with 1 by intermolecular HCl elimination to give the 1-chloro-3-hydroxysiloxane 9, hydrazine reacts to form the N,N′-bis(hydroxysilyl)hydrazine 10, methylhydrazine to yield the N-(hydroxysilyl)-N-methylhydrazine 11, and N,N′-dimethylhydrazine to give 9. The reaction of the dilithium salt 10a with F3SiN(SiMe3)2 leads to the formation of the seven-membered N2O2Si3 ring 12. The 1,5,3,7,2,4,6,8-dioxadiazatetrasilocanes 13 and 14 are obtained by LiF elimination from lithiated 5 and 7, respectively.
    Notes: Halogenfunktionelle Siloxane [(Me3C)2SiCl - O—SiHalR2, Hal = F, R = CMe3 (2), Hal = Cl, R = Ph (3)] werden durch Reaktion der Dihalogensilane mit (Me3C)2Si(Cl)OLi (1a) erhalten. Mit Ammoniak reagiert (Me3C)2Si(Cl)OH (1) glatt unter Bildung des Aminosilanols (Me3C)2Si(NH2)OH (4), dessen Lithiumsalz 4a mit Fluorsilanen die amino- und fluorfunktionellen Siloxane 5 - 8 [(Me3C)2Si(NH2) - O—SiFRR′, R = R′ = Me (5), R = R′ = CMe3 (6), R = F, R′ = CMe3 (7), R = F, R′ = N(SiMe3)2 (8)] bildet. Primäre Amine reagieren mit 1 unter intermolekularer HCl-Abspaltung zum 1-Chlor-3-hydroxysiloxan 9, Hydrazin zum N,N′-Bis(hydroxysilyl)hydrazin 10, Methylhydrazin zum N-(Hydroxysilyl)-N′-methyl-hydrazin 11 und N,N′-Dimethylhydrazin zu 9. Die Reaktion des Dilithiumsalzes 10a mit F3SiN(SiMe3)2 führt zur Bildung des siebengliedrigen N2O2Si3-Ringes 12. Durch LiF-Eliminierung aus lithiiertem 5 und 7 entstehen die 1,5,3,7,2,4,6,8-Dioxadiazatetrasilocane 13 und 14.
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  • 94
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 878-886 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Chemistry of Transition Metal Heterocyclic Complexes, II. Synthesis and Electrochemistry of Carbonyl Chromium Complexes in the Bithiophen SeriesThe (substituted) (bithiophene)tricarbonylchromium complexes 4a - g are formed in yields up to 95% upon treatment of tricarbonyltris(γ-picoline)chromium with 2,2′-bithiophene (1a) and its derivatives 1b - e and 1g, respectively, in the presence of the Lewis acid BF3. The oxidation of the new compounds, as investigated by means of cyclovoltammetry, is irreversible and effects decomposition of the complexes.
    Notes: Durch Umsetzung von Tricarbonyltris(γ-picolin)chrom (3) mit 2,2′-Bithiophen (1a) und seinen Derivaten 1b - e und 1g bilden sich in Gegenwart der Lewis-Säure BF3 die (substituierten) Bithiophen-Chromtricarbonyl-Komplexe 4a - g in Ausbeuten bis 95%. Die cyclovoltametrisch untersuchte Oxidation der neuen Verbindungen verläuft irreversibel unter Zerfall der Komplexe.
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  • 95
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Oxidative Aminomercurierung von 2-Propin-1-olen. Stereoselektive Synthese und Struktur von cis-[1,4]Oxazino[3,2-b]-1,4-oxazin-DerivatenDie Reaktion von 2-Propin-1-olen 1 mit 2-Aminoalkoholen 7 in Gegenwart von Quecksilber(II)-chlorid beginnt mit einer oxidativen Aminomercurierung, gefolgt von hoch stereo-selektiven Reaktionsschritten, die zu cis-[1,4]Oxazino[3,2-b]-1,4-oxazin-Derivaten 10 führen. Nach den Röntgenstrukturanalysen von 10c,f,g zeigen diese Verbindungen die gleiche Anordnung um die zentrale Bindung, und zwar so, daß die anomere Stabilisierung ein Maximum erreicht.
    Notes: The reactions of 2-Propin-1-ols 1 with 2-amino alcohols 7 and mercury(II) chloride start with an oxidative aminomercuration step followed by a series of highly stereoselective processes leading to cis-[1,4]oxazino[3,2-b]-1,4-oxazine derivatives 10. X-Ray analyses of 10c,f,g show that these compounds have the same geometrical arrangement around their central fusion bond in such a way that anomeric stabilisation reaches a maximum.
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  • 96
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Decabenzylgermanocene, -stannocene and -plumbocene. Synthesis and Structure of Air-stable Metallocenes of Main Group IVGermanium diiodide, tin dichloride, or lead diacetate reacts with pentabenzylcyclopentadienyllithium (1) to give decabenzylgermanocene (2), decabenzylstannocene (3) or decabenzylplumbocene (4), respectively. The air-stable metallocenes were characterized by IR, Raman, NMR, tin-119m-Mössbauer (3), and mass spectroscopy. The X-ray structural analysis shows for all three compounds an angle of 31 to 36° between the planes of the two cyclopentadienyl rings and a shielding of the lone pair of electrons at the metal atom by three of the ten benzyl groups each.
    Notes: Germaniumdiiodid, Zinndichlorid bzw. Bleidiacetat reagiert mit Pentabenzylcyclopentadienyllithium (1) unter Bildung von Decabenzylgermanocen (2), Decabenzylstannocen (3) bzw. Decabenzylplumbocen (4). Die luftstabilen Metallocene wurden durch IR-, Raman-, NMR-, 119mSn-Mößbauer- (3) und Massenspektren charakterisiert. Die Röntgenstrukturanalyse der Verbindungen zeigt, daß die Ebenen der beiden Cyclopentadienylringe einen Winkel zwischen 31 und 36° einschließen, und daß eine Abschirmung des freien Elektronenpaares am Metallatom jeweils durch drei der zehn Benzylgruppen erfolgt.
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  • 97
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2668-2677 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Asymmetric Reductive Amination of Cycloalkanones, 5. Synthesis and Absolute Configuration of 2-Substituted CyclopentanaminesIn an asymmetric synthesis 2-substituted cyclopentanamines are obtained from racemic cyclopentanones by means of reductive amination in a three-step procedure. Condensation of the ketones 3(n) with optically active 1-phenylethylamines yields imine mixtures 4(n), which are hydrogenated with Raney nickel to give the optically active, diastereomerically pure secondary amines 5(n). Hydrogenolysis with Palladium-on-charcoal leads to high grade enantiomerically pure primary amines 6(n) with good yields. The relative configuration of the amines 5(n) and 6(n) is elucidated by 1H and 13C NMR techniques. The absolute configuration is determined by X-ray analysis of the 4-bromobenzamide 8 of the primary amine (+)-6(n)e and with the help of CD of the salicylidenes 9(n). The kinetically controlled asymmetric hydrogenation with a first order transformation as proved reaction mechanism in the cyclohexanamine line is confirmed for this investigation. The hydrogenation runs like-induced to the cis-configurated amines 5(n) and 6(n), respectively.
    Additional Material: 5 Tab.
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  • 98
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 917-928 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Elektronen-Übertragungs-Reaktionen. Reaktion von Furanonen und Bifurandionen mit Kalium und SauerstoffBei der Behandlung von Furanonen (1a - c, 25, 34) und Bifurandionen (23, 37) mit Kalium in THF entstehen Radikalanion-Zwischenstufen, die mit Sauerstoff zu Superoxid reagieren, das seinerseits mit den Ausgangsfuranonen und -bifuranonen weiterreagiert. So ergab die Reaktion von 1a mit Kalium eine Mischung von 4-Oxo-2,2,4-triphenylbutansäure (7a), 1,3,3-Triphenyl-2-propen-1-on (11a) und Benzoesäure (12). Unter ähnlichen Bedingungen reagierte 11a selbst zu einer Mischung von Benzophenon (18a) und 12. Ähnliche Ergebnisse wurden im Falle von 1b und c erhalten. Das Bifurandion 23 ergab mit Kalium eine Mischung von 2(5H)-Furanon 25, 2,3-Diphenylpropensäure (31) und 12. 25 selbst reagierte mit Kalium unter ähnlichen Bedingungen zur selben Mischung von 31 und 12. 3-Phenyl-2(3H)-benzofuranon (34) führte mit Kalium jedoch zu keinem isolierbaren Produkt; nur Ausgangsmaterial wurde zurückgewonnen. Unter vergleichbaren Bedingungen lieferte das Bifurandion 37 das Fragmentierungsprodukt 34. Mit Hilfe der cyclischen Voltammetrie wurden die zu den Radikalanionen führenden Reduktionspotentiale gemessen. Die Radikalanion-Zwischenstufen wurden durch ihre Elektronenspektren charakterisiert.
    Notes: Treatment of furanones (1a - c, 25, 34) and bifurandiones (23, 37) with potassium in THF gave rise to radical anion intermediates, which reacted with oxygen to give superoxide and ultimately products derived through the reaction of superoxide with the starting furanones and bifurandiones. Thus, the reaction of 1a with potassium gave a mixture of 4-oxo-2,2,4-triphenylbutanoic acid (7a), 1,3,3-triphenyl-2-propen-1-one (11a), and benzoic acid (12). The reaction of 11a itself, under similar conditions, gave a mixture of benzophenone (18a) and 12. Similar reactions have been observed in the case of 1b and c. The bifurandione 23, on treatment with potassium, gave a mixture of the 2(5H)-furanone 25, 2,3-diphenylpropenoic acid (31), and 12. The reaction of 25 itself with potassium under similar conditions gave the same mixture of 31 and 12. Treatment of 3-phenyl-2(3H)-benzofuranone (34) with potassium, however, did not give any isolable product; only the starting material could be recovered. Under similar conditions, the bifurandione 37 gave the fragmentation product 34. Cyclic voltammetric studies have been employed to measure the reduction potentials, leading to radical anions, and these intermediates have been characterized through their electronic spectra.
    Additional Material: 1 Ill.
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  • 99
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 943-949 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaktionen von Uracilen, 7. Synthese und eine neue Sequenz thermischer [1,5]-sigmatroper Umlagerungen von 6-(Alkylamino)-5-ethenyluracilenNeue 6-(Alkylamino)-5-ethenyluracile (2d und 7) werden dargestellt, um Substituenteneffekte bei thermischen Reaktionen zu untersuchen. Ähnlich 2a werden 2d und 7 beim Erhitzen in Dowtherm® A und nach anschließender Verseifung in die 6-Amino-5-(ethoxycarbonyl[phenyl]ethyl)uracile 4 bzw. 8 übergeführt. Erhitzen in Xylol liefert die intermediären Imine 11 und 12. Deuterierungsexperimente belegen aufeinanderfolgende thermische [1,5]-H-Wanderungen (2a-D1 → 4-D1 und 4-D2; 2a′-D2 → 4′-D1). Die Mechanismen werden diskutiert.
    Notes: Additional 6-(alkylamino)-5-ethenyluracils (2d, 7) have been prepared for investigating substituent effects in thermal reactions. Like 2a, upon heating in Dowtherm® A 2d and 7 afford after saponification 6-amino-5-(ethoxycarbonyl[phenyl]ethyl)uracils 4 and 8, respectively. After refluxing in xylene the intermediary imines 11 and 12 can be isolated. Deuteration experiments reveal consecutive thermal [1,5]H-migrations (2a - D1 → 4-D1, and 4-D2; 2a′-D2 → 4′-D1). The mechanism is discussed.
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  • 100
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 960-970 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 1-Methylbenzvalene - Synthesis and Several Reactions1-Methylbenzvalene (1) has been obtained in preparatively useful quantities from the reaction of cyclopentadienyllithium with 1,1-dichloroethane and n-butyllithium. Hydrogenation of 1 by means of diimine afforded 1-methyltricyclo[3.1.0.02,6]hexane (3). Addition of benzonitrile oxide and 2,4,6-trimethylbenzonitrile oxide to the double bond of 1 gave rise to the formation of a mixture of the isomeric Δ2-isoxazoline derivatives 4 and 5. 4-Methyl-4H-1,2,4-triazole-3,5-dione and 1 reacted to give the rearranged adducts 6 - 8. At temperatures as low as 20°C 8 transformed slowly into the dihydrodiazasemibullvalene derivative 9. Using [6-D]-1-methylbenzvalene (1a) the mechanisms of the reactions leading to 6 - 9 have been studied.
    Notes: Aus der Reaktion von Cyclopentadienyllithium mit 1,1-Dichlorethan und n-Butyllithium ging in präparativ brauchbaren Mengen 1-Methylbenzvalen (1) hervor. Seine Hydrierung mit Diimin erbrachte 1-Methyltricyclo[3.1.0.02,6]hexan (3). Benzonitriloxid und 2,4,6-Trimethylbenzonitriloxid addierten sich an die Doppelbindung von 1 unter Bildung von Gemischen der isomeren Δ2-Isoxazolin-Derivate 4 und 5. 4-Methyl-4H-1,2,4-triazol-3,5-dion ergab mit 1 die umgelagerten Addukte 6 - 8. Schon bei 20°C wandelte sich 8 langsam in das Dihydrodiazasemibullvalen-Derivat 9 um. Durch Einsatz von [6-D]-1-Methylbenzvalen (1a) wurden die Mechanismen der zu 6 - 9 führenden Reaktionen untersucht.
    Additional Material: 1 Tab.
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