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  • 1995-1999  (682)
  • 1980-1984  (1.240)
  • 1998  (682)
  • 1984  (1.240)
  • General Chemistry  (1.505)
  • Atomic, Molecular and Optical Physics  (276)
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  • Ultrastructure
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Erscheinungszeitraum
  • 1995-1999  (682)
  • 1980-1984  (1.240)
Jahr
  • 1
    Digitale Medien
    Digitale Medien
    Springer
    Virchows Archiv 433 (1998), S. 443-447 
    ISSN: 1432-2307
    Schlagwort(e): Key words Apoptosis ; Crescent-shaped spaces ; Ultrastructure ; Nivalenol ; Thymus
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract  There have been many reports on the formation of apoptotic bodies, but little is known about the cellular pathological processes and the morphological changes involved. We induced apoptotic cell death by administering nivalenol (NIV), a trichothecene mycotoxin produced by Fusarium species, and investigated the ultrastructural process of formation of apoptotic bodies. The thymus was examined by electron microscopy 6, 12, and 18 h after administration. Apoptotic cell death was induced in the thymus of NIV-treated mice. The nuclei became invaginated and pinched off to give fragments, and crescent-shaped spaces (CSS) were found around the nuclear envelopes of these cells at quite an early stage. In some of these spaces, myelin figures were observed. We divided the process of formation into four stages and characterized each of them. These are easily recognized in morphological stages and are also useful for clarifying the apoptotic mechanism.
    Materialart: Digitale Medien
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  • 2
    Digitale Medien
    Digitale Medien
    Springer
    Acta neuropathologica 96 (1998), S. 97-101 
    ISSN: 1432-0533
    Schlagwort(e): Key words Brittany Spaniel dog ; Immunocytochemistry ; Purkinje cell ; Spinocerebellar degeneration ; Ultrastructure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract Eight Brittany Spaniel dogs, seven females and one male, between 7 and 14 years old presented with clinical neurological signs of spinocerebellar disease of about 6 months to 4 years duration. Clinically the dogs had a dramatic forward “saluting” movement of the thoracic limbs, hypermetria of the pelvic limbs, cerebellar ataxia and intention tremors. Terminally, dogs crawled in a crouched thoracic posture with neck extension. Lesions were confined to cerebellum, medulla oblongata and spinal cord. The most severe lesion was diffuse Purkinje cell loss with massive neurofilament accumulation in degenerating cells. There was some bilateral neuronal degeneration in the dorsal horns of the spinal cord and in the gracilis and cuneate nuclei. There was bilateral sporadic axonal degeneration in the dorsal columns and lateral and ventromedial areas of the spinal cord. The etiology of this syndrome was not determined.
    Materialart: Digitale Medien
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  • 3
    Digitale Medien
    Digitale Medien
    Springer
    Acta neuropathologica 95 (1998), S. 367-372 
    ISSN: 1432-0533
    Schlagwort(e): Key words Amyotrophic lateral sclerosis ; Heterotopic neuron ; Alpha motor neuron ; Immunocytochemistry ; Ultrastructure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract This report concerns a comparative immunocytochemical, ultrastructural and morphometric investigation on heterotopic neurons in the white matter of the spinal cords of 19 patients with amyotrophic lateral sclerosis (ALS) and 18 age-matched neurologically normal individuals. The study revealed that the heterotopic neurons were scattered in the white matter, often adjacent to gray matter, that they immunoreacted with the antibody to synaptophysin, and that there were synaptic apparatuses on the surface of their somata and their neuronal processes. Bunina bodies and ubiquitin-positive inclusions such as Lewy body-like inclusions and skein-like inclusions, characteristic of anterior horn neurons of ALS, were present in the cytoplasm of the patients’ heterotopic neurons in the anterior or lateral column of the white matter. These findings suggest that heterotopic neurons in the anterior or lateral column have the characteristics of alpha motor neurons. The average number of heterotopic neurons observed in ALS patients was generally less than in normal subjects. This reduction was correlated with the severity of neuronal loss. The heterotopic neurons in ALS were less susceptible to the degenerative process as compared with spinal cord anterior horn cells. We assume that in this disease the heterotopic neurons may be degenerated and their number diminished after or concomitantly with the depletion of anterior horn neurons.
    Materialart: Digitale Medien
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  • 4
    ISSN: 1432-0533
    Schlagwort(e): Key words Dentatorubral-pallidoluysian atrophy ; Nuclear inclusion ; Ubiquitin ; Immunohistochemistry ; Ultrastructure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract We examined the brains and spinal cords of seven patients with clinicopathologically and genetically confirmed hereditary dentatorubral-pallidoluysian atrophy (DRPLA) using an antibody against ubiquitin, and found small, round immunoreactive intranuclear inclusions in both neurons and glial cells in various brain regions. Ubiquitinated neuronal intranuclear inclusions (uNIIs) were consistently found in the striatum, the pontine nuclei, the inferior olivary complex, the cerebellar cortex and the dentate nucleus. Ubiquitinated glial intranuclear inclusions (uGIIs) were found less frequently than uNIIs. Most of the inclusion-bearing nuclei were of an astrocytic nature. Immunostaining with an antibody against DRPLA protein revealed similar immunoreactive neuronal and glial intranuclear inclusions, but in much smaller in numbers compared with uNIIs and uGIIs. Electron microscopy showed that such inclusions were composed of granular and filamentous structures. These findings strongly suggest that, in DRPLA, the occurrence of uNIIs and uGIIs is directly related to the causative gene abnormality (an expanded CAG repeat encoding polyglutamine), that neurons are affected much more widely than previously recognized and that glial cells are also involved in the disease process.
    Materialart: Digitale Medien
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  • 5
    ISSN: 1432-0533
    Schlagwort(e): Key words Congenital myopathy ; Muscle fibers ; Ultrastructure ; Myofibrillar disarray
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract A 44-year-old man presenting with dyspnoic attacks was found to be affected with congenital myopathy, rigid spine, restrictive respiratory insufficiency and cardiomyopathy. Muscle biopsy showed type 1 fiber predominance (65.7%) and hypotrophy, and characteristic changes in 43.9% of the type 1 fibers, consisting in alternating pale and dark staining on alkaline ATPase reacted sections in a mosaic pattern. Ultrastructural examination demonstrated bands of myofibrils at right angles or skew to the remaining myofibrils transversing the fibers. Myofibrillar disarray was always associated with loss of the Z-discs and actin filaments, and often with aggregation of mitochondria. The muscle biopsy findings in this patient suggest a new entity of congenital myopathy with clinical features of rigid spine, cardiomyopathy and restrictive respiratory insufficiency, characterized by peculiar abnormalities of ATPase staining in a mosaic pattern and, ultrastructurally, by zones of disorientation of the sarcomeres.
    Materialart: Digitale Medien
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  • 6
    ISSN: 1432-0568
    Schlagwort(e): Key words Adult-type Leydig cells ; Endothelium ; 3β-HSD ; Ultrastructure ; Differentiation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract  In the biosynthesis of steroid hormones 3β-hydroxysteroid dehydrogenase (3β-HSD) is a key enzyme. The present report describes the subcellular localization of the enzyme in the fetal-type Leydig cells, the fibroblast-like precursors of adult-type Leydig cells and in endothelial cells of interstitial capillaries. Histochemical methods for light microscopy and ultracytochemical methods for electron microscopy were used on rat testes of postnatal day 15. 3β-HSD reactivity was located at subcellular levels by means of the ferricyanide method. A specific, distinct localization of reaction product in the form of copper ferrocyanide precipitates was observed on the membranes of the smooth endoplasmic reticulum not only in the fetal-type Leydig cells and the fibroblast-like precursors of adult-type Leydig cells, but also focally in the endothelial cells of interstitial blood capillaries. Topographically, the 3β-HSD-positive precursors were most often found in the outer layer of the boundary tissue and surrounding interstitial blood vessels. The capillaries with 3β-HSD-positive endothelial cells were usually located in the vicinity of 3β-HSD-positive Leydig cells. For the first time, 3β-HSD has been located at the subcellular level in precursors of adult-type Leydig cells and focally in capillary endothelial cells associated with them. Due to the close association between 3β-HSD-positive vascular endothelial cells and Leydig cells a paracrine relationship between the two cell types may be involved in the acute regulation of steroidogenesis by blood-borne luteinizing hormone.
    Materialart: Digitale Medien
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  • 7
    ISSN: 1432-0533
    Schlagwort(e): Key words Anorexia nervosa ; Myopathy ; Muscle biopsy ; Ultrastructure ; Protein-energy malnutrition
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract Protein-energy malnutrition in anorexia nervosa is an under-recognised cause of muscle dysfunction. To characterise the skeletal myopathy that occurs in patients with severe anorexia nervosa, muscle function and structure were comprehensively examined in eight young adult female patients with severe (40%) self-induced weight loss. All of the patients showed impaired muscle function on strength and exercise measurement. The maximum voluntary contraction force for the patient group was significantly less than predicted values. Electromyography revealed myopathy in five of the patients, four of whom also had electro-physiological evidence of neuropathy. However, muscle biopsy specimens consistently showed myopathic changes with severe type 2 fibre atrophy but with no evidence of neuropathic changes. Ultrastructurally, there was separation and segmental loss of myofibrils and most biopsy samples contained abundant glycogen granules; we have previously reported that one of the most consistent biochemical abnormalities in these patients is impaired ischaemic lactate responses to forearm exercise. The result of severe protein-energy malnutrition on the musculo-skeletal system is a metabolic myopathy. Although the patients admitted to a variety of abnormal dieting behaviours, such as over-exercising and self-induced vomiting, no association was found between any of these and quantitative histological changes in the muscle biopsy samples. It is recommended that myopathy in anorexia nervosa be treated by instituting an appropriate refeeding programme.
    Materialart: Digitale Medien
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  • 8
    Digitale Medien
    Digitale Medien
    Springer
    Anatomy and embryology 197 (1998), S. 135-141 
    ISSN: 1432-0568
    Schlagwort(e): Key words Interstitial cells of Cajal ; Ultrastructure ; Gap junction ; Intestine ; Motility
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract  Interstitial cells forming many large gap junctions in the region of the deep muscular plexus of the rat small intestine were studied by electron microscopy and by three-dimensional cell models reconstructed from serial ultrathin sections. Two different profiles of cells were observed. Cells of the first profile are characterized by an elongated cell shape and by less electron-dense cytoplasm, containing many mitochondria, well-developed Golgi apparatus and free ribosomes. They mainly connect with smooth muscle cells of the main circular layer. In a three-dimensional cell model, the total area of the gap junctions occupies 1.3% of the cell surface. Cells of the second profile are characterized by the frequent occurrence of slender cytoplasmic processes, higher electron-dense cytoplasm, containing mitochondria, Golgie apparatus and well-developed rough endoplasmic reticulum, and numerous caveolae on the cell membrane. In this cell model, gap junctions occupy 0.8% of the cell surface. The ratio of gap junctions with the same profile of cells to the total gap junction area is 37.7%, which is more than three times greater than the 9.9% in cells of the first profile. These cells were closely associated with nerve terminals. It is likely that these cells with different profiles constitute subtypes with each other and cooperate for regulation of intestinal motility via the transmission of nerve signals.
    Materialart: Digitale Medien
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  • 9
    ISSN: 1432-0533
    Schlagwort(e): Key words Congenital myopathy ; morphometry ; Ultrastructure ; Fetal myogenesis
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract Centronuclear myopathy (CNM) is a congenital myopathy which manifests itself as a severe neonatal (also termed myotubular myopathy), early-onset, or adult form. The histological pattern of each is marked by a considerable number of nuclei of muscle fibers being internally placed. Owing to their remote resemblance to myotubes, and their expression of developmentally regulated proteins, most authors now favor the concept that myogenesis is arrested or delayed in this disease. We here present two muscle biopsy specimens of a patient with early-onset CNM, taken at the age of 5 months and 14 years, respectively. The first biopsy sample contained internally placed nuclei in 7% of the muscle fibers, abundant minute myotubes, and hypertrophic muscle fibers. The second biopsy sample showed internally placed nuclei in 40% of the muscle fibers, and hypotrophic fibers. We suggest that the histological findings in early-onset CNM are the result of a complex dynamic process, which includes a delay in maturation.
    Materialart: Digitale Medien
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  • 10
    ISSN: 1432-0533
    Schlagwort(e): Key words Aging ; Blood-brain barrier ; Horseradish peroxidase ; Senescence-accelerated mouse ; Ultrastructure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract The ultrastructural features of microvessels showing increased permeability to intravenously injected horseradish peroxidase (HRP) were examined in the olfactory bulbs of senescence-accelerated prone mice (SAMP8), which showed age-related deficits in learning and memory, and senescence-accelerated resistant mice (SAMR1), which did not show the age-related deficits. HRP was visualized with tetramethyl benzidine (TMB) and diaminobenzidine (DAB) for light and electron microscopic examination, respectively. In the olfactory bulbs of 13-month-old SAMP8 mice, the staining reaction with TMB for HRP appeared in the neuropil of central area (granule cell layer and subependymal layer), in the pia mater and in the vascular wall. Some vessels located in the central area showed several changes observed at the ultrastructural level. The cytoplasm of the endothelial cells, especially in the arterioles, was segmentally thickened and contained numerous vesicles and vacuoles, some of which were HRP positive. The endothelial cell surface was occasionally undulated with microvillous protrusions. Membranous inclusions within the basal lamina, suggesting the cellular (presumably pericytal) degeneration, were frequently observed, especially in venules. The collagen deposits were occasionally observed in the subendothelial space of some vessels. Perivascular cells with vacuolated inclusions or lipid-like droplets were present around some vessels in the central area of the olfactory bulbs of aged SAMP8 mice. On the other hand, in the microvessels located in the areas negative for HRP-TMB reaction, except the vessel walls, the cytoplasm of the endothelial cells with smooth luminal surface was flattened and some vesicles located there contained HRP-DAB reaction product. Weak staining reaction with TMB for HRP appeared also in the central area of the olfactory bulbs of 3-month-old SAMP8 mice and 3- and 13-month-old SAMR1 mice. The cytoplasm of the endothelial cells in the olfactory bulbs of these mice was focally thickened and contained some cytoplasmic vesicles. Occasionally, the endothelial cell surface was moderately undulated with few microvillous protrusions. Membranous inclusions within the basal lamina were not observed in these animals. These findings indicate that the endothelial cells and pericytes in some vessels located in the central area of the olfactory bulb of aged SAMP8 mice, which show staining reaction with TMB for HRP, are ultrastructurally changed, suggesting their altered functions.
    Materialart: Digitale Medien
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  • 11
    ISSN: 1432-069X
    Schlagwort(e): Key words Barrier function ; pH ; Stratum corneum ; Lamellar body ; Lipid content ; Ultrastructure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract Epidermal permeability barrier homeostasis requires the postsecretory processing of polar lipid precursors into nonpolar lipid products within the stratum corneum (SC) interstices by a family of lipid hydrolases. A specific requirement for β-glucocerebrosidase (β-GlcCer’ase), which exhibits a distinct acidic pH optimum, is particularly well documented. Therefore, we sought to determine whether the recovery of the barrier after acute insults requires acidification of the SC. We examined permeability barrier recovery by assessing changes in transepidermal water loss (TEWL), SC membrane ultrastructure utilizing ruthenium tetroxide (RuO 4 ) postfixation, and β-GlcCer’ase activity by in situ zymography at an acidic vs neutral pH. Barrier recovery proceeded normally when acetone-treated skin was exposed to solutions buffered to an acidic pH. In contrast, the initiation of barrier recovery was slowed when treated skin was exposed to neutral or alkaline pH, regardless of buffer composition. In addition, enhancement of the alkaline buffer-induced delay in barrier recovery occurred with Ca 2+ and K + inclusion in the buffer. Moreover, the pH-dependent alteration in barrier recovery appeared to occur through a mechanism that was independent of Ca 2+ - or K + -controlled lamellar body secretion, since both the formation and secretion of lamellar bodies proceeded comparably at pH 5.5 and pH 7.4. In contrast, exposure to pH 7.4 (but not pH 5.5) resulted in both the persistence of immature, extracellular lamellar membrane structures, and a marked decrease in the in situ activity of β-GlcCer’ase. These results suggest first that an acidic extracellular pH is necessary for the initiation of barrier recovery, and second that the delay in barrier recovery is a consequence of inhibition of postsecretory lipid processing.
    Materialart: Digitale Medien
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  • 12
    Digitale Medien
    Digitale Medien
    Springer
    Zeitschrift für Lebensmittel-Untersuchung und -Forschung 206 (1998), S. 38-43 
    ISSN: 1431-4630
    Schlagwort(e): Key words Starch ; Gels ; Kamaboko ; Surimi ; Gelatinization ; Ultrastructure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Abstract  The purpose of this work was to study the changes undergone by starch during heat-induced surimi gel preparation either with or without added egg white, and their effects on the structure of gels using light and scanning electron microscopy. Gels were made from SA-grade Alaska pollack (Theragra chalcogramma) surimi with: (1) salt (3%, w/w); (2) salt and waxy corn starch (3% and 5%, respectively w/w); or (3) salt, waxy corn starch and egg white (3%, 5% and 5%, respectively, w/w). Final moisture was adjusted to 73% or 83%. The gels were prepared by prior setting (40°C, 30 min, followed by 90°C, 30 min) or cooking (90°C, 30 min). The prepared gel was frozen and stored at –20°C (±1°C) until analysis. Samples were observed by light and scanning electron microscopy. The results show that the starch granules alter according to the processing conditions, with the predominance of crystalline or amorphous morphology depending upon the availability of heat and water. Large cavities formed in the protein gel matrix during setting can trap water; as a result, water availability is limited for starch to swell and gelatinize even in the high-moisture gel.
    Materialart: Digitale Medien
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  • 13
    Digitale Medien
    Digitale Medien
    Springer
    Der Pathologe 19 (1998), S. 373-378 
    ISSN: 1432-1963
    Schlagwort(e): Schlüsselwörter Metaplastische Brustdrüsenkarzinome ; Plattenepithelmetaplasie ; Plattenepithelkarzinom ; Immunhistologie ; Elektronenmikroskopie ; Zytophotometrie ; Key words Pure squamous cell carcinoma ; Mammary gland ; Squamous metaplasia ; Immunohistology ; Cytophotometry ; Ultrastructure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Beschreibung / Inhaltsverzeichnis: Summary Squamous metaplasia can be demonstrated in about 4% of all invasive carcinomas of the breast. Primary squamous cell carcinomas of the breast are rare, since they occur in less than 1% of all primary invasive breast carcinomas. In order to classify a breast tumor as a primary squamous cell carcinoma one must exclude an epidermal origin, especially from the nipple region and the possibility of metastatic infiltration of the breast by a squamous cell carcnoma from a different location. Causative and formal pathogenesis of primary squamous cell carcinoma of the breast is not clear. A pluripotent embryonal stem cell origin is discussed, considering the phylogenetic descent of the mammary gland from skin appendages. Squamous metaplasia is also suggested to be a precursor of squamous cell carcinoma. Here endocrine stimulation and chronic inflammation may both play an inductive role. The number of published cases of squamous cell carcinomas developing years and decades after implantation of silicon prostheses has increased in recent years. These tumors probably develop on top of squamous metaplasia induced by the inflammatory pseudocapsule. Estimating the prognosis and therapeutic management in patients with squamous cell carcinoma of the breast should follow the same guidelines as for other squamous cell cancers.
    Notizen: Zusammenfassung Plattenepithelmetaplasien werden bei etwa 4% aller invasiven Brustdrüsenkarzinome beschrieben. Reine Plattenepithelkarzinome der weiblichen Brustdrüse sind mit einem Anteil von wahrscheinlich unter 1% an allen invasiven epithelialen Tumoren der Mamma selten. Von einem primären Plattenepithelkarzinom der Brustdrüse darf nur gesprochen werden, wenn zum einen der Ursprung von der Epidermis, insbesondere auch im Bereich des Mamillentrichters ausgeschlossen ist und zum anderen keine metastatische Infiltration in die Brustdrüse durch ein Plattenepithelkarzinom anderer Organlokalisation vorliegt. Die kausale und formale Pathogenese der primären Plattenepithelkarzinome der Brustdrüse ist unklar. Zum einen wird ein Ursprung von pluripotenten embryonalen Stammzellen diskutiert, wobei bedacht wird, daß die Brustdrüse entwicklungsgeschichtlich ein Hautanhangsgebilde darstellt. Zum anderen werden Plattenepithelmetaplasien als Vorstufe der Plattenepithelkarzinome diskutiert, wobei neben einer endokrinen Induktion auch länger bestehende Entzündungsreize eine Rolle spielen sollen. In den letzten Jahren wird immer häufiger darüber berichtet, daß oft Jahrzehnte nach Implantation von Silikonprothesen periprothetische Plattenepithelkarzinome entstehen, die wahrscheinlich über die Stufe einer Plattenepithelmetaplasie der entzündlichen Prothesenpseudokapsel entstehen. Die Abschätzung der Prognose und therapeutische Maßnahmen bei primären Plattenepithelkarzinomen der Brustdrüse sollten an den Erfahrungen mit Plattenepithelkarzinomen anderer Organlokalisation ausgerichtet werden.
    Materialart: Digitale Medien
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  • 14
    Digitale Medien
    Digitale Medien
    Springer
    Sexual plant reproduction 11 (1998), S. 284-291 
    ISSN: 1432-2145
    Schlagwort(e): Key words Abies ; Egg cell ; Plastid inheritance ; RFLP ; Ultrastructure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract  The ultrastructure of egg cells in Abies alba was examined to elucidate the lack of maternal inheritance of plastids. Before fertilization, maternal plastids are absent in the perinuclar zone containing mainly mitochondria and smooth endoplasmic reticulum. During egg cell development the maternal plastids are transformed into large inclusions which are situated mostly towards the periphery of the egg cell, and finally disintegrate. As a consequence, they do not participate in zygote formation. RFLP analysis of cpDNA of parental trees and their F1 interspecific hybrids (A. alba×A. numidica, A. alba×A. nordmanniana, A. nordmanniana×A. Alba) using HindIII and BamHI showed a paternal mode of cpDNA inheritance. Paternal inheritance has also been found with PCR/RFLP analysis of cpDNA from parental trees and their hybrids (A. alba×A. pinsapo, A. pinsapo×A. alba, A. pinsapo×A. numidica) using ApaI and HaeIII digests, as well as in the crosses of A. cephalonica×A. nordmanniana, A. nordmanniana×A. cephalonica, A. cephalonica×A. numidica using TagI digests.
    Materialart: Digitale Medien
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  • 15
    Digitale Medien
    Digitale Medien
    Springer
    Sexual plant reproduction 11 (1998), S. 121-130 
    ISSN: 1432-2145
    Schlagwort(e): Key words Egg cell ; Parthenogenesis ; Synergid ; Ultrastructure ; Wheat ; Zygote
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract  The ultrastructure of the egg apparatus of the sexual (aestivum)-Salmon line (aS) and the isogenic but alloplasmic (kotschyi)-Salmon line (kS) of the Salmon system of wheat was studied by transmission electron microscopy 3 days before and during anthesis. Additionally, the zygotic stage of aS, 17 h after pollination, was included. Metabolic activity of egg cells from the sexual line aS was low 3 days before anthesis and increased dramatically after pollination and fertilization. This timing of increased activity was evident because of changes occurring in the egg cell nucleus and nucleolus, polysomes, endoplasmic reticulum and Golgi apparatus, and the completion of the cell wall around the zygote. In contrast to the sexual line, the egg cell of the parthenogenetic line showed high activity 3 days before anthesis. The metabolic and ultrastructural characters observed in the nucleus and cytoplasm of the kS line 3 days before and during anthesis corresponded with those of the isogenic sexual line aS during anthesis and 17 h after pollination, respectively. High metabolic activity observed in the persistent synergid of kS may be connected with the occurrence of additional embryos in seeds (twins) of this line.
    Materialart: Digitale Medien
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  • 16
    ISSN: 1432-072X
    Schlagwort(e): Key words Magnetic bacteria ; Biomineralization ; Magnetite ; 16S rRNA ; In situ hybridization ; Ultrastructure ; Electron microscopy
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract Natural enrichments of magnetic bacteria from the Itaipu lagoon near Rio de Janeiro were dominated by coccoid-to-ovoid morphotypes that produced unusually large magnetosomes. To determine the phylogenetic position of these unusual microorganisms, 16S rRNA genes were retrieved from bacteria magnetically separated from sediment of the Itaipu lagoon by in vitro amplification and cloning of PCR products into a plasmid vector. Partial sequencing of the obtained clones revealed two clusters of closely related sequences affiliated to a distinct lineage consisting exclusively of magnetic bacteria within the α-subclass of Proteobacteria. For a detailed phylogenetic analysis, several almost complete sequences of the 16S rRNA genes were determined. One representative clone of each cluster provided a PCR template for the in vitro transcription of group-specific polynucleotide probes complementary to a variable region of the 16S rRNA molecule. At least three different morphotypes of magnetic bacteria were reliably identified by post-embedding hybridization of ultra-thin sections. Electron microscopic analyses of hybridized cells enabled for the first time a detailed description of the morphological variety and ultrastructure of phylogenetically identified, uncultured magnetic bacteria. Two distinct coccoid bacteria were identified by the transcript probe complementary to the 16S rRNA sequence mabrj12, whereas the probe complementary to the sequence mabrj58 allowed the identification of an ovoid morphotype that displayed magnetosomes with the largest volumes observed to date.
    Materialart: Digitale Medien
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  • 17
    Digitale Medien
    Digitale Medien
    Springer
    Cell & tissue research 292 (1998), S. 275-282 
    ISSN: 1432-0878
    Schlagwort(e): Key words Interstitial cells (Cajal) ; Large intestine ; Fluorescent dyes ; Vital staining ; Ultrastructure ; Mouse (BALB/c)
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract  Interstitial cells of Cajal (ICCs) are believed to be a major element in generating the spontaneous rhythm of the gastrointestinal tract. A prominent problem in the study of these cells has been the difficulty in observing them in intact tissues. We used the lipophilic dye DiI to stain ICCs in the submucosal-circular muscle border of freshly dissected mouse colon. The placement of small DiI crystals in this area resulted in the labeling of ICC-like cells. Two main morphological cell types, viz., bipolar and multipolar, were noted. Bipolar cells had two primary processes emerging from the poles of an elongated soma. The mean length of these processes was 78.7 μm. These cells constituted 42.3% of the sample (n=105). Multipolar cells (54.3% of total) had a less elongated soma and extended 3–6 main processes whose mean length was 56.3 μm. These processes showed no preferred direction. The length of the primary processes of bipolar cells was 40% greater than that of multipolar cells (P〈0.02). Three cells (2.9%) had only one primary process. The DiI stain could be converted into a stable electron-opaque product. Electron-microscopic observations showed that these cells had the typical appearance of ICCs reported in previous studies. This staining method should be useful for physiological investigations of ICCs in gastrointestinal tissues.
    Materialart: Digitale Medien
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  • 18
    ISSN: 1432-0878
    Schlagwort(e): Key words Cutaneous scent glands ; Apocrine glands ; Myoepithelial cells ; Holocrine glands ; Ultrastructure ; Lectins ; Cytokeratins ; Impala ; Aepyceros melampus (Artiodactyla)
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract  The cutaneous glands of the forehead and the metatarsus were studied by histological and histochemical methods and electron microscopy in adult male and female impalas in various seasons of the year. All glandular areas consist of apocrine and holocrine glands, which, however, occur in different proportions. Our findings in the apocrine gland cells suggest (1) the synthesis and exocytosis of a glycoproteinaceous secretory product stored in secretory granules, (2) typical apocrine secretion of the transformed apical cytoplasm, and (3) transepithelial fluid transport. The Golgi apparatus and apical membrane have binding sites for several lectins (PNA, HPA, RCA I, WGA). Cytokeratins 7, 14 and 19 are expressed at various intracellular localizations, suggesting an active role in the secretory mechanisms. The glands of the male forehead show marked seasonal changes in activity that are correlated with the main phases of the reproductive cycle, with the highest cellular activity occurring during the rut in April/May. The female forehead glands are only moderately developed and do not undergo seasonal changes. The metatarsal glands are of equal size in males and females and show no seasonal changes in activity. This study supports the hypothesis that (1) forehead glands in the male have a signaling role in the rut and (2) the metatarsal glands have a more general, probably social role maintaining and restoring contact between herd members.
    Materialart: Digitale Medien
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  • 19
    Digitale Medien
    Digitale Medien
    Springer
    Cell & tissue research 293 (1998), S. 165-171 
    ISSN: 1432-0878
    Schlagwort(e): Key words Muscle injury ; Cytoskeleton ; Sarcomere organisation ; Immunohistochemistry ; Ultrastructure ; Rabbit (New Zealand White)
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract Immunohistochemical and electron-microscopic techniques were used to analyze the extensor digitorum longus muscles of New Zealand White rabbits 1 h, 1 day, 3, 7, and 28 days after repetitive eccentric contractions. Loss of the cytoskeletal protein desmin was the earliest manifestation of injury. Apart from 1 h post-exercise, all desmin-negative fibers stained positively with antibody to plasma fibronectin, indicating loss of cellular integrity accompanying cytoskeletal disruption. Fiber sizes were significantly increased from 1–7 days after exercise. The large (hyaline) fibers found in histological sections after repetitive eccentric contractions resulted from segmental hypercontraction of the fiber. This phenomenon occurred proximally and distally to plasma membrane lesions of the muscle fiber and necrosis and manifested itself as very short sarcomere lengths. Thus, in serial sections, staining characteristics, sizes and shapes of one and the same fiber often varied dramatically. We conclude that the following sequence of events occurs: cytoskeletal disruptions, loss of myofibrillar registry, i.e., Z-disk streaming and A-band disorganization, and loss of cell integrity as manifested by intracellular plasma fibronectin stain, hypercontracted regions, and invasion of cells. When a fiber is disrupted, the remaining intact fibers apparently take up the tension put on the muscle and later fewer fibers are subjected to eccentric contractions.
    Materialart: Digitale Medien
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  • 20
    Digitale Medien
    Digitale Medien
    Springer
    Cell & tissue research 294 (1998), S. 253-260 
    ISSN: 1432-0878
    Schlagwort(e): Key words P2X1 receptor ; Ultrastructure ; Cerebellum ; Rat (Wistar)
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract  The distribution of the P2X1 subtype of purinoceptors associated with the extracellular activities of ATP was studied in the rat cerebellum at the electron-microscope level. Receptors were labelled with peroxidase-antiperoxidase and the avidin-biotin-peroxidase complex for immunocytochemistry. Immunoreactivity to P2X1 receptors was localized in subpopulations of synapses between varicosities of parallel fibres of granule cells and dendritic spines of Purkinje cells. Unlabelled varicosities of parallel fibres formed asymmetric synapses with labelled dendritic spines, whereas labelled varicosities of parallel fibres formed asymmetric synapses with unlabelled dendritic spines. P2X1 immunoreactivity was also localized in some astrocyte processes. The functional significance of these findings is discussed.
    Materialart: Digitale Medien
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  • 21
    Digitale Medien
    Digitale Medien
    Springer
    Cell & tissue research 294 (1998), S. 367-375 
    ISSN: 1432-0878
    Schlagwort(e): Key words Neurons ; Glia ; Tracheae ; Wing ; Ultrastructure ; Moth ; Manduca sp.
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract  This ultrastructural examination of sensory nerves of the Manduca wing has revealed that extensive remodeling occurs among insect sensory neurons and their associated glial cells between pupation and adult emergence. Systematic counts of axons in particular wing nerves throughout adult development have shown that a decrease in axon number per nerve occurs after day 6. The neurons and glial cells that die are believed to be cells present at pupation that have no apparent sensory function but that probably function as guidance scaffolding for neurons and glia that are born after pupation. Despite the loss of several axons from each wing nerve, these nerves continue to grow in diameter during the latter half of adult development as some of the surviving axons increase severalfold in diameter. Each growing wing nerve in turn apparently functions as a scaffold for the proximal to distal growth of adult tracheae. A correspondence exists between adult nerve pathways and adult tracheal pathways, with each trachea maintaining intimate contact with a wing nerve along its entire length.
    Materialart: Digitale Medien
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  • 22
    Digitale Medien
    Digitale Medien
    Springer
    Cell & tissue research 291 (1998), S. 549-559 
    ISSN: 1432-0878
    Schlagwort(e): Key words Endolymphatic sac ; Ultrastructure ; Fluid transport ; Otoconia ; Newt ; Cynops pyrrhogaster (Urodela)
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract  The ultrastructure of the endolymphatic sac (ES) of the late stage larva of the Japanese red-bellied newt, Cynops pyrrhogaster (stage 57), was examined by light and transmission electron microscopy. The two endolymphatic sacs are located at the dorsal-medial side of the otic vesicle on the dorsal-lateral side of the midbrain in the cranial cavity. The wall of the sac is composed of a layer of cubical epithelial cells with loose, interposed intercellular spaces. The sac contains a large luminal cavity, in which endolymph and numerous otoconia are present. The epithelial cells of different portions of the sac have a similar structure. These cells contain an abundance of cytoplasmic organelles, including ribosomes, Golgi complexes, and numerous vesicles. Two types of vesicles are found in the epithelial cells: the “floccular” vesicle and the “granular” vesicle. The floccular vesicles are located in the supra- and lateral-nuclear cytoplasm and contain flocccular material. The granular vesicles have a fine granular substance and are usually situated apposed to the apical cell membrane. The granular vesicles are suggested to be secreted into the lumen, while the floccular vesicles are thought to be absorbed from the lumen and conveyed to the intercellular spaces by the epithelial cells. The apical surfaces of the epithelial cells bear numerous microvilli. Apparently floating cells, which bear long microvilli on the free surfaces, are observed in the lumen of the ES. Based on the fine structure, the function of the endolymphatic sac of the newt Cynops pyrrhogaster is discussed.
    Materialart: Digitale Medien
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  • 23
    Digitale Medien
    Digitale Medien
    Springer
    Cell & tissue research 293 (1998), S. 253-269 
    ISSN: 1432-0878
    Schlagwort(e): Key words Septate junctions ; Ultrastructure ; Permeability ; Ions ; Epithelium ; Photoreceptor ; Hirudo medicinalis (Hirudinea)
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract  The leech photoreceptor forms a unicellular epithelium: every cell surrounds an extracellular “vacuole” that is connected to the remaining extracellular space via narrow clefts containing pleated septate junctions. We analyzed the complete structural layout of all septa within the junctional complex in elastic brightfield stereo electron micrographs of semithin serial sections from photoreceptors infiltrated with colloidal lanthanum. The septa form tortuous interseptal corridors that are spatially continuous, and open ended basally and apically. Individual septa seem to be impermeable to lanthanum; interseptal corridors form the only diffusional pathway for this ion. The junctions form no diffusion barrier for the electron-dense tracer Ba2+, but they hinder the diffusion of various hydrophilic fluorescent dyes as demonstrated by confocal laser scanning microscopy (CLSM) of live cells. Even those dyes that penetrate gap junctions do not diffuse beyond the septate junctions. The aqueous diffusion pathway within the septal corridors is, therefore, less permeable than the gap-junctional pore. Our morphological results combined with published electrophysiological data suggest that the septa themselves are not completely tight for small physiologically relevant ions. We also examined, by CLSM, whether the septate junctions create a permeability barrier for the lateral diffusion of fluorescent lipophilic dyes incorporated into the peripheral membrane domain. AFC16, claimed to remain in the outer membrane leaflet, does not diffuse beyond the junctional region, whereas DiIC16, claimed to flip-flop, does. Thus, pleated septate junctions, like vertebrate tight junctions, contribute to the maintenance of cell polarity.
    Materialart: Digitale Medien
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  • 24
    ISSN: 1432-0878
    Schlagwort(e): Key words Angiogenesis ; Capillary growth ; Prazosin ; Shear stress ; Skeletal muscle ; Ultrastructure ; Rat
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract  Chronic vasodilatation represents a stimulus for capillary growth associated with increased luminal shear stress. We have examined the ultrastructure of more than 2000 capillaries to establish whether the sequence of angiogenesis in response to this stimulus is similar to that described during development and under pathological circumstances. Administration of the α1-blocker prazosin to rats for 2 weeks led to a greater capillary length density in extensor hallucis proprius muscles without any change in capillary tortuosity: J v(c,f)=262±54 compared with 350±17 mm–2, control compared with prazosin (P〈0.002). There were obvious signs of endothelial cell (EC) activation after prazosin treatment, including an increased proportion of capillaries with rough endoplasmic reticulum, large cytoplasmic vacuoles, thickened endothelium and an irregular luminal surface. Capillaries from control muscles had a maximum of three ECs in cross section, whereas four ECs were noted in 0.8+0.5% of capillaries after 1 week (n.s.) and 2.5±0.9% after 2 weeks (P〈0.01) of treatment. This could be due to elongation and/or migration of ECs, as cell proliferation has not been described at these time points. There was also an increase in the proportion of capillaries having a narrow, slit-like lumen (1.7±0.8% of controls; 7.1±1.9% at 1 week; 8.8±2.5% at 2 weeks; P〈0.02), some of which were smaller in size (less than 2 μm diameter) than in controls (3–5 μm) and/or “seamless”, i.e. lacking EC junctions. These may represent newly formed vessels. Focal discontinuity of the basement membrane and abluminal EC processes were rarely seen, and capillary growth by abluminal sprouting appeared to be very infrequent (less than 0.001% of profiles). Of more importance was growth starting from the luminal side. Significantly more thin cytoplasmic processes were observed protruding into the lumen of capillaries after 1 week (47.5±6.2%, P〈0.001) and 2 weeks of prazosin (34.2±5.5%, P〈0.05) than in control vessels (16.7±3.9%). Some of these traversed the entire lumen and connected with endothelium of the opposite side, probably involving membrane fusion, resulting in the appearance of a double lumen. Individual capillaries with a complete double lumen were observed after 2 weeks’ prazosin but comparatively rarely, in only four out of six muscles. These findings indicate a pattern of luminal growth which is completely different from intussusceptive growth previously described during development, and from the abluminal capillary sprouting seen under pathological circumstances.
    Materialart: Digitale Medien
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  • 25
    Digitale Medien
    Digitale Medien
    Springer
    Protoplasma 204 (1998), S. 155-169 
    ISSN: 1615-6102
    Schlagwort(e): Spores ; Ultrastructure ; Entorrhiza ; Microbotryum ; Tilletia ; Ustilago
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Summary The concept and nomenclature for the elements of teliospore walls in smut fungi are presented and a survey of teliosporogenesis is given, as seen by light and transmission electron microscopy. Four developmental types are distinguished: the Ustilago, Microbotryum, Tilletia, and Entorrhiza type. In the Ustilago type, sporogenous hyphae are completely segmented into teliospore initials which are embedded in a hyaline matrix formed by gelatinised hyphal walls (found in species ofAnthracoidea, Cintractia, Heterotolyposporium, Kuntzeomyces, Macalpinomyces, Melanopsichium, Sporisorium, Testicularia, Tolyposporium junci, Trichocintractia, and species ofUstilago infecting members of the family Poaceae). In the Microbotryum type, septate sporogenous hyphae are also completely segmented into teliospore initials, however, they are not surrounded by a hyaline matrix (Microbotryum, Sphacelotheca, Ustilago spp. infecting dicotyledons). A yeast-like budding of teliosporogenic cells is observed for some species ofMicrobotryum, Sphacelotheca, andUstilago infecting dicotyledons. In the Tilletia type, teliospores differentiate locally in the sporogenous hyphae, in an apical or intercalary position, without a hyaline matrix (Conidiosporomyces, Doassinga, Entyloma, Erratomyces, Ingoldiomyces, Neovossia, Oberwinkleria, Rhamphospora, Tilletia). In all these types, the teliospore initials first develop a hyaline sheath under which the ornamentation, the exosporium, sometimes a middle layer, and the endosporium are successively deposited by the fungal cell. In the Entorrhiza type, the teliospores develop inside vital host cells with the wall of the sporogenous hypha included into the teliospore wall. The fungus develops a middle layer and an electron-transparent endosporium inside the hyphal wall while a layer forming the ornamentation is deposited onto the hyphal wall, probably by vesicles of dictyosomes of the host cell.
    Materialart: Digitale Medien
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  • 26
    ISSN: 1615-6102
    Schlagwort(e): Neck cell proliferation ; Binucleate ; Douglas fir ; Conifers ; Genetic instability ; Ultrastructure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Summary To study the effect of culturing on megagametophytes of Douglas fir (Pseudotsuga menziesii) and hybrid larch (Larix × eurolepis), cones were collected at the time of fertilization and the megagametophytes were removed, then placed on medium. We used a modified Murashige and Skoog medium supplemented with 5% lactose and 10% polyethylene glycol 4000. A variety of cell types proliferated including prothallial, neck, and jacket cells. Some of these multiplying cells showed a binucleate condition. The prothallial cells of the apex divided and expanded. The neck cells formed clusters composed of more cells than normally found in situ; though otherwise they showed ultrastructural similarity to neck cells in situ. These neck cells had large numbers of active Golgi complexes, numerous large and small vacuoles, coated vesicles, smooth vesicles, a well-developed endoplasmic reticulum, and thickened cell walls. These are the first reports of neck cell multiplication and induction of a binucleate state for gymnosperm megagametophyte cells in vitro.
    Materialart: Digitale Medien
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  • 27
    Digitale Medien
    Digitale Medien
    Springer
    Protoplasma 201 (1998), S. 30-37 
    ISSN: 1615-6102
    Schlagwort(e): Cell-to-cell communication ; Plasmodesmata ; Ultrastructure ; Wounding ; 2-Deoxy-D-glucose
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Summary The transport of ions and metabolites through plasmodesmata has been thought to be controlled at the neck region where the cytoplasmic annulus is constricted and where callose has also been localised. In order to determine the possible structural and functional effects of callose, its deposition was inhibited through incubation of the plant tissue with 2-deoxy-D-glucose (DDG) for 1 h prior to fixation in 2.5% glutaraldehyde. The inhibition of callose formation was monitored through aniline blue-induced fluorescence of callose. The neck region of the plasmodesmata fromAllium cepa L. roots treated with DDG exhibited a funnel-shaped configuration. This is in contrast to the plasmodesmata from tissue not incubated with DDG, which exhibited constricted necks similar to those previously reported. Both initial dissection and glutaraldehyde fixation induced neck constriction in plasmodesmata, however, dissection of tissue increased the frequency of constrictions. The inhibition of callose formation by chemical means showed that the neck constrictions and raised collars in this area are artefacts due to physical wounding and glutaraldehyde fixation. The external electron-dense material observed when tannic acid is included in the primary fixative appears to be unrelated to the deposition of callose at the neck region.
    Materialart: Digitale Medien
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  • 28
    Digitale Medien
    Digitale Medien
    Springer
    Protoplasma 202 (1998), S. 23-37 
    ISSN: 1615-6102
    Schlagwort(e): Chloroplast development ; Cotton ; Fluorescence induction kinetics ; Ultrastructure ; Immunocytochemistry
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Summary Many of the studies of chloroplast ontogeny in higher plants have utilized suboptimal conditions of light and growth to assess development. In this study, we utilized structural, immunological, and physiological techniques to examine the development of the chloroplast in fieldgrown cotton (Gossypium hirsutum cv. “MD 51 ne”). Our youngest leaf sample developmentally was completely folded upon itself and about 0.5 cm in length; leaves of this same plastochron were followed for three weeks to the fully expanded leaf. The chloroplasts at the earliest stage monitored had almost all of the lamellae in small, relatively electron-opaque grana, with relatively few thylakoids which were not appressed on at least one surface. During the development of the thylakoids, the membranes increase in complexity, with considerable stroma lamellae development and an increase in the number of thylakoids per granum. Besides the increase in complexity, both the size and numbers of the chloroplast increase during the development of the leaf. Developmental changes in six thylakoid proteins, five stromal proteins, and one peroxisomal protein were monitored by quantitative immunocytochemistry. Even at the earliest stages of development, the plastids are equipped with the proteins required to carry out both light and dark reactions of photosynthesis. Several of the proteins follow three phases of accumulation: a relatively high density at early stages, a linear increase to keep step with chloroplast growth, and a final accumulation in the mature chloroplast. Photosystem-II(PS II)-related proteins are present at their highest densities early in development, with an accumulation of other parts of the photosynthetic apparatus at a latter stage. The early accumulation of PS-II-related proteins correlates with the much lower ratio of chlorophylla tob in the younger leaves and with the changes in fluorescence transients. These data indicate that some of the conclusions on chloroplast development based upon studies of intercalary meristems of monocots or the greening of etiolated plants may not be adequate to explain development of chloroplasts in leaves from apical meristems grown under natural conditions.
    Materialart: Digitale Medien
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  • 29
    Digitale Medien
    Digitale Medien
    Springer
    Protoplasma 201 (1998), S. 101-109 
    ISSN: 1615-6102
    Schlagwort(e): Kinetochore ; Kinetoplastida ; Intranuclear microtubules ; Mitosis ; Ultrastructure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Summary The three-dimensional ultrastructural organization of the mitotic apparatus ofDimastigella mimosa was studied by computer-aided, serial-section reconstruction. The nuclear envelope remains intact during nuclear division. During mitosis, chromosomes do not condense, whereas intranuclear microtubules are found in close association with six pairs of kinetochores. No discrete microtubule-organizing centers, except kinetochore pairs, could be found within the nucleus. The intranuclear microtubules form six separate bundles oriented at different angles to each other. Each bundle contains up to 8 tightly packed microtubules which push the daughter kinetochores apart. At late anaphase only, midzones of these bundles align along an extended interzonal spindle within the narrow isthmus between segregating progeny nuclei. The nuclear division inD. mimosa can be described as closed intranuclear mitosis with acentric and separate microtubular bundles and weakly condensed chromosomes.
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  • 30
    Digitale Medien
    Digitale Medien
    Springer
    Plant systematics and evolution 210 (1998), S. 25-39 
    ISSN: 1615-6110
    Schlagwort(e): Cyanophyta ; Cyanobacteria ; Cyanothece ; Synechococcus ; Cyanobium ; Ultrastructure ; nucleoids ; taxonomy
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract The fine structure of the type species of the genusCyanothece Komárek 1976,C. aeruginosa, is described and compared with the main cytological characteristics of morphologically related members of the generaCyanobium, Cyanobacterium andSynechococcus. Several morphological features, such as cell walls with thick outer layers containing a special type of vesicles, position of thylakoids, “keritomy” (net-like appearance of protoplast caused by arrangement of thylakoids, net-like nucleoids and/or by tendency to form intrathylakoidal spaces) and a special structure of mucilaginous envelopes were found to be characteristic of this genus, supporting its separate position among coccal cyanoprokaryotes (cyanobacteria, cyanophytes). The taxonomic significance of ultrastructural features in all mentioned genera is discussed.
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  • 31
    ISSN: 1615-6102
    Schlagwort(e): Spore balls ; Germ areas ; Ultrastructure ; Phylogeny
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Summary Special features of teliospores in smut fungi are described, including teliospore connections, appendages, and germ pores. Balls of teliospores in species of many different genera cohere by remnants of hyphal walls, sheaths, and sometimes interlocking ornamentation. Teliospores are connected in pairs in species ofMycosyrinx andGeminago by special local structures. Appendages can be formed locally by persistent material from the sheath (Cintractia, Anthracoidea, Sphacelotheca), thickened parts of the spore wall (e.g.,Georgefischeria, Jamesdicksonia, Rhamphospora, Tolyposporella), or persistent walls of sporogenous hyphae (Rhamphospora, genera of the Tilletia relationship). Species ofGeorgefischeria, Jamesdicksonia, andTolyposporella have teliospore walls composed of more than three layers of different electron density. “Germ areas” corresponding to thinner parts of the spore wall are known, e.g., for species ofAnthracoidea, Cintractia, andUstilago infecting members of the family Poaceae, while distinct germ pores, one per teliospore, are found in some species ofThecaphora, “Tolyposporium”, andSporisorium. Teliospores ofMycosyrinx cissi have a germination ring. Characteristics of teliospores are used to discuss the phylogeny of smut fungi. A phylogenetic tree in accordance with teliospore characteristics is compared to those obtained from ultrastructural characteristics of host-parasite interaction, of septal pores, and from sequence data. Aspects of teliospore development help to define taxa at a high systematic level (Entorrhizales, Ustilaginales, Tilletiales/Entylomatales, Microbotryaceae), while details of ornamentation ontogeny delimit groups of genera (e.g., genera related toUstilago on members of the Poaceae andSporisorium, Cintractia andAnthracoidea, Tilletia) or single genera (e.g.,Melanopsichium, Dermatosorus, Mycosyrinx, Doassinga, Rhamphospora). Types of ornamentation (warty, reticulate), middle layers, teliospore balls, and germ pores evolved repeatedly by convergence. The smut teliospore itself probably evolved independently at least twice, or perhaps three (or more) times, in the Microbotryales, in the Entorrhizales, and in a common ancestor of the remainder of the Ustilaginomycetes.
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  • 32
    ISSN: 1615-6102
    Schlagwort(e): Spores ; Ultrastructure ; Microbotryum ; Tilletia ; Tolyposporium ; Ustilago
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Summary The walls of mature teliospores and the development of ornamentation, as seen by transmission electron microscopy, are described for 37 genera of smut fungi, based on observations of ca. 120 species and on literature. Structural diversity of mature teliospore walls is due to differences in spore wall layers forming the spore wall (endosporium, middle layer, exosporium, ornamentation) and to different elements forming the ornamentation (exosporium, ornaments, sheath, hyphal wall, adjacent fungal cells, material of the host). During teliosporogenesis the outer layers are usually deposited first. At the beginning of the formation of the ornamentation the plasma membrane may be smooth or undulated carrying the developing ornaments on its tips or in its depressions. The ornamentation of some genera appears similar when seen by scanning electron microscopy, but can be the product of different developmental patterns (e.g., warts of species ofFarysia, Tilletia, andUstilago), however, warty and reticulate ornamentation can both be produced by similar developmental processes (shown, e.g., for species ofCintractia andTilletia). Typical structures of the mature teliospore wall and developmental patterns based on homologous similarities are described for the following groups of genera or species:Macalpinomyces, Melanopsichium, Sporisorium, andUstilago infecting members of the family Poaceae;Kuntzeomyces, Testicularia, andTrichocintractia; Anthracoidea, Cintractia, Heterotolyposporium piluliforme, andTolyposporium junci; Glomosporium, Sorosporium, andThecaphora; Conidiosporomyces, Erratomyces, Ingoldiomyces, Neovossia, Oberwinkleria, andTilletia; Entyloma, and genera of the Doassansia group;Liroa, Microbotryum, Sphacelotheca, Ustilago infecting dicotyledons, andZundeliomyces; Aurantiosporium, Fulvisporium, andUstilentyloma. Special characteristics of the teliospore wall were observed for the generaDermatosorus, Doassinga, Entorrhha, Farysia, Mycosyrinx, Rhamphospora, and some species ofTolyposporium.
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  • 33
    Digitale Medien
    Digitale Medien
    Springer
    Space science reviews 84 (1998), S. 199-206 
    ISSN: 1572-9672
    Schlagwort(e): Nuclear reactions ; Nucleosynthesis ; Abundances ; Stars:Evolution ; Interior ; Rotation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Physik
    Notizen: Abstract We first recall the observational and theoretical facts that constitute the so-called 3He problem. We then review the chemical anomalies that could be related to the destruction of 3He in red giants stars. We show how a simple consistent mechanism can lead to the destruction of 3He in low mass stars and simultaneously account for the low 12C/13C ratios and low lithium abundances observed in giant stars of different populations. This process should both naturally account for the recent measurements of 3He/H in galactic HII regions and allow for high values of 3He observed in some planetary nebulae. We propose a simple statistical estimation of the fraction of stars that may be affected by this process.
    Materialart: Digitale Medien
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  • 34
    ISSN: 1860-1499
    Schlagwort(e): Solitary fibrous tumor of the pleura ; Mesenchymal cell ; Immunohistochemistry ; CD 34 ; Ultrastructure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract A solitary fibrous tumor of the pleura (SFTP) in a 37-year-old woman was reported as a rare pleural tumor based on morphological, immunohistochemical, and electron microscopic studies. The results showed that the tumor was composed of spindle-shaped cells forming fascicular and interlacing patterns with a mixture of mature collagen. The tumor cells coexpressed vimentin and CD34 and lacked cytokeratin reactivity. Ultrastructurally, there were abundant collagenous fibrillae surrounding spindle-shaped cells in which the junctional complex, basement membrane-like structure, and microvilli were not seen. From literature review and observation of the morphological features around the tumor, we consider that the tumor originated from the stromal cells subjacent to the mesothelium.
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  • 35
    Digitale Medien
    Digitale Medien
    Springer
    Medical molecular morphology 31 (1998), S. 151-155 
    ISSN: 1860-1499
    Schlagwort(e): Serous adenocarcinoma ; Peritoneal neoplasm ; Immunohistochemistry ; Ultrastructure ; Case report
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract Two cases of serous surface carcinoma of the peritoneum (SSCP) are discussed. The first patient was a 48-year-old Japanese woman with abdominal pain and fullness. The second patient was a 66-year-old Japanese woman with abdominal fullness. In both patients, laparotomy revealed many tumor nodules on the peritoneal surface. However, the ovaries, the uterus, and other intraperitoneal organs were free from tumors. The serum levels of CA125 were excessively elevated. The tumor cells were arranged in a papillotubular pattern. Mitoses were frequent. Diastaseresistant PAS-positive, and hyaluronidase-resistant alcian blue-positive materials were observed. In immunohistochemistry, the tumor cells showed positive reactions for cytokeratin, EMA, CA125, and HBME-1, and, in contrast, negative reactions for CEA, thrombomodulin, vimentin, and HHF35. In analysis for Ber-EP4, all tumor cells of case 1 were negative, and a few tumor cells of case 2 were positive. Ultrastructurally, hobnail-shaped tumor cells rested on a continuous basal lamina. Each cell was attached to short desmosomes. Microvilli were slender, straight, and short, and some had core rootlets. Many primary lysosomes were aggregated in the basal portion of the cytoplasm. A few well-differentiated ciliated cells were present. These two cases were diagnosed as SSCP.
    Materialart: Digitale Medien
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  • 36
    ISSN: 1860-1499
    Schlagwort(e): Restitution ; Ultrastructure ; Cell migration ; Colon ; Saponin
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract The superficial colonic epithelia of rats were exposed to 1.0% saponin solution for 3 min and fixed at various periods thereafter. The repair or restitution process was observed by light as well as by transmission and scanning electron microscopy. The exposure of the luminal surface to saponin resulted in uniform and extensive damage to the superficial epithelial cells without affecting the cells in the crypts. At 3 min after saponin treatment, the damaged epithelial cells exfoliated from the mucosa and the basal lamina was exposed. Within 15 min, most of the exposed basal lamina was covered by squamous to low-cuboidal epithelial cells, probably migrating from the crypts. These epithelial cells extended large lamellipodia over the denuded basal lamina. After 15 min the damaged surface was completely covered with epithelial cells, which became columnar at 1 h. Tight junction protein ZO-1 became positive along the restituted epithelium. Proliferating-cell nuclear antigen (PCNA) staining showed that proliferation of epithelial cells occurred after the restitution. These results suggest that saponin treatment serves as a good model system to study colonic restitution, which is carried out by rapid migration from the remaining crypt cells, followed by cellular proliferation. Rapid formation of tight junctions spanning the damaged regions allows rapid restoration of the barrier function of the colonic epithelium.
    Materialart: Digitale Medien
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  • 37
    ISSN: 1434-193X
    Schlagwort(e): Photocycloaddition ; Ring opening ; Oxetanes ; 1,2-Diols ; Alkyldealkoxylation ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The ring opening of 3-isopropyl-2-phenyl-3-oxetanol (2a) by various nucleophiles has been studied. In the presence of BF3 as a Lewis acid, a clean reaction at the less substituted C-4 position was observed and the corresponding 1,2-diols 6-11 and 21-23 were isolated in diastereomerically pure form (47-97% yield). Alkyl-, aryl-, alkynyl- and alkenyllithium compounds proved to be suitable carbon nucleophiles. Deprotonated thiols were used as sulfur nucleophiles. An alkoxide derived from benzyl alcohol and an amide derived from benzylamine reacted less readily under these conditions, yielding the 1,2,3-trifunctional compounds 24 (42% yield) and 26 (54% yield). Other 2-phenyl-3-oxetanols such as 2b and 2c can also be employed as electrophiles, whereas 2-anisyl derivatives preferentially undergo rearrangement reactions, as exemplified by the conversion of oxetane 16 to the hydroxy ketone 17 (84% yield). The superior behaviour of 3-oxetanols as compared to their silyl derivatives in reactions with nucleophiles became evident from the reaction of 3-silyloxyoxetane 1a with alkyllithium reagents. A β elimination occurred upon treatment with nBuLi, which, after pericyclic ring opening and addition of nBuLi, yielded the allylic alcohol 20.
    Materialart: Digitale Medien
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  • 38
    ISSN: 1434-193X
    Schlagwort(e): Azoalkanes ; DBO ; Fluorescence quenching ; Exciplexes ; Hydrogen transfer ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The fluorescence of the DBO derivatives 1-3 is efficiently quenched by olefins and arenes, exciplex formation and hydrogen transfer operate as quenching mechanisms. The electron-accepting ester groups in the azoalkanes 1-3 promote significantly more effective quenching compared to the parent DBO. Steric hindrance accounts for the differences in the quenching efficiencies, but electronic effects dominate
    Materialart: Digitale Medien
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  • 39
    ISSN: 1434-193X
    Schlagwort(e): Mannich bases ; γ-Amino alcohols ; Grob fragmentation ; (Z)-Alkenes ; Oxetanes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Quaternized γ-amino alcohols 5 derived from ternary iminium salts 2 are stereospecifically converted into both unsaturated aldehydes/ketones 6 with a (Z)-C—C double bond in a Grob-type fragmentation and highly functionalized oxetanes 7 by intramolecular substitution.
    Materialart: Digitale Medien
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  • 40
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2201-2207 
    ISSN: 1434-193X
    Schlagwort(e): Antibiotics ; Asymmetric synthesis ; β-Lactams ; Michael additions ; Multicomponent reactions ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Lithium dialkylcuprates react either in a sequential one-pot or in a domino “three-component” fashion with chiral Michael acceptors, like Oppolzer's N-enoyl-2,10-camphorsultams 7 and 11 or ‘Evans’ N-enoyl-4-phenyl-1,3-oxazolidin-2-ones 8 and 13, and N-(methoxycarbonylmethylidene)(4-methoxyphenyl)amine 9 to afford the corresponding cis-3-alkyl-4-methoxycarbonyl-1-(4-methoxyphenyl)azetidin-2-ones 10, 14-15 in overall yields of 40-67% and enantiomeric excesses of 91-99%.
    Materialart: Digitale Medien
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  • 41
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2229-2235 
    ISSN: 1434-193X
    Schlagwort(e): 3-Nitro-ω-benzylideneacetophenone ; Carbanions ; Michael addition ; Intramolecular vicarious nucleophilic substitution of hydrogen ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 3-Nitro-ω-benzylideneacetophenone (1) reacts with carbanions containing leaving groups to give addition products to the electrophilic side chain. As a result of conjugated addition and subsequent intramolecular vicarious nucleophilic substitution of hydrogen (VNS) in the nitroaromatic ring of 1 in the position para to the nitro group, 4-cyano-7-nitro-3-phenyl-1,2,3,4-tetrahydronaphthalen-1-one and 4-cyano-7-nitro-3-phenylnaphth-1-ol are obtained. Smooth intramolecular VNS in the position para to the nitro group was observed for 4-chloro-1-(3-nitrophenyl)-3-phenyl-4-(p-tosyl)butanol.
    Materialart: Digitale Medien
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  • 42
    ISSN: 1434-193X
    Schlagwort(e): Conformation analysis ; Electrochemistry ; Nitrogen heterocycles ; Dimerization ; Mechanism ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: In aqueous media the one-electron reduction of the title compounds on a mercury pool generally gives rise to three dimers, which are distinguishable by HPL chromatography. From spectroscopic analyses it has been possible to propose a structure for these conformers and their stability has been studied. Two conformers are unstable, yielding the third conformer. A mechanism is proposed for this transformation.
    Materialart: Digitale Medien
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  • 43
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 837-846 
    ISSN: 1434-193X
    Schlagwort(e): AZT ; cycloSal-pro-nucleotide ; Prodrugs ; Nucleotide delivery ; HIV chemotherapy ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The application of our cycloSaligenyl- (cycloSal) pronucleotide concept to the approved anti-HIV dideoxynucleoside 3′-azido-3′-deoxythymidine AZT (1) is reported. This pro-nucleotide concept has been designed to deliver the corresponding 3′-azido-3′-deoxythymidine monophosphate AZTMP (2) by selective chemical hydrolysis from the lipophilic precursors cycloSal-AZTMP 4a-h. All derivatives 4a-h were synthesized using differently substituted salicyl alcohols 7a-h as starting materials. In hydrolysis studies, compounds 4 decomposed selectively releasing AZTMP (2) and the salicyl alcohols 7 following the designed tandem reaction. Furthermore, due to the electronic properties introduced by substituents, the half-lives of the triesters 4 could be ajusted over a wide range. Phosphotriesters 4 exhibited considerable biological activity in HIV-1 and HIV-2 infected wild-type human T-lymphocyte (CEM/O) cells, whereas, contrary to our expectations, nearly all activity was lost in HIV-2 infected thymidine-kinase-deficient CEM cells.
    Materialart: Digitale Medien
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  • 44
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 853-859 
    ISSN: 1434-193X
    Schlagwort(e): N-Alkylation ; Diketopiperazine building block ; Peptidomimetics ; RGD analogues ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: As a new scaffold for peptidomimetic synthesis, a highly constrained bifunctional diketopiperazine, 4, has been prepared by smooth N-alkylation with tert-butyl bromoacetate. As a first application, we describe herein the synthesis of new peptidomimetics of the Arg-Gly-Asp (RGD) sequence. The product 30, which shows a selective platelet-aggregation inhibiting activity, can be used as a lead for the preparation of more potent products.
    Materialart: Digitale Medien
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  • 45
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 871-876 
    ISSN: 1434-193X
    Schlagwort(e): Dioxirane ; Homolysis, induced ; Aminoxyl ; Oxidation ; Spin-trapping ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: In the reactions of dimethyldioxirane (1a) and methyl(trifluoromethyl)dioxirane (1b) with 2,2,6,6-tetramethylpiperidinyl-1-oxyl (2) (TEMPO) in acetone, the corresponding methoxyamine 1-methoxy-2,2,6,6-tetramethylpiperidine (5) is produced in ≥98% yield, both in air and under N2, and in the absence or presence of a hydrocarbon (adamantane). Kinetic experiments show that aminoxyl 2 triggers the radical decomposition of the dioxirane, in addition to scavenging methyl radicals derived therefrom. The reactions of an aminoxyl less prone to oxidation, namely 1,2-dihydro-2-methyl-2-phenyl-3H-indol-3-one-1-oxyl (4), with dioxiranes 1a and 1b in acetone have also been studied. In these cases, not only is the corresponding methoxyamine 8a produced (yield 12-16%), but quinoneimine-N-oxides 10 (yield 12-21%) and 11 (yield 18-19%) are also formed. Furthermore, significant amounts (8-14%) of the amine 9 (the product of deoxygenation of 4) can be isolated. These observations provide useful information concerning the free-radical mechanism that follows the initial attack by the aminoxyl at the dioxirane.
    Materialart: Digitale Medien
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  • 46
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2373-2377 
    ISSN: 1434-193X
    Schlagwort(e): Charge-transfer fluorescence ; Fluorogenic probe ; Fluorescence labelling ; Maleimide group ; Solvatochromism ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Structural modification of the highly fluorescent donor-bridge-acceptor molecule “Fluoroprobe” (FP) is shown to extend the excitation window to longer wavelengths. The resulting “Fluorotrope” (FT) shows appreciable absorption in the 350-420-nm range, so that visible (blue) light can be used for excitation. Further functionalization with a maleimide group results in the novel fluorogenic reagent MaleimidoFluorotrope (MFT) which yields fluorescent adducts with amines, thiols and other reactive groups that add to the double bond of the maleimide. The fluorescence wavelength of these adducts is extremely sensitive to the polarity and mobility of the medium.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 47
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2379-2387 
    ISSN: 1434-193X
    Schlagwort(e): β-Peptides ; Polylithiation of peptides ; Li-enolates of peptides ; Back-bone alkylation of β-peptides ; Diastereoselective alkylation of β-peptide enolates ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A series of N-Boc-protected β-tripeptide derivatives with or without N-methyl groups and with free or Me-ester-protected C terminus has been prepared (8-14, 16, 17). As with α-peptides (→ A), the β-peptide derivatives can be polylithiated (→ B, C). No epimerization of stereogenic centers and no β elimination (exception 17 → 24) is observed upon treatment with bases as strong as tBuLi. The C terminal ester Li-enolate moiety of tetralithio β-tripeptides (cf. C) can be selectively alkylated with methyl, benzyl and allyl halides, and with tert-butyl bromoacetate in yields ranging from 35-80% (8 → 18, 14 → 20-23).
    Materialart: Digitale Medien
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  • 48
    ISSN: 1434-193X
    Schlagwort(e): Natural products ; Steroids ; Chenodeoxycholic acid ; Brassinosteroid analogues ; Biological activity ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The synthesis and spectroscopic characterization of two new bioactive analogues of brassinosteroids with a 24-hydroxylated cholanic side chain, an A/B ring cis-junction and oxygenated functions in C-7 is described.
    Materialart: Digitale Medien
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  • 49
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2409-2416 
    ISSN: 1434-193X
    Schlagwort(e): Sulfur heterocycles ; Rearrangements ; Reductions ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The syntheses of 1,2-benzodithiino[5,4,3-cde][1,2]benzodithiin-2,7-diamine (1) and dithio-bridged benzidine 2 have been achieved. The starting material for the synthesis of 1 was 1,3-diiodo-5-nitrobenzene (15) which was transformed by conventional means into 1,2-bis[3,5-bis(ethylthio)phenyl]diazane (19). The benzidine rearrangement of 19 in the presence of HBF4 at -30 °C yielded 4,4′-diamino-2,2′,6,6′-tetraethylthiobiphenyl (20) in 50 % yield. Treatment of 20 with sodium in ammonia and work-up in the presence of air yielded 1. The latter compound could be reduced with LiAlH4 to the tetrathiol 20a. The starting material for the preparation of 2 was 3-chloro-1-iodo-5-nitrobenzene (23), a side product of the preparation of 15. It was transformed analogously to the preparation of 1 into 1,2-bis(3-ethylthiophenyl)diazane (28). The benzidine rearrangement of 28 in presence of HBF4 at -30 °C afforded 4,4′-diamino-2,2′-bis(ethylthio)biphenyl (29) in 49 % yield. Treatment of 29 with sodium in ammonia and work-up under aerobic conditions yielded 2. Quantitative reduction of 2 to the thiol 29a could be achieved with LiAlH4. The reversible electrochemical reduction of 1 on unmodified glassy carbon electrodes leads to a product to which the structure of 3 was assigned.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 50
    ISSN: 1434-193X
    Schlagwort(e): N-Heterocycles ; Porphyrins ; Radical cations ; N-Dealkylation ; Stereoelectronic effects ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Evidence for a stereoelectronic inhibition of deprotonation of the radical cation of N-benzylpiperidine is presented. This stereoelectronic effect, which is due to the cyclic structure of the precursor, provides a tool to differentiate hydrogen-atom- versus electron-transfer routes in the biomimetic oxidative N-dealkylation of tertiary amines: the electron-transfer route appears to be the operating mechanism.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 51
    ISSN: 1434-193X
    Schlagwort(e): Colchicine ; 10-Ethylthiocolchicide, diene properties of ; π-Facial diastereoselectivity ; Consecutive [4+2],[3+2] cycloadditions ; Atropisomerism ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Cycloaddition reactions of the facially dissymmetric diene moiety of (-)-(M,7S)-colchicine (5) and (-)-(M,7S)-10-ethylthiocolchicide (9) to various alkynes have been studied. With 5 and the dienophilic benzyne (3), dimethyl acetylenedicarboxylate (DMAD) (4) and cyclooctyne (6) as starting materials all cycloadditions could be realized with high regioselectivity at the 8,12-positions of the alkaloid. The approach of the dienophiles preferentially occurred toward the syn π-face of the diene. In contrast to the cycloaddition mode of 5 the ethylthiocolchicide 9 surprisingly reacted in a different manner. With benzyne as starting material a novel [3+2] cycloaddition of the thioenol ether moiety of 9 towards the dipolarophilic benzyne is supposed, affording the unexpected colchicide 10 after [1,5]H shift of the primarily formed cycloadduct followed by cleavage of the C-S linkage. With DMAD (4) and cyclooctyne (6) the reaction course is more complex. In a consecutive [4+2]/[3+2] cycloaddition (or vice versa) followed by a thermally induced cycloreversion of a not identified intermediate DMAD (4) gives rise to the polycyclic thiophene derivative 13 and the novel allocolchicinoid 14. In a similar way cyclooctyne (6) yielded three products, the thiophene-annulated homobarrelenones 18 and 19 and the tetracyclic allocolchicinoid 21. The structures of the novel colchicine derivatives were assigned on the basis of spectral data, those of the cycloadducts 1 and 19 were verified by X-ray crystallography. For the unprecedented formation of the various allocolchicinoids by consecutive [4+2]/[3+2] cycloadditions plausible reaction pathways are suggested, as far as possible. In addition the inhibitory effects on the tubulin polymerization reaction in vitro of 10, 14, and 21 are reported.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 52
    ISSN: 1434-193X
    Schlagwort(e): Paclitaxel (Taxol®) ; Paclitaxel CD-ring ; High-pressure Diels-Alder reactions ; Furan cycloadditions ; Ether cleavage in 7-oxabicyclo[2.2.1]heptanes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The high-pressure promoted Diels-Alder reactions between several furans and citraconic anhydride have been studied and the cycloadducts obtained have been explored in new straightforward routes to the CD-ring fragment of paclitaxel. The reaction between furan and citraconic anhydride afforded the exo cycloadduct diastereoselectively, whereas a variety of 2-substituted furans afforded approximate 1:1 mixtures of exo regioisomers. Separation of both regioisomers was accomplished after either diastereoselective esterification or regioselective reduction of the anhydride function. Ether cleavage of the bicyclic compounds by either high-pressure promoted ether cleavage or Boord elimination afforded several potential CD-ring precursors which can be used in the total synthesis of paclitaxel analogues.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 53
    ISSN: 1434-193X
    Schlagwort(e): Camphoracetyl chloride ; Lactols, fused ; Lactones, fused ; Pseudoacid chlorides ; Reagents, stereoselective ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: endo-Fused lactone 3 was obtained in high yield from the camphoracetic acid 2 with thionyl chloride and a subsequent reduction of intermediate 5 with tributyltin hydride. The structure of 5 was elaborated and some aspects of the mechanism of its formation and reactivity were investigated. Lactone 3 serves as key intermediate for lactol 1 which is a useful reagent in racemate resolution and asymmetric synthesis.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 54
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2609-2615 
    ISSN: 1434-193X
    Schlagwort(e): Supramolecular chemistry ; Domino reactions ; Bipyridines ; 1,x-Cyclohexanediones ; Mannich bases ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A one-pot reaction using 1,x-cyclohexanediones, a Mannich base (or its hydrochloride), and ammonium acetate delivers novel pyridines or 3,3′-bridged bipyridine compounds 8, 16, 18, 20, and 22. This strategy offers a great flexibility in the design of new building blocks, e.g. in supramolecular chemistry and underlines the efficiency of domino reactions.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 55
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2603-2607 
    ISSN: 1434-193X
    Schlagwort(e): Fluoro analogs of vitamin A ; Horner-Wittig reaction ; Fluoroisoprenoid building blocks ; Stereoselectivity ; Hydrolysis of chlorofluorocyclopropanes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: An improved method for the preparation of ethyl 2-fluoro-3-methyl-2-butenoate (3) is described. The two stereoisomers [(E)-4 and (Z)-4] obtained after γ-bromination can be separated and can be individually converted into the corresponding diethyl phosphonates. The PO-ylides generated by α-deprotonation of the latter lose their stereochemical integrity by rapid torsional equilibration of the ester tail. Thus, Horner-Wittig reactions accomplished with benzaldehyde and (Z)- or (E)-(β-ionylidene)-acetaldehyde lead inevitably to stereorandomization at the terminal, ethoxycarbonyl-bearing double bond affording (E)- and (Z)-isomers in 50:50 to 15:85 ratios, depending on the reaction conditions. The new double bond, however, is formed with perfect trans-selectivity.
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  • 56
    ISSN: 1434-193X
    Schlagwort(e): Alkaloids ; Total synthesis/Pumiliotoxin ; PTX-C ; PTX isomers ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A method is described for the synthesis of pumiliotoxin C (1a) and related stereoisomeric compounds 1c-1f. Starting from (+)- or (-)-3-methylcyclohexanone (6a,b), the oxo esters 7a and 7b were prepared. Condensation with (+)- or (-)-3-aminohexanol (8a,b) gave the stereoisomeric 3-aminoacrylates 9a, 9b and 9c. The hydroxy group of the amino-acrylates was transformed into bromide using the tosylate method. Cyclization of the bromides led to unsaturated quinoline ring systems. Finally, decarboxylation and catalytic hydrogenation gave the different cis- and trans-fused stereoisomeric alkaloids of the pumiliotoxin C type. The structures were verified by X-ray analysis.
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  • 57
    ISSN: 1434-193X
    Schlagwort(e): Lawesson's reagent ; Thiolation of cyclic ketones ; Anchimeric effect ; cis-Bicyclo[3.3.0]octane-3,7-diones ; 9-Thiatricyclo[3.3.1.03,7]nonane ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A simple and efficient approach to the 9-thiatricyclo[3.3.1.03,7]nonane ring system (5) has been found by treating cis-bicyclo[3.3.0]octane-3,7-diones (1) with Lawesson's reagent or phosphorus pentasulfide. When dione 1 is treated with Lawesson's reagent tetramethyl 3(4aH)oxo-1,4-dihydrophenanthro[9,10-a]pentalene-1,2,4,4a-tetracarboxylate (6) is obtained as a by-product as shown by X-ray structural analysis.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 58
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2667-2672 
    ISSN: 1434-193X
    Schlagwort(e): Pyrazolidin-3-ones ; Optical activity ; Asymmetric synthesis ; Ring transformation ; Hydrazines ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Enantiopure α-alkylidenelactones 7 were prepared by a Wittig reaction from α-bromolactones 4 and chiral aldehydes 6. Compounds 7 react with hydrazines 9 by stereoselective Michael-like addition and ring-chain transformation affording optically active 4-(ω-hydroxyalkyl)pyrazolidin-3-ones 11.
    Zusätzliches Material: 5 Ill.
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  • 59
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2673-2676 
    ISSN: 1434-193X
    Schlagwort(e): Aromatic aldehydes ; Pinacol coupling ; Radical reactions ; Reagent control ; Titanium ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A novel concept for conductingtransition-metal-catalyzed radical reactions that allows highly diastereoselective titanocene-catalyzed pinacol couplings is described.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 60
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2677-2682 
    ISSN: 1434-193X
    Schlagwort(e): Terpenoid lactones ; Antifeedants ; Limonene ; Claisen rearrangement ; Iodolactonization ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Four enantiomeric pairs of spirolactones were obtained in a four step synthesis from (+) and (-) limonene. The Claisen rearrangement and iodolactonization were the key steps of the syntheses presented. The structures of products were confirmed by X-ray crystallography of 11, 18b, and 19.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 61
    ISSN: 1434-193X
    Schlagwort(e): Phosphole ; Phosphanorbornadiene ; Stille cross-coupling ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The reaction of alkynylstannanes with 1-phenyl-3,4-dimethylphosphole at 150 °C affords the corresponding 2-stannyl-1-phosphanorbornadienes (2a, b), in fair yield. Oxidation under mild conditions affords the corresponding phosphane oxides (3a, b), whereas more drastic conditions (H2O2, 15% in toluene at 80 °C) induce the oxidative cleavage of the P-CH2 bond of the bridge to give a bicyclic phosphinate such as 4. Treatement of 4 by iodine leads to a tin → iodine exchange. The X-ray crystal structure analysis of the resulting 1-phospha-2-oxabicyclo[2.2.2]octa-5,7-diene 1-oxide confirms the functionalisation at the α-position and the relief of ring strain taking place upon insertion of oxygen into the P-CH2 bond of the norbornadiene. The 2-stannyl-1-phosphanorbornadiene 1-oxides (3a, b) readily undergo tin → iodine exchange. The resulting 2-iodo derivatives (6a, b) can be cross-coupled with 2-furyl-, 2-thienyl-, 2-pyrrolyl-, phenylethynyl-, and vinyl-tributylstannanes to give the corresponding 2-functional 1-phosphanorbornadiene 1-oxides in excellent yields (80-95%)
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 62
    ISSN: 1434-193X
    Schlagwort(e): Asymmetric synthesis ; Density functional calculations ; Cycloadditions ; Dihydropyrans ; Enantioselective oxidations ; Sulfur heterocycles ; Sulfoxides ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The 4-benzylidene-3-oxo[1,3]oxathiolan-5-ones 13-15, which were derived from the 3-oxo[1,3]oxathiolan-5-ones 9-11 by Knoevenagel condensation with the aldehydes 12, cyclize in an intramolecular hetero Diels-Alder reaction with high yield and excellent endo/exo as well as induced diastereoselectivity to give the hetero Diels-Alder adducts 16-18. The preferred formation of the Knoevenagel products 13-15 with a (Z) configuration was predicted with DFT calculations (B3LYP-6-311+G*) using the model systems 28 and 29. In addition B3LYP-6-31G*/sB3LYP/3-21G(*) calculations on transition structures for the hetero Diels-Alder reaction of 29 and 30 allowed a good correlation with the experimental results, which show that an endo attack of the dienophile syn to the S-O group in 13-15 leads to the main products.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 63
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2759-2767 
    ISSN: 1434-193X
    Schlagwort(e): Phosphorus phthalocyanines ; Triazatetrabenzcorroles ; Dihydroxyphosphorus(V) phthalocyanine hydroxides ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The previously reported reaction of phthalocyanines [H2(pc)] with PBr3, which was claimed to give a phosphorus(III) phthalocyanine “(PcPIII)”, has been reinvestigated in detail with both unsubstituted and alkyl-substituted phthalocyanines, 1-4. The products exhibit unusual electronic and mass spectra compared to normal phthalocyanines and have been identified as oxophosphorus(V) triazatetrabenzcorroles 5-8. The corresponding dihydroxyphosphorus(V) phthalocyanine hydroxides 9-12 have also been synthesized for the first time by insertion of phosphorus(V) into phthalocyanines and have been characterized in detail. The different reactivities of PBr3 and POX3 (X = Cl, Br) toward phthalocyanines are discussed.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 64
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2769-2773 
    ISSN: 1434-193X
    Schlagwort(e): Rubicenes ; Cyclization ; Polycyclic aromatic hydrocarbons ; Arenes ; Synthetic methods ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The synthesis of novel disubstituted rubicenes 1a-k is described. Starting from 1,5-dichloroanthraquinone and aryllithium reagents 3, the diol adducts 4 are reduced and the resulting diarylanthracenes 5 are cyclized to afford the title compounds in fair to good overall yield.
    Materialart: Digitale Medien
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  • 65
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 37-41 
    ISSN: 1434-1948
    Schlagwort(e): Tripodal P ligands ; Rhodium ; Water-soluble complexes ; Immobilization ; Biphasic hydroformylation ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The synthesis of the water-soluble tripodal phosphane ligand cis,cis-1,3,5-(PPh2)3-1,3,5-[CH2(OCH2CH2)xOCH3]C6H6 (x = 30-160) (5) has been achieved in a four-step reaction sequence. The alcohol Mo(CO)3[cis,cis-1,3,5-(PPh2)3-1,3,5-(CH2OH)3C6H6] (1) is converted to the corresponding alcoholate 2, which forms the polyethylene glycol derivative 3 in a polyaddition reaction with oxirane. After methylation of the end groups of 3, the ligand 5 is obtained by a combined photochemical/oxidative demolybdenation reaction. The water-soluble tripodal phosphane 5 and the methoxymethyl functionalized tripodal ligand 6 react with Rh(PPh3)3(CO)H to form the water-soluble and water-insoluble rhodium carbonyl hydrido complexes 5a and 6a, respectively. The catalytic activity of the rhodium complex 5a in the hydroformylation of 1-hexene was found to be comparable in a single-phase system (1-hexene/methanol) with that in the biphasic system (1-hexene/water). Only traces of alcohol were found, which demonstrates that the catalyst 5a displays higher selectivity in hydroformylation than in hydrogenation.
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  • 66
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 55-59 
    ISSN: 1434-1948
    Schlagwort(e): Arsaalkenes ; Arsenic ligands ; Carbonyl complexes ; Chromium ; Iron ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Reaction of equimolar amounts of the metalloarsaalkene [(η5-C5Me5)(CO)2FeAs=C(NMe2)2] (1) with the carbonyl complexes [Ni(CO)4], [Fe2(CO)9], and [{(Z)-cyclooctene}Cr(CO)5], respectively, affords the adducts [(η5-C5Me5)(CO)2FeAs{M(CO)n}=C(NMe2)2] with [M(CO)n] = [Ni(CO)3] (2); [Fe(CO)4] (3), and [Cr(CO)5] (4). These feature η1 coordination of the arsaalkene ligand via the arsenic atom. The molecular structures of the complexes 3 and 4 have been determined by X-ray diffraction analyses.
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  • 67
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 155-157 
    ISSN: 1434-1948
    Schlagwort(e): Bite angle ; Catalysis ; P ligands ; Palladium ; Cross-coupling ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The effect of the natural bite angle (βn) of diphosphane ligands on catalyst selectivity and activity in the palladium-catalyzed cross-coupling of sec-butyl magnesium chloride with bromobenzene was investigated. The calculated natural bite angles range from 78° for dppe (1,2-bisdiphenylphosphanoethane) to 110° for Xantphos. The natural bite angle of diphosphane ligands has a large effect on catalyst selectivity and activity. Both rate and selectivity of the cross-coupling reaction increase with increasing bite angle and reach a maximum value with DPEphos (βn = 102.7° ). Larger bite angles of the diphosphane ligands result in a decreased selectivity and activity.
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  • 68
    ISSN: 1434-1948
    Schlagwort(e): Ligand field spectra ; Phosphonate complexes ; X-ray structures ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The synthesis and characterization of transition-metal coordination compounds containing the ligand diethyl 2-quinolylmethylphosphonate (2-qmpe) is described. Complexes of CoII, MnII, NiII, CdII, and ZnII were found to be mutually isomorphous according to their X-ray powder diffraction patterns and IR spectra. The new coordination compounds were identified and characterized by elemental analysis, magnetic measurements, infrared and ligand-field spectra. The crystal structures of the complexes [M(2-qmpe)4(H2O)2](ClO4)2 (M = Ni, 1; Mn, 2) reveal six-coordinate [M(2-qmpe)4(H2O)2] cations with the qmpe ligand coordinating via the oxygen rather than via the nitrogen atom, as well as lattice perchlorate anions. The metal ion is octahedrally surrounded by the four oxygen atoms of the four organic ligands. The non-participation of the pyridine nitrogen atom is unusual. The two water molecules occupy the fifth and the sixth coordination sites in a trans configuration. The coordinated water molecules are strongly hydrogen-bonded to the pyridine nitrogen atom of the 2-qmpe, further stabilizing the solid-state structure. The geometry of the metal ion can be described as distorted octahedral. For the CuII complex, a hydroxo-bridged dinuclear structure of the type [Cu(2-qmpe)2(OH)(H2O)2]2(ClO4)2 is proposed, based on its spectroscopic and magnetic properties. Ligand-field spectra of the Co and Ni compounds were found to be in agreement with the tetragonally distorted octahedral geometry.
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  • 69
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 191-202 
    ISSN: 1434-1948
    Schlagwort(e): Polynuclear complexes ; Carbene complexes ; Bridging ligands ; Alkynyl complexes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The sequential reaction of two equivalents of the dimethylamino(ethynyl)carbene complexes [(CO)5M=C(NMe2)C≡CH] [M = W (1a), Cr (1b)] with two equivalents of nBuLi and one equivalent of a transition metal dichloride, [Cl2M′(Ln)], affords trinuclear biscarbene complexes of the type [(CO)5M=C(NMe2)C≡C-M′(Ln)-C≡CC(NMe)2=M(CO)5] [M′(Ln) = Ni(PEt3)2 (2a, b), Pd(PEt3)2 (3a, b), Pt(PEt3)2 (4a, b), Fe(dmpe)2 (6a), Hg (8a), Ti(η5-C5H5)2 (9a, b)] [dmpe = 1,2-bis(dimethylphosphino)ethane]. Treatment of 1a with equimolar amounts of first nBuLi and then [Cl2M′(Ln)] results in the formation of the monosubstitution products [(CO)5W=C(NMe2)C≡CM′(Ln)] [M′(Ln) = trans-Pd(PEt3)2Cl (5a), trans-Fe(dmpe)2Cl (7a)]. Additionally, the synthesis of the heterobimetallicethynylcarbene complex [(CO)5W=C(NMe2)C≡CPd(PEt3)2C≡CH] (10a), starting from 1a and [ClPd(PEt3)2C≡CH], is described. When three equivalents of 1a are treated, first with three equivalents of nBuLi and then with one equivalent of the trihalides PCl3 or BBr3, the novel tris(ethynylcarbene) complexes [{(CO)5W=C(NMe2)C≡C}3E] [E = B (11a), P (12a)] are obtained. The reaction of four equivalents of 1a,b with four equivalents of nBuLi, followed by addition of one equivalent of a group 14 tetrachloride [M′Cl4], yields the novel tetrakis(ethynylcarbene) complexes [{(CO)5M=C(NMe2)C≡C}4M′] [M′ = Si (13a, b), Ge (14a), Sn (15a, b)]. The complexes 8a, 9a, 12a, and 15a were characterized by X-ray structural analyses. All spectroscopic and structural data suggest that the carbene fragments and the central transition metal or heteroatom in these new bis-, tris-, and tetrakis(ethynylcarbene) complexes interact only weakly.
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  • 70
    ISSN: 1434-1948
    Schlagwort(e): Rhenium ; Oxacyclocarbene complexes ; Vinylidene comlexes ; Alkynols ; Tripodal ligands ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Various β-, γ-, and δ-alkynols have been reacted with the 16e- fragment [(triphos)Re(CO)2]+ generated in situ by H2 elimination from [(triphos)Re(CO)2(η2-H2)]BF4 [triphos = MeC(CH2PPh2)3]. Irrespective of the length of the alkyl chain between the C≡C and OH functional groups in the ω-alkynol, 2-oxacyclocarbene complexes are obtained. These include the 2-oxacyclopentylidene derivatives [(triphos)Re(CO)2{=CCH2CH2CH2O}]BF4 and [(triphos)Re(CO)2{=CCH2CH2CH(Me)O}]BF4, the 2-oxacyclohexylidene dervivatives [(triphos)Re(CO)2{=CCH2CH2CH2CH2O}]BF4 and[(triphos)Re(CO)2{=CCH2CH2CH2CH(Me)O}]BF4, and the 2-oxacycloheptylidene complex [(triphos)Re(CO)2{=CCH2CH2- CH2CH2CH2O}]BF4. The latter compound contains a unprecedented seven-membered oxacarbene ring. The rhenium-assisted δ-alkynol to 2-oxacyloheptylidene rearrangement proceeds via the hydroxybutylvinylidene kinetic intermediate [(triphos)Re(CO)2{C=C(H)CH2CH2CH2CH2OH}]BF4, which has been characterized in both the solid state and solution. An X-ray analysis has been carried out on a single crystal of [(triphos)Re(CO)2{=CCH2CH2CH(Me)O}]BF4. The structure of this complex consists of [(triphos)Re(CO)2{=CCH2CH2CH(Me)O}]+ cations and tetrafluoroborate anions with no interspersed solvent molecules. A facial triphos ligand, two cis-disposed carbonyl groups and a 2-oxacyclopentylidene ligand coordinate the Re centre in a slightly distorted octahedral environment.
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  • 71
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 237-244 
    ISSN: 1434-1948
    Schlagwort(e): Titanium complexes ; Amido-cyclopentadienyl ligand ; Titanium alkyl ; Intramolecular coordination ; Ethene polymerization ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Titanium complexes containing a linked isopropyl- or benzylamido(tetramethylcyclopentadienyl) ligand C5Me4SiMe2NR (R = iPr, CH2Ph,) and one bidentate organyl group C6H4(CH2NMe2)-2, CH2C6H4(NMe2)-2, and {η5-C5H3(CH2NMe2)-2}Fe(η5-C5H5) were prepared by salt metathesis of the corresponding dichloro complex Ti(η5:η1-C5Me4SiMe2NR)Cl2 with the lithium organyl. Single crystal X-ray structural analysis of Ti(η5:η1-C5Me4SiMe2NCH2Ph)- {C6H4(CH2NMe2)-2}Cl and of Ti(η5:η1-C5Me4SiMe2NiPr){CH2C6H4(NMe2)-2}Cl revealed the presence of intramolecular coordination with square pyramidal geometry around titanium. In the ferrocenyl derivative Ti(η5:η1-C5Me4SiMe2NCH2Ph)[{η5-C5H3(CH2NMe2)-2}Fe(η5-C5H5)]Cl the NMe2 group is not bonded at the titanium atom. Ethene polymerization catalyzed by these complexes upon activation with methylaluminoxane was examined.
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  • 72
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 271-274 
    ISSN: 1434-1948
    Schlagwort(e): Zinc complexes ; Pyrazolylborate ligands ; Hydrolytic cleavage ; Diphosphate ; Sulfonatophosphate ; Disulfonate ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Three (pyrazolylborate)zinc hydroxide complexes Tp*Zn-OH were used as hydrolytic reagents to cleave the P-O-P, P-O-S, and S-O-S linkages of organic diphosphates, sulfonatophosphates, and disulfonates. The resulting complexes of the types Tp*Zn-OPO(OR)2 and Tp*Zn-OSO2R could also be obtained by condensation reactions between Tp*Zn-OH and HO-PO(OR)2 or HO-SO2R. Two of them were characterized by structure determinations.
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  • 73
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 283-289 
    ISSN: 1434-1948
    Schlagwort(e): Gold ; Chalcogenide ; Flux reaction ; Structure determination ; Metal-metal bonding ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The novel compounds K2AuPS4 (1), Tl2AuPS4 (2), K2AuAsS4 (3), and KAu5P2S8 (4) have been synthesized by direct reaction of the elements with a molten alkaline polythiophosphate(arsenate) flux at 550°C. The crystal structures of these compounds have been determined by single-crystal X-ray diffraction techniques. 1, 2, and 3 crystallize in the monoclinic space group P21/m. The structures of 1, 2, and 3 consist of infinite, one-dimensional anionic chains running along the crystallographic b axis. The chains are separated by potassium or thallium ions. Neighbouring Au atoms are bridged by MS43- tetrahedra (M = P, As) in a trans orientation. Compound 4 crystallizes in the space group P21/c. The anionic chains of 4 are built up from linear AuS2 dumbbell units and PS43- tetrahedra. The chains extend along the [110] and [110] direction and are separated by charge balancing K+ cations. Each of the compounds was investigated by differential thermal analysis, FT-IR, and solid-state UV/Vis diffuse reflectance spectroscopy.
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  • 74
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 299-303 
    ISSN: 1434-1948
    Schlagwort(e): Calix[4]arenes ; Calix[4]arene complexes ; Molybdenum ; Tungsten ; Metal-metal bonding ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Addition of p-tert-butylcalix[4]arene LH4 to the dinuclear compounds M2(NMe2)6 (M = Mo, W) results in the formation of [NH2Me2]2[L2M2] 1 (M = Mo) and 2 (M = W). Both compounds have been characterized by spectroscopic methods and single-crystal X-ray diffraction. The metal-metal distances of 1 and 2, of 2.194(1) Å and 2.293(1) Å, respectively, are consistent with the retention of the M≡M triple bond. Both „ate” complexes contain a [M≡M]6+ dimetal core, supported by two bridging μ2-κ2O,κ2O-calix[4]arene ligands in the solid state. These compounds are the first examples of a formally fourfold deprotonated calix[4]arene acting as a μ2-κ2O,κ2O bridging ligand for two transition metal centres. The calix[4]arenes in 1 and 2 are distorted from a cone conformation in the uncomplexed ligand, to an elliptical cone section. 1H-NMR data at variable temperatures suggest fluxional behaviour of 1 and 2 in solution.
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  • 75
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 331-337 
    ISSN: 1434-1948
    Schlagwort(e): Bis(pentamethylcyclopentadienyl)phosphanes ; Aminobis(pentamethylcyclopentadienyl)phosphanes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The bis(1,2,3,4,5-pentamethyl-1,3-cyclopentadien-1-yl)phosphanes 3-7 are formed in good yields by the reaction of the halogenophosphanes 2a or 2b with the appropriate nucleophile. Following another route, the dialkylaminobis(pentamethylcyclopentadienyl)phosphanes 11a-c have been synthesized by the treatment of dichloro(dialkylamino)phosphanes with two equivalents of (pentamethylcyclopentadienyl)lithium. The compounds 3-11 have been characterized by multinuclear NMR spectroscopy and 3, 5, 6, and 11a have also been characterized by single-crystal X-ray diffraction studies. The molecular structure of 11a is governed by steric congestion, which typically would lead to a parallel arrangement of the two pentamethylcyclopentadienyl ligands at the phosphorus atom. However, surprisingly, the crystal structure of the (dimethylamino)phosphane 11a, exhibits a tilted, rather than a parallel, conformation of the pentamethylcyclopentadienyl groups [tilt angle: 130.6(1)°].
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  • 76
    ISSN: 1434-1948
    Schlagwort(e): Palladium ; Platinum ; Bidentate nitrogen ligands ; p-Quinone ; Alkenes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Compounds of the type M(N∩N-κN)(nq)2 and M2(μ2-N∩N)(μ2-pbq)2, in which nq = 1,4-naphthoquinone, pbq = 1,4-benzoquinone, and N∩N is a monodentate or bridging ligand of the α-diimine type, were obtained from reactions of Pd(dba)2 in toluene with the 3,3′-annelated-2,2′-bipyridines: 4,5-diazafluoren-9-one (dafo) and 4,5-diazafluorene (dafe) in the presence of the appropriate p-quinone. In the corresponding reactions with 2,2′-bipyridine (bpy), 1,10-phenanthroline (phen), 2,2′-bipyrimidine (bpym), N,N′-dicyclohexyl-1,4-diaza-1,3-butadiene (chex-dab), bis[N-(o,o′-diisopropyl)phenylimino]acenaphthene (o,o′-iPr2-bian) and 5,6-dihydro-1,10-phenanthroline (dh-phen) only complexes of the type M(N∩N-κ2N)(Q) were formed (Q = nq, pbq). The structures of the complexes have been established by NMR in solution and by X-ray diffraction in the solid state; crystal structures of Pd(bpy-κ2N)(η2-pbq) (1) Pd(dafo-κN)(η2-nq)2 (14) and Pd2(μ2-dafo)(μ2,η2:η2-pbq)2 (16) have been determined. Of the ligands, dafo and dafe are the only ones apt to form complexes containing a monodentate or bridging N∩N ligand. This behaviour is ascribed to the geometrical constraints of dafo and dafe; the annelation by one carbon atom at the 3,3′-positions in these ligands causes an increase in bite angle from approximately 77° to 82°.
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  • 77
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 367-373 
    ISSN: 1434-1948
    Schlagwort(e): Phthalocyanines ; Indium ; Indium-carbon bond ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The synthesis of highly soluble chloro(phthalocyaninato)indium(III) complexes RxPcInCl (3a: R1 = tert-butyl, R2 = H, x = 4 and 4a: R1 = R2 = n-pentyl, x = 8), and their reactions with R′MgBr [R′ = p-trifluoromethylphenyl- (b), m-trifluoromethylphenyl- (c), p-fluorophenyl- (d), perfluorophenyl- (e)] leading to the stable σ-bonded aryl(phthalocyaninato)indium(III) complexes 3b-e, 4b-e are described. All compounds were characterized by IR, UV/Vis, MS, 1H, 13C and 19F NMR as well as elemental analyses. Phenyl(phthalocyaninato)indium(III) (4f) was prepared by the reaction of (n-C5H11)8PcInCl (4a) with PhLi. The high solubility of the complexes 3a-e and 4a-f is, aside from the influence of the peripheral substituents, considered to be derived from the large dipole moments present which are due to the strongly electron withdrawing axial ligands, and from the lower tendency of axially substituted phthalocyaninato metal complexes to form aggregates.
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  • 78
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 381-388 
    ISSN: 1434-1948
    Schlagwort(e): Phosphanes ; Phosphorus ylides ; Nucleophilic addition ; Structure elucidation ; NMR spectroscopy ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Chlorophosphanyl and dichlorophosphanyl alkylidene- and benzylidenephosphoranes 6 and 8 are converted by reaction with LiAlH4 to the respective phosphanes 7 and 9. The former can be isolated, but decompose on heating or on protonation to give the ylidyl diphosphane 11 and the phosphonium ylide or phosphonium salt, respectively. The final products are the cyclooligophosphanes 15-17. Only the C-tert-butyl derivative 7c is stable in both regards. The conformation of the RPH group in 7 as compared to that of the RPCl group in 6 clearly reflects their different interaction with the ylide moiety.
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  • 79
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 407-414 
    ISSN: 1434-1948
    Schlagwort(e): Ruthenium ; Phosphorus ; Triphos complexes ; Fluxionality ; Arm-off dissociation ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Structural fluxionality is apparent in the 1H- and 31P-NMR spectra of compounds of the type [Ru(L)(MeCN)(triphos)](CF3SO3), 2-5, at 25°C, where L represents a diorganyldithiocarbamate or a heterocyclic κ2N,S coordinating thioamide. In contrast, complexes [Ru(Et2NCS2)(Y)(triphos)]n+ (6, n = 1, Y = CO; 7, n = 0, Y = CN-; 8, n = 0, Y = H-) are stereochemically rigid in solution at this temperature, indicating that MeCN dissociation must occur for the crowded octahedral coordination spheres of 2-5. Reaction of [Ru(MeCN)3(triphos)](CF3SO3)2, 1, with Na(Et2NCS2) at a 1:2 molar ratio yields [Ru(Et2NCS2-κ2S)(Et2NCS2-κS)(triphos)], 9, which slowly converts to [Ru(Et2NCS2-κ2S)2(triphosO-κ2P)], 10, on recrystallization from ethanol/acetone under air [triphosO is O=P(Ph)2CH2C(CH3)(CH2PPh2)2]. A similar κ3P→κ2P arm-off dissociation leads to the formation of [Ru(mpy-κ2N,S)2(triphosO-κ2P)] (13) and [Ru(mmim-κ2N,S)2(triphosO-κ2P)] (14) (Hmpy = 2-mercaptopyridine, Hmmim = 2-mercapto-1-methylimidazole). Crystal structures are reported for [Ru(mbt-κ2N,S)(MeCN)(triphos-κ3P)](CF3SO3) (4) (Hmbt = 2-mercaptobenzothiazole), [Ru(mpym-κ2N,S)(mpym-κS)(triphos-κ3P)] (11) (Hmpym = 2-mercaptopyrimidine) and 14, the latter of which is present as the OC-6-13 isomer.
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  • 80
    ISSN: 1434-1948
    Schlagwort(e): Alkyne complexes ; Titanium ; Zirconium ; Coordination mode ; Metallacycles ; Cyclopentadienes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The influence of metals, alkyne substituents, Cp substitution and additional ligands on the stability of bridged and unbridged η2-alkyne-titanocene and -zirconocene complexes has been investigated. The reduction of the complex [(η5-C5H4)-SiMe2-(η5-C5H4)]TiCl2 with magnesium in the presence of tolan (PhC2Ph) does not give the expected alkyne-titanocene complex [(η5-C5H4)-SiMe2-(η5-C5H4)]Ti(η2-PhC2Ph) but by coupling of two tolan molecules the corresponding titanacyclopentadiene [(η5-C5H4)-SiMe2-(η5-C5H4)]TiC4Ph4 (1) was obtained. In the analogous reaction with Me3SiC2SiMe3 the stable η2-alkyne complex without additional ligands [(η5-C5H4)-SiMe2-(η5-C5H4)]Ti(η2-Me3SiC2SiMe3) (2) was formed, due to the sterical influence of the alkyne substituents. The compounds without additional ligands (thi)2Ti(η2-PhC2Ph) (3) and (thi)2Ti(η2- Me3SiC2SiMe3) (5) were isolated from the unbridged titanocene complex (thi)2TiCl2 (thi = tetrahydroindenyl). Two equivalents of complex 3 reacted with one equivalent of water to yield the dimeric alkylidene-μ-oxo complex [(thi)2Ti(CPh=CHPh)]2(μ-O) (6). The reaction of the unbridged zirconocene compound (thi)2ZrCl2 gave the alkyne complex (thi)2Zr(THF)(η2-Me3- SiC2SiMe3) (7) which is stabilized by THF. At higher temperature THF was eliminated from the orange complex 7 forming the green complex (thi)2Zr(η2-Me3SiC2SiMe3). This behaviour was investigated in detail using NMR spectroscopy and compared to similar complexes such as Cp2Zr(η2-Me3SiC2SiMe3) (not stable without THF), (ebthi)2Zr(η2-Me3SiC2SiMe3) (ebthi = ethylenebistetrahydroindenyl; stable without THF) and Cp*2Zr(η2-Me3SiC2SiMe3) (Cp* = pentamethyl-Cp, stable without THF). All complexes were characterized by spectroscopic methods. X-ray structural determinations were conducted for the complexes 1, 3 and 7. Compound 3 is the first example of a structurally characterized tolan-titanocene complex without additional ligands.
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  • 81
    ISSN: 1434-1948
    Schlagwort(e): Calixarene ; Phosphinite ; Calixphosphane ; Transition metals ; X-ray diffraction ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A cone-shaped calix[4]arene-derived monophosphinite, 25,27-di(ethoxycarbonylmethoxy)-26-hydroxy-28-(diphenylphosphinooxy)calix[4]arene (L1), has been prepared in two steps from calix[4]arene. Treatment of L1 with [AuCl(tetrahydrothiophene)] in tetrahydrofuran gave the phosphinite complex [AuClL1] (1). Reaction of [PdCl2(PhCN)2] with two equivalents of L1 gave selectively trans-[PdCl2L12] (2). Complex 2 · 2 CH2Cl2 crystallizes in the triclinic space group P1¯. The molecule is centrosymmetric, leading to a divergent array of the two calixarene moieties. The palladium atom resides outside both cones. As a result of steric interactions, the meta and para carbon atoms of the PPh2-bearing aryl ring are significantly pushed to the interior of the cavity. The related platinum complex trans-[PtCl2L122] (3), was obtained similarly from [PtCl2(PhCN)2] and presents in the solid state a structure which is isomorphous to that of 2. The diphosphinite 25,27-di(ethoxycarbonylmethoxy)-26,28-bis(diphenylphosphinoxy)calix[4]arene (cone) (L2) has also been prepared and reacts with [PtCl2(PhCN)2] to yield oligomeric material.
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  • 82
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 501-504 
    ISSN: 1434-1948
    Schlagwort(e): Metallomesogens ; Azo compounds ; Palladium ; Platinum ; Cyclopentadienyl complexes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The mesogenic 4,4′-bis[4-(n-octyloxy)benzoyloxy]azobenzene (HL) ligand reacts with [(PhCN)2PdCl2] to give the dinuclear cyclometalated complex [(μ-Cl)(L)Pd]2 (1), from which the mononuclear half-sandwich [(η5-C5H5)(L)Pd] (2) species has been obtained by reaction with Tl(C5H5). The PtII analogue of 2, [(η5-C5H5)(L)Pt] (4), has been prepared in a similar manner starting from [(μ-Cl)(L)Pt]2 (3). Both dinuclear complexes 1 and 3 display a smectic C phase (SC) stable over 80°C. Whereas 4 is the first example of an 18-electron PtII mesogen, both mononuclear 2 and 4 are mesomorphic materials that exhibit a nematic phase spanning a wide temperature range.
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  • 83
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 523-536 
    ISSN: 1434-1948
    Schlagwort(e): Quantum chemistry ; Intermetallic compounds ; Transition metal cluster compounds ; Crystallography ; Electronic structure ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The “coloring problem,” as applied to the field of solid state chemistry, addresses the issues of structural preference as well as the distribution of different elements within a given structure. Both the connectivity and arrangement of elements in a solid affect physical and chemical properties, so a clear understanding of the forces controlling how elements will arrange themselves in a solid state structure creates the ability to predict structure-composition-property relationships. There are two fundamental energetic contributions that influence how elements in a structure order: the site energy and the bond energy. This review examines how these two parts of the total electronic energy work together to influence the observed structures, compositions, and properties of intermetallics and transition metal cluster compounds.
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  • 84
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 559-563 
    ISSN: 1434-1948
    Schlagwort(e): Metal(II) complexes ; Octanuclear complexes ; Supramolecular chemistry ; Zinc ; Cadmium ; Manganese ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The reaction of H2L1 and H2L2 with divalent metal ions leads to octanuclear bis(triple-helical) metal(II) complexes of the general composition [Zn8O2L26] (3) and [M8O2L16] (4: M = Cd2+; 5: M = Mn2+). NMR studies of the diamagnetic cadmium complex 4c show six equivalent ligands. Unambiguous characterisation of 5b was achieved by X-ray crystallographic analysis.
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  • 85
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 575-578 
    ISSN: 1434-1948
    Schlagwort(e): Phosphorus heterocycles ; 2H-Azaphosphirene complexes ; Carbene complexes ; Tungsten ; Cyclizations ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The syntheses of 3-heteroaryl-substituted 2H-azaphosphirene pentacarbonyltungsten complexes are reported. The products were characterized by multinuclear NMR spectroscopy (1H, 13C, 15N, 31P, 183W); the structure of the 3-N-methylpyrryl-substituted 2H-azaphosphirene complex was determined by single-crystal X-ray structure analysis.
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  • 86
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 657-662 
    ISSN: 1434-1948
    Schlagwort(e): Cadmium ; Crown compounds ; Pentafluorophenyl ; Potassium ; S ligands ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Bis(pentafluorophenyl)cadmium, [Cd(C6F5)2], reacts with equimolar amounts of triphenylmethanethiol, TrtSH, in toluene to give [{Cd(C6F5)(STrt)}4] · 1.5 tol (1). The cuboidal complex of 1 has been transformed into the heterometallic cuboidal complex [{Cd(C6F5)(STrt)}3(OH)K(THF)3] (2) by reaction with KOH in tetrahydrofuran. In the presence of 18-crown-6, the compound [K(18-crown-6)(THF)2][{Cd(C6F5)- (STrt)}3(OH)] · THF (3) has been obtained instead of 2. X-ray structure analysis shows the anion of 3 to be an incomplete cuboidal complex, which alternatively can be described as a cyclic trimer of the {Cd(C6F5)(STrt)} unit stabilized by a μ3-hydroxo ligand. The compound [K(18-crown-6)(THF)2][Cd(C6F5)(STrt)2] (4) has been isolated from reaction mixtures containing 1, KSTrt and 18-crown-6. The cadmium atom in 4 is three-coordinated, in contrast to the cadmium atoms in 1-3, which are situated in strongly distorted coordination tetrahedra. Intramolecular C6H5···C6F5···C6H5 stacks in 4 are interpreted as resulting from attractive ligand-ligand interactions. Spectroscopic data, particularly from 13C-NMR and IR spectra, are consistent with the order of ligand deficiency: 1 〉 2 〉 3 〉 4. The macrocyclic, eight-coordinate complex [K(18-crown-6)(THF)2]+ in 3 and 4 contains trans arranged THF ligands.
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  • 87
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 745-749 
    ISSN: 1434-1948
    Schlagwort(e): Gallium ; Silicon ; Heterocycles ; Main group elements ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The reaction of Ga2X4· 2 dioxane with four equivalents of (Me3Si)3SiLi(thf)3 (= hypersilyllithium) affords for X = Br a 1,3,2,4-disiladigalletane together with tetrahedral hypersilylgallium(I). For X = Cl an anionic 1,2,3,4-silatrigalletanate, a four-membered heterocycle with a Ga3 unit, is isolated. These primary examples of gallium/group-14 heterocycles have been investigated by NMR spectroscopy as well as by X-ray single-crystal structure analysis. In addition, the synthesis and structure of bis(hypersilyl)gallium chloride is described. This monomeric molecule has a nearly T-shaped Si2GaCl framework.
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  • 88
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 761-769 
    ISSN: 1434-1948
    Schlagwort(e): Organometallics ; Boron ; Lithium ; Tin ; Metal-metal exchange ; Electrophilic reagents ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: With the purpose of preparing novel mono- and bidentate organoboron Lewis acids, the scope and limitations of synthesizing the requisite organoboranes by the boron-tin exchange between a boron halide and the appropriate organostannane have been examined in detail. The following organotin derivatives have been obtained either from the corresponding RMgBr or RLi reagent and MenSnCl4-n or from a Barbier procedure using the organic halide, Me3SnCl and magnesium metal: 1,2-bis(trimethylstannyl)ethyne, o-, m-, and p-bis(trimethyl-stannyl)benzenes, α,o-bis(trimethylstannyl)toluene, α,α-bis(trimethylstannyl)-o-xylene, and 2,2-dimethyl-2-stannaindane. The individual interaction of the 1,2-bis(trimethylstannyl)ethyne and the isomeric bis(trimethylstannyl)benzenes with Et2BBr produced the corresponding bis(diethylboryl)-derivatives. By contrast, with Et2BCl the α,o-bis(trimethylstannyl)toluene gave only o-diethylboryl-α-trimethylstannyltoluene and with BCl3 the α,α′-bis(trimethylstannyl)-o-xylene formed only,-bis-(chlorodimethylstannyl)-o-xylene. Furthermore, in the attempted double boron-tin exchange between o-bis(trimethylstannyl)benzene and BCl3, an unprecedented rearrangement of the 1-(dichloroboryl)-2-(trimethylstan-nyl)benzene intermediate into its 1-[chloro(methyl)boryl]-2-(chlorodimethylstannyl) isomer was observed. Likewise, o-bis(trimethylstannyl)benzene with PhBCl2 produced by a similar rearrangement 1-[methyl(phenyl)boryl]-2-(chloro-dimethylstannyl)benzene. The thermolysis of such boranes led variously to definite dimers or ill-defined oligomers. Preliminary studies of the properties of these organoboranes have identified the heightened Lewis acidity of 1,2-bis(diethylboryl)ethyne and the π-electron delocalization involving the 2pz-boron orbitals in the 9,10-dihydro-9,10-diboraanthracene system. Finally, an electronic mechanism for the boron-tin exchange has been developed to account for the selectivity of the boron halide's attack at unsaturated carbon-tin bonds.
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  • 89
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 799-805 
    ISSN: 1434-1948
    Schlagwort(e): Aminoalcohol ligands ; Hydrogen bonds ; Magnetic properties ; Oxo complexes ; Vanadium ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The aminoalcohol ligands diethanolamine (H2dea) and triethanolamine (H3tea) react with [VO(acac)2] to yield the tetranuclear oxovanadium(IV) complexes [{VO(dea)}2{VO(acac)}2(μ2-OMe)2] (1) and [{VO(Htea)}2{VO(acac)}2(μ2-OMe)2] (2). In the case of the potentially bridging aminoalcohol ligands N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine (H4edte) and N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine (H4edtp) the corresponding oxovanadium(IV) complexes could not be isolated. Instead after air oxidation the ligand supported binuclear oxovanadium(V) complexes [{VO(acac)}2(edte)] (3) and [{VO(acac)}2(edtp)] (4) are obtained. The reaction of the ligand H4edtp with ammonium meta-vanadate in methanol solution leads to the methoxy bridged binuclear oxovanadium(V) complex [(VO)2(edtp)(μ2-OMe)2] (5). The tetranuclear oxovanadium(IV) complexes can be isolated as crystalline compounds 1 · 2 MeOH and 2 · 2 MeOH and have been characterized by IR, UV/Vis, and ESR spectroscopy as well as cyclic voltammetry and magnetic susceptibility measurements. Single-crystal diffraction studies reveal that the complexes 1 and 2 contain a tetranuclear {(VO)4(μ3-OR)2(μ2-OR)4}2+ core composed of three different types of edge-shared binuclear units, whereas the oxovanadium(V) complexes 3, 4, and 5 posses binuclear structures, that are either ligand supported as in the case of 3 and 4 or contain a μ2-methoxy bridged{(VO)2(μ2-OR)2}4+ core as in the case of 5. ESR and magnetic data indicate a singlet ground state for 1 · 2 MeOH and 2 · 2 MeOH, although competing ferromagnetic exchange interactions are operative within the tetranuclear core structure. In the solid state compounds 1 · 2 MeOH and 2 · 2 MeOH hydrogen bridged supramolecular structures are found. The hydrogen bonding scheme of both compounds leads to the formation of a similar chain arrangement of the tetranuclear complexes 1 and 2.
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  • 90
    ISSN: 1434-1948
    Schlagwort(e): Silicon ; Phosphorus ; Oligophosphides and -phosphanes ; NMR spectra ; X-ray structure analysis ; Ab initio calculations ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The violet THF adduct (tBu3Si)2P3Na(THF)4 (1a) of the triphosphide (tBu3Si)2P3Na (1) is prepared, (i) by protolysis of the tetraphosphide (tBu3Si)2P4Na2 (2) with an equimolar amount of CF3CO2H in THF (transformation of 2 into 1), (ii) by the reaction of tBu3SiNa and the oligophosphane (tBu3SiP3)n in THF (building-down of Pn), and (iii) by the action of tBu3SiNa on PCl3 in THF (building-up of Pn). According to X-ray structural analysis, the SiPPPSi skeleton of the anionic part [tBu3SiPPPSitBu3]- of 1a is W-shaped with two P-P 11/2 bonds; in addition, 1a contains a planar deltoid P3Na backbone with the 4 THF molecules coordinated to Na. The protolysis of 1a leads to cyclotriphosphane (tBu3Si)2P3H (11), and the oxidation of 1a leads to 1,1′-bicyclotriphosphane (tBu3Si)2P3-P3(SitBu3)2 (12) as the main product and bicyclo[3.1.0]hexaphosphane (tBu3Si)4P6 (13) as an isomer of 12. The structures of 11, 12, and 13 as well as the structure of 1a have been unambiguously determined by 31P-NMR studies. Ab initio structure and energy calculations show that the acyclic P3H2- with allylic conjugation and P-P 11/2 bonds is thermodynamically more stable than the cyclic isomer whereas, in contrast, the neutral compound P3H3 prefers the cyclic form. The exceptional downfield shift of the NMR signal of the central phosphorus in 1a is in agreement with DFT NMR calculations for a model compound [H3SiPPPSiH3]Na with P-P 11/2 bonds.
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  • 91
    ISSN: 1434-1948
    Schlagwort(e): Trinuclear triangulo palladium complex ; 2-Hydroxyacetophenone N4-ethylthiosemicarbazone ; Dimethylformamide aggregation ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The X-ray crystal structure of a palladium(II) complex of 2-hydroxyacetophenone N4-ethylthiosemicarbazone (H2Ap4E) shows it to be a triangular,trinuclear complex with bridging thiosemicarbazonato sulfur atoms. This species can be formed from a monomer on dissolution in DMF or directly from Li2PdCl4 and the thiosemicarbazone in methanol-ammonia solution.
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  • 92
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 889-895 
    ISSN: 1434-1948
    Schlagwort(e): Zirconocene ; Metallocene cation ; Isonitrile insertion ; Isonitrile complex ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Hydrozirconation of propyne followed by treatment with propynyllithium yields the (σ-propenyl)(σ-propynyl)zir-conocene complex 11. Its treatment with the organometallic Lewis acid B(C6F5)3 results in transfer of the σ-propynyl group from zirconium to boron followed by insertion of the alkynylborate triple bond into the zirconium carbon bond of the remaining metallaallyl cation to furnish the zirconocene-(μ-hydrocarbyl)borate betaine complex 14. This reacts with three molar equivalents of tert-butyl isocyanide to give 16. Complex 16 contains a five-membered carbocyclic ring, formed by carbon-carbon coupling of the former propenyl and propynyl groups with the C≡N-R reagent, to which a (η2-iminoacyl)(ĸ-tert-butyl isocyanide)zirconocene moiety is attached. Complex 16 was characterized by an X-ray crystal structure analysis.
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  • 93
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 921-926 
    ISSN: 1434-1948
    Schlagwort(e): Aluminium ; Chelates ; Lewis acids ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Sodium nitrite (NaNO2) dissolves readily in THF, when the methylene-bridged dialuminium compound R2Al-CH2-AlR2 [R = CH(SiMe3)2] 1 with two coordinatively unsaturated aluminium atoms is added. Compound 1 reacts as a chelating Lewis acid, and, as shown by a crystal structure deter-mination of the [Na([18]crown-6)(Et2O)]+ derivative 5c, a compound (5) is formed, in which one oxygen atom and the nitrogen atom of the nitrite ion are each coordinated by one aluminium atom to form a five-membered Al2CNO hetero-cycle. The second oxygen atom of the nitrite anion is not affected. Similarly, lithium nitrate (LiNO3) reacts with 1 to yield a THF soluble product (6a). Single crystals were obtain-ed of the [Li(N,N′,N′′-trimethyltriazinane)2]+ derivative 6c, whose structure shows each aluminium atom to be coordinated by one oxygen atom of the nitrate ion to give a six-membered Al2CNO2 heterocycle.
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  • 94
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 957-963 
    ISSN: 1434-1948
    Schlagwort(e): Amino acids ; Bioinorganic chemistry ; Copper ; Luminescence ; Ruthenium ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A series of heterobimetallic complexes [{Ru(bipy)2}m-AA{Cu(phen)(H2O)}](PF6)3 (m-AA = Nω-(4-carbonyl-4′-methyl-2,2′-bipyridyl)-L-α,ω-diamino acid; diamino acid (AA): 1b, L-2,3-diaminopropionic acid; 2b, L-2,4-diaminobutyric acid; 3b, L-ornithine, 4b, L-lysine) has been synthesized and characterized starting from the 2,2′-bipyridineruthenium(II)-substituted amino acids [{Ru(bipy)2}m-AA-αN-tBoc]2+ (αN-tBoc-1a-4a, αN-tBoc = Nα-tert-butoxycarbonyl). The metal centers in 1b-4b are bridged by insulating alkyl chains. Consequently, spectroscopic and electrochemical investi-gations confirmed the absence of any appreciable ground-state coupling between ruthenium(II) and copper(II). However, the luminescence of 1b-4b is significantly quenched compared to that of the parent compounds 1a-4a. Quenching was found to proceed only intramolecularly and to be most efficient in 1b with the shortest alkyl spacer. Equilibrium constants for the formation of 1b-4b were determined from luminescence titrations of the respective ruthenium-substituted amino acid with [Cu(phen)(NO3)2]. The complexes 2b-4b (K = 1.61-2.08 × 107M-1) were found to be significantly more stable than 1b (K = 5.7 × 106M -1). This is explained by a stronger electrostatic repulsion between the two metal centers in the latter compound.
    Materialart: Digitale Medien
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  • 95
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 905-911 
    ISSN: 1434-1948
    Schlagwort(e): Phosphane complexes ; Alkaline earth metal compounds ; Phosphanomethanides ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The reaction of lithium[bis(dimethylphosphanyl)(trimethyl-silyl)methanide] Li[(PMe2)2C(SiMe3)] with BeCl2 gave the homoleptic compound Be[(PMe2)2C(SiMe3)]2 (5) with four beryllium-phosphorus bonds constituting a distorted tetrahedron around the beryllium center. The reaction of MgCl2 with Li[(PMe2)2C(SiMe3)] resulted in the formation of the bis-chelate complex Mg[(PMe2)2C(SiMe3)]2 · 2 THF (7), where the distorted cis-octahedral magnesium center is additionally coordinated by two THF ligands. In the reaction of 7 with an additional equivalent of Li[C(PMe2)2(SiMe3)], THF is released and the magnesate anion {Mg[(PMe2)2C-(SiMe3)]3}- (8) was obtained. This compound is not only the first reported hexacoordinated magnesate, but also the first magnesium compound with six magnesium-phosphorus bonds. With CaCl2 and Li[C(PMe2)2(SiMe3)], a heptacoor-dinated complex Ca[(PMe2)2C(SiMe3)]2 · 3 THF (10) with three coordinating THF ligands was isolated. The complexes were characterized using 9Be{1H}-, 31P{1H}-, 1H-, 13C{1H}-NMR spectroscopy, and elemental analysis and by X-ray diffraction. The neutral compounds are highly soluble in nonpolar solvents.
    Materialart: Digitale Medien
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  • 96
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 941-949 
    ISSN: 1434-1948
    Schlagwort(e): Lithium tetrahydridoborate diethyl ether (1:1) ; Lithium tetrahydridoborate diveron (1:1) ; Lithium tetrahydridoborate dimethoxyethane (1:2) ; Lithium tetrahydridoborate triglyme (1:1) ; Lithium tetrahydridoborate tetrahydrofuran (1:3) ; Lithium tetrahydridoborate 1,3-dioxolane (1:1) ; Hydride-bridge bonding ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: LiBH4 · OEt2 (1) and LiBH4 · O(Me)CMe3 (2) form double-stranded chains in the solid state. While 3 hydrides of the BH4 group in 1 bind to three different Li atoms through Li···H-B interactions, the fourth H atom interacts with three adjacent Li centers. In contrast, in compound 2 there are two single Li···H-B bonds and two doubly bridging hydrogen atoms, the latter again interacting with three lithium centers. Moreover, the arrangements of the ether molecules in 1 and 2 are different. LiBH4 · 2 DME (3) (DME = dimethoxyethane) forms a molecular lattice, in which the BH4- anions are present in Li···H2BH2 bridges. The same structural feature is present in LiBH4 · TG (4) (TG = triglyme = triethylene glycol dimethyl ether), but the TG molecule coordinates to two Li centers through two of its four oxygen atoms in such a manner that a chain structure results. The compound LiBH4 · 3 THF (5) exists as discrete molecules in the lattice. Its BH4- anion is triply bridging to the Li center. In contrast, LiBH4·C3H6O2 (6) (1,3-dioxolane) is polymeric. Due to the presence of two μ22-BH4 groups, a chain of the type ···Li(H2BH2)Li(H2BH2)··· is formed, and the 1,3-dioxolane molecules connect the chains through Li-O coordination to form a three-dimensional array. In spite of the variations in the bonding of the BH4 group to Li centers, the Li atoms are hexacoordinated in 3 to 6 but are heptacoordinated in 1 and 2.
    Materialart: Digitale Medien
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  • 97
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 977-982 
    ISSN: 1434-1948
    Schlagwort(e): Helicates ; Oligobipyridine ligands ; Self-recognition ; NMR titration ; Self-assembly ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Oligobipyridine ligands containing one or two imine bridges were found to form double helicates by treatment with copper(I) or silver(I). The properties of the complexes are similar to those of oxapropylene-bridged oligobipyridines. Titration of a mixture of the bis(bipyridine) and the tris(bipyridine) ligands with silver(I) hexafluorophosphate showed that helicates formed with strict self-recognition.
    Materialart: Digitale Medien
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  • 98
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 983-987 
    ISSN: 1434-1948
    Schlagwort(e): Telluroles ; Neutralization-reionization mass spectrometry ; DFT calculations ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 2,2-Dichloro-1,3-dichalcogena-2-telluroles of sulfur and selenium, C6H4[XTe(Cl)2Y] with X, Y = S, Se, serve as precursors to generate the cation radicals of 1,3-dichalcogena-2-telluroles C6H4[XTeY]+• as well as the corresponding neutral counterparts by means of neutralization-reionization mass spectrometry. These neutral 2-telluroles are intrinsically stable for at least 1 μs in the gas phase. The most abundant fragmentation channel at the neutral and cationic stages is due to loss of atomic tellurium to afford the corresponding benzo-1,2-dichalcogena-cyclobutenes. For the latter, partial isomerization to the related dichalcogena-ortho-quinones is indicated by the mass-spectrometric fragmentation pattern.
    Materialart: Digitale Medien
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  • 99
    ISSN: 1434-1948
    Schlagwort(e): Ab initio calculations ; π interactions ; Agostic interactions ; Electronic structure ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Rotational barriers and π conjugation effects have been studied in H2X-YR systems (X = Al, B; Y = O, S; R = H, CH3) by means of ab initio calculations at the MP4/6-311G**//MP2/6-311G** level. In non-substituted systems H2X-YH, it is shown that the rotational barrier depends on three factors: (i) π conjugation strength between the X vacant p orbital and the Y p-lone pair; (ii) the opening ability of the Y-valence angle and (iii) a possible direct interaction between X and the Y hydrogen substituent. The conjugation stabilization has been estimated through Valence Bond calculations and is found to decrease in the order BO (22.6 kcal/mol), BS (16.6 kcal/mol), AlO (10.2 kcal/mol), and AlS (8.1 kcal/mol). Study of the methylated systems confirm the results found in unsubstituted species. The most important feature is the location of a deconjugated secondary minimum for H2B-SCH3 species. An acute B-S-C angle (69.6°) is found, thus evidencing a direct H···B agostic interaction with a four-membered (BSCH) heterocycle. To further evidence our analysis, additional calculations have been performed on carbocationic species H2C+-YR (Y = O, S; R = H, CH3) for which the H2C+ moiety is a strong π acceptor. As expected, the C+-O and C+-S conjugation are strong (about 60 kcal/mol). Only two minima have been located for the H2C+-OCH3 species. In the sulfur case, the Potential Energy Surface (PES) is more complicated and six stationary points have been characterized. A strong agostic interaction is found for a secondary deconjugated minimum for which an hydrogen symmetrically bridges the two carbon atoms. A schematic energy profile connecting the various extrema is given for this cationic species.
    Materialart: Digitale Medien
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  • 100
    ISSN: 1434-1948
    Schlagwort(e): Cyclopentadienes ; Magnesium ; Metalations ; NMR spectroscopy ; Sandwich complexes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The reaction of n/sec-dibutyl magnesium with 6-methyl-6-phenyl- and 6,6-dicyclopropylfulvene gives the β-hydride transfer products 1,1′-bis(1-phenylethyl)- and 1,1′-bis-(dicyclopropylmethyl)magnesocene, respectively. The latter crystallizes in the eclipsed conformation, whereas the first one shows an anti conformation in the solid state. Dimethyl-magnesium deprotonates 6-methyl-6-phenylfulvene with formation of 1,1′-bis(1-phenylethen-1-yl)magnesocene, which decomposes upon isolation. The deprotonation of 6,6-dicyclopropylfulvene with MgMe2 in thf solution yields [bis(tetrahydrofuran-O)][iro{cyclopropane-1,2′(1′-η5-cyclopentadienyl-1′,3′,3′-tricyclopropyl-1′,2′,3′,3a′-tetrahydropentalene)}-3a′-6′-η2-enyl]magnesium. In the absence of β-hydrogen atoms at the organometallic reagent as well as at the fulvene the addition reaction is the only possible reaction pathway. Thus, one Mg-C bond of MgMe2 adds to tetramethylfulvene to give quantitatively dimeric methylmagnesium ethyltetramethylcyclopentadienide. The bridging methyl groups are sterically shielded against further attack of the fulvene.
    Materialart: Digitale Medien
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