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  • 1990-1994  (832)
  • 1975-1979
  • 1890-1899
  • 1991  (832)
  • Inorganic Chemistry  (773)
  • Electron microscopy
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  • 1990-1994  (832)
  • 1975-1979
  • 1890-1899
Year
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Lasers in medical science 6 (1991), S. 363-366 
    ISSN: 1435-604X
    Keywords: Laser vascular welding ; Tissue fusion ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine , Physics , Technology
    Notes: Abstract The central problem in microsurgery is the reconstruction of small vessels. The long operating time, foreign body granuloma formation around the suture material as well as aneurysmal alterations of the vessel wall after conventional suture technique make the search for alternatives indispensable. Some of these disadvantages can be avoided as demonstrated by our animal experiments and histological examinations in laser-assisted anastomosing. The aim of this study is to show these aspects in connection with laser application and compare them with conventional suture techniques.
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  • 2
    ISSN: 1572-8773
    Keywords: Ferritin ; Thalassemia ; Ferrihydrite ; Crystallinity ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Summary The cores of ferritins isolated from different organs of human subjects withβ-thalassemia/hemoglobin E (β-thal/HbE) disease have different size distributions and crystallinities depending on the source organ. These patients have not been treated by hypertransfusion regimen or iron chelation therapy.β-Thal/HbE spleens and livers yield ferritin cores which are less crystalline than those isolated from normal spleens and livers, reflecting the more rapid deposition of iron in the diseased state. Ferritins isolated from the hearts and pancreases ofβ-thal/HbE subjects were found to have larger, more crystalline cores than those from theβ-thal/HbE livers and spleens, possibly as a consequence of the role of the heart and pancreas as long-term iron deposition sites in this iron overload pathology.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1432-2307
    Keywords: Neurenteric cyst ; Enterogenous cyst ; Cilia ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Claw-like projections and related structures on cilium tips in neurenteric cyst epithelium are described. The ciliary claws are about 20 nm in length and just beneath them four parallel electron-dense areas or lines are discernible. Similar structures were also observed in another case of neurenteric cyst. These structures are very similar to those reported previously, and it is suggested that they are commonly present in various ciliated epithelia in Man.
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  • 4
    ISSN: 1432-2307
    Keywords: Alveolar soft-part sarcoma ; Uterus ; Myometrium ; Immunocytochemistry ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary A case of alveolar soft-part sarcoma located in the uterine corpus is reported. It was an incidental finding in the hysterectomy specimen of a 40-year-old woman. Light and electron microscopic examination revealed periodic-acid-Schiff-positive, diastase-resistant, membrane-bound cytoplasmic granules and crystalloids. Tumour cells expressed immunoreactivity with vimentin, desmin, cytokeratins, NK1/C3 and HMB-45 antibodies. Four years postoperatively, the patient is still alive without evidence of disease. Differential diagnoses, immunocytochemistry and clinical management of uterine alveolar soft-part sarcoma are discussed and the literature reviewed.
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  • 5
    ISSN: 1432-2307
    Keywords: Transgenic mice ; Glucagonomas ; Immunohistochemistry ; Electron microscopy ; Radioimmunoassay
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Pancreatic tumours of transgenic mice carrying a glucagon-promoted simian virus 40 (SV40) T antigen oncogene have been analysed by histological, histochemical, ultrastructural and radioimmunological means. Seven transgenic mice were examined revealing dysplastic and neoplastic lesions in the endocrine pancreas. Four tumours were identified, one of which metastasized to periadrenal spaces and paravertebral lymph nodes. Benign tumours were composed of argyrophilic, endocrine cells reactive to a range of antibodies against neuroendocrine markers (neuron-specific enolase, protein gene product 9.5, chromogranin A, synaptophysin and protein 7B2) and different fragments of the proglucagon molecule (glucagon, glicentin, glucagon-like polypeptides 1 and 2). A few tumour cells expressed pancreatic polypeptide, somatostatin or insulin. Conventional ultrastructural analysis and immunogold labelling revealed typical glucagon-immunoreactive alpha granules which co-stored glicentin and glucagon-like polypeptides 1 and 2. The malignant primary tumour and its metastases were composed mainly of cells which did not show immunoreactivity for neuroendocrine markers or peptides. Atypical, glucagon-immunogold labelled granules were detected at electron microscopy in differentiated tumour cells and C-type retroviral particles in the largest tumour population of degranulated cells. The transgene-encoded oncoprotein SV40 large T-antigen was detected in the nuclei of well-differentiated tumour cells and in alpha cells of some dysplastic islets. All tumour-bearing mice showed high levels of circulating glucagon-like immunoreactivity. Transgenic mice harbouring the glucagon-promoted SV40 T antigen oncogene may provide a model for human glucagonoma.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Virchows Archiv 418 (1991), S. 387-400 
    ISSN: 1432-2307
    Keywords: Submandibular gland ; Tissue culture ; Electron microscopy ; Proliferating cells
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Fragments of rat submandibular gland (organoids) which maintained the topological organization of the parent tissue were cultured in a three-dimensional collagen gel matrix for up to 30 days. At 48 h, vigorous peripheral outgrowth had occurred around each organoid. This was accompanied by central necrosis and the bridging of adjacent organoids. By day 5, large cyst-like spaces occupied the centre of many organoids. Bromodeoxyuridine labelling indicated that a considerable proportion of the lining cells were proliferating. Organoid growth peaked at between 5 and 10 days. Thereafter, the number of viable colonies and proliferating cells declined. Addition of isoproterenol after 24 h culture resulted in marked morphological alterations, with earlier and more prolific outgrowth and a greater tendency for organoids to flatten and grow out over the surface of the gel with squamous differentiation. Ultrastructurally, nuclear and cytoplasmic features of isoproterenol-treated and untreated cultures were similar. The secretory granules and extensive rough endoplasmic reticulum of terminal tubule cells, evident in organoids immediately after isolation, were infrequent after 24 h and absent by 48 h. Similar alterations occurred in the few acinar cells, so by 5 days the cultures were composed entirely of a uniform population of primitive, dedifferentiated cells. Further uses of this culture systems will include the study of diseases and disorders of the salivary glands as well as normal growth and differentiation pathways.
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  • 7
    ISSN: 1432-2307
    Keywords: Corticopontine tract degeneration ; Olivopontocerebellar atrophy ; Electron microscopy ; Morphometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Nine cases of sporadic olivopontocerebellar atrophy [Déjérine-Thomas type, multisystemic atrophy (MSA)] were examined histologically and electron microscopically with special reference to the corticopontine tract. Five of nine cases showed degeneration of the myelinated nerve fibres in this tract. More severe degeneration of the fibres at the level of the pons than the crus cerebri indicates that degeneration of the fibres may start axodistally. Electron microscopy revealed selective involvement of large fibres in olivopontocerebellar atrophy, in contrast to unselective axonal atrophy in dentatorubropallidoluysian atrophy. The problem whether the degeneration of the tract is primary or secondary due to the loss of the pontine neurons remains open. We believe the former to be most likely. Degeneration of the corticopontine fibres should be added to the list of neuropathological findings in sporadic olivopontocerebellar atrophy.
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  • 8
    ISSN: 1432-2307
    Keywords: Large cell anaplastic lymphoma ; Electron microscopy ; Immunophenotyping
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Eleven cases of large cell anaplastic lymphoma (T typen=5, B typen=4, 0 typen=2) were investigated using electron microscopy and immunophenotyping on formalin-fixed paraffin sections and frozen sections of fresh tissue, to determine whether morphological criteria exist for the discrimination of T, B, and 0 phenotypes. Tumour cell lineage could not be established from ultrastructural features. On paraffin material monoclonal B-cell markers Ki-B5 and L-26 served as reliable tools for recognizing the B phenotype of large cell anaplastic lymphomas (previously determined on fresh material), whereas monoclonal antibodies MT1 (CD43) and UCHL1 (CD45RO) were of limited value in lineage determination.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 1432-2307
    Keywords: Membranous lipodystrophy ; Nasu-Hakola disease ; Lipid and glyconconjugate ; Cytochemistry ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary In order to assess the lipid and glycoconjugate characteristics of membranous lipodystrophy, a 29-year-old male with this disease was studied using an ultrastructural cytochemical approach. The specific membranocystic lesions of the disease are composed of cystic spaces and the lining membranes. The membranes were observed to have a two-layered character: microtubular structures in the layer adjacent to the spaces and a central amorphous zone. Lipid staining and the lipase digestion test revealed triglycerides localized not only in the cystic spaces but also in the microtubular structures. Lectin histochemical examintion of carbohydrate components demonstrated thatMaclura pomifera agglutinin bound strongly to the membranes, whileGriffonia simplicifolia I,G. simplicifolia II,Concanavalia ensiformis andTriticum vulgaris agglutinin reacted weakly. Our results indicate the presence of triglycerides and carbohydrates with mainlyα-D-galactose residues in the distinctive membranocystic lesions, in particular in the microtubular structures.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Urological research 19 (1991), S. 353-356 
    ISSN: 1434-0879
    Keywords: Bladder cancer ; Electron microscopy ; Photodynamic therapy ; Photosan ; Phototoxicity ; Tumor selectivity ; Video fluorescence microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The uptake of photosan and the intracellular sites of photoradiation-induced damage were investigated in vitro in bladder carcinoma cells and in normal bladder cells. Cells were examined by phase contrast, fluorescence and electron microscopy. The concentration of photosan, measured in μg/106 cells, showed a good correlation to the incubation time. At all incubation times, control cells showed a lower uptake when compared with tumor cells. Following photodynamic therapy (PDT), phase-contrast microscopy revealed marked changes in tumor cells, whereas only minor effects could be detected at the cell membrane of the control cells. Following PDT, most of the investigated cells showed onanges of the mitochondria and cytoplasma. These changes consisted of dissolution of the cristae, predominantly in the central part of the mitochondria. Twenty-four hours after PDT the shape of the mitochondria had changed markedly and the cristae were found to be completely destroyed. Moreover, the cystoplasma showed numerous vacuoles, and the number of mitochondria was decreased compared to non-treated cells.
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  • 11
    ISSN: 1432-0533
    Keywords: Amyotrophic lateral sclerosis ; Bunina body ; Clarke's nucleus ; Onuf's nucleus ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary We report the autopsy findings of an 81-year-old patient with short-course sporadic amyotrophic lateral sclerosis lasting approximately 5 months. Pathological findings were probably very early. Light microscopy showed abundant eosinophilic Bunina type inclusions widely distributed not only in the motor neurons of the spinal cord and brain stem but also in neurons of the Onuf's and Clarke's nuclei. Fine structural study revealed that the inclusions seen in the Clarke's nuclei were identical to Bunina bodies observed in anterior horn cells. A direct connection between axonal swelling and perikaryon was often seen in the facial and hypoglossal nuclei and in the spinal cord. Ubiquitin-positive Lewy body-like inclusions and central chromatolysis-like changes were also found in the anterior horn cells.
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  • 12
    ISSN: 1432-0568
    Keywords: Pyramidal neurons ; Motor cortex ; Synapses ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The morphological characteristics and distribution of synapses on a small pyramidal neuron in layer III of the cat motor cortex have been studied by combining intracellular HRP staining and electron microscopic examination. The stained neuron showed spiny apical and basal dendritic profiles under the light microscope, and exhibited the morphological features of a pyramidal neuron. Ultrastructural analysis indicated that about 80% of the presynaptic terminals formed asymmetrical synapses with spines of distal apical and basal dendrites. On proximal apical dendrites, 64% of the synapses were found to make contact with spines, and 16.7% of the synapses were of symmetrical type and formed with dendritic shafts. Two types of terminal could be identified on the soma; they were alternately located and established symmetrical and asymmetrical synaptic contacts respectively. Possible functional implications are discussed.
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 184 (1991), S. 337-343 
    ISSN: 1432-0568
    Keywords: Costo-uterine muscle ; Innervation ; Fluorescence histochemistry ; Electron microscopy ; Morphometry ; Rat (Wistar)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The costo-uterine muscle provides a skeletal attachment to the longitudinal myometrial layer of the uterine horn. In this study we investigated the possibility that the muscle is responsive to sex steroid hormones. In rats of 4 weeks of age, injected with oestradiol for 5 days, the cross-sectional area of nucleated muscle cell profiles was significantly increased. A significant increase in the sectional area of muscle cells was also demonstrated in the costo-uterine muscle of 16-week-old rats, on the 20th day of gestation, compared with nonpregnant rats in dioestrus and of the same age. In oestrogen-treated and in pregnant rats, there was also an increase in muscle cell length. As to the innervation of the costo-uterine muscle, in glyoxylic acid-treated whole-mount and cryostat preparations, we found not only perivascular nerve fibres, but also a few nerve fibres innervating the muscle proper. The pattern of innervation was unchanged after oestrogen treatment and during pregnancy. In the electron microscope, axonal varicosities were observed in the proximity of both vascular and non-vascular muscle cells.
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  • 14
    ISSN: 1432-0568
    Keywords: Spinal nerves ; Dorsal column nuclei ; Nerve degeneration ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Ultrastructural changes in the gracile nucleus of the rat have been examined after peripheral nerve injury. The sciatic nerve of adult rats was transected at mid-thigh level, and after survival times ranging from 1 day to 32 weeks sections from the gracile nucleus were prepared for electron microscopic examination. Unoperated animals served as controls. Atypical profiles were regularly observed in the experimental cases at post-operative survival times from 3 days up to 32 weeks. It was sometimes not possible to classify these as pre-terminal axons or terminals, because synaptic contacts could not be identified. The two most common changes throughout the entire post-operative period were greatly expanded myelinated axons, or unmyelinated profiles containing numerous mitochondria, osmiophilic dense bodies and vacuoles. Atypical profiles were occasionally observed in unoperated control animals. The results clearly show that various types of degenerative changes occur in the gracile nucleus after peripheral nerve injury. These changes differ markedly from previously described transganglionic changes in other systems. It cannot be excluded that some of the changes reflect growth-related reactions, although the typical features of axon regeneration could not be found.
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  • 15
    ISSN: 1432-0533
    Keywords: Hirano bodies ; Unit lamellae ; Alzheimer's disease ; Rapid-freeze, deep-etch and replica ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary To clarify the yet controversial fine structure of Hirano bodies, we made three-dimensional observations of the tissues from the right hippocampus obtained at autopsy of elderly patients by the quick-freeze, deep-etch and replica method. The basic structure of Hirano bodies was a unit lamella, a closely attached pair of sheets composed of parallel-running smooth filaments, 10 to 12 nm in diameter with 12-nm interspaces. In the unit lamella, filaments from each of the overlapping sheets crossed obliquely at acute or obtuse angles to form lattice-like meshworks. The unit lamellae were arranged in a folded, waved or concentric manner, and connected or supported by cross-linking filaments of the same width. The distance between these unit lamellae was about 50 nm. Occasionally the sheets were separated or fused making layers of one to three sheets. At the periphery of the bodies parallel filaments were dispersed into individual filaments of similar size or directly attached to the cytoplasmic membrane.
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  • 16
    ISSN: 1432-0533
    Keywords: Amyotrophic lateral sclerosis ; Bunina body ; Onuf's nucleus ; Ubiquitin ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary We examined the Onufrowicz nucleus (Onuf's nucleus) of ten sporadic amyotrophic lateral sclerosis (ALS) patients with light and electron microscopic and immunohistochemical methods. Neurons in the Onuf's nucleus of ALS patients were better preserved than those in anterior horn cells. However, some showed morphological changes in the nucleus, namely, central chromatolytic changes, Bunina bodies, ubiquitin-positive filaments and spheroids. The Onuf's neurons of ALS patients showed more argentophilia than those of non-ALS patients. Electron microscopic observations revealed that neurofilaments were relatively more numerous in the Onuf's neurons of ALS patients. Bunina bodies and degenerated neurites were also seen in the Onuf's nucleus. In conclusion, the Onuf's nucleus in sporadic ALS patients showed some morphological changes similar to those noted in anterior horn cells.
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  • 17
    ISSN: 1432-0533
    Keywords: Alzheimer-type dementia ; Senile plaques ; Amyloid β/A4 protein ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary We compared the ultrastructure between diffuse and primitive plaques in the brains of senile dementia, using pairs of routine electron microscopic ultrathin sections and adjacent semithin sections, which were immunolabeled for β protein. In the frontal cortex, amyloid fibrils were rarely seen in a minority of diffuse plaques, suggesting an initial stage of the diffuse plaques. A majority of the diffuse plaques had electrondense material and/or amyloid fibrils between cell processes in part of but not the entire β/A4-immunoreactive areas. Small degenerating neurites were often seen with apparent amyloid fibrils in the diffuse plaques, and these were considered to be in an advanced stage. The size and number of degenerating neurites were proportional to the amount of amyloid. Bundles of amyloid fibrils were occasionally surrounded by astroglial processes forming gap junctions. Neurons were found within some diffuse plaques, but capillaries were rarely seen. In contrast, in the temporal cortex, the diffuse plaques were smaller, and even these small ones had apparent amyloid fibrils. The amount of amyloid correlated significantly with plaque size in the temporal cortices, but not in the frontal cortices. Most of the diffuse plaques of the frontal lobe remained as advanced diffuse plaques (apparent amyloid with occasional astroglia and some degenerating neurites) for a long time, and did not transformed into primitive plaques, whereas the temporal diffuse plaques tended to transform into primitive plaques.
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  • 18
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 183 (1991), S. 105-110 
    ISSN: 1432-0568
    Keywords: Initial axon segment ; Microtubules ; Cross-bridges ; Golgi apparatus ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The initial axon segments and the cell bodies of Purkinje cells were examined in electron microscopic serial sections and toluidine blue semithin sections of goldfish cerebellum. We observed two characteristic cytoplasmic features different from those of other vertebrate neurons. 1. The areas of Nissl substance and Golgi apparatus are sharply divided in the periphery and center of the cytoplasm. 2. Microtubules fasciculated by cross-bridges in the axon hillock and initial axon segment remain bundled in the perikaryon, pass near the eccentric nucleus, and enter into the Golgi area of the central cytoplasm, where they are surrounded by mitochondria. We suggest that the intracellular fasciculated microtubules may establish a prepared pathway for fast anterograde and retrograde transport to and from the Golgi area of the cell body.
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  • 19
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 183 (1991), S. 475-481 
    ISSN: 1432-0568
    Keywords: Elastic-like tissue ; Elasmobranch ; Glomerular capillary wall ; Kidney ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Elastic-like tissue composed of tubular microfibrils continuous with, and disappearing into, amorphous material is present in the connective tissue space of the glomerular capillary wall of the river ray (freshwater elasmobranch) kidney. The amorphous material is stained by tannic acid but not by uranyl acetate. Structures with similar morphology and staining characteristics are also found in the subendothelial connective tissue layer of renal arteries in this species. Comparative ultrastructural observations of kidneys from marine rays show elastic-like tissue in the arterial wall but not in the glomerular vessels.
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  • 20
    ISSN: 1432-0533
    Keywords: Primitive neuroectodermal tumor ; Cytokeratin immunohistochemistry ; Double labelling ; Electron microscopy ; Immunoblotting
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Eleven primitive neuroectodermal tumor (PNET) biopsies from infants under the age of 3 years were studied for the presence of various differentiation markers for neuroectodermal stem cells. Special emphasis was placed on the expression of cytokeratin proteins. The tumor cells expressed different cytokeratin proteins (CK8, CK13, CK18, CK19, KL1, AE1/AE3, MNF16) in 3 of 11 cases. These cases were furthermore characterized by a strong expression of glial fibrillary acidic protein, S-100 protein and vimentin. Vimentin and cytokeratin proteins were co-expressed; cross-reactivity between these two intermediate filaments could be excluded by immunoblotting. It is noteworthy that the three positive tumors were all from infants in their 1st year. We assume that PNETs in early infancy are characterized by a particularly wide range of differentiation patterns. The presence of cytokeratin proteins in these cases seems to be associated with the expression of vimentin and must be regarded as an indicator of an early developmental stage of the tumor cells.
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  • 21
    Electronic Resource
    Electronic Resource
    Springer
    Archives of dermatological research 283 (1991), S. 211-218 
    ISSN: 1432-069X
    Keywords: Ichthyosis ; Histopathology ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary In the hetereogeneous group of recessive congenital ichthyoses the disorder of desquamation seems to be a basic problem. Desquamation is strongly dependent on the normal lipid metabolism of the keratinocytes. We describe a group of patients who have a typical clinical picture of large scale ichthyosis and cholesterol clefts in the thickened corneal layer, evidencing a disturbance of the lipid metabolism of the skin. The corneocytes also show a thin or absent cornified envelope, which could indicate a disturbance of protein synthesis. These patients have a severe ichthyosis, but good general health and no associated symptoms. This disorder has recently been named ‘ichthyosis congenita type II’ by the Heidelberg group on the basis of electron microscopic findings. According to the present examination this group corresponds clinically to the currently used diagnosis ‘lamellar ichthyosis’.
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  • 22
    Electronic Resource
    Electronic Resource
    Springer
    Archives of dermatological research 283 (1991), S. 377-381 
    ISSN: 1432-069X
    Keywords: Savinase ; Proteolytic enzyme ; Human plantar skin ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The effect of the proteolytic enzyme savinase on human plantar skin in vitro was examined by light and electron microscopy to elucidate the morphological involvement of activated savinase in human epidermis. Light microscopic examination of incubated skin fragments demonstrated that the histological changes produced by savinase in the epidermis, including the stratum corneum, depended upon pH value, enzyme concentration and incubation time. After incubation in 0.1% savinase in phosphate buffer, pH 8.0, for 2 h at 35
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  • 23
    ISSN: 1432-1106
    Keywords: Corticothalamic projection ; Somatosensory system ; Barrel ; Phaseolus vulgaris ; leucoagglutinin ; Electron microscopy ; Mouse ; Synaptic glomerulus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary By means of tracing with the lectin Phaseolusvulgaris leucoagglutinin (PHA-L), we examined in the thalamus of the mouse, the axon terminals of fibers originating in the barrel cortex. Vibratome sections of the brain were subjected to PHA-L immunocytochemistry and processed for light and electron microscopy. We observed small (0.5–0.8 μm in diameter) varicosities of labeled fibers in the nucleus ventrobasalis (VB) and the nucleus posterior (PO) as well as labeled giant terminals (3–5 μm in diameter) in PO. The analysis involved examination of serial sections and computer-aided reconstruction of several terminals. The small varicosities in VB appear to be small axon terminals forming distinct asymmetric synapses with small dendritic profiles. Some labeled terminals are apposed to, but not synaptically related with, the cell bodies of neurons in VB that are retrogradely labeled with PHA-L. The small varicosities seen with the light microscope in PO are terminals forming asymmetric synapses with dendritic shafts. The giant terminals in PO appear as large, vesicle-filled profiles forming part of synaptic glomeruli, i.e. complexes of one corticothalamic terminal engulfing several excrescences of a single dendrite. A giant terminal forms several asymmetric synapses (about 8) with these excrescences, as well as numerous (up to 15) puncta adhaerentia. The glomeruli are enveloped in glial lamellae, and they are often found at the bifurcations of primary dendritic segments. We suggest that the small terminals in VB are in the service of feedback signalling from the barrel cortex to its principal thalamic relay nucleus; the functional importance of this projection may reside in increased spatio-temporal discrimination. We interpret the giant terminals in PO as elements serving feed-forward processing, allowing the barrel cortex to influence, via PO, parts of the motor pathway modulating the animal's ongoing behavior.
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  • 24
    ISSN: 1432-1106
    Keywords: Serotonin ; Tyrosine hydroxylase ; Electron microscopy ; Thalamus ; Cat ; Monkey
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Immunocytochemical methods have been combined with serial thin section analysis to study the synaptic organization of serotonin (5-HT) and tyrosine hydroxylase (TH) immunoreactive terminals in the ventral posterior nucleus of the cat and monkey thalamus. One hundred 5-HT immunoreactive terminals from the cat and approximately forty 5-HT and TH immunoreactive terminals from the monkey were selected for analysis in serial thin sections. Only 7–10% of the immunoreactive terminals could be revealed to form conventional synaptic contacts. Most of these could be identified as the asymmetrical type. Dendritic shafts belonging to relay neurons were the major targets of these monoamine immunoreactive terminals. The remainder made intimate membrane associations with relay cell dendrites and somata or with presynaptic dendrites of interneurons, but no overt membrane specializations could be detected. The present results suggest that the modulation of thalamocortical relay function by brainstem monoamine pathways in the somatosensory thalamus may occur by release of transmitters at atypical contact sites.
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  • 25
    ISSN: 1432-0738
    Keywords: Bis (tributyltin) oxide ; Corneal edema ; Electron microscopy ; X-ray microanalysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Comeal edema induced by bis (tributyltin) oxide (TBTO) was studied with an electron microscope and the accumulation sites of tin were determined with an X-ray microanalyzer. Male Wistar rats received an intramuscular injection of 0.5 ml/kg TBTO. After time intervals of 2,4, 6, 8, 10, 12 h after injection, corneas were isolated and provided for electron microscopy. Corneas from untreated rats served as controls. Marked swelling of mitochondria in the corneal endothelial cells occurred at 4 h after TBTO injection. The corneal edema appeared in the endothelial layer and the stroma at 6 h after injection. By X-ray microanalysis, Sn peaks were obtained from swollen mitochondria in the endothelial cells. At 12 h after TBTO injection, edematous swelling of the corneal tissue became more advanced. These results indicated that parenterally administered TBTO accumulated in the mitochondria of corneal endothelial cells. The direct toxic effects of TBTO on the mitochondria might cause the interference with active pump function of endothelial cells and induced the corneal edema.
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  • 26
    ISSN: 1432-0738
    Keywords: αNi3S2 ; βNiS ; Rat lymphocytes ; Electron microscopy ; Energy dispersive spectrometry ; Sulfur phosphorus shift ; Biological transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The uptake, the biological transformation and the interaction with cellular constituents of αNi3S2 and βNiS have been studied in vitro and in vivo on rat lymphocytes. βNiS crystals are phagocytized in vitro and no structural degradation is observed within the first 3 days of exposure. Energy dispersive spectrometry (EDS) reveals a slight dissolution characterized by the loss of sulfur. αNi3S2 is degraded in the extracellular space to minute particles (50–100 nm) covering the cell membrane. Smaller intracellular particles (10–30 nm) are found selectively bound to mitochondria, endoplasmic reticulum, Golgi vesicles, nuclear membranes, and the euchromatinic part of nuclei. EDS analyses reveal that the particles bound to cell membranes and euchromatin no longer contain sulfur but phosphorus and nickel as inorganic compounds. This observation suggests the formation of a Ni/P complex with the phosphate groups either of membranous phospholipids or of nuclear RNA or DNA. A similar uptake and transformation process of αNi3S2 is observed on lymphocytes after in vivo incubation. This leads us to consider lymphocytes as target cells, as compared with other cell types where the αNi3S2 uptake occurs only partially. The present findings show a difference of uptake and biological transformation between αNi3S2 and βNiS. The identical results obtained after in vitro and in vivo bioassays enhance the in vitro experiments, at least for this cell type.
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  • 27
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    Machine vision and applications 4 (1991), S. 271-285 
    ISSN: 1432-1769
    Keywords: Electron microscopy ; three-dimensional vision ; surface reconstruction ; stereo ; shape from shading ; dynamic programming
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science
    Notes: Abstract The computational reconstruction of surface topographies from scanning electron microscope (SEM) images has been extensively investigated in the past, but fundamental image processing problems still exist. Since conventional approaches adapted from general-purpose image processing have not sufficiently met the requirements in terms of resolution and reliability, we have explored combining different methods to obtain better results. This paper presents a least-squares combination of conventional stereoscopy with “shape from shading” and a way of obtaining self-consistent surface profiles from stereoscopy and “stereo-intrinsic shape from shading” using dynamic programming techniques. Results are presented showing how this combined analysis of multi-sensorial data yields improvements of the reconstructed surface topography that cannot be obtained from individual sensor signals alone.
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  • 28
    ISSN: 1432-072X
    Keywords: Soluble NAD-dependent hydrogenase ; Alcaligenes eutrophus ; Nocardia opaca ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The soluble NAD-dependent hydrogenase (hydrogen-NAD oxidoreductase, EC 1.12.1.2), consisting of four non-identical subunits, was isolated from Alcaligenes eutrophus H16 and from Nocardia opaca 1b and analyzed by a HPLC gel permeation technique and electron microscopy. The tetrameric enzyme particles from both origins, as determined from negatively stained electron microscopic samples, were found to be elongated and very similar in shape and size. The A. eutrophus enzyme was measured in more detail. It exhibited dimensions of 12.7 nm by 5.5 nm (axial ratio 2.3:1). Dissociation into smaller particles and unspecific aggregation combined with partial inactivation were observed in the presence of the inhibitor NADH. Kept in buffer without added nickel, the enzyme was partially dissociated. Reassociation of tetramers without restored enzyme activity was achieved by addition of 0.5 mM NiCl2. A working model for the structural organization of the tetrameric enzyme particle is presented.
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  • 29
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    Child's nervous system 7 (1991), S. 442-447 
    ISSN: 1433-0350
    Keywords: Acetazolamide ; Carbonic anhydrase activity ; Choroid plexus ; Electron microscopy ; Serotonin ; Tetrabenazine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The carbonic anhydrase (CA) activities in the choroid plexus of dogs were investigated by electron microscopy, and the effects of 5-hydroxytryptophan (5-HTP) on them were examined to elucidate the participation of serotonin in the production of cerebrospinal fluid. The reaction products yielded by the method employed proved to be CA activity by elimination tests using acetazolamide (Diamox). Following administration of 5-HTP, the CA activities fell to 43.3% of the control value, that is, approximately 56% of the CA activities in the choroid plexus were affected by serotonin. When tetrabenazine (TBZ) was administered, the CA activities in the choroid plexus decreased to 22.4% of the control value. These results suggest that the CA activity in the choroid plexus is remarkably suppressed when nervous control of the choroid plexus is disturbed by the administration of a monoamine denervator such as TBZ. The present data indicate that the serotonergic inhibitory effect on the CA activity in the choroid plexus may be less predominant than that of TBZ and acetazolamide.
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  • 30
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    Cell & tissue research 265 (1991), S. 517-525 
    ISSN: 1432-0878
    Keywords: Spermiogenesis ; Spermatids ; DNA ; Immunocytochemistry ; Electron microscopy ; Bovine ; Mouse ; Rabbit
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary DNA distribution in mouse, rabbit and bull spermatids was analyzed by electron microscopy, after using a Feulgen-like HCl-osmium ammine procedure, and after immunocytochemistry with anti-DNA antibodies. In addition, nucleic acids were visualized with the intercalating dye ethidium bromide and phosphotungstic acid. The parts of DNA displaying a beta helix configuration (possibly A-T rich parts) were identified by epifluorescence microscopy after staining with Hoechst 33258. In all 3 species, young spermatid nuclei were seen to have large areas poor in DNA, as well as DNA-rich areas, which were mostly concentrated into a peripheral layer close to the acrosome and into one or several masses, displaying species-specific locations. These DNA-rich areas were stained with Hoechst 33258. Elongating spermatid nuclei contained homogeneously distributed DNA, and this was evident following both immunocytochemistry and nucleic acid histochemistry in all 3 species. However, the distribution appeared more heterogeneous after the Feulgen-like procedure, and was accompanied by a disappearance of Hoechst-fluorescence. In fully elongated spermatids, all nuclear areas stained with Hoechst 33258, while the 3 other techniques labeled either all or species-specific parts of the condensed chromatin. The reasons for these variable reactions are discussed in terms of technique specificities, DNA configuration and nucleoprotein moiety replacements.
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  • 31
    ISSN: 1432-0878
    Keywords: Calbindin ; Neurohypophysis ; Development, ontogenetic ; Immunohistochemistry ; In-situ hybridization ; Electron microscopy ; Rat (Wistar)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Spot 35 protein is a Ca-binding protein originating from the rat cerebellum; it is now referred to spot 35-calbindin. This protein is expressed in immature pituicytes of the neurohypophyseal anlage in the E11–E18 rat embryo. The gene expression of spot 35-calbindin was detected by in-situ hybridization analysis only at stage E11–E12. Profiles of spot 35-positive nerve fibers of a neurosecretory nature were found in anlage at stage E16. At this stage, some immature pituicytes are partially immunopositive for spot 35-calbindin only in their peripheral cytoplasm; others are immunonegative. At birth and thereafter through adulthood, abundant nerve fibers are the sole structures immunoreactive for spot 35-calbindin; all the pituicytes are immunonegative, resulting in a light-microscopic appearance of numerous immunonegative round profiles, corresponding to pituicytes, and capillaries embedded in the granularly immunostained neurohypophysis. The present findings suggest that, during specific embryonic stages, immature pituicytes exert some as yet unidentified roles related to Ca-mediated functions involving the expression of spot 35-calbindin.
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  • 32
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    Cell & tissue research 266 (1991), S. 563-578 
    ISSN: 1432-0878
    Keywords: Xenografted human carcinomas ; Basal lamina ; Development, following heterotransplantation ; Electron microscopy ; Immunofluorescence microscopy ; Man ; Mouse (NMRI, nu/nu)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The development of the basal lamina (BL), the key structure of the basement membrane (BM), was investigated in three xenografted human carcinomas of the sigmoid colon (CA 1), the lung (L 261), and the hypopharynx (H-Stg 1) following heterotransplantation to athymic mice. The study involved the use of electron microscopy and indirect immunofluorescence techniques employing highly specific antibodies against the intrinsic BL components, heparan sulfate proteoglycan, laminin and type-IV collagen. Following transplantation, the extracellular matrix material of the transplanted tumors decomposed and was phagocytozed by invading macrophages within 1 to 2 days. During this stage, no specific binding of the applied antibodies to BL components could be detected within the xenografts. Following the ingrowth of host-derived connective tissue between days 2 to 6, small fluorescence-positive granules appeared within the cytoplasm and around those tumor cells that were located close to the invaded strands of connective tissue. Ultrastructurally, typical secretory granules were detectable in the cytoplasm of many xenografted carcinoma cells. Thereafter, a tannic acid-positive, patchy material appeared in the extracellular space of CA 1 and L 261 and aggregated to form small fragments of a discontinuous BL. In the H-Stg 1 xenografts, this material assembled to form continuous mono-, bi- and multilayered structures. Large amounts of excess BL material remained accumulated in the L 261 and H-Stg 1 xenografts until the end of the observation period (day 24). These findings reveal that discontinuities of the BL occur independent of the active invasion processes of tumor cells, since xenografted human carcinomas neither grow invasively nor metastasize in nude mice. Moreover, they confirm that these discontinuities are not caused by a quantitatively insufficient production of BL material, but rather arise from qualitative imbalances of the composition of the synthesized BL material.
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  • 33
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    Cell & tissue research 263 (1991), S. 311-324 
    ISSN: 1432-0878
    Keywords: Dental root surface ; Periodontal fiber fringe ; Dentino-cemental junction ; Electron microscopy ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The development of acellular extrinsic fiber cementum (AEFC) has never before been studied in human teeth. We have therefore examined the initiation of AEFC in the form of a collagenous fiber fringe and its attachment to the underlying dentinal matrix, in precisely selected, erupting human premolars with roots developed to 50%–60% of their final length. Freshly extracted teeth were prefixed in Karnovsky's fixative, decalcified in EDTA and subdivided into about 10 blocks each, cut from the mesial and distal root surfaces, vertical to and along the root axis. The blocks were postfixed in osmium tetroxide, embedded in Epon and cut for light- and electron-microscopic investigation. Starting at the advancing edge of the root, within a region extending about 1 mm coronal to this edge, fibroblast-like cells were seen closely covering the external root surface. Along the first 100 μm from the root edge, these cells extended cytoplasmic processes and contacted the dentinal collagen fibrils. Between these cells and the dentinal matrix, new collagen fibrils and very short collagen fibers gradually developed. Within the second 100 μm from the root edge, this resulted in the formation of a cell-fiber fringe network. Newly formed fibers of the fringe were directly attached to the non-mineralized matrix containing dentinal collagen fibrils and could be distinguished from the latter by differences in fibril orientation. During the process of dentin mineralization, the transitional zone between the fiber-fringe base and the dentinal matrix, i.e., the future dentino-cemental junction, also mineralized. It is suggested that this fiber fringe is the base of AEFC, which later increases in thickness by fiber extension and subsequent mineralization.
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  • 34
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    Cell & tissue research 263 (1991), S. 325-336 
    ISSN: 1432-0878
    Keywords: Cementum ; Fiber fringe ; Periodontal ligament fibers ; Dentino-cemental junction ; Electron microscopy ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The present study describes for the first time the development of early acellular extrinsic fiber cementum (AEFC) until its establishment on human teeth. Precisely selected premolars with roots developed to 50%–100% of their final length were prefixed in Karnovsky's fixative and most of them were decalcified in EDTA. Their roots were subdivided into about 10 blocks each, cut from the mesial and distal root surfaces. Following osmication, these blocks were embedded in Epon and sectioned for light-and transmission electron microscopy. Some blocks were cut non-demineralized. From semithin stained sections, the density of the collagenous fiber fringe protruding from the root surface was measured by using the Videoplan-system. After initiation of this fiber fringe and its attachment to the dentinal root surface followed by mineralization, the fringe gradually increased in length and subsequently became mineralized. Fringe elongation and the advancement of the mineralization front appeared to progress proportionally. Thus, in all stages of AEFC development, a short fiber fringe covered the mineralized AEFC. Its density remained constant, irrespective of AEFC thickness. The latter gradually increased and reached an early maximum of 15–20 μm in the cervical region. At this stage, the AEFC fringe appeared to fuse with the future dentogingival or other collagen fibers of the tooth supporting apparatus. Mineralization of the fringe commenced with isolated, spherical or globular centers, which later fused with the mineralization front and became incorporated in AEFC.
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  • 35
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    Cell & tissue research 264 (1991), S. 215-219 
    ISSN: 1432-0878
    Keywords: Erythroblast ; Cytokinesis ; Cytoplasmic bridge ; Fetal liver ; Erythropoiesis ; Electron microscopy ; dd Mice
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary A unique cytoplasmic connection between erythroblasts was studied by electron microscopy in mouse hemopoietic tissues (fetal liver, fetal and neonatal spleen and adult bone marrow). Many pairs of interphase erythroblasts were connected by a “cytoplasmic bridge” that was very thin and sometimes long in comparison with telophase bridges. The stage of maturation of the cells in a pair was similar. Small numbers of microtubules ran along the cytoplasmic bridge; a mid-body was not seen. The plasma membrane at approximately the middle of the bridge bulged to form a ring-shaped ridge filled with dense amorphous substances; this was called a “bulging ring”. Thus, the cytoplasmic bridge between erythroblasts did not morphologically correspond to the telophase bridge in the usual cytokinesis. Cytoplasmic bridges were observed in various differentiating stages of erythroblasts, whereas other cell types of the hemopoietic lineage did not have such a bridge. The cytoplasmic bridge is unique to erythroblasts and provides an evidence for the atypical cytokinesis of the erythroblastic lineage.
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  • 36
    ISSN: 1432-0878
    Keywords: Oocytes ; Meiosis ; Energy metabolism ; Protein synthesis ; Nuclear envelope ; Electron microscopy ; Mouse (Swiss)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary In the absence of a suitable energy source, mouse oocytes cultured in vitro resume, but fail to complete, meiotic maturation. However, little is known about the underlying mechanisms leading to this meiotic failure. We utilized pyruvate-deficient medium to test for the role of pyruvate throughout the meiotic maturation process. Germinal vesicle-stage (GV) oocytes underwent germinal vesicle breakdown (GVBD), but failed to form a polar body when cultured continuously in pyruvate-free medium. However, when GV oocytes were preincubated for 4 h in pyruvate-free medium containing dibutyryl cyclic adenosine monophosphate (dbcAMP) and then cultured in pyruvate-free medium, GVBD was markedly inhibited. Preincubation of GV oocytes in dbcAMP and cycloheximide, followed by culture in cycloheximide only, also inhibited GVBD. A longer preincubation period was required in the cycloheximide-dbcAMP case (12 h) than in pyruvate-free-dbcAMP medium situation (4 h). Strikingly, reassembly of the nuclear membrane without polar body formation was observed following GVBD in oocytes continuously cultured in pyruvate-free medium. The reassembled nuclear membrane increased in size with continued culture, and it surrounded partially-decondensed chromatin. Nuclear membrane reassembly also occurred in oocytes which had undergone GVBD during continuous culture in medium containing only cycloheximide. Reformation of nuclear membranes after GVBD was confirmed by electron-microscopic analyses of oocytes cultured in pyruvate-free medium or in the presence of cycloheximide. We conclude that both pyruvate and protein synthesis are required for nuclear membrane disassembly, whereas lack of pyruvate or protein synthesis is associated with interruption of the metaphase state and reassembly of the nuclear membrane. The evidence suggests that assembly and maintenance of an intact nucleus and its disintegration are all amenable to regulation by pyruvate, possibly via mechanism(s) involving protein synthesis.
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  • 37
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    Cell & tissue research 265 (1991), S. 113-120 
    ISSN: 1432-0878
    Keywords: Blood-brain barrier ; Glia ; Meninges ; Electron microscopy ; Skate, Raja erinacea (Elasmobranchii)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary This report gives the results of the first electron-microscopic examination of the cell layers covering the outer brain surface and the inner surface of the cartilaginous skull in the skate, Raja erinacea. The perivascular glial blood-brain barrier — a characteristic of elasmobranchs — extends to the outer surface of the brain. This outer barrier layer is surrounded, in turn, by a subarachnoid compartment (depth: 30–40 μm), containing loose connective tissue and blood vessels; by an arachnoid-like epithelium (10–15 cell layers), impermeable to horseradish peroxidase; and, by perimeningeal fluid, a fluid with a slow turnover rate and a protein composition different from plasma. The inside of the skull, facing the perimeningeal fluid, is covered by a multilayered (10–15 layers) cuboidal epithelium, also impermeable to horseradish peroxidase. Closely apposed cells in the luminal layer of this epithelium have apical microvilli and numerous vesicular profiles, containing material of moderate electron density. These observations may explain, in terms of structure, the regulated protein content of perimeningeal fluid and the restricted exchange of solutes between brain and perimeningeal fluid in elasmobranchs.
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  • 38
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    Cell & tissue research 266 (1991), S. 11-22 
    ISSN: 1432-0878
    Keywords: Basement membrane ; Proximal tubule ; Hydraulic pressure ; Mechanical stress ; Electron microscopy ; Rat (Sprague-Dawley)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The ultrastructure of the basement membrane of the rat proximal tubule was observed by transmission electron microscopy after the use of a cold dehydration technique. The basement membrane of the P1 segment is thick and possesses several structural specializations that are rare in other basement membranes; these include intraepithelial ridges, dense bars, and basement membrane vesicles. The intraepithelial ridges are found in the intercellular spaces between interdigitating processes of the proximal tubule cells. The ridges and the interdigitating processes run circumferentially around the tubule. The dense bars are frequently found in the intraepithelial ridges. They are especially prominent on the concave side of the tubular bends and to a lesser extent near sites where intracellular actin filaments anchor onto the basal cell membranes. The basement membrane vesicles are bounded by unit membranes; they are variable in both their electron density and their size. They are usually found in association with dense bars, and the grade of their accumulation is positively correlated with the development of the dense bars. These three specializations have no topographical relationship with the interstitial structures, such as fibrobalasts and collagen fibrils. The specializations are best developed on the concave side of tubular bends where the circumferential stresses caused by the intraluminal hydraulic pressure are presumably the largest; we therefore propose that they are an adaptation to, or a manifestation of, the increased wall stress in the proximal tubule.
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  • 39
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    Cell & tissue research 263 (1991), S. 195-198 
    ISSN: 1432-0878
    Keywords: Pancreas, endocrine ; Islets of Langerhans ; Immunocytochemistry ; Endocrine cells four types ; Electron microscopy ; Sminthopsis crassicaudata (Marsupialia)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The endocrine pancreas of the Australian fattailed dunnart, Sminthopsis crassicaudata, was investigated by means of electron-microscopic immunocytochemistry using the protein A-gold technique on London resin (LR) white-embedded tissue. The primary antibodies used were raised against insulin, glucagon, somatostatin and pancreatic polypeptide. The morphology of the secretory granules differed in the four cell types. The insulin cells are pleomorphic, and the secretory granules composed of an electron-dense core surrounded by an electron-lucen halo. The glucago cells possess granules with an electron-dense core usually surrounded by a halo of less dense granular material. Somatostatin cells have large, less dense secretory granules. The pancreatic polypeptide cells show small, dense secretory granules. In order for an ultrastructural study to be considered reliable for the definite identification of endocrine cell types, it is essential that it be corroborated by immunocytochemical data at the light-or preferably electron-microscopic level. Recent developments in immuno-electron-microscopic techniques have contributed to a better knowledge of cells responsible for the secretion of a wide variety of hormones, as in this study.
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  • 40
    ISSN: 1432-0878
    Keywords: Transverse (T-) tubules ; Muscle, cardiac ; Electron microscopy ; Morphometry ; Rabbit (Lagomorpha)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The goal of the present investigation was to compare quantitatively the distribution of T-tubules between regions of the myocardium. The volume fraction and surface density of T-tubules in rabbit right atrial free wall, left atrial free wall, right ventricular free wall, left ventricular free wall, right ventricular papillary muscle, and left ventricular papillary muscle were measured using established, electron-microscopic, morphometric techniques. T-tubules were delineated using wheat-germ agglutinin conjugated to horseradish peroxidase as a tracer. No significant differences were found in the morphometric parameters between any two ventricular samples or between atrial samples. Furthermore, little difference between T-tubule volume fraction or surface density was found between individual animals for any given site. Both volume fraction and surface density of ventricular T-tubules were more than ten-times their values in atrial tissue (volume fraction: 3.43%±0.35 vs. 0.20±0.09; surface density: 2.46 μm2/μm3±0.11 vs 0.10±0.04). Measurements show that there is greater variation of T-tubule volume fraction and surface density within atrial samples than within ventricular samples. This suggests greater inhomogeneity in T-tubule distribution in atrial myocardium than in ventricular myocardium. Morphometric data also indicate that the mean diameter of atrial T-tubules is greater than that of ventricular T-tubules while qualitative observations show that atrial T-tubules are distributed less regularly and have a larger longitudinal component to their organization than those in the ventricular myocardium.
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  • 41
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    Cell & tissue research 264 (1991), S. 321-328 
    ISSN: 1432-0878
    Keywords: Tooth pulp ; NGF receptor ; Calcitonin gene-related peptide ; Substance P ; Neuropeptide Y ; Immunocytochemistry ; Electron microscopy ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The distribution of nerve growth factor receptor (NGF receptor)-like immunoreactivity in pulps of developing primary and mature permanent cat canine teeth was examined, by use of a monoclonal antibody against NGF receptor detected by fluorescence immunohistochemistry and pre-embedding immunocytochemical light- and electron microscopy. Both primary and permanent pulps contained a vast number of NGF receptor-like immunoreactive nerves. Immunolabelling appeared to be localized both to axons and Schwann cells. In addition, many blood vessel walls in immature primary tooth pulps showed NGF receptor-like immunoreactivity, in contrast to permanent pulps where blood vessels rarely were NGF receptor-immunoreactive. Double-labelling immunofluorescence experiments revealed that in the permanent pulp a majority of the NGF receptor-positive nerves also showed calcitonin gene-related peptide (CGRP)-like immunoreactivity, and many showed substance P-like immunoreactivity. However, nerve fibers with neuropeptide Y-like immunoreactivity lacked NGF receptor-like immunoreactivity. In developing primary tooth pulps fewer NGF receptor-positive nerves were CGRP-like immunoreactive or substance P-like immunoreactive, as compared to the permanent pulp. Neuropeptide Y-like immunoreactive nerve fibers were not detected in the primary tooth pulp. The results suggest a role for nerve growth factor in both developing and mature sensory nerves of the tooth pulp.
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  • 42
    ISSN: 1432-0878
    Keywords: Adrenal autotransplants ; Sodium restriction ; Mineralocorticoid hormones ; Electron microscopy ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Regenerated adrenocortical nodules were obtained by implanting fragments of the capsular tissue of excised adrenal glands into the musculus gracilis of rats (Belloni et al. 1990). Five months after the operation, operated rats showed a normal basal blood level of corticosterone, but a very low concentration of circulating aldosterone associated with a slightly increased plasma renin activity (PRA). Regenerated nodules were well encapsulated and some septa extended into the parenchyma from the connective-tissue capsule. The majority of parenchymal cells were similar to those of the zonae fasciculata and reticularis of the normal adrenal gland, while zona glomerulosa-like cells were exclusively located around septa (juxta-septal zone; JZ). In vitro studies demonstrated that nodules were functioning as far as glucocorticoid production was concerned, while mineralocorticoid yield was very low. Prolonged sodium restriction significantly increased PRA and plasma aldosterone concentration, and provoked a marked hypertrophy of JZ, which was due to increases in both the number and average volume of JZ cells. Accordingly, the in vitro basal production of aldosterone and other 18-hydroxylated steroids was notably enhanced. The plasma level of corticosterone, as well as zona fasciculata/reticularis-like cells and in vitro production of glucocorticoids by regenerated nodules were not affected. These findings, indicating that autotransplanted adrenocortical nodules respond to a prolonged sodium restriction similar to the normal adrenal glands, suggest that the relative deficit in mineralocorticoid production is not due to an intrinsic defect of the zona glomerulosa-like JZ, but is probably caused by the impairment of its adequate stimulation under basal conditions. The hypothesis is advanced that the lack of splanchnic nerve supply and chromaffin medullary tissue in regenerated nodules may be the cause of such an impairment.
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  • 43
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    Cell & tissue research 265 (1991), S. 261-273 
    ISSN: 1432-0878
    Keywords: Endocrine pancreas ; Immunization ; Insulin ; Glucagon ; Somatostatin ; Electron microscopy ; Rabbit (Chinchilla, Ch: b Ch)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary An active or passive immunization against hormones and the subsequent neutralization of hormones by circulating antibodies is a valuable tool for the identification of hormonal action. To recognize presumed local (autocrine, paracrine) effects exerted by pancreatic hormones, the endocrine pancreas of rabbits was investigated electron-microscopically after long-term immunization against glucagon or somatostatin. Glucagon immunization resulted in hyperplasia and hypertrophy of glucagon- (A-) cells and in their increased metabolic activities: They showed prominent nucleoli, increased amounts of endoplasmic reticulum, Golgi areas, and mitochondria. These changes were paralleled by alterations in secretion granules (increased size, decreased hormonal content), increased numbers of lysosomes (crinophagic bodies), and an increment of the filamentous system. Basically, these findings point to an autocrine regulation of A-cells. Following somatostatin immunization, somatostatin- (D-) cells were hyperplastic but unchanged in their metabolic state. Instead, insulin-(B-) cells and A-cells exhibited equivalents of increased cellular activities (parameters, see above). This stimulation most probably is caused by cancelled paracrine (inhibitory) effects of somatostatin. The changes observed after both immunizations were differently expressed in morphologically heterogeneous islet types (size, angioarchitecture, cellular composition, microtopology of the various cell types). It is concluded, therefore, that the regulation of islets is not uniform. Autocrine and paracrine effects exerted by islet hormones are of different significance in individual islets, or they interfere differently with other regulatory signals.
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  • 44
    ISSN: 1432-0878
    Keywords: Electron microscopy ; Scanning electron microscopy ; Lectin-gold particles ; Cytology ; Glycoproteins ; Imaginal discs ; Tissue culture ; Plodia interpunctella (Insecta)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The Indian meal-moth cell line, IAL-PID2, established from larval wing discs was examined from the 250th to the 300th passages. The cultured cells retain various structural and functional qualities of epidermal cells. Under hormone-free conditions PID2 cells grow as a monolayer of round or spindle-shaped cells. They appear as weakly active epidermal cells. The endoplasmic reticulum and Golgi apparatus are poorly developed and secretory activity is reduced. Culture conditions resulted in considerable cellular expansions, abundance of storage products (glycogen, lipids), and hypertrophy of the lysosomal system. The PID2 cell line retains the ability to respond to ecdysteroids; 20-hydroxyecdysone treatment (2×10-6 M) triggered morphogenetic and secretory processes. Cells formed pseudoepithelial aggregates interconnected and linked by desmosome-like structures. The hormone-stimulated cells are involved in the biosynthesis of N-acetyl-D-glucosamine-rich glycoproteins. The glycosylation sites were located, by use of WGA-gold particles, on cellular expansions and all along the plasma membrane. The possible significance of these glycoproteins is discussed.
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  • 45
    ISSN: 1615-2573
    Keywords: Isolated heart ; Extended perfusion ; Oxygen-carrying solutions ; Electron microscopy ; Preservation and edema
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract In a comparative study, we investigated whether or not removed and non-beating hearts could be preserved in vitro by continuous perfusion with oxygen-carrying solutions (blood, perfluoro-carbon emulsion) and simultaneous substitution with specific substrates. We used 18 mongrel dogs subdivided into 2 groups (1st group: perfluorocarbon emulsion; 2nd group: blood); the perfusion time was 9 h. In addition to parameters to control the medium of the perfusion solution, we measured parameters that would allow us to assess the success of the extended perfusion. These parameters were high-energy phosphates and, in particular, electron optical analysis. At the end of the perfusion period, electron optical analysis revealed a mild and reversible ischemic reaction by the myocardial cells in both groups. However, statistical analysis showed (1) a significant increase in the ischemic reaction for both groups over the perfusion period (P=0.02), and (2) a significant, even more pronounced ischemic reaction in the subendocardial myocardium (P=0.025). It should be noted that distinctly interstitial edema developed during the perfusion period and that this would appear to be a fairly critical problem with extended continuous isolated heart perfusion.
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  • 46
    ISSN: 1615-6102
    Keywords: Adiantum capillus veneris ; Meristematic root cells ; Microtubule organization ; Immunofluorescence microscopy ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary The interphase meristematic root cells ofAdiantum capillus venerispossess a well developed cytoskeleton of cortical microtubules (Mts), which disappear at prophase. The preprophase-prophase cells display a well organized preprophase microtubule band (PMB) and a perinuclear Mt system. The observations favour the suggestion that the cell edges included in the PMB cortical zone possess a Mt organizing capacity and thus play an important role in PMB formation. The perinuclear Mts are probably organized on the nuclear surface. The preprophase-prophase nuclei often form protrusions towards the PMB cortical zone and the spindle poles, assuming a conical or rhomboid shape. Mts may be involved in this nuclear shaping. Reinstallation of cortical Mts in dividing cells begins about the middle of cytokinesis with the reappearance of short Mts on the cell surface. When cytokinesis terminates, numerous Mts line the postcytokinetic daughter wall. Many of them converge or form clusters in the cytoplasm occupying the junctions of the new and the old walls. In the examined fern, the cortical Mt arrays seem to be initiated in the cortex of post-cytokinetic root cells. A transitory radial perinuclear Mt array, comparable to that found in post-telophase root cells of flowering plants, was not observed inA. capillus veneris.
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  • 47
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    Molecular genetics and genomics 228 (1991), S. 335-344 
    ISSN: 1617-4623
    Keywords: Saccharomyces cerevisiae ; DNA interstrand cross-links ; DNA repair ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary The repair of interstrand cross-links induced by 8-methoxypsoralen plus UVA (365 nm) radiation DNA was analyzed in diploid strains of the yeast Saccharomyces cerevisiae. The strains employed were the wild-type D7 and derivatives homozygous for the rad18-1 or the rad3-12 mutation. Alkaline step-elution and electron microscopy were performed to follow the process of induction and removal of photoinduced crosslinks. In accordance with previous reports, the D7 rad3-12 strain failed to remove the induced lesions and could not incise cross-links. The strain D7 rad18-1 was nearly as efficient in the removal of 8-MOP photoadducts after 2 h of post-treatment incubation as the D7 RAD+ wild-type strain. However, as demonstrated by alkaline step-elution and electron microscopic analysis, the first incision step at DNA cross-links was three times more effective in D7 rad18-1 than in D7 RAD+. This is consistent with the hypothesis that the RAD18 gene product is involved in the filling of gaps resulting from persistent non-informational DNA lesions generated by the endonucleolytic processing of DNA cross-links. Absence of this gene product may lead to extensive strand breakage and decreased recognition of such lesions by structural repair systems.
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  • 48
    ISSN: 1573-7284
    Keywords: Creutzfeldt-Jakob disease ; Electron microscopy ; Myelinated axon
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract We report the ultrastructural pathology of myelinated axons in mice infected experimentally with the Fujisaki strain of Creutzfeldt-Jakob disease (CJD). Initially the myelin sheath was separated into several concentric bands, and cellular processes penetrated between layers of myelin and lifted away the outermost lamella. Then a complicated labyrinth of the concentric cellular processes, clearly belonging to either astrocytes or macrophages, invested myelinated axons. In terminal stages axons completely denuded of myelin were seen in the center of concentric networks of cellular processes. Myelin remnants were seen within astrocytes and macrophages. We conclude that the mechanism(s) of damage to myelinated axons in CID may be similar to that operating in immunologically mediated demyelinating disorders.
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  • 49
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    European archives of oto-rhino-laryngology and head & neck 248 (1991), S. 436-441 
    ISSN: 1434-4726
    Keywords: Merkel cell carcinoma ; Neuroendocrine carcinoma ; Bowen's disease ; Immunohistochemistry ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The Merkel cell carcinoma occurs primarily in the skin of the head and neck, and develops in the dermis with a trabecular growth pattern. Immunohistochemistry reveals positive staining for neuron-specific enolase, neurofilaments, cytokeratin and chromogranin A. Electron microscopically, the tumor cells contain dense-core granules, spinous cytoplasmic processes, desmosomes, zonulae adherentes and paranuclear filament aggregates besides frequent mitoses, focal necroses and lymphocyte and plasma cell infiltrates. The Merkel cell carcinoma is often co-existent with other malignancies such as squamous cell carcinoma or, as in the present study, with Bowen's disease. The definite diagnosis of the Merkel cell carcinoma can be effected only by electron microscopic examination of the tumor.
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  • 50
    ISSN: 0009-2940
    Keywords: Manganese-mediated cyclization ; Nine-membered carbocycles ; Manganese complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photochemical Reactions of Transition Metal Organyl Complexes with Olefines, 31). - [4 + 5] Cycloaddition of Conjugated Dienes to Tricarbonyl(η5-2,4-dimethyl-2,4-pentadienyl)manganeseTricarbonyl(η5-2,4-dimethyl-2,4-pentadienyl)manganese [1] reacts photochemically with the acyclic conjugated dienes 1,3-butadiene [A], 2-methyl-1,3-butadiene [B], (E)-1,3-pentadiene (C), (E,E)-2,4-hexadiene (D), 2,4-dimethyl-1,3-pentadiene (E), 2,4-hexadien-1-ol (F), and methyl 2,4-hexadienoate (G) in a formal [4 + 5] cycloaddition to give tricarbonylmanganese complexes with η3:2-2,6-cyclononadien-1-yl ligands (2A-2G). In addition, the reaction of 1 with A yields thermolabile [η3:2:2-1-(3-butene-1,2-diyl)-1,3-dimethyl-2,6-cyclononadiene]dicarbonylmanganese (3A) and E,E and E,Z isomers of [η3-1-(2-butene-1,1-diyl)-1,3-dimethyl-2,6-cyclononadiene]tetracarbonylmanganese (4A, 4A] as byproducts. Similarly, 1 reacts with B to form tetracarbonyl[η3-1-(3-methyl-2-butene-1,1-diyl)-1,3,6-trimethyl1-2,6-cyclononadiene]manganese (4B) in a side reaction. The crystal and molecular structures of tricarbonyl(η3:2-1,3,5,5,7-pentamethyl-2,6-cyclononadien-1-yl]manganese (2E) and of 3A are determined by X-ray structure analyses. In each of the formally octahedral complexes unusual long manganese-carbon bonds are found for one coordinated CC double bond of the hydrocarbon ligands.
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  • 51
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 17-23 
    ISSN: 0009-2940
    Keywords: (Borole)nickel complexes ; Nucleophilic substitution at boron ; 1H-Borole ; Dihydro-1H-borolediide ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Derivatives of Borole, XVI1), - Bis(borole)nickel Complexes2)The dilithium 1-(dialkylamino)dihydroborolediides Li2[C4H4-BNR2] 2a, b: R = Me, Et) react with NiCl2 · DME to give bis(borole)nickel complexes Ni(C4H4BNR2)2. Nucleophilic substitution reactions are used to produce a large variety of derivatives Ni(C4H4BR)2 1 (e.g. R = H, tBu, F, Cl, Br, I, OH, OMe). Treatment of Ni(C4H4BCl)2 (tg) with LiO(CH2)3OLi in THF produces a polymer and a dinuclear complex (μ-{η5:η5-[(CH2)3(OBC4H4)2]}2Ni2 (3) which crystallizes from CH2Cl2 as solvate 3 · CH2Cl2. The complexes 1g and 3 · CH2Cl2 are characterized by X-ray diffraction work. Barriers to internal ring-ring rotation are measured by variable-temperature NMR spectroscopy. The B - H bond of Ni(C4H4BH)2 (1a) is remarkably inert and does not react with H2O or with carboxylic acids in THF at room temperature. With PhCHO slow formation of the benzyloxy compound Ni(C4H4BOCH2Ph)2 (1 m) is observed at 100°C. For typical complexes such as the phenyl derivative 1e cyclic voltammetry in CH2Cl2 reveals an irreversible oxidation at 1.32 and a quasi-reversible reduction at -1.37 V vs. SCE.
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  • 52
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 25-29 
    ISSN: 0009-2940
    Keywords: Borole complexes ; {η5-[1-(Diisopropylamino)borole]}metal complexes, internal rotation of, protonation of ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Derivatives of Borole, XVII1). - {η5-[1-(Diisopropylamino)borole]}metal Complexes: Syntheses, Protonation, Internal RotationNew complexes M(CO)4L (M = Cr, W), cis-M(CO)2L2 [M = Mo, W (not isolated)], and (COD)NiL have been prepared from the Diels-Alder dimer L2, where L is 1-(diisopropylamino)borole, C4H4BNiPr2. Complexes of L can be protonated at the nitrogen atom to give stable salts such as [Cr(CO)4(LH)]BF4, [Fe(CO)3(LH)]BF4, [(C6Me6)Ru(LH)]BF4, and [CpCo(LH)]BF4; B  -  N bond dissociation is not observed. Barriers to internal rotation have been determined by variable temperature NMR spectroscopy for Cr(CO)4L, (COD)NiL, and NiL2. Three processes have been identified: rotation of the NiPr2 group around the B  -  N bond, gear-mesh rotation of the isopropyl groups around the C  -  N bonds, and rotation of L with respect to the counter ligands.
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  • 53
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 51-61 
    ISSN: 0009-2940
    Keywords: Selenocarbonyl compounds, perfluorinated ; 1,3-Diselenetanes, perhalogenated ; 2-Selenabicyclo[2.2.1]hept-5-enes ; 1,3-Diselenetan-2-ylium hexafluoroarsenates ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Preparation of (Perfluoroalkyl)halogeno-1,3-diselenetanes from the Corresponding Selenocarbonyl Fluorides and Reactions with Boron Trichloride or Arsenic Pentafluoride1)Reactions of Hg(SeRt)2 (Rt = C2F5, C3F7, CF3) with (C2H5)2 All or All3 in octamethylcyclotetrasiloxane produce the unstable perfluoroalkaneselenocarbonyl fluorides 1 [R1 = CF3 (1 a), C2F5 (1 b), CF3Se (1 c)]. These compounds are very reactive and polymerize to rubberlike products. On heating the polymers decompose almost quantitatively to the monomers or dimers. In CFCl3 solution 1 dimerizes at 20°C in sunlight to the corresponding cis/trans-1,3-diselenetanes 2. The structure of 2 b is determined by single crystal X-ray diffraction. Different selenocarbonyl derivatives add to unsymmetrically substituted 1,3-diselenetanes 3. 1 a and 1 b react with cyclopentadiene to form the [4 + 2] cycloaddition products 4a and 4c. Halogen exchange reactions take place between 2a  -  d and BCl3. The cis-isomers react much faster than the trans-isomers to give a mixture of cis-, trans-forms of 5. When 2c,d is treated with BCl3 it is possible to isolate and characterize the pure trans-isomer 2d, which is separated by preparative gas chromatography from 5c,d. Fluorine abstraction with formation of 1,3-diselenetan-2-ylium ions (6a  -  f) are accomplished by reactions of 2 or 3 with AsF5 in SO2.
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  • 54
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 87-88 
    ISSN: 0009-2940
    Keywords: Alkylidenesulfur difluoride oxide ; Carbon-sulfur double bond ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hg[C(COF) = SF2 = O]2 is prepared by the reaction of FCO — CH = SF2 = O with HgF2. This compound represents the third known example of an alkylidenesulfur difluoride oxide. Its molecular structure is the same as that of the most abundant of the three isomers of FCO-CH = SF2 = O. This is assumed to be the result of weak intramolecular Hg… O contacts. With the exception of the fluorine atoms bound to sulfur, all atoms lie approximately in one plane.
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  • 55
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 103-109 
    ISSN: 0009-2940
    Keywords: Asteranes ; Cage compounds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Asteranes, XXII1).  -  Synthesis of a Double Tetraasterane: Nonacyclo[10.8.0.02,11.04,9.04,19.06,17.07,16.09,14.014,19]eicosane1,4,5,8-Tetrahydronaphthalene-2,3-dicarboxylic anhydride (9) is dimerized by UV light in dioxane yielding four isomeric [2 + 2] adducts whose methyl ester derivatives are elucidated spectroscopically. The structures of the major products 14 and 16 have been confirmed by X-ray structure analysis. Degradation of the carboxylic groups of 14 afforded the title compound 5.
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  • 56
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 157-162 
    ISSN: 0009-2940
    Keywords: Fluoro compounds, aromatic ; Nitrite exchange by fluoride ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of Aromatic Fluoro Compounds by Nucleophilic Exchange of Nitro Groups by FluorideThe synthesis of aromatic fluoro compounds from the respective nitro compounds by nucleophilic substitution of nitrite by fluoride is described. Reasonable yields in case of nonactivated nitro compounds are only obtained if the nitrite formed in the reaction is eliminated by acylation. 1-Fluoro-3-nitrobenzene (2) was obtained from 1,3-dinitrobenzene (1), and 1-fluoro-3,5-dinitrobenzene (9) as well as 1,3-difluoro-5-nitrobenzene (10) from 1,3,5-trinitrobenzene (8) in yields up to 92% by reaction of nitro compounds with potassium fluoride in sulfolane at 180 - 200°C in the presence of phthaloyl dichloride (6); 1,2-difluoro-4-nitrobenzene (12) was formed in 58% yield from 2,4-dinitro-1-fluorobenzene (11) in the presence of pyromellitoyl tetrachloride (13).
    Additional Material: 2 Tab.
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  • 57
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 13-16 
    ISSN: 0009-2940
    Keywords: Diphosphines, tetrakis(diisopropylamino) ; Phosphinous anhydrides ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis and Structure of Bis[bis(diisopropylamino)phosphino]chalcogenidesPhosphorodiamidous chalcogeno-anhydrides [(R2N)2P]2X (R = Me2CH; X = S, Se, Te) (2a-c) have been obtained by insertion of elemental sulfur, selenium, or tellurium into the P-P bond of the corresponding diphosphane (1). The structure of 2a and 2c has been confirmed by an X-ray diffraction.
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  • 58
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 31-38 
    ISSN: 0009-2940
    Keywords: Fluorosulfonium salts, reaction with nucleophiles ; (Perfluoroakyl)(dimethylamino)sulfonium salts, preparation and structures of ; Methoxysulfinyl hexafluoroarsenate, alkylation with ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (Perfluoroalkyl)(dimethylamino)sulfonium HexafluoroarsenatesMeN = S(CF3)2 (5) is alkylated by Me3O⊕ AsF⊖6 to Me2N-S(CF3)⊕2 AsF⊖6 (4). From 5 and MeOSO⊕ AsF⊖6 (6) MeOS(O)-N(Me)S(CF3)⊕2 AsF⊖6 (7) is formed as a relatively stable primary product. Decomposition of 7 gives the expected 4 only in poor yield. Nucleophilic substitution of the sulfur-bonded fluorine in CF3SF⊕2 AsF⊖6 (8) by Me3SiNMe2 yields CF3S(NMe2)⊕2 AsF⊖6 (9). Similarly, (CF3)2CFSF⊕2 AsF⊖6 (10) reacts with dimethyl(trimethylsilyl)amine to give (CF3)2CFS(NMe2)⊕2 AsF⊖6 (11). The structures of 4 and 9 are elucidated by X-ray analyses, and the influence of the substituents on the bonding is discussed.
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  • 59
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 63-67 
    ISSN: 0009-2940
    Keywords: Dinuclear gold complex ; Silyl complex ; Gold-gold interaction ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Transition-Metal Silyl Complexes, 361).  -  On the Question of Gold-Gold Interactions in Ph2P[CH2]t(2)PPh2-Bridged Dinuclear Gold Silyl ComplexesDinuclear silyl gold complexes of the type dppm(AuSiR3)2 (1) or dppe(AuSiR3)2 (2) are prepared by the reaction of dppm-(AuCl)2 or dppe(AuCl)2 with two equivalents of LiSi(aryl)3 or LiSi(SiMe3)3 The complex dppe[AuSi(SiMe3)3]2 (2 c) exhibits crystallographic inversion symmetry, and therefore the distance between both gold atoms is a maximum. In dppm-(AuSiPh3)2 (1b) a gold-gold interaction between both gold atoms is observed [Au  -  Au 316.80(3) pm].
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  • 60
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 149-156 
    ISSN: 0009-2940
    Keywords: Cyclobutene, ring-opening ; Poly Diels-Alder reaction ; Molecules, double-stranded ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cyclobutene Ring Opening: A Useful Reaction for the Synthesis of Double-Stranded MoleculesSyntheses and ring-opening reactions of the compounds endo-5a - e and 9a - c, all containing cyclobutene rings, are described. From these experiments it is concluded that compound 9a is a useful AB-type Diels-Alder monomer for the synthesis of well-defined double-stranded molecules. The stereochemistry of the adducts endo-4b and endo-5d is determined by X-ray structure analysis.
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  • 61
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 175-184 
    ISSN: 0009-2940
    Keywords: α-Enones, regioselective 1,2-addition of dimethyl phosphite to ; Allylic rearrangement of dialkyl (1-hydroxy-2-alkenyl)phosphonates ; 1-Alkenylphosphonates, 3-acetyloxy- ; 1-Alkenylphosphonates, 3-hydroxy- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of Dialkyl Phosphites with α-Enones, I. - Synthesis and Allylic Rearrangement of Dimethyl (1-Hydroxy-2-alkenyl)- and (1-Hydroxy-2-cycloalkenyl)phosphonatesVarious β,γ-unsaturated α-hydroxyphosphonates 3 are prepared in good yields by NaOCH3-catalyzed regioselective 1,2-addition of dimethyl phosphite to acyclic and cyclic α-enones at -35°C. On acid-catalyzed acetylation, the allylic α-hydroxyphosphonates 3 (R1, R2 + H) rearrange under thermodynamic control; yielding the new 3-acetyloxy-1-(cyclo)alkenyl derivatives 8, from which the transposed allylic alcohols 11 are readily obtained. Using shorter reaction times, acetylation of compounds 3 affords mixtures of 1- and 3-acetylated products, 10 and 8, respectively.
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 207-212 
    ISSN: 0009-2940
    Keywords: 2,3,6-Trioxypentafulvenes ; Keto-enol tautomerism ; Push-pull system ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Syntheses of 2,3,6-trioxypentafulvenes with a free position at the ring are described, in which the protection of the C-3 hydroxy group as methoxy or acetoxy derivative has been required. The difference in the behavior of the title compounds in relation to the previously reported 1,4-disubstituted 2,3,6-trihydroxypentafulvenes 2a-e, which only exhibit enol forms, is discussed and attributed to the disappearance of the push-pull system formed by the C-3 enol group and the C-4 electron-withdrawing substituent.
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  • 63
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 233-235 
    ISSN: 0009-2940
    Keywords: Hexaoxacyclotriacontadodecaenes ; Macrocycles ; 2,2-Bis(2-furyl)propane ; 2,5-Bis[1-(2-furyl)-1-methylethyl]furan ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New O6 Macrocycles with 2,2-Bis(2-furyl)propane UnitsThe macrocycles 3a and 6 are prepared in 29 and 16% yield by cyclization of dilithiated 2,2-bis(2-furyl)propane (1) and 2,5-bis[1-(2-furyl) 1-methylethyl]furan (5), respectively, with ethyl N,N-dimethylcarbamate (2).
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 237-240 
    ISSN: 0009-2940
    Keywords: Bicyclo[3.2.1]oct-6-yl cations ; Wagner-Meerwein rearrangements ; Alkyl-bridged ions ; Conformational effects ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rearrangements of 1,4,4- and 2,2,5-Trimethylbicyclo[3.2.1]oct-6-yl Cations1,4,4-Trimethylbicyclo[3.2.1]oct-6-yl cations (18) are generated from the tosylhydrazone 7, by nitrous acid deamination of the amines 6 and 8, and by acetolysis of the brosylates 21 and 24. The product distributions are but slightly affected by the configuration (exo vs. endo) of the leaving groups. The predominant product, 1,4,4-trimethylbicyclo[3.2.1]octan-exo-6-ol (11) is formed without significant redistribution of a 6-2H label. The degenerate Wagner-Meerwein rearrangement of the parent bicyclo[3.2.1]oct-6-yl cation is virtually eliminated by the presence of two methyl groups at C-4. Enhanced conformational strain, raising the barrier to ring flipping, accounts for these observations. Minor products (12, 13) arise from a 7,6-hydride shift of 18, followed by Wagner-Meerwein rearrangement. When the 2,2,5-trimethylbicyclo[3.2.1]oct-6-yl cation (19) is generated directly from the tosylhydrazone 17, the tertiary alcohol 13 is obtained as the major product. The conformational barrier to Wagner-Meerwein rearrangement is compensated by the incipient stabilization of the tertiary carbocation 20.
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 403-405 
    ISSN: 0009-2940
    Keywords: 1,2-Dihydropentalenes ; 1,5-Dihydropentalenes ; Rearrangements ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An efficient one-pot synthesis of 3-substituted 1-phenyl-1,2-dihydropentalenes from α,β-unsaturated ketones is described. These compounds can be rearranged to their 1,5-dihydro isomers using different methods such as acid catalysis and vacuum-flash thermolysis or by chromatography on alumina.
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 417-421 
    ISSN: 0009-2940
    Keywords: Methylenephosphines ; Voltammetry, cyclic ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Electrochemical investigations on a selection of methylenephosphines 1 and related systems are reported. They are shown to possess an irreversible oxidation and reduction wave. An exception is diaminodiphosphene, which reversibly forms a radical anion. A relative ordering of frontier orbitals is possible, based on the redox properties of these systems.
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  • 67
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 321-327 
    ISSN: 0009-2940
    Keywords: Trifluororthocarbonates of potassium, rubidium, cesium ; Phase transitions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Crystal Structures of Potassium, Rubidium, and Cesium Trifluororthocarbonate and a Remark Concerning the Barium Sulfate Type1)Crystals of potassium, rubidium, and cesium trifluororthocarbonate (9a, 9b, and 9c) have been grown by Ostwald ripening in CH3CN applying a COF2 pressure of 3 bar. According to X-ray single-crystal structure analysis, 9a, 9b, and 9c belong to the baryte-structure family with an pseudotetrahedral anion being dynamically disordered at room temperature. All of the title compounds undergo a phase transition into a monoclinic, completely ordered low-temperature form, which has been refined for 9c. The C - O bond seems to be shortened by polar interactions. The results obtained with 9a, 9b, and 9c at room temperature indicate that the type of disorder found in 9 might be generally present in baryte-type compounds.
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  • 68
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 339-345 
    ISSN: 0009-2940
    Keywords: Photoadditions ; Caffeine derivatives ; Calculations, AM1 ; Diradicals ; Propellanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Selectivities in Photoadditions with Multifunctional Caffeine DerivativesElectronically excited stilbene (21*), 4,4′-dichlorostilbene (1*), and 4,4′-dimethoxystilbene (18*) are trapped by caffeine derivatives 2, 13, or 22 with variable results. While 1* and 2 react predominantly at the imino double bond (substitutive and fragmentating additions), 1* or 18* and 13 produce mostly propellanes by [2 + 2] photocycloaddition, which hydrolyze or may be hydrolyzed. 21* and the relatively electron-poor compound 22 produce mostly propellanes, which always show a preponderance of the syn-10, anti-11 stereoisomers. These selectivities as well as the competition with reactions at the imino double bonds are rationalized on the basis of diradical mechanisms with the aid of semiempirical AM1 calculations. Earlier results on closely related transformations are also discussed.
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  • 69
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 377-381 
    ISSN: 0009-2940
    Keywords: Phosphorus compounds, organic ; Phosphorus heterocycles ; Arbuzov rearrangement ; Mechanism, SN2, SN1 ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Addition Reactions of Phosphorus Nucleophiles to BenzothieteTrialkyl phosphites 4 add to the o-quinoid form 2 of benzothiete (1) to yield the phosphonates 6. An intermolecular migration of an alkyl group from oxygen to sulfur is the most important feature of this transformation. The rearrangement - related to the Arbuzov reaction - can be avoided in a two-step process by the subsequent action of PCl3 and alcohol; thus the phosphonates 10 are generated. Analogous to 2 → 6, dimethyl phenylphosphinate (11) furnishes 13. In contrast, the cyclic esters 14a-d form 2:1 adducts, namely the 12- to 15-membered heterocyclic compounds 17a - d. An intramolecular rearrangement in a 1:1 adduct is only observed for the 1,3,2-dioxaphosphepine 14e, a benzylic system which allows an SN1 process generating the 1,6,2-oxathiaphosphecine 18e. A similar rearrangement at a tertiary carbon center is prevented by the competitive addition of water (1 + 14f → 20).
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  • 70
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 391-396 
    ISSN: 0009-2940
    Keywords: Ozonolysis ; Cycloalkylidenecycloalkanes ; Dispiro-1,2,4-trioxolanes ; Thermolysis ; Photolysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dispiro-1,2,4-trioxolanes by Ozonolysis of Cycloalkylidenecycloalkanes on PolyethyleneOzonolyses of symmetrical (1b - d) and of unsymmetrical cycloalkylidenecycloalkanes (8a, b) afforded the dispiro-1,2,4-trioxolanes 4b - d and 9a, b, respectively. Their thermal decompositions gave mixtures of the cyclic ketones (3) and lactones (6). Photolyses afforded in addition to 3 and 6 the cyclic anhydrides 13, which are isomeric with the corresponding dispiro-1,2,4-trioxolanes.
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  • 71
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 665-669 
    ISSN: 0009-2940
    Keywords: Semideltic acid ; Cyclopropenylium cations ; Pseudooxocarbon anions ; Semideltate anions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pseudooxocarbon Anions of Semideltic AcidNovel pseudooxocarbon anions of semideltic acid (2) can easily be obtained by stepwise substitution of the dimethylamino groups of the cyclopropenium perchlorate 8. Treatment of 8 with cyanamide or malononitrile in the presence of triethylamine leads to the triafulvenes 9 and 13. Two cyanoimino groups are successfully introduced into the cyclopropenylium system by treating 9 with excess cyanamide/potassium ethoxide. Under the same conditions malononitrile reacts with 13 to yield the potassium salts 14 and 17. The thioamide 26 of semideltic acid is obtained by treating the triphenylphosphonium salt 24 with H2S/pyridine and subsequent hydrolysis of the intermediate 25. With the anions of cyanamide or malononitrile ring-opening reaction of the cyclopropenylium system of 24 occurs to yield the push-pull phosphonium salts 28 and 29.
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  • 72
    ISSN: 0009-2940
    Keywords: Ethylene-bridged metal complexes ; Ethanediyl complexes ; Manganese, Rhenium, Ruthenium, Osmium carbonyls ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hydrocarbon-Bridged Metal complexes, XVIII. - Heterometallic Ethylene-Bridged Complexes (OC)5ReCH2CH2Mn(CO)5, (OC)5ReCH2CH2Ru(CO)2Cp, (OC)5ReCH2CH2Os(CO)4CH2CH2Re(CO)5 and (OC)5ReCH2CH2CH2Os(CO)4Os(CO)4(CO)4Os(CO)4CH2CH2Re(CO)5Addition of [(OC)5Re(C2H4)]+ to the carbonylmetallates [Mn(CO)5]-, [RuCp(CO)2]-, [Os(CO)4]2-, [Os3(CO)12]2- affords the title complexes in a directed way. The dynamic behaviour of (OC)5ReCH2CH2Mn(CO)5 in solution is attributed to a dyotropic exchange of the pentacarbonylmetal groups on the CH2CH2 bridge.
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  • 73
    ISSN: 0009-2940
    Keywords: [2.2.2]Paracyclophane ligand ; (η6)π Complexes ; Arsenic(III) complexes ; Antimony(III) complexes ; Bismuth(III) complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Arsenic(III), Antimony(III), and Bismuth(III) Trihalide Complexes of [2.2.2]Paracyclophane: From Weak van der Waals Coordination to Strongly Directional π Complexation with Single or Double External η6 Coordination[2.2.2]Paracyclophane forms the adducts C24H24·AsCl3 (1), C24H24·(SbCl3)2·1/2 C6H6 (2), and C24H24·(BiCl3)3·C6H6 (3). For solutions in polar solvents NMR spectra indicate extensive dissociation and/or fluxionality. In the crystals adduct 1 features a weak addition of the AsCl3 molecule to one open side of a paracyclophane molecule with long intermolecular contacts approaching C3v symmetry. - Crystalline 2 shows SbCl3 coordination to two of the benzene rings of the hydrocarbon in a quasi-centered η6 mode, while one of the benzene rings remains uncoordinated. Chlorine-bridging between antimony atoms leads to tetrameric units (SbCI3)4 in the lattice. - In the bismuth compound 3 each benzene ring of the hydrocarbon is engaged in centroid (η6)π complexation, with the BiCl3 units crosslinked by chlorine bridges. The average of the Bi-ring distances (3.08,2.98, and 2.99 Å) is shorter than for the Sb-ring distances in 2 (3.047 and 3.050 Å), indicating stronger bonding. The crystal benzene is not coordinating.
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  • 74
    ISSN: 0009-2940
    Keywords: Metallacyclic organoaluminium, -gallium and -indium compounds ; MOVPE precursors ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Intramolecularly base-stabilized four-coordinated metallacyclic organoaluminium, -gallium, and -indium compounds C5H10-Al(CH2)3NMe2 (4), C4H8Ga(CH2)3NMe2 (5), C5H10Ga(CH2)3N-Me2 (6), C5H10GaCH2CH(Me)CH2NMe2 (7), C4H8Ga(CH2)4NMe2 (8), C5H10Ga(CH2)4NMe2 (9), EtAl[(CH2)3]2NMe (10), MeGa-[(CH2)3]2NMe (11), EtGa[(CH2)3]2NMe (12), MeIn[(CH2)3]2NMe (13), and (14) have been synthesized by the reaction of [3-(dimethylamino)propyl]aluminium dichloride (1), [3-(dimethylamino)propyl]gallium dichloride (2), [3-(dimethylamino)-2-methylpropyl]gallium dichloride (3), or [4-(dimethylamino)butyl)gallium dichloride with the respective bis-Grignard reagents or by the reaction of the organometal dichlorides RMCl2 with bis[3-(chloromagnesio)propyl]methylamine or with N,N′-bis[3-(chloromagnesio)propyl]-N,N′-dimethyl ethylenediamine. Aluminium or gallium trichloride reacts with tris[3-(chloromagnesio)propyl]amine to give Al[(CH2)3]3N (15) and Ga[(CH2)3]3N (16). The 1H-, 13C-NMR and mass spectra of the new compounds as well as the X-ray crystal structure of 16 are discussed. 4, 6, and 12 have been tested successfully as MOVPE precursors.
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  • 75
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1143-1148 
    ISSN: 0009-2940
    Keywords: Ironcarbonyl complexes ; ortho-Metallation ; o-Semidine rearrangement ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Iron Carbonyl Induced o-Semidine Rearrangement of 1-Alkyl-2-aryldiazenesIrradiation of pentacarbonyl iron in the presence of Me3C - N=N - Ar (Ar=phenyl, p-tolyl, p-CH3OC6H4) produces in the first step ortho-metallated complexes of the type Me3C - N - N(H)RC6H3Fe(CO)3Fe(CO)3 (2a-c, R=H, Me, MeO). In a thermal consecutive step these intermediates undergo an o-semidine rearrangement to Me3C - NFe(CO)3 - Fe(CO)3N(H)RC6H3 (1a-c). The structure of 1a has been elucidated by X-ray structure analysis. Dynamic 13C-NMR spectra indicate restricted rotation of the Me3C group and hindered carbonyl scrambling for the latter and former complexes, respectively.
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  • 76
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1161-1162 
    ISSN: 0009-2940
    Keywords: Semiconductor ; Photocatalysis ; Carbon dioxide ; Formate ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Carbon dioxide is catalytically reduced to formate in a suspension of zinc sulfide in water/2,5-dihydrofuran when irradiated (λ ≥ 290 nm). Turnover rates are in the range of 1.5 monolayers CO2/h. No reaction occurs at pH=12, and a very slow one at pH=3.2,5-Dihydrofuran functions as reducing agent which is oxidized to dehydro dimers. When it is substituted by 2-propanol, no CO2 reduction is observed. Semiconductor photocatalysis by a two-electron transfer from zinc sulfide to adsorbed hydrogen carbonate is assumed as the key step of CO2 fixation.
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  • 77
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1181-1186 
    ISSN: 0009-2940
    Keywords: Stereoselective cyclizations ; Ethers, cyclic ; Dipolar cycloaddition ; Nitro olefins ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A convenient conversion of aldehydes via nitroolefins 2 into cyclic ethers 6 fused to an isoxazoline ring involves formation of unsaturated nitroalkyl ethers 4 and subsequent intramolecular cycloaddition of an in situ-formed nitrile oxide olefin. The cyclization proceeds with stereoselective formation of trans over cis isomers in the tetrahydrofuran series and opposite stereoselectivity in the tetrahydropyran and hexahydrooxepine series, depending on the substituent R in the original nitro compound, thus providing access to stereoselectively functionalized cyclic ethers.
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  • 78
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1223-1227 
    ISSN: 0009-2940
    Keywords: Cesium effect ; Clathrate ; Cyclophanes ; Acetylene, diphenyl ; Rigid-group principle ; Tolane ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Intra- and Extraannularly Functionalized [2.2.2]Phanes: Syntheses and PropertiesThe severely strained new cyclophanes 7b-f, consisting of bridged tolane subunits and bearing intraannular substituents R, were prepared mainly to study steric interactions of R with the “π cloud” of the triple bond. These compounds exist in a rigid twisted conformation, whereas the unsubstituted reference compound 7a and the extraannularly functionalized azo compound 9 show C2 symmetry. 9 forms a 1 : 1 clathrate with toluene.
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  • 79
    ISSN: 0009-2940
    Keywords: Carbenoids ; Bromine-lithium exchange ; Asymmetric induction ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bromine-lithium exchange in 1,1-dibromo-3-(trimethylsilyl-oxy)alkanes 4 and 6 affords the carbenoids 8 and 14, which have been added to ketones, aldehydes, arylboronates, and silylating agents. Diastereoselectivity in the generation and trapping of the carbenoids ranged between 70 - 90% for 8 and 〉90% for 14.
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  • 80
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1271-1289 
    ISSN: 0009-2940
    Keywords: Dibenzo compounds, rigid face-to-face ; Photocycloadditions, [6 + 6] Benzo, Benzo ; Pagodanes, 4,9,14,19-tetrafunctionalized ; Functional Group Manipulations ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Various 4,9,14,19-tetrafunctionalized pagodanes are prepared by a de novo route commencing from appropriately substituted isodrin analogues (3, 4). With the 14,19-dimethoxypagodane-4,9-dicarboxylic esters 30/31, isolated after 16 one-pot operations (ca. 40 functional changes) in ca. 6.5% overall yield (ca. 84% per operation, ca. 93% per functional change), the scope for further functional group manipulations on the pagodane sphere is explored (e.g. diketone dicarboxylic ester 35, dimethoxy diketone 37, tetraketone 41). In two face-to-face dibenzo substrates (17, 49), clean photoequilibration with the corresponding syn-o,o'-dibenzo isomers (19, 50) (75: 25 and 80: 20, resp.) is observed upon direct excitation (λ=254 nm).
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  • 81
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1311-1312 
    ISSN: 0009-2940
    Keywords: Anthracene adducts ; Sulfine, chloro(trichloromethyl)- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of Chloro(trichloromethyl)sulfine, Cl3C(Cl)C=SOThe unstable trichlorothioacetyl chloride (2) could be trapped by a Diels-Alder reaction with anthracene to form the adduct 3, which in turn could be oxidized to the corresponding sulfine adduct 4. Finnaly, chloro(trichloromethyl)sulfine (5) was prepared in good yield by vacuum thermolysis (retro Diels-Alder reaction) of 4.
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  • 82
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1207-1213 
    ISSN: 0009-2940
    Keywords: Diazirines ; Phosphaalkynes ; Carbenes ; Phosphirenes ; [2 + 1] Cycloaddition ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Organophosphorus Compounds, 48. - 1-Halogen-1H-phosphirenes from Phosphaalkynes and ChlorocarbenesHalogen-substituted carbenes (7a - i), generated by thermolysis of diazirines (11a-i), add onto phosphaalkynes (8a-c) to form the title compounds (10a-1). Initially formed 2H-phosphirenes (9) could not be detected as their subsequent conversion to the 1H-isomers 10 by a 1,3-halogen shift is very fast. Hydrolysis of 10c,e,g-i and k yields vinylphosphonous acids (17a - e). 1-Chloro-1H-phosphirenes are transformed by nucleophilic substitution into fluoro (10a,c,e → 19a-c), bromo (10c,e → 20a,b), and iodo analogs (10c,e → 21a,b) with the help of silver tetrafluoroborate, trimethylsilyl bromide, and trimethylsilyl iodide, respectively. A crystal structure analysis of 10c is reported.
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  • 83
    ISSN: 0009-2940
    Keywords: Carbene complexes of chromium and tungsten ; 1-Metalla-1,3,5-trienes ; 1-Metalla-1,3-dien-5-ynes ; Insertion of alkynes into M=C and C=C bonds ; [2 + 2] Cycloaddition reactions of carbene complexes and alkynes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Organic Syntheses via Transition Metal Complexes, 51. - 1-Metalla-1,3,5-trienes and 1-Metalla-1,3-dien-5-ynes of Chromium and Tungsten by Insertion of Alkynes into M=C and C=C Bonds of 1-Metalla-1,3-dienes and 1-Metalla-1-en-3-ynes, respectively1-Metalla-1,3,5-trienes LnM=C(NEt2)-C(Me)—C(OEt)-CH=CHPh (3,4) and LnM=C(OEt)- CH=C(NEt2) - C(Me)=CHPh [5, LnM=Cr(CO)5 (a), W(CO)5 (b)] are obtained for the first time from the corresponding 1-metalla-1,3-dienes LnM=C(OEt) - CH=CHPh (1a, b) under very mild conditions by the insertion of the electron-rich alkyne Et2N-C ≡ C - Me (2) into the M=C and the C=C bonds, respectively, of 1. The chelate complex (6b) and the cyclobutenyl carbene complex 7b are isolated as minor side products. 1-Metalla-1,3-dien-5-ynes LnM=C(NEt2) - C(Me)=C(OEt) - C ≡ CPh [9, 10, LnM=Cr(CO)5 (a), W(CO)5 (b)] are formed with high regio- and stereoselectivity on insertion of 2 into the M=C bonds of 1-metalla-1-en-3-ynes 8. X-ray data are given for the tungsten complex 3b.
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  • 84
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1265-1270 
    ISSN: 0009-2940
    Keywords: Gas-phase pyrolysis ; Tandem mass spectrometry ; Carbonates ; Alkyl migration ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Gas-phase pyrolysis of dimethyl carbonate and its mono-, di-, and trithio analogs has been performed in the temperature range from 1253 to 1404 K applying the gas phase Curie-point pyrolysis technique. Real-time analyses have been carried out by means of mass-spectrometric techniques. The possible isomerizations of the ester functions have been studied by collisional activation mass spectrometry in combination with appropriate D, 18O, and 34S labeling. It is demonstrated that methyl group migrations can be induced pyrolytically in cases where oxygen-to-oxygen or oxygen-to-sulfur isomerizations are involved; in contrast, sulfur-to-oxygen as well as sulfur-to-sulfur isomerizations apparently do not take place.
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  • 85
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    Berichte der deutschen chemischen Gesellschaft 124 (1991) 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 86
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1379-1395 
    ISSN: 0009-2940
    Keywords: Vinyl anions, chiral ; Umpolung ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The vinyllithium reagent 13 and its enantiomer are generated by a bromine/lithium exchange reaction starting from dibromoalkenes 11 and 12, both available from the corresponding enantiomer of alkyl lactate. When 13 is allowed to react with aldehydes or with acetophenone, a highly stereoselective addition to the Re face of the carbonyl compounds occurs to give predominantly the diastereomers 15. Alkenes 25a,c, accessible by another bromine/lithium exchange reaction of 15a,d and subsequent protonation, can be cleaved by ozonolysis followed by reduction to afford carbinols 27a, b in 〉 98% ee. The sequence corresponds to a stereoselective introduction of a methanol d1 synthon (⊖CH2OH) or, as shown by other examples, of acyl and formyl d1 synthons (⊖CRO and ⊕CHO) into prochiral carbonyl compounds. As a consequence, 13 and its enantiomer may be regarded as highly stereoselective reagents for "carbonyl umpolung". A series of further vinyllithium reagents, 38a-g and 54/55, is treated with benzaldehyde, but none of those displays comparable enantiofacial selectivity. The prerequisites to the highly stereoselective reactions of 13 and its enantiomer are briefly discussed.
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  • 87
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1411-1414 
    ISSN: 0009-2940
    Keywords: Propane-1,2,3-trione, 1,3-diphenyl- ; Electron diffraction ; Gas-crystal structure comparison ; Conformation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The molecular structure of 1,3-diphenylpropane-1,2,3-trione (diphenyl triketone) has been determined by gas-phase electron diffraction at 130°C nozzle temperature. It has been found that the phenyl rings are nearly coplanar with the adjacent carbonyl groups, and the two Cph-C(O)-C(O)-C(O) dihedral angles are - 129.5 ± 0.8 and - 107.1 ± 0.8° (0° corresponds to the syn form). Bond distances (rg, Å) and bond angles (deg) with estimated total errors are C—H 1.105 ± 0.006, O = C 1.213 ± 0.003, 〈 Cph-Cph〉 1.404± 0.003, Cph-C(O) 1.478 ± 0.005, C(O)-C(O) 1.558 ± 0.004, Cph-C(O)-C(O) 120.0 ± 0.3, Cph—C(O)=O 120.8 ± 0.4, C(O)-C(O)-C(O) 117.3 ± 0.4, Cph-Cph(CO)-Cph 119.8 ± 0.6. Although there is a general agreement between the gas-phase and crystal molecular structures there are some notable differences. One of the benzene rings is slightly turned about the Cph-C(O) axis in the opposite direction in the gas molecule as compared to the crystal. This causes a marked shortening of the O… H intramolecular contact (to 2.18 Á) between the central oxygen and an ortho-hydrogen.
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  • 88
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1431-1434 
    ISSN: 0009-2940
    Keywords: Proton transfer ; Fragmentation of rings ; Aryllithium ; Carbanions ; Imines ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title carbanions 1 are shown to lose nitrogen to afford ortho-carbiminophenyl anions 4 which can be protonated by inter- or intramolecular proton transfer or react inter- or intramolecularly with other types of electrophilic center.
    Additional Material: 1 Tab.
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  • 89
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1453-1460 
    ISSN: 0009-2940
    Keywords: Shock tube technique ; Oxygen scavanger ; Heat of formation ; Allyl resonance energy ; Radical disproportionation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Heat of Formation of the Allyl and Methallyl RadicalThe decomposition of 1,5-hexadiene (1), 2-methyl-1,5-hexadiene (7), and 2,5-dimethyl-1,5-hexadiene (5) into allyl- (2) and methallyl radicals (6) was studied by means of the shoke tube technique with and without oxygen as scavanger. From these data and from the temperature dependence of the equilibria 1 ⇌ 2 and 5 ⇌ 6, measured between 600 and 800°C, the heat of formation of the allyl (2) and methallyl radical (6) as well as the activation parameters for the recombination and disproportionation of these radicals have been deduced.
    Additional Material: 4 Ill.
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  • 90
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1461-1470 
    ISSN: 0009-2940
    Keywords: Allyl stabilisation energy ; Calculations, force field ; Rotational barrier, intrinsic ; Gas-phase kinetics ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rotational Barriers of Vinyl-Substituted OlefinesFor the vinyl-substituted olefines 1 - 14 activation parameters for the geometrical isomerisation have been determined in the gas-phase. By comparison of these barriers with the corresponding ones of the isolated double bonds, each corrected by the contribution of the steric energy to the ground and transition state, a value of 13.5 ± 1.1 kcal mol-1 for the allyl stabilisation energy (ASE), defined as replacement of alkyl by vinyl, has been derived.
    Additional Material: 2 Ill.
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  • 91
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1471-1475 
    ISSN: 0009-2940
    Keywords: Polyacetylenes ; Cross conjugation ; Alkenes, tetraethynyl ; π-Systems, planar ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New Planar π-Systems, II1). - On the Preparation and Structure of Tetrakis(phenylethynyl)etheneThe preparation of tetrakis(phenylethynyl)ethene (1 b) has been repeated. Among various routes to this highly unsaturated cross-conjugated π-system, the dimerization of bromide 2 via the carbene 3 is the most simple one. Full spectroscopic data for 1 b are reported for the first time, as is its X-ray structural analysis at - 95°C.
    Additional Material: 2 Ill.
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  • 92
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1485-1487 
    ISSN: 0009-2940
    Keywords: Thioketenes ; Flash-vacuum pyrolysis ; Diels-Alder reaction ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Flash-vacuum pyrolysis of 2,4-bis(dichloromethylene)-1,3-dithietane (1) at 820°C furnishes dichlorothioketene (2a) which may be trapped with cyclopentadiene (3) in a [4+2] cycloaddition. The constitution 4a of the product is confirmed by an X-ray structural analysis of the related cycloadduct 4b.
    Additional Material: 1 Ill.
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  • 93
    ISSN: 0009-2940
    Keywords: Spirosilicates, zwitterionic ; Bond cleavage, Si - C ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bis[2,3-naphthalenediolato(2 - )](pyrrolidiniomethyl)silicate Acetonitrile Solvate: Synthesis and Crystal and Molecular Structure of a Zwitterionic λ5-SpirosilicateThe zwitterionic spirocyclic bis[2,3-naphthalenediolato[2-)](pyrrolidiniomethyl)silicate (3) was synthesized and the crystal and molecular structure of its acetonitrile solvate 3 · CH3CN investigated. 3 was prepared by reaction of trimethoxy(pyrrolidinomethyl)silane (8) or dimethoxy(methyl)(pyrrolidinomethyl)silane (8) or dimethoxy(methyl)(pyrrolidinomethyl)silane (9) with 2,3-dihydroxynaphthalene in acetonitrile. Reaction 9 → 3 involves a remarkable Si - C cleavage with formation of CH4. The pentacoordinate silicon atom of 3 · CH3CN is surrounded by 4 oxygen atoms and 1 carbon atom, the latter being in an equatorial position. The coordination polyhedron can be described as a distorted trigonal bipyramid (the structure is displaced by 20.5% from the trigonal bipyramid towards the square pyramid). The crystal lattice of 3·CH3CN contains centrosymmetric dimers of 3, built up by intermolecular N - H … O hydrogen bonds.
    Additional Material: 2 Ill.
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  • 94
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    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1517-1520 
    ISSN: 0009-2940
    Keywords: Diiminosuccinonitrile ; 2H-Imidazoles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chemistry of Cyanogen: Reactions of Diiminosuccinonitrile (DISN) with Sulfenyl Chlorides, Chlorotrimethylsilane and Ring Closure to Trifluoromethyl-Substituted 2H-Imidazoles4,5-Dicyano-2-hydroxy-2-(trifluoromethyl)-2H-imidazole (1) is easily prepared by treating DISN with trifluoroacetic anhydride. In the presence of 4-(dimethylamino)pyridine, however, the O-acylated derivative 2 is formed in excellent yield, while the reaction of 1 with chlorotrimethylsilane affords the O-silylated product 6. A bi-1,2,5-thiadiazole of the formula S2(CN)4Cl2 (5) is the final reaction product, when DISN is treated with sulfur dichloride in the presence of “naked” chloride ions. On the other hand the non-heterocyclic N-sulfenyl derivative 4 has readily been obtained, when DISN is treated with F3CSCl instead. Finally a procedure is described to convert DISN into the corresponding N-silylated diimine 3.
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  • 95
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1575-1577 
    ISSN: 0009-2940
    Keywords: Oxidative coupling of cyclopentadienide anion ; Dihydrofulvalene, molecular structure ; Migration of trimethylsilyl group ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of 1,2,4-tris(trimethylsilyl)cyclopentadienyllithium with ferric chloride in THF at -95°C leads to the formation of a thermally sensitive iron(III) complex which decomposes to the new dihydrofulvalene derivative 3,7-dihydro-1,3,3,5,7,7-hexakis(trimethylsilyl)fulvalene (1).
    Additional Material: 1 Ill.
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  • 96
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1677-1678 
    ISSN: 0009-2940
    Keywords: Cyclopentadienes, chiral ; Quinone adducts ; Diels-Alder reactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Diels-Alder adduct obtained by addition of quinone to the chiral cyclopentadiene 2 undergoes regioselective and stereoselective reduction after hydrogenation. The 4-hydroxy ketone 3 thus formed yields the title compound 1 in a thermal retro Diels-Alder process.
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  • 97
    ISSN: 0009-2940
    Keywords: P - P bond ; Alkyne insertion ; Diphosphamolybdacyclopentene ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Metal-Containing Heterocycles: Preparation, Properties, Reactions, LXXV1).  -  Synthesis of a Diphosphamolybdacyclopentene by Alkyne Insertion into the P - P Bond of a DiphosphamolybdacyclopropaneInsertion of the alkyne RC≡CR (R = CO2Me) into the P - P bond of the diphosphamolybdacyclopropane (5-C5H5)-(OC)2Mo-PPh2-PAr (2) [Ar = 2,4,6-(tBu)3C6H2] results in the formation of the thermally and kinetically stable diphosphamolybdacyclopentene (η5-C5H5)(OC)2Mo-PPh2-RC = CR-PAr (3), which is characterized on the basis of mass, IR, 31P{1H}-, 1H-, and 13C{1H}-NMR spectra.
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  • 98
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1733-1738 
    ISSN: 0009-2940
    Keywords: Phthalocyanine ; Ruthenium complexes ; Pyridines ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Soluble Bisaxially Substituted (Phthalocyaninato)ruthenium ComplexesSeveral attempts to prepare (tBu4Pc)Ru only led to an impure product (tBu4Pc)RuLx. This reacts quantitatively with pyridine to form (tBu4Pc)Ru(py)2, easily purified by chromatography. In addition the preparation of (tBu4Pc)RuL2 with L = pyridine, 2-picoline (2-pic), 3-picoline (3-pic), 4-picoline (4-pic), 2,5-lutidine (2,5-lut), and 2,6-lutidine (2,6-lut), respectively, is described. All complexes are characterized by spectroscopic methods including 1H-NMR spectroscopy. Not even in the cases of (tBu4Pc)RuL2 with L = 2-pic and 2,5-lut, a careful removal of the ligands L by thermogravimetric methods (TG/DTA) leads to pure (tBu4Pc)Ru. For comparison, the bisadducts PcRuL2 with L = pyridine, picolines (2-pic, 3-pic, 4-pic), lutidines (2,3-lut, 2,5-lut, 2,6-lut), and chloropyridines (2-Clpy and 3-Clpy), respectively, are prepared by treatment of PcRu with an excess of the ligand. For the first time (phthalocyaninato)iron complexes PcFeL2 with sterically hindered axial ligands, e.g. PcFe(2-pic)2, are prepared and characterized by 57Fe Mößbauer spectroscopy.
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  • 99
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1809-1817 
    ISSN: 0009-2940
    Keywords: Lithiation ; Mannich reaction ; Alkylation ; Grignard reaction ; Condensation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Phenols and naphthols are benzotriazolylmethylated by 1-(hydroxymethyl)-1H-benzotriazole (13) (a formaldehyde derivative) in the o- or (if both o-positions are occupied) in the p-position. The reaction can be extended to other aldehydes in the case of the naphthols. The methylene group in the o-(benzotriazolylmethyl)phenols can be lithiated (but only after trimethylsilyl protection of the hydroxy group) and then substituted by various electrophiles. The benzotriazole residues in both the primary products and in their substituted derivatives can be displaced by the alkyl anions of Grignard reagents or by hydride ions allowing the elaboration of many new types of substituted phenols.
    Additional Material: 5 Tab.
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  • 100
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1827-1830 
    ISSN: 0009-2940
    Keywords: Cyclopropannelation ; Bicyclo[3.3.0]octane derivatives ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To facilitate the synthesis of tetracycles containing the framework 2, the reaction of the tetrabromide 8 with cyanide and bis(phenylsulfonyl)methane under various conditions was investigated. Instead of the expected twofold bridging, novel cyclopropa derivatives were obtained. Product formation is a consequence of the stereochemistry of the starting material 8, with the exo configuration of the bromomethyl substituents being the crucial factor.
    Additional Material: 1 Ill.
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