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  • 1990-1994  (262)
  • 1985-1989
  • 1970-1974  (176)
  • 1850-1859
  • 1991  (262)
  • 1972  (176)
  • Physical Chemistry  (266)
  • Ultrastructure
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  • 1990-1994  (262)
  • 1985-1989
  • 1970-1974  (176)
  • 1850-1859
Year
Keywords
  • 1
    Electronic Resource
    Electronic Resource
    Diethylene glycol (DEG)-associated myocardial changes: A pilot investigation of chronic intoxication in guinea-pigs (1991)
    Springer
    International journal of legal medicine 104 (1991), S. 93-97 
    Details
    ISSN: 1437-1596
    Keywords: Diethylene glycol ; Intoxication ; Myocardium ; Myocytolysis ; Ultrastructure ; Mitochondria ; Guinea pig ; Diethylenglycol ; Intoxikation ; Myokard ; Myozytolyse ; Ultrastruktur ; Mitochondrien ; Meerschweinchen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine , Law
    Description / Table of Contents: Zusammenfassung Das Myokard von Meerschweinchen, welche mit subletalen Mengen von Diethylenglycol über eine Zeitdauer von 2–11 Tagen gefüttert worden waren, wurde mikroskopisch und elektronenmikroskopisch untersucht. Eine Koagulationsmyozytolyse und Verlust von Myofibrillen war fleckförmig verstreut über das Myokard. Diese Veränderungen waren in den Kontrollen nicht zu beobachten. Die begleitenden ultrastrukturellen Veränderungen bestanden in Schwellung, Pleomorphie, Hyperplasie von Mitochondrien, begleitet von einer Erweiterung der interfibrillären Räume und Verlagerung, Verzerrung und Ruptur angrenzender Fibrillen.
    Notes: Summary The myocardium of guinea pigs fed on sublethal doses of diethylene glycol (DEG) over a period of 2–11 days was examined for microscopical and ultrastructural changes. Coagulative myocytolysis and loss of myofibrils, not observed in the controls, was patchily distributed throughout the myocardium. The accompanying ultrastructural features included swelling, pleomorphism and hyperplasia of mitochondria with an associated distension of the interfibrillary spaces and a displacement, distortion and rupture of adjacent myofibrils.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01626038
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  • 2
    Electronic Resource
    Electronic Resource
    Effect of dopamine agonist medication on prolactin producing pituitary adenomas (1991)
    Springer
    Virchows Archiv 418 (1991), S. 439-446 
    Details
    ISSN: 1432-2307
    Keywords: Bromocriptine ; Pituitary neoplasm ; Prolactin ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Conventional light microscopy, immunocyto-chemistry, electron microscopy and in situ hybridization were used to evaluate the effect of dopamine agonists (bromocriptine-LAR and bromocriptine) on the morphology of surgically removed prolactin (PRL)-producing pituitary adenomas. Dopamine agonist therapy resulted in decrease of serum PRL, clinical improvement and tumour shrinkage. Using light and electron microscopy cellular atrophy, interstitial and perivascular fibrosis were noted; in several tumours connective tissue accumulation was pronounced. The cellular response was not uniform. In some adenomas populations of large cells and small cells were distinguished. The large cells contained immunoreactive PRL and expressed the PRL gene indicating resistance to dopamine agonists. It appears that these cells retained the potential to secrete PRL and proliferate despite exposure to dopamine agonists. In the small cells, PRL immunoreactivity and PRL gene expression decreased providing evidence that both PRL release and synthesis were blocked. Small cells can persist in tumours after discontinuation of dopamine agonist medication suggesting these small cells are irreversibly suppressed and are not capable of regaining their endocrine function and proliferative capability. The formation of irreversibly suppressed PRL cells may explain why some PRL-producing adenomas do not recur after withdrawal of dopamine agonists.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01605931
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  • 3
    Electronic Resource
    Electronic Resource
    Immunohistochemical characterization of HLA-DR-antigen positive dendritic cells in phaeochromocytomas and paragangliomas as a prognostic marker (1991)
    Springer
    Virchows Archiv 418 (1991), S. 33-39 
    Details
    ISSN: 1432-2307
    Keywords: HLA-DR ; Phaeochromocytomas ; Paragangliomas ; Immunohistochemistry ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Twelve cases of phaeochromocytoma (PCC) and four cases of paraganglioma (PGG) were studied by immunohistochemistry and immunoelectron microscopy in order to demonstrate HLA-DR (Ia)-antigen-positive dendritic cells (IaDCs). Dense infiltration of IaDCs was detected in the majority of PCCs revealing high urinary or serum catecholamine levels, but in aggressively growing PCCs, a familial PCC and all PGGs, few IaDCs were demonstrated. Interestingly, these IaDCs were negative for S-100 protein. Although S-100-protein-positive sustentacular-like cells (SCs), morphologically similar to IaDCs, were also present, these were clearly distinguished from IaDCs by our double immunostaining method. Ultrastructurally, IaDCs had smooth or slightly indented nuclei and contained a moderate amount of endoplasmic reticulum, small mitochondria and vacuoles, extending elongated cytoplasmic processes. These results suggest that determination of the quantity of IaDCs is a highly effective method of assessing the character of PCCs, in particular, their prognosis.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01600242
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  • 4
    Electronic Resource
    Electronic Resource
    Cell-mediated cytotoxicity in acute rat cardiac allograft rejection: An immunological and ultrastructural study (1991)
    Springer
    Virchows Archiv 418 (1991), S. 41-50 
    Details
    ISSN: 1432-2307
    Keywords: Cell-mediated cardiocyte injury ; Acute cardiac allograft rejection ; Mononuclear cellular infiltration ; Immunohistochemistry ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary To clarify the immune mechanism of cytotoxicity in acute cardiac allograft rejection, we observed interactions between cardiocytes and mononuclear cells using immunohistochemistry and light and electron microscopy. All allografted WKA rat hearts transplanted to F344 recipients stopped beating by the 7th day after the transplantation. The population of helper/inducer T cells (Th) and IL2R+ cells was large for the first 3 days, whereas that of cytotoxic/suppressor T cells (Tc-s) and macrophages increased from the 4th day. TheTh/Tc-s ratios were more than 2.0 until the 3rd day, then decreased to less than 1.0. In circulating T lymphocytes; theTh/Tc-s ratios were under 1.0 on the 1st, 6th and 7th days. Electron microscopically IL2R+ cells, Tc-s and macrophages were often seen in close contact with the plasma membrane of the cardiocytes. The majority of IL2R+ cells are NK cells, Tc-s andTh. Of these, the population of Tc-s was small until the 3rd day. Thus, NK cells play a pivotal role in the early stage of the rejection, and Tc-s and macrophages then aggravate cell-mediated cardiocyte injury.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01600243
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  • 5
    Electronic Resource
    Electronic Resource
    Ultrastructure of oesophageal melanocytosis (1991)
    Springer
    Virchows Archiv 418 (1991), S. 515-522 
    Details
    ISSN: 1432-2307
    Keywords: Oesophagus ; Melanocyte ; Melanoma ; Ultrastructure ; Endoscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Four examples of an endoscopically detected oesophageal melanotic lesion were examined by light microscopy, light microscope histochemistry and transmission electron microscopy, and were compared with 13 control samples of normal oesophageal epithelium. By light microscopy, pigmented melanocytes lacking atypia and mitoses were observed amongst the keratinocytes in the basal layer of the oesophageal mucosa. Junctional activity was absent. The mechanism of pigmentation was studied and found to consist of: an increase in the number of melanocytes in the basal layer of the mucosa, an increase in the quantity of melanin in these melanocytes, transfer of melanin from melanocytes to keratinocytes and to macrophages and fibroblasts in the tunica propria. Since all the lesions demonstrated increased numbers of both melanocytes and melanosomes, the term oesophagealmelanocytosis rather thanmelanosis is suggested, to emphasise the essential character of the lesion as a cellular proliferation. The value of sampling these pigmented lesions during endoscopy is emphasised as a means of obtaining well-preserved material for the evaluation of a lesion which some authorities have viewed as a possible precursor for oesophageal malignant melanoma.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01606502
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  • 6
    Electronic Resource
    Electronic Resource
    Ultrastructural abnormalities of mitochondria and deficiency of myocardial cytochromec oxidase in a patient with ventricular tachycardia (1991)
    Springer
    Virchows Archiv 419 (1991), S. 63-68 
    Details
    ISSN: 1432-2307
    Keywords: Mitochondrial cardiomyopathy ; Ultrastructure ; Cytochromec oxidase deficiency ; Ventricular tachycardia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary A 30-year-old woman presented with lifethreatening ventricular tachycardia without overt heart disease. Ultrastructural investigation of endomyocardial biopsy disclosed abnormally structured and often enlarged mitochondria. Morphometry revealed the ratio of volume density of mitochondria to myofibrils to be markedly increased to 0.667 as compared with five controls (mean: 0.46; range: 0.445–0.479). Investigation of mitochondrial respiratory chain enzymes revealed a 90% reduction in activity of cytochromec oxidase. Our data suggest that mitochondrial cardiomyopathy may induce malignant ventricular arrhythmias.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01600154
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  • 7
    Electronic Resource
    Electronic Resource
    Varicocele in the rat: a new experimental model (1991)
    Springer
    Urological research 19 (1991), S. 319-322 
    Details
    ISSN: 1434-0879
    Keywords: Varicocele ; Rat, Histology ; Ultrastructure ; Temperature ; Infertility
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary With no consistent animal prototype for the study of varicocele, we set out to create a model in the rat by complete ligation of the main branch of left spermatic vein (MBSV) or by partial ligation of the left renal vein. Three months later, the histology, ultrastructure and temperature of the testis and epididymis were studied. Microscopically, spermatogenic arrest was the most frequent anomaly seen. The most frequently noted ultrastructural change of the testis was distension of smooth endoplasmic reticula in Sertoli cells. The microvilli of columnar epithelia in epididymis were sparse and showed local defects. Lesions and increased temperatures in the testis and epididymis induced by the ligation of the left MBSV were similar to those seen in partial ligation of the left renal veins, with no significant differences between left and right. Significant differences were found, however, on comparison with the controls.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00299069
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  • 8
    Electronic Resource
    Electronic Resource
    Morphology of the synovium during its differentiation and development in the mouse knee joint (1991)
    Springer
    Anatomy and embryology 183 (1991), S. 537-544 
    Details
    ISSN: 1432-0568
    Keywords: Synovial membrane ; Development ; Ultrastructure ; Scanning electron microscopy ; Mouse
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The prenatal and postnatal development of the mouse knee joint was investigated by transmission and scanning electron microscopy. In the prenatal stage, following the appearance of a narrow intercellular cleft between two skeletal elements on the 16th fetal day, clefting extended into the lateral synovial mesenchyme. In some regions, the extension of the cleft was very rapid, but in a certain region (future fat pad region), it was somewhat slower. Macrophage-like cells appeared in the synovial mesenchyme on the 16th fetal day, and then increased in number, and were distributed as if they were clustering around the presumptive clefting zone in the future fat pad region on the 17th–18th fetal day. This suggests that macrophage-like cells may participate in joint development, as they phagocytize and remove some kinds of solid extracellular matrix, and facilitate the cleft extension. In the early postnatal stage, scanning electron microscopic observations showed that there were two different types of cell in the synovial lining. One of them exhibited a surface morphology corresponding to that of macrophages: a spherical cell body and numerous pseudopodia. The other type of cell exhibited various cell shapes with many cytoplasmic processes extending along the synovial surface.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00187902
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  • 9
    Electronic Resource
    Electronic Resource
    Endothelial heterogeneity in the chick wing bud: A morphometric study (1991)
    Springer
    Anatomy and embryology 184 (1991), S. 47-53 
    Details
    ISSN: 1432-0568
    Keywords: Wing bud ; Endothelial cell ; Development ; Ultrastructure ; Morphometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The microvascular endothelium of the chick wing bud at stages 22, 27, and 32 was evaluated by ultrastructural morphometry. The rationale for this study is based on the hypothesis that endothelial cells exhibit variation in structure and function during cytodifferentiation. The microvessels had a luminal diameter range such that they were classified as capillaries. The thin continuous endothelium was devoid of a basal lamina. The endothelium had a very small number of plasmalemmal vesicles; vacuoles were however present for all stages and in some cases were abundant. The temporal findings were that endothelial cell thickness increases, plasmalemmal vesicle densities decrease, and the densities of cytoplasmic vacuoles increase. The spatial results were that endothelial cells in proximal regions of the limb have a greater thickness, contain fewer vesicles and have more vacuoles than those in distal regions. In general, these results indicate that endothelial ultrastructural heterogeneity occurs within a 31/2 day timespan of wing bud development. The discussion considers the results with regard to recent reports on endothelial cell heterogeneity.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01744260
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  • 10
    Electronic Resource
    Electronic Resource
    Development of taste organs inRana temporaria (1991)
    Springer
    Anatomy and embryology 184 (1991), S. 363-369 
    Details
    ISSN: 1432-0568
    Keywords: Taste organs ; Amphibia ; Development ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary In tadpoles ofRana temporaria two successive generations of taste organs: taste buds (TBs) and taste disks were studied. The TBs are located in the apices of oral premetamorphic papillae. Each TB consists of vertically elongated receptor cells (probably taste) and supporting cells. No basal (Merkel) cells were observed there. Morphologically, two types of receptor cells have been distinguished in a TB. Complete synaptic structures were observed in the TBs between the 30th and 41st of Gosner's (1960) developmental stages, though synaptic vesicles occur already at stage 26. The taste disks consist of taste cells, supporting cells and basal cells. Dense-core synaptic vesicles occur in the gustatory cells at stage 41, but complete synaptic structures were not observed earlier than at stage 45. Synaptic junctions observed at some of the gustatory cells seem to be reciprocal (bidirectional).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00957898
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  • 11
    Electronic Resource
    Electronic Resource
    The anatomy and fine structure of the echidnaTachyglossus aculeatus snout with respect to its different trigeminal sensory receptors including the electroreceptors (1991)
    Springer
    Anatomy and embryology 184 (1991), S. 371-393 
    Details
    ISSN: 1432-0568
    Keywords: Tachyglossus aculeatus (echidna) ; Echidna bill ; Sensory receptors ; Electroreceptor ; Mechanoreceptor ; Trigeminal nerve ; Monotreme ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The gross anatomy and nerve supply of the bill of echidna (Tachyglossus aculeatus) is described in relation to its function as an outstanding sensory organ. The sensory innervation of the skin of the echidna snout was investigated by means of frontal serial sections, after decalcification of the specimens. A comprehensive light and electron microscopic description of the location and fine structure of cutaneous sensory receptors of the trigeminal system was made by this means. The encapsulated and non-encapsulated Ruffini receptors, the types of other free receptors in the connective tissue and the Merkel cell receptor do not differ morphologically from those of higher mammals, whereas the pacinian-like corpuscle shows a unique organization of its outer core. This is composed of large perineural cells containing a unique reticulum of parallel-orientated endoplasmic membranes. Lamellated corpuscles, seen in isolation or in association with push rods, are numerous in the snout and in the tip of the tongue of echidna. Push rod receptor organs occur in the hairless skin of the bill with a very dense array at its rostral end and in the pseudopalatal ridges. Gland duct receptors are restricted to the skin adjacent to the nostrils and the mouth opening, including the pseudopalatal plates. Only about one quarter of the total number of 400 seromucous glands receive a sensory innervation of their intraepidermal duct segment. Within each innervated gland two types of receptor terminals are identified. The distributions of the different receptor types are mapped for different regions of the skin, the mucous membrane of the nasal and oral vestibule and the tip of the tongue. The fine structure of nerve terminals is discussed from a comparative anatomical point of view, and some speculations are made about possible transduction processes that underlie the known electrophysiological properties. The sensory organs such as the “push rod” and “gland duct receptor”, and most of their sensory terminals, are less differentiated in echidna snout than in the platypus (Ornithorhynchus anatinus) bill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00957899
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  • 12
    Electronic Resource
    Electronic Resource
    Immunocytochemical and ultrastructural studies of hyaline inclusions in sporadic motor neuron disease (1991)
    Springer
    Acta neuropathologica 82 (1991), S. 295-301 
    Details
    ISSN: 1432-0533
    Keywords: Hyaline inclusions ; Motor neuron disease ; Amyotrophic lateral sclerosis ; Immunocytochemistry ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary We investigated hyaline inclusion bodies (HI) immunocytochemically and ultrastructurally in six cases of sporadic motor neuron disease (MND). All HI contained large amounts of ubiquitin and some HI were stained at the core or the center with anti-neurofilament antibody, with the surrounding halo unstained. No HI were stained with antibodies raised against cytoskeletal proteins such as high-molecular weight microtubule-associated proteins and phosphorylated tau. Ultrastructurally, HI were chiefly composed of filaments measuring about 20 nm in diameter thicker than neurofilaments, and contained fine granules and frequently one or more of four characteristic profiles, i.e., small electron-dense materials resembling Bunina bodies, bundles of tubular filaments measuring approximately 20 nm in diameter, large electron-dense cores, and focal accumulations of randomly arranged neurofilaments. Hyaline inclusions can be regarded as one of the characteristic markers for sporadic MND as well as familial amyotrophic lateral sclerosis. Hyaline inclusions have a markedly heterogeneous ultrastructure and, therefore, differences in immunoreactivity with antineurofilament antibodies are not unexpected.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00308815
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  • 13
    Electronic Resource
    Electronic Resource
    Meningiomas differentiating to arachnoid trabecular cells: a proposal for histological subtype “arachnoid trabecular cell meningioma” (1991)
    Springer
    Acta neuropathologica 82 (1991), S. 327-330 
    Details
    ISSN: 1432-0533
    Keywords: Meningioma ; Microcystic meningioma ; Vacuolated meningioma ; Arachnoid trabecular cell ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Three cases of meningiomas which had abundant small vacuoles in the tumor tissue are reported. By electron microscopy, the tumor cells exhibited long and thin processes, the tips of which were united by desmosomes. The tumor tissue was revealed to have wide extracellular spaces which corresponded to the vacuoles observed by light microscopy. In previous literature, various terms have been used when referring to this meningioma, such as microcystic meningioma or vacuolated meningioma. Since the ultrastructure of the tumor showed similarity to that of normal arachnoid trabecular cells, we propose to call the tumor “arachnoid trabecular cell meningioma” denoting its morphological nature clearly.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00296542
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  • 14
    Electronic Resource
    Electronic Resource
    Galactosialidosis: neuropathological findings in a case of the late-infantile type (1991)
    Springer
    Acta neuropathologica 82 (1991), S. 331-339 
    Details
    ISSN: 1432-0533
    Keywords: Galactosialidosis ; Neuronal storage disease ; Neuropathology ; Ultrastructure ; Neuronal loss
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The neuropathological findings in a 13-year-old Japanese male showing decrease of sialidase and β-galactosidase activities are reported. The patient was the product of normal pregnancy to consanguineous parents. He started to sit at 8 months, stand at 20 months and walk at the age of 2; mental retardation, visual disturbance, cerebellar ataxia, myoclonus and epilepsy developed by the age of 10, and he died at 13. Neuropathological investigation revealed neuronal loss and storage. Severe loss of neurons was observed in the thalamus, globus pallidus, lateral geniculate body, gracile nucleus, Purkinje and retinal ganglion cells. Marked ballooning was seen in the Betz cells and neurons in the basal forebrain, the motor neurons in the cranial nerve nuclei and spinal cord, and in the trigeminal and spinal ganglia. The storage material varied in staining from region to region and from neuron to neuron. Electron microscopic investigation revealed a variety of intracytoplasmic and intranuclear inclusions: membranous cytoplasmic bodies, parallel, wavy-lamellar or tortuous tubular structures, lipofuscin-like irregular-shaped pleomorphic bodies, and cytoplasmic vacuoles with fine granules and lamellar materials. The severity of the neuronal loss did not seem to correlate with the amount of the storage materials, but with the presence of tortuous tubular inclusion.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00296543
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  • 15
    Electronic Resource
    Electronic Resource
    Intramedullary secretory gangliocytoma (1991)
    Springer
    Acta neuropathologica 82 (1991), S. 402-407 
    Details
    ISSN: 1432-0533
    Keywords: Gangliocytoma ; Ultrastructure ; Catecholamines ; Hypertension ; Spinal cord
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary An 8-year-old boy developed severe systemic hypertension during resection of an intramedullary tumor. The histological, ultrastructural and immunocytochemical characteristics of the tumor are those of a gangliocytoma. Based on the demonstration of tyrosine hydroxylase in neuronal tumor cells, it is postulated that catecholamine secretion was responsible for the systemic hypertension.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00296552
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  • 16
    Electronic Resource
    Electronic Resource
    Immunocytochemical and ultrastructural studies of Werdnig-Hoffmann disease (1991)
    Springer
    Acta neuropathologica 81 (1991), S. 408-417 
    Details
    ISSN: 1432-0533
    Keywords: Werdnig-Hoffmann disease ; Immunocytochemistry ; Ultrastructure ; Cytoskeleton ; Ubiquitin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Neuronal alterations in two cases of Werdnig-Hoffmann disease (WH) were investigated immunocytochemically and ultrastructurally. Ballooned neurons (BNs) were found in anterior horn, Clarke's column, dorsal root ganglion and thalamus. Anti-phosphorylated neurofilament antibodies preferentially stained the peripheral perikarya and proximal neuronal processes of BNs, whereas anti-ubiquitin antibodies preferentially stained the central perikarya of BNs. Ultrastructurally, BNs showed degenerative changes ranging from a diffuse increase of neurofilaments to a centrally accentuated accumulation of mitochondria and vesicular or membranous profiles. Our studies suggest that ubiquitinated degradation products accumulate in the center of the BN's perikaryon and displace aberrantly phosphorylated neurofilaments to the periphery. BNs in WH probably reflect an intrinsic alteration in the metabolism of neurofilaments that is associated with regressive changes in the neuron and eventually neuronal death.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00293462
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  • 17
    Electronic Resource
    Electronic Resource
    The effect of denervation on the morphology of regenerating rat soleus muscles (1991)
    Springer
    Acta neuropathologica 82 (1991), S. 21-32 
    Details
    ISSN: 1432-0533
    Keywords: Muscle ; Regeneration ; Denervation ; Ultrastructure ; Snake toxin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary This study examines the level to which muscle regeneration proceeds in the absence of innervation. Regeneration was monitored in rat soleus muscles following localised injection of a snake toxin, notexin. Muscles which had been concomittantly denervated were compared with those that were normally innervated. Until 3–4 days following toxin administration regeneration is identical in both groups. The muscles contain new myotubes in place of the degenerated “parent” fibres. Thereafter, the non-denervated muscles grow rapidly and by 28 days their myofibres attain the size of those from the contralateral controls. Growth of denervated regenerating muscles, however, is retarded and is superseded by a gradual atrophy. In such muscles we further identify ultrastructural abnormalities from 7 days post-injection. These a re loss of individual myosin filaments and the presence of immature and abnormal configurations of the transverse system and triads. We, thus, conclude that innervation is an obligatory requirement for the restoration of normal myofibrillar and sarcotubular morphology, as well as growth, but is not necessary for the neo-formation of myofibres.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00310919
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  • 18
    Electronic Resource
    Electronic Resource
    Bone marrow transplant in a case of mucopolysaccharidosis I Scheie phenotype: skin ultrastructure before and after transplantation (1991)
    Springer
    Acta neuropathologica 82 (1991), S. 33-38 
    Details
    ISSN: 1432-0533
    Keywords: MPS I-S ; Skin biopsy ; Ultrastructure ; Bone marrow transplant
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary An 11-year-old girl with mucopolysaccharidosis I Scheie phenotype (MPS I-S) received a bone marrow transplant (BMT) from her heterozygous HLA-identical LMC-non-reactive mother. Multidisciplinary studies were carried out and results evaluated 21 months after transplantation. Herein we report the ultrastructural findings pre-and post-BMT in skin. Multidisciplinary studies are commonly used to evaluate the benefits of metabolic correction following BMT in some MPS and other inherited metabolic disorders, and changes in morphology have been described in liver and few other tissues. In this case, we elected skin, since connective tissue is universally involved in MPS and is safely and easily obtainable. Comparison of skin biopsy specimens taken before and after BMT showed a considerable change in dermal fibroblast morphology, with marked reduction in cell size and the number and size of abnormal lysosomes, thus indicating the clearance of storage. Our results demonstrate that dermal cells respond to enzyme replacement therapy in MPS I-S, with the clearance of glycosaminoglycan lysosomal accumulation in connective tissue fibroblasts, which had near-normal morphology 21 months after BMT. Therefore, the practice of skin biopsy after BMT in MPS and other metabolic disorders in which dermal cells are involved should be encouraged.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00310920
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  • 19
    Electronic Resource
    Electronic Resource
    Idiopathic prolactin cell hyperplasia of the pituitary mimicking prolactin cell adenoma: a morphological study including immunocytochemistry, electron microscopy, and in situ hybridization (1991)
    Springer
    Acta neuropathologica 82 (1991), S. 147-151 
    Details
    ISSN: 1432-0533
    Keywords: Hyperplasia ; Pituitary ; Pathology ; Prolactin ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Prolactin cell adenoma is the most frequently found lesion in surgically removed pituitaries of patients with hyperprolactinemia. However, in several instances, instead of prolactin cell adenoma, other lesions are encountered by morphological investigation. We report here the morphological findings in a patient with hyperprolactinemia who underwent transsphenoidal pituitary surgery for suspected prolactin cell adenoma. A morphological diagnosis of tumor could not be confirmed and massive diffuse prolactin cell hyperplasia was identified. The aim of this publication is to describe the lesion by histology, immunocytochemistry, electron microscopy, and in situ hybridization and to call attention to primary prolactin cell hyperplasia which can mimic prolactin cell adenoma.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00293958
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  • 20
    Electronic Resource
    Electronic Resource
    Fulminant blastomycosis with blastomycotic infection of a cerebral glioma (1991)
    Springer
    Acta neuropathologica 82 (1991), S. 420-424 
    Details
    ISSN: 1432-0533
    Keywords: Blastomycosis ; North American Blastomy-cosis ; Brain tumor ; Opportunistic infection ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Except for isolated case reports, blastomycosis has not been identified as a significant problem in immunosuppressed patients. We describe an unusual case with blastomycotic infection of a cerebral glioma in a 56-year-old man who underwent radiotherapy for his tumor and died of fulminant blastomycotic pneumonia. This is believed to be the first reported case of Blastomyces dermatitidis infection of a cerebral glioma. The light microscopic and ultrastructural features of B. dermatitidis, the giant forms of which were encountered in our patient, are described, and the role of immuno-suppression due to steroid therapy in the pathogenesis of this fulminant infection are reviewed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00296555
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  • 21
    Electronic Resource
    Electronic Resource
    Scrapie inoculation of mice: light and electron microscopy of the superior colliculi (1991)
    Springer
    Acta neuropathologica 81 (1991), S. 562-571 
    Details
    ISSN: 1432-0533
    Keywords: Scrapie ; Ultrastructure ; Vacuolation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Ultrastructural examination of the superior colliculi of mice intraocularly inoculated with the ME7 strain of scrapie showed vacuolation early in the course of infection. Brains were examined between 85–260 days after monocular inoculation with scrapie. The mean incubation period for the development of clinical disease was 302 days. Vacuolation was seen initially in the contralateral superior colliculus and subsequently in the ipsilateral colliculus. In coded trails light microscopical vacuolation was seen from 218 days but ultrastructural examination showed that sparse vacuoles were inconsistently present in either or both of the ipsilateral and contralateral colliculi from 85 days; frequent vacuoles were seen from 190 days. Scrapie-induced vacuoles were differentiated from vacuoles present in control tissue by the presence of loculation or by a limiting double membrane which showed protrusion or proliferation of the innermost lamella. Vacuolation was seen in neuronal perikarya, myelinated fibres, dendrites and axonal presynaptic terminals. Vacuoles of myelinated fibres were observed within myelin and possibly also in the inner tongue of oligodendroglial cytoplasm. Whorled membrane configurations were also seen. Tubulovesicular particles, 40 nm in diameter, were recognised in two scrapie-infected mice. It is suggested that some scrapie vacuoles arise as a result of incorporation of abnormal membrane into organelles, possibly mitochondria, in neuronal perikarya and neurites and probably also within oligodendroglial cytoplasm and myelin.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00310139
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  • 22
    Electronic Resource
    Electronic Resource
    Histopathogenesis of inflammatory linear verrucose epidermal naevus: histochemistry, immunohistochemistry and ultrastructure (1991)
    Springer
    Archives of dermatological research 283 (1991), S. 491-499 
    Details
    ISSN: 1432-069X
    Keywords: Inflammatory linear epidermal naevus ; Keratinization ; DACM ; Involucrin ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Skin lesions of three patients with inflammatory linear verrucose epidermal naevus (ILVEN) were examined. Histologically, orthokeratosis and parakeratosis were alternately seen in the acanthotic epidermis. By N-(7-dimethylamino-4-methyl-3-coumarinyl)maleimide staining, the horny cells in the parakeratotic epidermis showed a cytoplasmic SH pattern and a weak membranous SS pattern. The orthokeratotic epidermis revealed an increased involucrin expression, whereas the parakeratotic epidermis showed almost no involucrin expression. Ultrastructurally, in the parakeratotic epidermis, the living keratinocytes had prominent Golgi apparatuses and vesicles in the cytoplasm. In the intercellular spaces in the upper spinous layer through to the lower horny layer, an electron dense, homogeneous substance was deposited. The cytoplasm of the horny cells was filled with keratin filaments and contained remnants of nucleus and cytoplasmic membrane structures, and some lipid droplets. The marginal band formation was incomplete. Most of these ultrastructural abnormalities were not found in the orthokeratotic epidermis. There are both similarities and differences in histopathogenesis of the parakeratotic epidermis between ILVEN and psoriasis. A unique finding was the lack of involucrin expression in the ILVEN parakeratotic epidermis.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00371921
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  • 23
    Electronic Resource
    Electronic Resource
    The rhino mouse model: the effects of topically applied all-trans retinoic acid and CD271 on the fine structure of the epidermis and utricle wall of pseudocomedones (1991)
    Springer
    Archives of dermatological research 283 (1991), S. 100-107 
    Details
    ISSN: 1432-069X
    Keywords: Rhino mouse skin ; All-trans retinoic acid ; CD271 ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The histological and ultrastructural effects following 3 weeks' topical treatment with two agents (all-trans retinoic acid and a new synthetic retinoid-like substance, CD271) were evaluated on the epidermis and the epithelial wall of the pseudocomedones in rhino mouse skin. The comedolytic effects of these drugs were similar, and consisted of a reduction of the utricular diameter, with normalization of follicular units. Morphological examinations revealed a hyperplastic response with an increase in the number of cell layers of both epidermis and follicular epithelium, and modifications in keratinocyte differentiation. Ultrastructural changes in the epidermis and epithelial wall were observed mainly in the granular and horny layers, with increased desquamation, and a decrease in the cohesiveness of corneocytes. During the first week of treatment, some cutaneous toxic effects were noticed, but they normalized within two weeks. On the other hand, a fine granular material persisted in the intercellular spaces. It is confirmed that the skin of the rhino mouse is a good model for the evaluation of the comedolytic effects of drugs. Moreover, it reveals the specific effects of retinoids on epidermal differentiation. We have demonstrated that topically applied CD271 induces modifications similar to those obtained with all-trans retinoic acid. It is thus concluded that CD271 is a potentially effective anti-acne agent.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00371617
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  • 24
    Electronic Resource
    Electronic Resource
    Ultrastructural study of the skin in Sjögren — Larsson syndrome (1991)
    Springer
    Archives of dermatological research 283 (1991), S. 141-148 
    Details
    ISSN: 1432-069X
    Keywords: Sjögren ; Larsson syndrome ; Ichthyosis ; Ultrastructure ; Lamellar body ; Keratinization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The ichthyosiform skin and the uninvolved skin of a 5-year-old Japanese female with Sjögren — Larsson syndrome were examined by light and electron microscopy to elucidate the keratinization disorder. Light microscopically, the epidermis of the ichthyosiform skin showed acanthosis, papillomatosis and hyperkeratosis. The horny cells had a basket-weave appearance. The granular cell layer was slightly thickened. Slight round cell infiltration and vascular dilatation were seen in the upper dermis. The uninvolved skin was histologically normal. Electron microscopically, in both ichthyosiform and uninolved skin, abnormal lamellar or membranous inclusions were present in the cytoplasm of horny cells of the epidermis. These inclusions appeared to be derived from some of the lamellar bodies and/or abnormal membranous structures found in the cytoplasm of spinous and granular cells. Mitochondria in the epidermal basal cells were more numerous in the ichthyosiform skin than in the uninvolved skin. These findings indicate that, whether the skin is involved or not, the epidermis of the patient with this disorder may always have a structural abnormality, which may be genetically determined. Local environmental factors may play a role in inducing the acanthosis and papillomatosis of the epidermis.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00372053
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  • 25
    Electronic Resource
    Electronic Resource
    Are accessory nuclei involved in the establishment of developmental gradients in hymenopteran oocytes? (1991)
    Springer
    Development genes and evolution 199 (1991), S. 423-426 
    Details
    ISSN: 1432-041X
    Keywords: Oogenesis ; Accessory nuclei ; Developmental gradients ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary In the oocytes ofTenthredo olivacea, accessory nuclei (AN) are formed by budding from the nuclear envelope of the oocyte nucleus. Newly formed AN contain electron-dense material of nuclear origin and are surrounded by a double envelope devoid of pores. Such structures are subsequently transported to the peripheral ooplasm (periplasm), where they grow to reach a final diameter of 5 µm. In the envelopes of advanced AN nuclear pores arise. Through these pores “nuage” material is extruded into the surrounding periplasm. These findings are discussed with respect to a possible involvement of AN in the establishment of developmental gradients in hymenopteran oocytes.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01705853
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  • 26
    Electronic Resource
    Electronic Resource
    The origin of the nascent blastocoele in preimplantation mouse embryos ultrastructural cytochemistry and effect of chloroquine (1991)
    Springer
    Development genes and evolution 200 (1991), S. 77-85 
    Details
    ISSN: 1432-041X
    Keywords: Lysosomes ; Ultrastructure ; Chloroquine ; Blastocyst ; Mouse
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Mouse morulae are known to undergo cavitation as soon as some external cells have entered the sixth cell cycle (Garbutt et al. 1987). Since the early cytological features of cavitation are still unclear, we undertook a careful ultrastructural analysis of late morulae-nascent blastocysts. In addition, since maturation of lysosomes might be involved in the first step of cavity formation, we focused our attention on these organelles by means of the cytochemical localization of trimetaphosphatase activity and by the study of the effects of chloroquine on precavitation embryos. Our results suggest that cavitation starts in a few external cells (presumably competent cells entering the sixth cell cycle), by the chloroquine-sensitive formation of degradative autophagic vacuoles engulfing lipid droplets and vacuoles containing osmiophilic material. These complex structures enlarge (as a result of lipid metabolism?) and so transform into intrablastomeric cavities which, by means of a membrane fusion process, very rapidly become extracellular cavities that coalesce. The abembryonic pole of the blastocyst is determined in this way. Moreover, we suggest that the juxtacoelic cytoplasmic processes covering the inner cell mass (ICM) cells, which are known to restrict the expression of their totipotency during early cavitation (Fleming et al. 1984), are the latest remnants of the walls of the growing intrablastomeric cavities.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00637187
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  • 27
    Electronic Resource
    Electronic Resource
    Contributions of sodium and chloride to ultrastructural damage after dendrotomy (1991)
    Springer
    Experimental brain research 86 (1991), S. 60-72 
    Details
    ISSN: 1432-1106
    Keywords: Trauma ; Neuron ; Sodium ; Chloride ; Ultrastructure ; Mouse
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary To determine the contributions of sodium and chloride to ultrastructural changes after mechanical injury, we amputated primary dendrites of cultured mouse spinal neurons in low calcium medium in which sodium chloride had been replaced with either choline chloride or sodium isethionate or sodium propionate. Uninjured cultured neurons were also exposed to the sodium ionophore, monensin. A third set of neurons was injured in medium in which all sodium and calcium chloride had been replaced with sucrose. Neurons injured in low-calcium, low-sodium medium exhibited few ultrastructural changes, except very near the lesion, where there was some dilation of mitochondria and cisternae of the smooth endoplasmic reticulum (SER). Mitochondria in other regions of the neurons developed an electron opaque matrix, and those nearer to the lesion converted to the condensed configuration, characterized by expanded intracristal spaces as well as a dense matrix. If sodium but not chloride was present in the medium, there was some dilation of the Golgi cisternae after injury, as well as some increased electron opacity of the mitochondria. Monensin treated neurons also exhibited dilation of the Golgi cisternae. Neurons injured in sucrose-substituted medium showed none of the changes associated with injury in normal culture medium. These results indicate that sodium influx through the lesion is involved in the dilation of the SER, which is seen even in low-calcium medium, and that a permeant anion, such as chloride, is also involved. This dilation of the SER may result from uptake of calcium released from mitochondria in response to elevated cytosolic sodium. Dilation of the Golgi cisternae appears to be a response only to elevated intracellular sodium. Condensation of the mitochondria after injury is thought to be due to increased demands for ATP synthesis and may involve a “futile cycling” of calcium across the mitochondrial membrane, involving sodium-mediated calcium release in response to elevated intracellular calcium.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00231040
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  • 28
    Electronic Resource
    Electronic Resource
    Secretory tapetum of Brassica oleracea L.: polarity and ultrastructural features (1991)
    Springer
    Sexual plant reproduction 4 (1991), S. 28-35 
    Details
    ISSN: 1432-2145
    Keywords: Tapetal cells ; Brassica oleracea L ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary The ultrastructure of the secretory, binucleate tapetum of Brassica oleracea in the micro spore mother cell (MMC) stage through to the mature pollen stage is reported. The tapetal cells differentiate as highly specialized cells whose development is involved in lipid accumulation in their final stage. They start breaking down just before anther dehiscence. Nuclei with dispersed chromatin, large nucleoli and many ribosomes in the cytoplasm characterize the tapetal cells. The wall-bearing tapetum phase ends at the tetrade stage. The dissolution of tapetal walls begins from the inner tangential wall oriented towards the loculus and proceeds gradually along the radial walls to the outer tangential one. The plasmodesmata transversing the radial walls between tapetal cells persist until the mature microspore, long after loss of the inner tangential wall. After wall dissolution, the tapetal protoplasts retain their integrity and position within the anther locule. The tapetal cell membrane is in direct contact with the exine of the microspores/pollen grains and forms tubular evaginations that increase its surface area and appear to be involved in the translocation of solutes from the tapetal cells to the microspores/ pollen grains. The tapetal cells exhibit a polarity expressed by spatial differentiation in the radial direction.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00194568
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  • 29
    Electronic Resource
    Electronic Resource
    Brassica napus pollen development during generative cell and sperm cell formation (1991)
    Springer
    Sexual plant reproduction 4 (1991), S. 176-181 
    Details
    ISSN: 1432-2145
    Keywords: Pollen ; Brassica napus ; Mitoses ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Brassica napus pollen development during the formation of the generative cell and sperm cells is analysed with light and electron microscopy. The generative cell is formed as a small lenticular cell attached to the intine, as a result of the unequal first mitosis. After detaching itself from the intine, the generative cell becomes spherical, and its wall morphology changes. Simultaneously, the vegetative nucleus enlarges, becomes euchromatic and forms a large nucleolus. In addition, the cytoplasm of the vegetative cell develops a complex ultrastructure that is characterized by an extensive RER organized in stacks, numerous dictyosomes and Golgi vesicles and a large quantity of lipid bodies. Microbodies, which are present at the mature stage, are not yet formed. The generative cell undergoes an equal division which results in two spindle-shaped sperm cells. This cell division occurs through the concerted action of cell constriction and cell plate formation. The two sperm cells remain enveloped within one continuous vegetative plasma membrane. One sperm cell becomes anchored onto the vegetative nucleus by a long extension enclosed within a deep invagination of the vegetative nucleus. Plastid inheritance appears to be strictly maternal since the sperm cells do not contain plastids; plastids are excluded from the generative cell even in the first mitosis.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00190001
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  • 30
    Electronic Resource
    Electronic Resource
    Ultrastructure of the micropyle and its relationship to pollen tube growth and synergid degeneration in sunflower (1991)
    Springer
    Sexual plant reproduction 4 (1991), S. 166-175 
    Details
    ISSN: 1432-2145
    Keywords: Helianthus annuus ; Ultrastructure ; Micropyle ; Pollen tube ; Synergid degeneration
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Ultrastructural studies made on the micropyle of sunflower before and after pollination resulted in the following observations. (1) The micropyle is closed instead of a hole or canal. The inner epidermis of the integument on both sides of the micropyle is in close contact at the apex of the ovule. The boundary between the two sides consists of two layers of epidermal cuticle. (2) The micropyle contains a transmitting tissue. The micropyle is composed of an intercellular matrix produced by the epidermal cells of the integument. (3) The micropyle is asymmetrical, and is much wider on the side proximal to the funicle. On the funicle side the cells adjacent to the micropyle are similar to those of the transmitting tissue: they have large amounts of intercellular matrix and contain abundant dictyosomes, rough ER, and starch grains, and provide an appropriate environment for growth of the pollen tubes. The cells distal to the funicle are rich in rough ER and lipid bodies; they lack large intercellular spaces. (4) The micropyle is variable in the axial direction, i.e., it is much larger and more asymmetric at the level distal to the embryo sac than at a level close to the embryo sac. After pollination, one to four pollen tubes are seen in a micropyle. During their passage through the micropyle, most pollen tubes are restricted to the side proximal to the funicle. There is a greater tendency (81%) for the degenerate synergid to be located toward the funicle, i.e., at the same side as the pollen tube pathway. The data indicate a close relationship between micropyle organization, orientation of pollen tube growth, and synergid degeneration.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00190000
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  • 31
    Electronic Resource
    Electronic Resource
    Sperm cells of the pollen tubes of Brassica: Ultrastructure and isolation (1991)
    Springer
    Sexual plant reproduction 4 (1991), S. 226-234 
    Details
    ISSN: 1432-2145
    Keywords: Male germ unit ; Sperm cells ; Isolation ; Pollen tubes ; Brassica napus ; Pollen-tube inner plasma membrane ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Sperm cells of pollen tubes grown both in vivo and in vitro form a male germ unit. Extensions from both sperm cells of each pollen tube are closely associated with the tube nucleus. A high yield (2.7 × 104. 20 mg−1 pollen grains germinated) of intact sperm cells was obtained following release by osmotic shock from pollen tubes grown in vitro. Structural integrity of isolated sperm was maintained by isolation at low temperature in an osmotically balanced medium. At 4° C many isolated sperm pairs were still enclosed within the pollentube inner plasma membrane. Sperm cells not enclosed within this membrane no longer remained connected as a pair. During isolation vesicles formed on the sperm cell surface from disruption of the fibrillar components bridging the periplasmic space. Both in the pollen tube and after isolation the sperm nucleus is in close association with at least one region of the sperm plasma membrane. Sperm isolated at room temperature showed the presence of nucleopores, and nuclei were euchromatic, instead of heterochromatic as in intact sperm in the pollen tube.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00190009
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  • 32
    Electronic Resource
    Electronic Resource
    Microsporogenesis and tapetal development in fertile and cytoplasmic male-sterile sugar beet (Beta vulgaris L.) (1991)
    Springer
    Sexual plant reproduction 4 (1991), S. 215-225 
    Details
    ISSN: 1432-2145
    Keywords: Cytoplasmic male sterility ; Beta vulgaris ; Microsporogenesis ; Tapetum ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary The development of sporogenous and tapetal cells in the anthers of male-fertile and cytoplasmic male-sterile sugar beet (Beta vulgaris L.) plants was studied using light and transmission electron microscopy. In general, male-sterile anthers showed a much greater variability in developmental pattern than male-fertile anthers. The earliest deviation from normal anther development was observed to occur in sterile anthers at meiotic early prophase: there was a degeneration or irregular proliferation of the tapetal cells. Other early aberrant events were the occurrence of numerous small vesicles in the microspore mother cells (MMC) and a disorganized chromatin condensation. Deviations that occurred in sterile anthers at later developmental stages included: (1) less distinct inner structures in the mitochondria of both MMC and tapetal cells from middle prophase onwards. (2) dilated ER and nuclear membranes at MMC prophase, in some cases associated with the formation of protein bodies. (3) breakdown of cell walls in MMCs and tapetal cells at late meiotic prophase. (4) no massive increase in tapetal ER at the tetrad stage. (5) a general dissolution of membranes, first in the MMC, then in the tapetum. (6) abortion of microspores and the occurrence of a plasmodial tapetum in anthers reaching the microspore stage. (7) no distinct degeneration of tapetal cells after microspore formation. Thus, it seems that the factors that lead to abortive microsporogenesis are structurally expressed at widely different times during anther development. Aberrant patterns are not restricted to the tetrad stage but occur at early prophase.
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    URL: http://dx.doi.org/10.1007/BF00190008
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  • 33
    Electronic Resource
    Electronic Resource
    Fluoride effects on leaf cell ultrastructure of olive trees growing in the vicinity of the Aluminium Factory of Greece (1991)
    Springer
    Trees 5 (1991), S. 83-89 
    Details
    ISSN: 1432-2285
    Keywords: Air pollutants ; Chloroplasts ; Fluoride ; Olive tree leaves ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Summary Leaves of olive trees growing in the vicinity of the Aluminium Factory of Greece were ultrastructurally investigated in order to determine any malformations caused by environmental air pollutants, especially hydrogen fluoride, in comparison with control samples and normal seasonal senescence. Estimation of some elements accumulated by these leaves showed that they contained high amounts of F and Al attributable to the operation of the nearby factory. The most seriously effected cell components were found to be the mesophyll chloroplasts that show a dilation of the intrathylakoid space, increase of the number of plastoglobuli, discoloration of plastoglobuli, accumulation of large starch grains and an overall disorganized appearance of the organelle. The nuclear crystalloid inclusions have unusual shapes, while the vacuoles contain a fibrillar/granular material that increases their electron density. It is concluded that the ultrastructural malformations are caused by a combination of environmental stresses and air pollutants.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00227489
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  • 34
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    Electronic Resource
    Different epithelia in the distal human male urethra (1991)
    Springer
    Cell & tissue research 264 (1991), S. 23-32 
    Details
    ISSN: 1432-0878
    Keywords: Male urethra ; Urethral epithelium ; Immunocytochemistry ; Ultrastructure ; Man
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The distal segment of the human male urethra, in particular the fossa navicularis, was studied with light- and electron microscopy as well as by means of histochemical and immunocytochemical methods. The fossa navicularis of the urethra contains a circumscribed zone of extremely thick, non-keratinized stratified squamous epithelium composed of cells containing a large amount of glycogen. These cells lack acid phosphatase activity and lysozyme-like immunoreactivity, both of which can be demonstrated to varying extents in the other zones of the distal male urethra. These glycogen-rich cells are considered to be the substrate for an endogenous flora of lactobacteria, whereas the acid-phosphatase activity and the lysozyme-like immunoreactivity indicate the presence of macrophages and the secretion of bactericidal agents at the epithelial surface. These observations suggest that the different zones with heterogeneous properties in the distal male urethra probably represent a defense system against the invasion of pathogenic microorganisms. Moreover, the glycogen-rich zone, which resembles the glycogen-rich epithelium of the vagina, is estrogen-dependent. This is demonstrated in cases of sex reversal in which after long-lasting estrogen treatment the glycogen-rich zone becomes extremely extended by displacement of the neighbouring epithelium.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00305719
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  • 35
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    Electronic Resource
    Ultrastructure of melatonin-responsive cells in the ovine pars tuberalis (1991)
    Springer
    Cell & tissue research 263 (1991), S. 529-534 
    Details
    ISSN: 1432-0878
    Keywords: Melatonin ; Pituitary gland, pars tuberalis ; Secretory cells ; Cyclic AMP ; Ultrastructure ; Cell culture ; Sheep
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Functional receptors for melatonin have been localized and characterized on the pars tuberalis (PT) of a number of mammalian species, but the cell-type responsive to melatonin is unknown. The ultrastructure of the ovine pars tuberalis has been examined and these findings correlated with the functional response of the gland to melatonin. This study revealed that two secretory cell types predominate in the ovine PT, which differ in the abundance of dense-core granules. The most abundant of the cells are either agranular or very sparsely granulated and represent 90% of the total population, with the remaining 10% being composed of cells with abundant dense-core vesicles. Few follicular cells were observed. This ratio of secretory cell-types persisted in primary culture, with the two types non-separable by Percoll gradient centrifugation. Using forskolin, as a non-specific stimulant of adenylate cyclase, melatonin was shown to inhibit the formation of cyclic AMP by 80–90% in cells both before and after Percoll centrifugation. The results demonstrate that the agranular secretory cells of the ovine pars tuberalis are the melatonin responsive cell-type of this gland.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00327285
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  • 36
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    Electronic Resource
    Ultrastructure and distribution of somatostatin-like immunoreactive neurons and nerve fibres in the coeliac ganglion of cats (1991)
    Springer
    Cell & tissue research 263 (1991), S. 567-572 
    Details
    ISSN: 1432-0878
    Keywords: Somatostatin ; Coeliac ganglion ; Autonomic innervation ; Ultrastructure ; Cat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Somatostatin-like immunoreactivity was localized in nerve cell bodies and nerve terminals in the cat coeliac ganglion. Two types of somatostatin-immunoreactive cell bodies were revealed, the first being large (diameter 35 μm), numerous and weakly labelled, where—as the second was considerably smaller (diameter 10.4 μm), sparsely distributed and heavily stained. The immunoreactive nerve terminals were in synaptic contact with many immunonegative large neurons and dendrites. However, in a few cases, somatostatin-immunoreactive nerve terminals could also be observed on the surface of lightly stained neurons. Transection of vagal or mesenteric nerve failed to affect the distribution or density of somatostatin-like immunoreactive nerve terminals. These results demonstrate the existence of a synaptic input to the principal neurons of the coeliac ganglion of the cat by somatostatin-containing nerve terminals and suggest that this peptide may act as a neuromodulator or neurotransmitter. It is proposed that somatostatin-positive neurons provide intrinsic projections to other somatostatin-positive and to somatostatin-negative neurons throughout the coeliac ganglion, thereby creating a complex interneuronal system.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00327290
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  • 37
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    Electronic Resource
    Islets of preadipocytes highly committed to differentiation in cultures of adherent rat adipocytes (1991)
    Springer
    Cell & tissue research 264 (1991), S. 243-251 
    Details
    ISSN: 1432-0878
    Keywords: Preadipocytes ; Adipocyte precursor cells ; Adipose tissue ; Differentiation-cell cultures ; Ultrastructure ; Rat (Fischer 344)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Cultures of adherent mature adipocytes, obtained from collagenase-digests of adipose tissue of the rat, invaribly contain rapidly proliferating, fibroblastlike cells despite the washing and centrifugation procedures empolyed during isolation of the fat cells. Such spindle-like cells originate from low-density structures, which we term “islets”, that are present, together with the mature adipocytes, in the floating layer of the digest of adipose tissue. Islets are found in preparations from adult (3–4 months old) as well as aging (17–24 months old) rats. By light-and electron microscopy, the islets appear as clusters of closely associated cells containing a variable amount of lipid-like material. Cells of endothelial or pericytic origin are also present in the islets. Within a few hours of culture, the islets give rise to those spindle-like cells that have been seen to proliferate in the cultures. By 36–48 hours, such cells begin to accumulate lipid droplets and, by 150 hours, assume the morphology of small mature adipocytes (diameter 20–35 μm) with a large central lipid droplet. The pattern of differentiation of these cells recalls that of preadipocytes derived from the stromal-vascular fraction of adipose tissue digests. Nonetheless, the extent and rapidity of their adipose conversion, as well as the culture conditions necessary for differentiation, are different and suggest that these cells are a substantially uniform subpopulation of adipocyte-precursor cells highly committed to differentiation.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00313961
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    Electronic Resource
    Postnatal changes in the ultrastructure of the rat olfactory epithelium: the supranuclear region of the supporting cells (1991)
    Springer
    Cell & tissue research 265 (1991), S. 193-196 
    Details
    ISSN: 1432-0878
    Keywords: Postnatal development ; Olfactory epithelium ; Supporting cells ; Receptor cell dendrites ; Ultrastructure ; Rat (Wistar)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The present electron-microscopical study reports ultrastructural changes occurring in the supranuclear region of the supporting cells of the rat olfactory epithelium during the first 16 days of postnatal life. These changes are concerned with the enclosure of receptor cell dendrites and an increase in the amount of smooth endoplasmic reticulum, which has a specific distribution in the supporting cell. An increase in microvillous projections at the free cell surface is also observed. Moreover, this report demonstrates that the cytoarchitecture of the apical portion of the olfactory epithelium at the 16th day of postnatal life is similar, with respect to the relationship between supporting cells and receptor cell dendrites, to that of adult animals.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00318154
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  • 39
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    Electronic Resource
    Diversity of ultrastructure in different phenotypes of cultured microvessel endothelial cells isolated from bovine corpus luteum (1991)
    Springer
    Cell & tissue research 266 (1991), S. 37-49 
    Details
    ISSN: 1432-0878
    Keywords: Microvessel endothelial cells ; Cell culture ; Corpus luteum ; Ultrastructure ; Cow
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Five different types of cultured microvessel endothelial cells defined by use of light microscopy and scanning electron microscopy in a preceding study were investigated by transmission electron microscopy. Type-1 cells displayed a deep invagination of the cell membrane or a single cilium. Granules of low electron density were abundant. A perinuclear ring of intermediate filaments occurred. Cultures of type-2 cells were subdivided into phenotype A, reminiscent of cell-type 1, and into phenotype B, assumed to be vascular smooth muscle cells. Many highly electron-dense granules appeared in late postconfluent cultures of both phenotypes. Cell-type 3 was conspicuous because of a large intracytoplasmic vacuole. Lysosomes with curvilinear bodies were found in cell-types 3 and 4. Both cell types developed a peripheral regular network of microfilaments. Cell-type 5 showed vesiculation of the rough endoplasmic reticulum, lipid droplets and a peripheral felt-like belt of microfilaments. Tubular forms seen in late postconfluent cultures of cell-types 1 to 3 displayed a core of extracellular matrix. Pseudotubular forms of cell-type 4 contained apoptotic bodies. Thus, as seen at the ultrastructural level, different features are maintained by cultured microvessel endothelial cells, suggesting that they have different inherent properties.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00678709
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  • 40
    Electronic Resource
    Electronic Resource
    Effect of cytokines on thymic hematopoietic precursors (1991)
    Springer
    Cell & tissue research 264 (1991), S. 369-375 
    Details
    ISSN: 1432-0878
    Keywords: Thymus ; CD4- ; CD8- ; thymocyte ; Thymic hematopoietic precursors ; Cytokines ; Ultrastructure ; Mouse (DBA/2, H-2d)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary We have previously shown that the interaction of thymocytes with thymic accessory cells (macrophages and/or interdigitating cells) is one of the factors required for thymocyte activation. Precursors of both thymic accessory cell and thymocytes are included in the CD4- CD8- Mac-1- Ia- subpopulation, and their respective maturation and/or activation may be modulated by granulocyte-macrophage colony-stimulating factor, interleukin 1 and interleukin 2. When CD4- CD8- thymic cells are activated with granulocyte-macrophage colony-stimulating factor plus interleukin 2, both macrophages and interdigitating-like cells are present, as shown by electron microscopy. When activated with interleukin 1 plus interleukin 2, the interdigitating-like cells is the only accessory cell present. In both culture conditions, large clusters are formed between interdigitating cells and lymphoid cells. These results have led us to propose two-step signals for thymocyte proliferation: first, the maturation of macrophages under granulocyte-macrophage colony-stimulating factor control and the production of interleukin 1, and secondly, the maturation of interdigitating cells under interleukin 1 control, their clustering with thymocytes which are then activated.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00313976
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  • 41
    Electronic Resource
    Electronic Resource
    The fine structure of lamellate cells in the brain of amphioxus (Branchiostoma lanceolatum, Cephalochordata) (1991)
    Springer
    Cell & tissue research 263 (1991), S. 597-600 
    Details
    ISSN: 1432-0878
    Keywords: Lamellate cell ; Ultrastructure ; Ciliary photoreceptors ; Nervous system, prochordates ; Branchiostoma lanceolatum (Acrania)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The lamellate cells of amphioxus have round nuclei, and cytoplasm with many mitochondria and a large amount of glycogen. Each of these cells projects a highly modified, branched cilium into the central canal, where it characteristically forms lamellar structures. Primary branches and secondary lamellae often contain accessory microtubules that are not derived from the axonema. The functional and evolutionary significance of this cell type is discussed in relation to the ciliary photoreceptors found in other chordates.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00327295
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  • 42
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    Electronic Resource
    Cell types in the fetal pars tuberalis of the human adenohypophysis at mid-gestation (1991)
    Springer
    Cell & tissue research 264 (1991), S. 161-165 
    Details
    ISSN: 1432-0878
    Keywords: Adenohypophysis ; Pars tuberalis ; Ultrastructure ; Immunohistochemistry ; Fetal ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The pars tuberalis of the adenohypophysis was investigated in three human fetuses at mid-gestation by electron microscopy or immunohistochemistry. In addition to gonadotrophs and thyrotrophs, identified by immunohistochemistry and ultrastructural morphology, electron microscopy revealed the existence of an additional differentiated cell type closely resembling “pars tuberalis-specific” cells known from other species. The role of this cell type in the human endocrine regulation remains to be elucidated.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00305734
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  • 43
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    Effect of 1,10-phenanthroline on ultrastructure of pea leaves (1991)
    Springer
    Protoplasma 161 (1991), S. 23-30 
    Details
    ISSN: 1615-6102
    Keywords: 1,10-Phenanthroline ; Photodynamic herbicides ; Pisum sativum ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary We have examined ultrastructural changes of mesophyll cells in pea leaves induced by the photodynamic herbicide 1,10-phenanthroline (Phe). Dark incubation of pea plants did not cause any damage in plants or changes in the ultrastructure of mesophyll cells. Two hours of illumination after pretreatment with Phe caused photooxidative damage in plant but was not sufficient to markedly change the ultrastructure, although dilation of endoplasmic reticulum (ER) cisternae occurred. Illumination for 12 h caused inhibition of grana formation in pretreated plants. These ultrastructural changes and the inhibition of chlorophyll (Chl) accumulation may be due to the inhibition of transport of certain proteins to the plastids, diminished accumulation of chlorophyll proteins (e.g., LHCP) and a decrease in activity of the chlorophyll synthetase.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01328894
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  • 44
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    Electronic Resource
    Intercellular permeability inAbutilon nectary trichomes (1991)
    Springer
    Protoplasma 161 (1991), S. 150-159 
    Details
    ISSN: 1615-6102
    Keywords: Abutilon ; Lucifer Yellow ; Microinjection ; Nectary ; Transport ; Trichome ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Intercellular transport was examined in nectary hairs ofAbutilon slriatum var.thompsonii using dye-uptake and microinjection followed by fluorescence and electron microscopy. Dye-uptake experiments demonstrated that both Lucifer Yellow CH (LYCH) and diaminobenzidine (DAB) move centrifugally along an apoplastic pathway from the sepellary tissue towards the tip cell. Further, fluorescence of LYCH could also be detected inside the cells of the nectary trichome. When LYCH or LYCH/DAB were microinjected into the tip cell, the dye spread in a centripetal direction towards the stalk cell. Electron microscopical investigations of microinjected nectary hairs revealed numerous electron-opaque globules in the cytoplasm of the nectary hair cells. In addition, multivesicular bodies, nuclei with opaque regions and changes in the rough endoplasmic reticulum (RER) were seen in nectary hair cells even at very low concentrations of injected dye. Ultrastructural investigations provided evidence for cytological changes in microinjected nectary hairs.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01322727
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  • 45
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    Electronic Resource
    Ultrastructure of the vegetative organisation and initial stages of silica plate deposition in the soil testate amoebaCorythion dubium (1991)
    Springer
    Protoplasma 163 (1991), S. 136-144 
    Details
    ISSN: 1615-6102
    Keywords: Corythion dubium ; Silica deposition ; Testate amoeba ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary The siliceous body plates ofCorythion dubium are bound by a band of organic cement which is thickest at the lateral margins. The anterior vacuolar cytoplasm is separated by a pigment zone, which forms a dark band in the mid-body region, from the compact posterior region containing a typical vesicular nucleus surrounded by a region of dense endoplasmic reticulum. A pellicular basket of microtubules surrounds the posterior cytoplasm. The large Golgi complex lies between the nucleus and the fundus. Numerous coated and uncoated vesicles from the Golgi cisternae are seen in the peripheral cytoplasm alongside developing plates. These small siliceous plates are enclosed in silicon deposition vesicles lying in surface ruffles of the plasmalemma, often in association with a pair of microtubules. Observations are made on the formation of these vesicles and the early stages of silica deposition. A comparison is drawn between silica deposition inC. dubium and choanoflagellates where there is a similar association between silicon deposition vesicles and microtubules.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01323337
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  • 46
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    Effects of heat shock and thermoadaptation on the ultrastructure of cowpea (Vigna unguiculata) cells (1991)
    Springer
    Protoplasma 163 (1991), S. 125-135 
    Details
    ISSN: 1615-6102
    Keywords: Cowpea ; Heat shock ; Thermoadaptation ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Suspension culture cells of cowpea (Vigna unguiculata) were examined using transmission electron microscopy to characterize morphological changes associated with hyperthermal stress. Cultures maintained at 26°C (unadapted cells) and 38°C (thermoadapted cells) were examined before and after exposure to elevated temperatures of 34°C and 45°C, respectively. Observations indicate that while there were significant ultrastructural differences between unadapted and thermoadapted cells, the following structural modifications in response to heat stress were observed in cells of both cultures: (a) almost a complete loss of polyribosomes, rough ER, and dictyosomes, (b) migration of intracellular waste material (presumably proteinaceous in composition) into the cell vacuole, (c) swelling of the nucleolus with assumed accumulation of preribosomal RNP granules, and (d) retraction of the tonoplast from the cytoplasm into the vacuoles of some cells. Heat shock granules (two size classes) were observed in the cytoplasm of stressed thermoadapted cells along with hollow-cored granules within the leucoplasts. Apart from a few minor differences, the morphological modifications that were made in apparent response to hyperthermal stress were remarkably similar in both cultures.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01323336
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  • 47
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    Ontogeny and ultrastructure of spontaneous nodules in alfalfa (Medicago sativa) (1991)
    Springer
    Protoplasma 162 (1991), S. 1-11 
    Details
    ISSN: 1615-6102
    Keywords: Rhizobium meliloti ; Development ; Symbiosis ; Nitrogen fixation ; Ultrastructure ; Spontaneous nodule
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary The development of spontaneous nodules, formed in the absence ofRhizobium and combined nitrogen, on alfalfa (Medicago sativa L. cv. Vernal) was investigated at the light and electron microscopic level and compared to that ofRhizobium-induced normal nodules. Spontaneous nodules were initiated from cortical cell divisions in the inner cortex next to the endodermis, i.e., the site of normal nodule development. These nodules, on uninoculated roots, were white multilobed structures, histologically composed of nodule meristems, cortex, endodermis, central zone and vascular strands. Nodules were devoid of intercellular or intracellular bacteria confirming microbiological tests. Early development of spontaneous nodules was initiated by series of anticlinal followed by periclinal divisions of dedifferentiated cells in the inner cortex of the root. These cells formed the nodular meristem from which the nodule developed. The cells in the nodule meristems divided unequally and differentiated into two distinct cell types, one larger type being filled with numerous membrane-bound starch grains, and the other smaller type with very few starch grains. There were no infection threads or bacteria in the spontaneous nodules at any stage of development. This size differentiation is suggestive of the different cell sizes seen inRhizobium-induced nodules, where the larger cell type harbours the invading bacteria and the smaller type is essential in supportive metabolic roles. The ontogenic studies further support the claim that these structures are nodules rather than aberrant lateral roots, and that plant possess all the genetic information needed to develop a nodule with distinct cell types. Our results suggest that bacteria and therefore theirnod genes are not necessarily involved in the ontogeny and morphogenesis of spontaneous and normal nodules in alfalfa.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01403895
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  • 48
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    Electronic Resource
    The occurrence and ultrastructure of a mechanoreceptor in the human cricopharyngeus muscle (1991)
    Springer
    European archives of oto-rhino-laryngology and head & neck 248 (1991), S. 144-146 
    Details
    ISSN: 1434-4726
    Keywords: Cricopharyngeus muscle ; Golgi tendon organ ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary An encapsulated nerve structure resembling the Golgi tendon organ was found in a human cricopharyngeus muscle near the cricoid cartilage where muscle fibers terminate. The capsule consisted of lamellated flattened cells with a basal lamina. Capsular cells separated the lumen into small compartments which contained myelinated and/or nonmyelinated nerve fibers. Nonmyelinated nerve fibers were also found in the interlamellar spaces of the capsular cells. Some nonmyelinated nerve fibers were dilated and contained abundant mitochondria, being partly surrounded by a Schwann cell sheath and embedded in collagen bundles. These features indicate that the nerve structure is a mechanoreceptor similar to the Golgi tendon organ. Its location and structure indicate that it is placed to detect the tension of the cricopharyngeus muscle.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00178924
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  • 49
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    Electronic Resource
    Origin of apparent swain-schaad deviations in criteria for tunneling (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 361-366 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Vibrational analysis calculations have been conducted in an effort to understand the origins of apparently anomalous relationships reported between kH/kT and kD/kT kinetic isotope effects. The actual isotopic substitutions used in previous work are more complex than a simple comparison between H/T and D/T isotope effects. The relationships between the actual isotope effects determined in these studies amount to tests of two standards of conventional isotope effect theory, the rule of the geometric mean (or the lack of isotope effects on isotope effects) and the Swain - Schaad rule. Model calculations illustrate the importance of violations of the rule of the geometric mean (over Swain - Schaad deviations) arising in models that incorporate both explicit reaction-coordinate coupling of two isotopic sites and reaction-coordinate tunneling. Implications for experimental studies of turneling using apparent Swain - Schaad exponents are discussed.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610040607
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  • 50
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    The schiff base between pyridoxal-5′-phosphate (PLP) and hexylamine. Formation of the unprotonated form of the imine by reaction of the unprotonated PLP and free amine (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 372-380 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Electrochemical and spectrophotometric studies of the pyridoxal-5′ -phosphate hexylamine Schiff base (PHSB) in strongly basic media were carried out. The equilibrium constant and rate constants of the formation and hydrolysis of the unprotonated imine from the unprotonated pyridoxal-5′ -phosphate and free amine were determined by linearscan cyclic voltammetry. The acid-base dissociation constant of the imine group was obtained by spectrophotometric measurements. Absorption bands for the free imine and the conjugate acid are characterized by a log-normal distribution. These studies are for general application to the quantitative characterization of non-enzymatic model compounds.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610040609
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  • 51
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    Factors affecting the reversibility of the electrophilic step in olefin bromination. The case of 5H-dibenzo [a, d] cycloheptene (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 387-398 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The tendency of ion-pair intermediates generated by treatment of trans-10-bromo-10, 11-dihydro-11-hydroxy-5H-dibenzo [a, d] cycloheptene (5) with HBr to release Br2 giving 5H-dibenzo [a, d,] cycloheptene (1) has been evaluated. The observed 9:1 ratio between ion-pair collapse to the trans-dibromide (7) and Br2 release to olefin 1, as compared with the 3:7 ratio found with the 5H-dibenz [b, f] azepine-5-carbonyl chloride system, has been interpreted as indicating a much lower propensity for reversibility of ion-pair formation in the bromination of 1. The structural parameters obtained by x-ray diffraction of the dibromide 7 show for this compound an angle strain at C-10 and C-11 analogous to that found in trans-10, 11-dibromo-10, 11-dihydro-5H-dibenz [b, f,] azepine-5-carbonyl chloride. Olefin 1 adds Br2 in 1,2-dichloroethane at 25°C according to a third-order rate law, with k3 = 30(3) M-2 s-1. About 10% of 5-bromo-5H,-dibenzo [a, d] cycloheptene, arising from collapse of a dibenzo [a, d] tropylium ion intermediate (9), is formed in this reaction besides the expected trans-dibromide 7. Spectral evidence for the formation of 9, arising by rearrangement of a first formed weakly bridged ionic intermediate in the reaction of 1 with Br2, is presented. the results obtained with the 5H-dibenzo [a, d,] cycloheptene system have been rationalized on the basis of the formation of very weakly bridged intermediates having a much lower tendency to revert back to olefin and Br2 with respect to the corresponding symmetrically bridged bromonium ions.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610040611
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  • 52
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    SRN1 Reactions of nucleophiles with radical clocks: Rate constants for some radical-nucleophile reactions (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 404-412 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Treatment of o-3-(but-3-enyloxy)benzene (1) with anions -SPh, -PPh2 and -PO(OEt)2 in ammonia, acetonitrile or dimethyl sulphoxide gives both direct substitution and cyclized products. The formation of the latter confirms the intermediacy of the o-3-(but-3-enyloxy)phenyl radical (2) and confirms that the reactions follow the SRN1 pathway. The kinetics of the coupling of the aryl radical 2 were determined by comparison with the known rate of cyclization of 2. Similar experiments with the neopentyl bromide, 6-bromo-5,5-dimethylhex-1-ene, and its 3-oxa derivative also gave cyclized and uncyclized products, thus confirming that the SRN1 mechanism applies to the reactions. Approximate rate constants for the coupling of a neopentyl radical with the nucleophiles -SPh and -PPh2 have thus been determined.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610040703
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  • 53
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    Short Communications. Biphenyl-3,4′-Dinitrene (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 459-462 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photolysis of biphenyl-3,4′ -diazide in a rigid glassy matrix at 77 K yields quintet state biphenyl-3,4′ -dinitrene with zero-field splitting parameters of |D/hc- = 0.153 cm-1 and |E/hc| = 0.019 cm-1 determined by electron spin resonance spectroscopic studies. Curie plot studies are consistent with assigning the quintet to be the ground state in this species. This finding confirms qualitative connectivity-based predictions for this general connectivity type of openshell system, and is in qualitative agreement with spectral INDO-CI computational predictions for both planar and twisted geometries of the dinitrene.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610040708
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  • 54
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    The α-bromocyclohexanone ring: The relationship between its conformation and the ultraviolet and infrared absorption of the keto group (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 420-438 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of diterpenoids whose C-ring was an α-bromocyclohexanone showed a discontinuity in the relationship between the Br—C—C=O torsion angle and the Br…O contact distance at about 50°, below which the Br…O distance remained effectively constant at about 3.0 Å. This effect is caused by the non-compressibility of the van der Waals radii of the Br and O atoms. Analysis of the parameters for all compounds in the Cambridge Data File containing an α-bromocyclohexanone ring confirmed this phenomenon. Once the Br…O distance approaches 3.0 Å, the Br—C—C and C—C=O angles are forced open to accommodate the Br…O compression strain as the torsion angle is further reduced. An approximate value of the Br…O distance, d in Å, can be estimated for any torsion angle, ø, by the empirical equation d2 = R - S cos φ + T cos2 φ where R = 11.73, S = 3.62 and T = 0.75. There is a linear relationship between the Br…O separation and both the infrared vibration frequency v and the ultraviolet absorption wavelength δmax of the C=O group: the greater the distance, the lower is the frequency v and longer the wavelength δmax. Thus measurement of the ultraviolet and infrared spectra of a compound containing an α-bromocyclohexanone system can yield information about the Br…O distance and hence the conformation of the six-membered ring. There are also systematic trends in the effect on the spectroscopic properties of the keto group that accompany changing the halogen from fluorine through to iodine. When the halogen is axial, its electronegativity has a maximum influence on the C=O vibration frequency by a ‘through-bond’ inductive process. When the halogen is equatorial, it exerts a steric compression on the non-bonded electrons in the 2p orbital of the oxygen atom. This enhances hybridization to the sp2 state and this simultaneously strengthens the C=O bond and enlarges the n → π* energy gap. This ‘through-space’ influence is simply a process of steric compression, dependent on the size of the halogen atom. It accounts well for all of the systematic trends in both infrared and ultraviolet frequencies of the C=O group when the halogen is equatorial and eclipses the C=O bond.
    Additional Material: 11 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610040705
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    Masthead (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991) 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610040801
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  • 56
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    Treatment of electrostatic effects within the molecular mechanics method. 3. Double bonds and conjugated systems (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 467-478 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The previously developed general method (IDME), which includes calculation of electrostatic and solvation effects on conformational equilibria, has been extended to molecules containing double bonds and conjugated systems. It was applied in connection with MM2 studies to the calculation of the charge distributions and dipole moments, and to the conformational energies of some β-substituted cyclohexenes, exo-methylenecyclohexanes and benzocycloheptenes. Conformational equilibria and dipole moments were well calculated. It was concluded that electrostatic interactions do not play a major role in determining conformational preferences in these compounds. On the other hand, the energies of the preferred conformations of the ten-membered ring in (E)-3β-acetoxy-5,10-seco-1(10)-cholesten-5-one are poorly calculated without the IDME procedure, and fairly well with it.
    Additional Material: 6 Ill.
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    Theoretical models for the reduction of arylmethyl halides by triorganotin hydridesPreliminary presentation of results at combined 45th Northwest-10th Rocky Mountain Regional Meeting of the American Chemical Society, Salt Lake City, UT, 13 June 1990. (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 485-491 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two mechanistic pathways have been proposed for halogen atom transfer from the benzylic positions of halomethylarenes to triorganotin radicals. These are direct atom abstraction, which might involve an extremely polar transition state, and single electron transfer followed by bond cleavage. AM1 semi-empirical calculations have been utilized to model the rate-determining step of these processes. A wide range of related families of compounds have been studied, including substituted halomethylbenzes, selected halomethyl-substituted polycyclic aromatic hydrocarbons and oxygen- and nitrogen-containing chloromethyl-substituted heteroaromatic systems. Although these calculations are relatively simple, the present results corroborate the view that chlorine and bromine atom transfer from the benzylic position to triorganotin radicals involves a direct atom abstraction in the rate-determining step whereas reduction of the corresponding iodides proceeds via an electron-transfer mechanism.
    Additional Material: 8 Tab.
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    Ambident electrophilicity of alkyl aryl phosphates (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 516-522 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hydrolysis of dimethyl aryl phosphates, (MeO)2P(O)OAr where the ArO group is derived from N-methyl-8-hydroxyquinolinium or 4-hydroxy-(N,N,N-trimethylanilinium) ion, proceeds with the cleavage of the P—OAr and Me—O bonds. The effect of external factors on the relative contributions of those two reaction pathways was studied. The increase in temperature favours, owing to the difference in activation entropies, the reaction at carbon. The addition acetone to the aqueous reaction medium slows down the reaction at carbon more rapidly than the reaction at phosphorus, indicating higher hydration requirements of the dealkylation transition state. In water-triffuoracetic acid mixtures only the P—OAr bond cleavage is acid catalysed; the catalytic effect is superimposed on the general, decelerating medium effect. Specific nucleophilic catalysis was demonstrated for the Me—O bond fission by thiosulphate ion (ca 60-fold acceleration), and for the reaction at phosphorus by fluoride ion (ca 500-fold acceleration).
    Additional Material: 6 Tab.
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    URL: http://dx.doi.org/10.1002/poc.610040807
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    Masthead (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991) 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610040901
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    Short communication. Structural studies of bromine adducts of 1,2- and 1,4-bis(phenylseleno)benzenes. Evidence for the (TB, MC) structure of 1,2-(PhSeBr2)2C6H4 (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 523-525 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 1,2-Bis(phenylseleno)benzene reacted with equimolar amount of bromine to yield a trigonal bipyramidal (TB) adduct, in contrast to the molecular complex (MC) structure of selenanthrene with bromine. Whereas the structure of 1,4-(PhSeBr2)2C6H4 was (TB, TB) at the two selenium atoms, that of the 1,2-derivative was demonstrated to be (TB, MC), the first example of an MC structure of PhSeC6H4Y with Br2 [Y = 2-PhBr2Se(TB)]. Both electronic and steric effects of the group must play an important role in MC formation. Rapid structural exchange in this tetrabromide, (TB, MC) ⇄ (MC, TB), was also observed.
    Additional Material: 2 Tab.
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    URL: http://dx.doi.org/10.1002/poc.610040808
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    Conformations of pentan-1-OL, hexan-1-OL and their thio analogues (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 536-540 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Empirical linear relationships between standard Gibbs free energy, ΔG298°, and parachor and between standard entropy, S298°, and parachor are presented for the aliphatic series H(CH2)nX with X = CH3, CH=CH2, C≡CH, Cl, OH, SH, SCH3 and SC2H5. In the series with X = OH and SH significant deviations of points for n = 4 and 5 are observed. INDO quantum-chemical analysis points to the formation of cyclic conformers of butan-1-ol, pentan-1-ol and their corresponding thio analogues. The formation energy of the cyclic conformers (higher for thiols than for alcohols) is proportional to the sum of deviations from the linearity of the points under discussion.
    Additional Material: 3 Ill.
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    Review commentary. Solvation, the electrophilic driving force of ionic bromination of ethylenic compounds. The addition-solvolysis analogy (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 527-535 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solvation is the main driving force of electrophilic bromination since it is impossible to obtain a bromonium ion from bromine and alkene in the gas phase, whereas it is a very fast reaction in solution. The role of a protic solvent in this addition was investigated experimentally by extended Winstein-Grunwald relationships, kinetic solvent isotope effects and R, the rate ratios in two solvents of similar ionizing powers but different nucleophilicities. It is shown that electrostatic medium effects and electrophilic assistance to bromide ion departure are the main rate-determining factors of the reaction. These two contributions are roughly independent of the double bond substituents. Nucleophilic solvent assistance to positive charge development is also found; however, it provides only a small acceleration, the magnitude of which depends on alkene structure. This nucleophilic solvent involvement is annulled when crowded substituents inhibit approach of the solvent to the cationic part of the transition state or when positive charge is delocalized by conjugated electron-donating groups. These several solvent roles are identical in nature and in magnitude with those observed in heterolytic solvolysis. In halogenated solvents, the driving force of bromination arises from catalysis by a second bromine molecule which assists heterolysis of the bromine-bromine bond, leading to the bromonium-tribromide ion pair. Similar halogen catalysis occurs also in some solvolyses. Finally, return is also found in both reactions; reversible formation of bromonium ions is observed when their nucleophilic attack, the productforming last step, is made energetically difficult either by steric inhibition or by poor nucleophilicity of the trapping nucleophiles. Similarities and differences between electrophilic bromine addition and limiting solvolysis are discussed in terms of respective intermediate stabilities and heats of formation.
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    Photochemical transformations. 49.For Part 48, see Ref. 1. Solvent effects on singlet ionic and triplet photoreactions of some bridged polycyclic chlorides: Comparison with ground-state reactionsDedicated to Professor Kurt Schaffner on his 60th birthday. (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 541-546 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Direct irradiations of 2-chloro-6,7 : 8,9-dibenzotricyclo [3.2.2.02,4] nona-6,8-diene (5-Cl) were conducted in cyclohexane, acetic acid and wet acetonitrile. The products are 1-methylfluoranthene (8) in all three solvents, the allylic chlorides 8-chloro-7-methylene-2,3 : 5,6-dibenzobicyclo [2.2.2] octa-2,5-diene (3-Cl) and 7-chloromethyl-2,3 : 5,6-dibenzobicyclo [2.2.2] octa-2,5,7-triene (2-Cl) in acetic acid and acetonitrile and solvolysis product amides in wet acetonitrile. Compound 5-Cl had previously been shown to be the product of triplet sensitization of 2-Cl and 3-Cl, so that the singlet reaction reverses that of the triplet. The formation of 8 from 5-Cl was quenched with piperylene, whereas that of the allylic chlorides was not. Quantum yields of products and singlet lifetimes in the three solvents were measured. The solvent effects are discussed. Deuterium-labeling results on the formation of 5-Cl from 2-Cl and of 8 from 5-Cl are reported.
    Additional Material: 1 Tab.
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    Steric effects of alkyl groups: A ‘cone angle’ approach (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 611-617 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A ‘cone angle’, θR, is defined for an alkyl group (R), which is proposed as a measure of the steric effect exerted by the group. The θR values for some 57 groups have been calculated mathematically by constructing the corresponding Corey - Pauling - Koltun molecular models. The variation in θR with the bulk of a group is satisfactory. However not all types of alkyl groups can be accommodated in this cone angle approach. In the case of the groups for which the cone angle can be measured, correspondences between θR and the two existing steric parameters (Taft's Es scale and Dubois' E′s scale) have been established. For some 23 alkyl groups θR has been used to explain the variation in the rate constant of the base-catalysed hydrolysis of RCOOEt with the nature of R. Our studies independently substantiate the basic assumptions of the Taft - Ingold hypothesis that, while the base-catalysed ester hydrolysis is mostly controlled by the steric and electronic effects of the R group, the acid-catalysed one is controlled almost solely be the steric effect.
    Additional Material: 5 Ill.
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    Effect of hexadecyltrimethylammonium bromide micelles on the hydrolysis of substituted benzoate esters (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 13-18 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The alkaline hydrolysis of nine para-substituted phenyl esters of para-substituted benzoates was studied in the presence and absence of hexadecyltrimethylammonium bromide (CTAB) micelles. The second-order rate constant for alkaline hydrolysis in CTAB micelles (K2m) was calculated using a pseudo-phase ion-exchange model. the substituent effect on the second-order rate constant in the aqueous phase (k2w) and on k2m was analysed using Hammett's σ ρ plots. The calculated ρ values in micelles were 0.8 unit. larger than those in water. The effective low dielectric constant in the micellar surface may be responsible for the general effect of increasing the sensitivity of reactions to the electronic effect of substituents in micelles.
    Additional Material: 4 Ill.
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    1,5-Sigmatropic shifts of bromine over a cyclopentadiene ring (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 31-47 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The intrinsic mechanism of circumambulatory rearrangements of 5-bromo-5-methyl-1,2,3,4-tetramethoxycarbonylcyclopentadiene, 5-bromo-1,2,3,4 5-pentamethoxycarbonylcyclopentadien and 5-bromo- 1,2,3,4,5-pentaphenylcyclopentadiene due to sigmatropic shifts of bromine over the cyclopentadiene ring was proved, using the dynamic 13C and 1H NMR technique, to be governed by successive intramolecular 1,5-sigmatropic shifts. Semi-empirical AM1 and MINDO/3 calculations of reactions paths performed for fluoro-, chloro- and bromocyclopentadienes are in accord with the conclusion of a preference for a 1,5- over a 1,3-shift reaction path of halogen migration over a cyclopentadiene system. Intramolecular 1,5-sigmatropic shifts of chlorine in 5-chloro-5-methyl-1,2,3,4-tetramethoxycarbonylcyclopentadiene with the free energy barrier of ΔG298+ = 26.1 kcal mol-1 were studied using 1H NMR spectroscopy.
    Additional Material: 7 Ill.
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    Masthead (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991) 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610040201
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    Specific micellar rate effects on unimolecular decarboxylation and cyclization (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 71-76 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Decarboxylation of 6-nitrobenzisoxazole-3-carboxylate ion and cyclization of o-3-halopropyloxyloxyphenoxide ion (PhY7) (Y = Br, I) are accelerated by aqueous cationic and zwitterionic micelles. For cationic micelles the rate enhancements (kM′kW′) increase with increasing bulk of the surfactant head groups but are largest for decarboxylation. There are good linear free energy relationships between micellar effects on these reactions and the plots of log kM′ for cyclization against log kM′ for decarboxylation have slopes of 0.46 and 0.64 for Y = Br and I, respectively. Surfactants that have twin tail or tri-N-alkylbenzyloxy head groups do not fit the relationship. Despite mechanistic differences between decarboxylation and cyclization (an intramolecular SN2 reaction), similar factors control micellar effects on these reactions. In the absence of surfactant there is only a qualitative relationship between free energies of activation of cyclization and decarboxylation in different solvents.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610040202
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    Aromaticity as a multi-dimensional phenomenon (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 163-169 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The classification of aromaticity criteria is studied. New aromaticity criteria are developed and discussed. A statistical analysis of such criteria is presented and compared with a similar analysis of the recent literature. It is shown that aromaticity is at least a two-dimensional phenomenon. The classification of the compounds depends on the type of criteria included in the analysis.
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    URL: http://dx.doi.org/10.1002/poc.610040307
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    AB initio MO study of the halogen cation basicities of some organic bases (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 177-191 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hartree - Fock calculations were performed to investigate the structure and relative stabilities of complexes between halogen cations and first- and second-row bases. It is shown by means of both a qualitative perturbation molecular orbital treatment and a topological analysis of the electronic charge density that second-row bases present enhanced halogen cation basicities compared with first-row bases. In this respect the results predict that although the fluorine cation basicity of water is smaller than its proton affinity, the fluorine cation basicities of SH2, thioether, phosphine and trimethylphosphine are considerably higher than their proton basicities. Similarly, phosphine and trimethylphosphine should have chlorine cation basicities greater than their proton affinities, in contrast with ammonia and trimethylamine. The results also show that fluorine and chlorine cation basicities are more sensitive to methyl substitution than proton affinities.
    Additional Material: 6 Ill.
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    Micellar effects on the alkaline hydrolysis of N-alkyl-4-cyanopyridinium ions. An example of micelle-induced regiochemical selectivity (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 207-216 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rates of the reaction of N-alkyl-4-cyanopyridinium (RCP) ions [alkyl = CH3 (MCP), n-C4H9 (BCP), n-C8H17 (OCP), n-C12H25 (DCP)] with OH- ion in water are independent of chain length and RCP concentration up to 0.001 M. The ratios of the concentrations of the reaction products, N-alkyl-4-pyridone (P) and N-alkyl-4-carboxamidopyridinium (A), P/A, are similar for all substrates. In water the P/A ratios increase with pH, reaching a plateau value of ca 2 at pH ≥ 13. Added salts slightly decrease the reaction rate and do not affect the P/A ratios. In aqueous solutions, addition of dioxane increases both rates and P/A ratios. Micelles of hexadecyltrimethylammonium bromide (cetyltrimethylammonium bromide; CTAB) and 3-(N,N-dimethyl dodecyl ammonium)propane-1-sulphonate (SDP) catalyse the alkaline hydrolysis of OCP and DCP and increase the yield of pyridone with BCP, OCP and DCP. In micellar CTAB and SDP the attack of OH- on RCP occurs almost exclusively at the 4-position of the pyridinium ring. Sodium dodecyl sulphate micelles inhibit the reaction and produce small changes in the P/A ratio. The regiochemical selectivity produced by micelles, leading to a preference for the attack of OH- at the pyridinium ring, was rationalized in terms of the low effective dielectric constant at the micelle-water interface.
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    Structure, topological electron density analysis and aromaticity of 4-heterosubstituted methylenecyclopropenes: X= X=CH2, NH, O, SiH2, PH and S (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 242-250 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structures of a series of heterosubstituted methylenecyclopropenes and methylenecyclopropanes were optimized at the HF/6-31G* level. All methylenecyclopropenes are planar except for the silicon analogue, which is bent at both C-3 and Si. The planar silicon structure is a transition state. The relative aromaticity of these compounds were evaluated using the C-1—C-3 bond length, the integrated charge on C-3 and the heteroatom, and delocalization energy. Second-row systems have slightly larger delocalization energies than their first-row counterparts, owing to their larger polarizability. Using these criteria, methylenecyclopropene and the silicon analogue are not aromatic and the N, O, P and S analogues are moderately aromatic. The planar silicon analogue is antiaromatic and bends from planarity to reduce this antiaromaticity.
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    Kinetics and mechanism of the alcoholyses of ethyl fluorosulphate (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 251-259 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The alcoholyses of ethyl fluorosulphate in methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and n-pentyl alcohols in the initial concentrations and temperature ranges of (1-10) 10-3 M and - 15.00 to 22.00 °C, respectively, were studied. The reactions follow pseudo-first-order kinetic laws up to at least ca 75 per cent ester conversions. At 10°C the experimental rate constant for ethanolysis is similar to that of ethyl triflate but much smaller than for its hydrolysis. The reactivity of the ester is ca 104-105 times higher than that of alkyl halides and benzenesulphonates. In alcohol-benzene and alcohol-acetone mixtures the ΔH≠ and ΔS≠ activation parameters are only slightly affected by the media composition. The effect of the ‘lyate ion’ on the kinetics of these reactions were investigated and the effects of changes in the dielectric constant of the media were evaluated. It is concluded that the alcoholyses of the ester fulfil the requirements for predominant SN2-type mechanism, where the reaction ground states are more polar than the corresponding transition states.
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    NMR study of polycrystalline azoles (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 271-276 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polycrystalline pyrazole, imidazole and benzotriazole were investigated by 1H and 2H NMR spectroscopy. In addition to the usual broad line of the 1H NMR signal due to the dipole-dipole interaction, a significantly narrowed component (δν = 1-2 kHz) of a complex triplet structure was detected in all three compounds. To interpret this observation, a mechanism with virtually complete averaging of the dipole-dipole interaction for a small part of the sample protons is suggested. The mechanism is based on proton interaction with the unpaired electron of a short-lived radical of the type Az· or (H-Az·-H).
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    URL: http://dx.doi.org/10.1002/poc.610040503
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    Gas-phase acidity of some α-keto aldoximes: Experiment and theory (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 285-292 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experimental gas-phase acidities of 2-oxopropanaloximes, XCH2COCH=NOH (X = H, CH3S, CH3SO, CH3SO2; compounds 1-4), were determined by Fourier transform ion cyclotron resonance (FT-ICR) spectrometry. The values are δ Gacid° = 1401, 1381, 1360 and 1351 kJ mol-1 for 1, 2, 3, and 4, respectively. Molecular orbital calculations using the semi-empirical AM1 method provided information on the geometry and relative energy of neutrals species 1-4 and their conjugate bases, together with charge distributions and entropies of deprotonation. It is demonstrated that the proton abstraction occurs preferentially at the oxime function; the formation of an enolate as a conjugate base is unfavourable by 70-140 kJ mol-1. The large variation of the gas-phase acidities for 1-4 is explained in terms of the field/inductive empirical substituent constant σF. The variation of solution acidities appears to be comparatively strongly attenuated. This attenuation is attributed mainly to charge delocalization in the anion, which was confirmed by charge density calculations.
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    Depurination of (dien)Pt(II) complexes of purine deoxyribonucleosides. Comparison with the effects of (dien)Pd(II) ion complexing (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 301-309 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: First-order rate constants for the hydrolytic depurination of 2′-deoxyinosine and its various (dien)Pt(II) ion complexes were measured over the acidic pH range. The rate profiles obtained indicate that the uncomplexed nucleoside and its N1-(dien)Pt(II) complex are depurinated via mono- and di-protonated species, whereas the N7-(dien)Pt(II) and N1, N7-di(dien)Pt(II) complexes exhibit significant spontaneous hydrolysis, which competes with a markedly retarded acid-catalysed reaction. Rate constants for the various partial reactions were calculated and the results were employed to explain the effects that (dien)Pd(II) ion exerted on depurination rates of the same compounds. Similar measurements were carried out with the N1, N7-di(dien)Pt(II) complex of 2′-deoxyadenosine in order to further the understanding of the previously reported rate-enhancing effect of (dien)Pd(II) ion on the depurination of 2′-deoxyadenosine.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610040507
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    Crystallographic studies of intra- and inter- molecular interactions. Part VI. Crystal and molecular structure of N,N′-dimethyl-N′-phenylsulphonylformamidine. Equalization of CN bond lengths in the amidine fragment as a result of substituent effects due to push-pull (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 331-335 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystal and molecular structure of N,N-dimethyl-N′-phenylsulphonylformamidine is solved by direct methods and refined to R = 0.041 for 935 reflections, Equalization of CN bond lengths in the amidine fragment is discussed in terms of a push - pull effect operating between the N,N-dimethyl and SO2Ph groups. A significant role of the substituent at the functional carbon on the degree of π-electron delocalization on the NCN fragment is interpreted by use of the HOSE model.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610040602
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  • 78
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    Orientation of benzoic acid and terephthalic acid on an alumina surface and their reactivities observed by infrared spectroscopy (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 346-352 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The orientation of benzoic acid and terephthalic acid on alumina was ascertained by IR measurements. Benzoic acid was chemisorbed as a carboxylate anion with a vertical conformation of the benzene ring (0 〈 θ 〈 1.0) and as a mixture of the anion and the acid (1.0 〈 θ). Terephthalic acid was chemisorbed as a mixture of monocarboxylate anion (hydrogenterephthalate) and dicarboxylate anion (0 〈 θ 〈 0.3), as the monocarboxylate anion with a vertical conformation of benzene ring (0.3 〈 θ 〈 1.0) and a mixture of the monocarboxylate anion and terephthalic acid (1.0 〈 θ). The carboxyl group of expected hydrogenterephthalate adsorbed through the carboxylate anion on alumina (θ = 0.8 : 0.37 mmol g-1 alumina) readily reacted with dimethyl sulphate to form monomethyl terephthalate selectively.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610040605
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  • 79
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    Influence of some steric and electronic effects on the mechanism of SNAr reactions in dimethyl sulphoxide (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 367-371 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reactions of 1-chloro- and 1-fluoro-2,4-dinitrobenzenes with aniline and 4-methylaniline in dimethyl sulphoxide are not base catalysed. When the nucleophile is 2-methylaniline, the reaction of the fluoro compound is base catalysed whereas that of the chloro compound is not. The reactions of 1-bromo-2-fluoro- and 1-bromo-2-chloro-3,5-dinitrobenzenes with both aniline and 2-methylaniline are not base catalysed. These results indicate that, in certain cases, the incidence or absence of base catalysis in aromatic nucleophilic substitution (SNAr) reactions in dipolar aprotic solvents results from an interplay of steric and electronic factors as they affect the magnitude of the (k2 + k3 [B])/k-1 ratio.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610040608
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  • 80
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    Controlling factors determining addition and reduction products in the grignard reaction of substituted benzophenones, acetophenone and fluorenone with ‘EtMgBr’ (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 381-386 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Addition (Add.) vs reduction (Red.) products in the reactions of substituted benzophenones, acetophenone and fluorenone with ‘EtMgBr’ were compared in diethyl ether, 1,2-dimethoxyethane and tetrahydrofuran. Plots of log (Add./Red.) vs σ-values or the oxidation potentials of ketones showed characteristic upward curves depending on the polarity of the solvents. The results are discussed on the basis of both the combined effects of the stability of the monomeric radical ion pair and the dimeric radical ion pair derived from ketone and ‘EtMgBr’, and the well known Schlenk equilibrium of ‘EtMgBr’ in solutions.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610040610
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  • 81
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    Micellar rate effects on reactions of hydroxide ion with phosphinate and thiophosphinate esters (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 618-628 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cationic micelles of cetyltrimethylammonium chloride, bromide and mesylate (CTACl, CTABr, CTAOMs) speed reactions of OH- with phosphinate and thiophosphinate esters: Ph2PO.OPh (1a), Ph2PO.OC6H4NO2-p (1b), Ph(i-Pr)PO.OC6H4NO2-p (1c), Ph2PO.SEt (2a), Ph2PO.SPh (2b), (EtO)2PO.SPh (2c) and (EtO)2PS.OC6H4NO2-p (Parathion, 3). First-order rate constants go through maxima with increasing [surfactant]. The rate - surfactant profiles are fitted quantitatively in terms of a kinetic model that treats the distribution of OH- between aqueous and micellar pseudo-phases in terms of coulombic and non-coulombic ion-micelle interactions. Second-order rate constants at the micellar surface are lower than in water by factors that range from 0.035 for 1a to 0.7 for 1c. The thiophenyl derivative (2b) is more reactive than the corresponding phenoxy derivative (1a) and it is more reactive than the corresponding thioethyl derivative (2a). Parathion (3) is the least reactive substrate in both water and micelles.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610041006
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    Semiempirical SCF-MO calculations of kinetic isotope effects (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 635-638 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Carbon and deuterium kinetic isotope effects (KIEs) on the isomerization of methyl isocyanide were calculated by using the geometries and force fields obtained with MNDO, AM1 and PM3 Hamiltonians. These theoretical KIE values were compared with the corresponding experimental values. None of the hamiltonians used proved to be superior to any of the others. The best agreement for the carbon isotope effect was obtained by using the PM3 method; however, the deuterium isotope effect obtained by this method gave the poorest fit to the experimental data. The opposite is true when the MNDO Hamiltonian was used.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610041008
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    Relationships between electronic substituent parameters (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 629-634 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Core-electron energies for sulphur in a series of 2-substituted thiophenes have been used to investigate the relationship between electronic substituent parameters as developed by Taft and Topsom and by Charton. Initial- and final-state energies are analysed in terms of familiar substituent effects, such as field, delocalization and polarizability. The results show that the data correlate equally well with both sets of parameters and that there are many common features between the two methods. Both agree that resonance delocalization contributes significantly to the initial state, but has virtually no effect on the final state. In connection with this investigation we have also correlated the parameters for 31 substituents that are parameterized in the two approaches. The results of this more general study indicate some real differences between these and suggest that neither of the parameterizations incorporates all the electronic effects.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/poc.610041007
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    The effect of pressure on swern-moffatt oxidations (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 639-642 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rates of oxidation of cyclohexanol by dimethyl sulphoxide in conjunction both with acetic anhydride and with dicyclohexylcarbodiimide have been measured with variation of both temperature and pressure. Activation volumes were found to be -25 and -34 cm3 mol-1, respectively, and the absence of an α—d PKIE was noted. The reaction mechanism is discussed in the context of these values.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610041009
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  • 85
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    Masthead (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991) 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610041101
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  • 86
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    Short communication. Synthesis and properties of 4-cyano-1-(7-carboxyheptadecyl)pyridinium bromide: A probe of the ionic composition near the surface of positively charged micelles (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 643-646 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 4-Cyano-1-(7-carboxyheptadecyl)pyridinium bromide (CCHP) was synthesized using standard procedures. The rates and product distribution of the reaction between OH- ion and CCHP are very similar to those previously obtained with alkyl-substituted 4-cyanopyridinium ions. The effect of hexadecyltrimethylammonium bromide micelles on the rate and product distribution of CCHP indicated that the cyanopyridinium ring of this compound is distal to the surface of the micelle. CCHP constitutes a probe for ionic composition in the vicinity of positively charged micelles.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610041010
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  • 87
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    Molecular mechanics (MM3) calculations on disulfides (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 659-666 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An MM3 parameter set was developed for disulfides so as to permit the force field representation of these molecules with respect to geometries, including conformations, vibrational spectra and heats of formation.
    Additional Material: 13 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610041103
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  • 88
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    Molecular Mechanics (MM3) calculations on sulfides (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 647-658 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structures of eleven sulfide compounds including methanethiol, ethanethiol, dimethyl sulfide, ethyl methyl sulfide, di-tert-butyl sulfide, thiacyclopentane, thiacyclobutane, 5-thiabicyclo [2.1.1] hexane and 7-thiabicyclo [2.2.1] heptane have been calculated to agree with experimental data, along with the vibrational spectra of the first three of these. The heats of formation of 24 sulfides (including mercaptans) have also been calculated to agree with experimental data. In general, the force field for sulfides seems to be similar in accuracy with that for hydrocarbons.
    Additional Material: 19 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610041102
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  • 89
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    Protolytic equilibria of several 4-acyl-substituted 1-phenyl-3-methylpyrazol-5-ones in dioxane-water mixtures (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 667-674 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermodynamic proton ionization constants, TpKa, of several 4-acyl-substituted pyrazol-5-ones [acyl = trifluoroacetyl (HPMTFP), acetyl (HPMAP), hexanoyl (HPMHP)] were determined in various dioxane-water mixtures at 25 and 35 ± 0.1°C. The TpKa values were determined by glass-electrode potentiometry and refined by using the extensive weighted least-squares FORTRAN program TPKA. Both extrapolation and leastsquares methods were used to obtain TpKa values in pure water (0%). All three acyl derivatives are weak monoprotic acids with TpKa values between 2.5 and 3.9, following the order HPMTFP 〈 HPMAP ≤ HPMHP. The TpKa values do not vary linearly with the reciprocal of the dielectic constant of the medium; however, a plot of TpKa versus the mole fraction of dioxane, n2, is linear at a given temperature. Values of standard free energy (ΔG°), enthalpy (ΔH°) and entropy (ΔS°) changes associated with their protolytic equilibria were also calculated. Temperature, medium and substituent effects are briefly discussed.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610041104
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  • 90
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    Molecular and electronic structure of substituted bithiophenes (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 675-680 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Several substituted bithiophenes were prepared and their electronic structure studied by photoelectron spectroscopy and semi-empirical MO calculations. Comparison of the spectra of related molecules and analysis of calculated molecular geometries gave an indication of molecular conformations in the gas phase.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610041105
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  • 91
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    Structural studies of 1,3-di(N,N-dimethylformamidyl)-2-cyanoguanidine. The case of a strongly lewis basic nitrogen atom in the cyano group VIII. Crystallographic studies of intra- and inter-molecular interactions (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 689-692 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610041107
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  • 92
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    Synthesis and NMR study of 5-furylmethylenehydantoins and 5-thienylmethylenehydantoins (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 681-688 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two series of 5-furylmethylenehydantoins and 5-thienylmethylenehydantoins were prepared and their 1H and 13C NMR spectra studied in comparison with those of compounds in the analogous 5-aryl- and 5-pyridyl- series. Differences in the effects of the aromatic, six- or five-membered heteroaromatic rings are discussed. Spectral analysis enables Z/E configurations to be assigned with confidence and conformational preferences to be qualitatively deduced. Some interesting solvent effects were also observed.
    Additional Material: 5 Tab.
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    URL: http://dx.doi.org/10.1002/poc.610041106
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    Masthead (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991) 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610041201
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    Topological aspects of chemical reactivity. Evans-dewar principle in terms of molecular similarity approach (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 701-705 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Evans-Dewar concept of aromaticity of transition states is given new theoretical support in terms of the similarity approach to chemical reactivity. The principal goal of this approach consists in providing a simple, chemically lucid justification for the legitimacy of the original intuitively formulated concept.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/poc.610041109
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  • 95
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    Z/E, photoisomerization of 5-arylmethylenehydantoins and 5-pyridylmethylenehydantoins (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 707-713 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Z/E photoisomerization of a series of 5-arylmethylenehydantoins and a series of 5-pyridylmethylenehydantoins by direct irradiation in methanol or ethanol solvent was investigated. The isomeric ratios at the photostationary state are dependent on the excitation wavelength and are related to the relative absorption coefficients of the two isomers. Measurements of quantum yields show the absence of quenching effects by oxygen or azulene, suggesting that triplet states either are not involved or are too short-lived for quenching to be observed. Preparative photoisomerization provides a route to the isomer which is not isolated or obtained only as a minor product by the usual method of synthesis.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610041202
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  • 96
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    Reactivity and reaction patterns of alkyl alkoxybenzene radical cations. Mechanistic pathways of the reactions between 2,5-DI-tert-Butyl-1, 4-Dimethoxybenzene and perfluorodiacyl peroxides (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 1-6 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the reactions of 2,5-di-tert-butyl-1,4-dimethoxybezene (1) with different oxidants, the radical cation 1+. is always detectable by EPR. However, the observed reactivity of 1+. depends greatly on the oxidation systems employed. In S2O82-—Cu2+—HOAc and Ce4+—HOAc systems (HOAc = acetic acid), 1+. appears to have long lifetimes and does not undergo fragmentation spontaneously. In contrast, in (RFCO2)2—CF2CICFCI2 (F113) systems, the readily formed 1+. is short-lived, and large amounts of de-tert-butylation products have been isolated. Experimental results imply that the C—C bond cleavage involved in de-tert-butylation could be a consequence of an attack by perfluoroacyloxy radical on 1+. in their original solvent cage. The fact that addition of methanol to the reaction mixture leads to the formation of a large amount of tBuOCH3 (46%) and other evidence suggest that the tert-butyl group leaves as a carbocation. On the basis of these results, we conclude that the reactions of 1 with (RFCO2)2 are initiated by electron transfer and followed by a fast coupling of various radical species, namely, 1+. with RFCO2 or with RF in the solvent cage, to form σ-complexes which collapse or react with nucleophiles to yield the final products.
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    URL: http://dx.doi.org/10.1002/poc.610040102
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  • 97
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    Interactions between tetracyanoethylene and rauwolfia alkaloids (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 25-30 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Interactions of the Rauwolfia alkaloids yohimbine, corynanthine, ajmalicine and reserpine with tetracyanoethylene were investigated by UV - visible spectroscopy. The results suggest the instantaneous formation of blue complexes whose thermodynamic and spectroscopic properties closely resemble those of 1 : 1 charge-transfer complexes of tetracyanoethylene with indole derivatives. The complexes are stable when the piperidinic nitrogen atom of the alkaloids is protonated or methylated. In contrast, those of the free bases rapidly decompose to give the corresponding 3,4-dehydro derivatives. The kinetics of these reactions have been studied and a mechanism is proposed.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610040106
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  • 98
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    Acid hydrolysis of 2-substituted 3-methyl-tetrahydro-1,3-oxazines: Simple models for tertiary glycosylamines (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 53-57 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The hydrolytic decomposition of 2-phenyl- and 2-isopropyl-3-methyltetrahydro-1,3-oxazines to 3-methylaminopropan-1-ol and appropriate aldehydes was studied by 1H NMR and UV spectroscopy in acidic solutions. The time-dependent spectra confirmed that the formation of the final products was preceded by an equilibration of three components, the two Schiff base intermediates and the starting material, of which the former produced a carbinolamine which in turn underwent heterolysis to the final products.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610040109
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    Potentiometric and spectroscopic investigations of the aqueous phase acid-base chemistry of urazoles and substituted urazoles (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 67-69 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Aqueous-phase equilibrium acidity constants have been determined for urazole (1,2,4-triazolidine-3,5-dione), several substituted urazoles and other selected imides. Aqueous phase pKa values for urazole (5.8), 1-methylurazole (5.3), 4-methylurazole (5.7) and 1,4-dimethylurazole (5.3) indicate that (in water) the methyl group acidifies the urazole moiety when bonded to N-1 but has little effect on acidity when bonded to N-4. Aqueous phase pKa values for hydantoin (9.0) and 1-methylhydantoin (9.1) suggest that a 1-methyl substituent has little effect on the acidity of the imide proton present in hydantoin. These data, combined with aqueous phase pKa values for 1,2-dimethylurazole (7.5), a substituted urazole lacking amide protons, indicate that an amide proton in urazole (i.e. the proton bound to either N-1 or N-2 in urazole) is ca 1.5 pKa units more acidic than the imide proton (i.e. the proton bound to N-4). Changes in 13C NMR chemical shifts for the carbonyl carbon atoms present in variously substituted D2O phase urazoles, hydantoins, succinimide and their conjugate bases also confirm that amide N—H bonds found in urazole and 1-methylurazole are weaker, in a heterolytic acid - base sense, than imide N—H bonds.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610040111
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    Activation and thermodynamic parameters of nucleophilic substitution. Reaction of alkyl halides with solid salts under phase-transfer catalysis conditions (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 341-345 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The paper is concerned with the effect of temperature and the nature of a solid ionophore (MCl, where M = Li, Na, K, Rb or Cs) on the rate and equilibrium constants in the process of substitution of chlorine for bromine in hexyl bromide. The non-linearity of the log k vs 1/T, dependence is shown to be linked with a change in the physical meaning of the constants with temperature variations. This is attributed to the occurrence of a strong exothermic process consisting in the formation of a kinetically independent intermediate, that precedes the limiting stage. A mechanism including the formation of two stable ternary complexes coordinated on the solid-phase surface, one of which is structurally close to the starting reagents and the other to the final reaction products, is proposed. The observed activation energies, enthalpies of formation of the ternary complex and activation energies of the limiting stages for the forward and reverse substitution processes were calculated. Thermal effects of the substitution in the presence of various solid MCl species were determined from the thermodynamic data and observed activation energies for both reaction types. The substitution is shown to involve a limiting stage represented by a transition between the ternary complexes. A linear relationship between the activation energy for the limiting stage and the solid ionophore crystalline lattice was established, suggesting incorporation of the solid salt molecule into the transition reaction state. Potential energy changes in the course of substitution in the presence of the various MCl solid salts are discussed. The Bell - Evans - Polyani principle is shown to hold for these studies.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610040604
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