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  • 1
    ISSN: 1432-2307
    Keywords: Human cutaneous leishmaniasis ; Skin ; Immunohistochemistry ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary To characterize the in situ cellular immune response in localized cutaneous leishmaniasis (LCL), the authors studied frozen skin biopsies from 50 patients with LCL due toLeishmania braziliensis guyanensis. A panel of 31 monoclonal antibodies was used, which defined the number and distribution of inflammatory cell subsets. Skin inflammatory infiltrates were composed of T cells (with a local CD4/CD8 ratio of 1.05±0.7 vs 1.48±0.3 in peripheral blood), macrophages and a smaller number of B cells, natural killer cells and granulocytes. Most of the T cells expressed activation markers (interleukin-2 and transferrin receptors, HLA-DR+) and an increase in T-cell-receptorγδ expression was noted. Analysis of the CD4+ subpopulations with newly available reagents showed that helper T cells (CD4+CD45RO+) exceeded the suppressor/inducer subset (CD4+CD45RA+) by 1.4∶1. There were no differences between local immune variables from patients with primary infection (45 patients) and those with recurrence (5). In 7 patients, biopsies were analysed before and 1 month after specific treatment, and did not show significant differences except for a small increase of dermal CD1a+ (Langerhans) cells/mm2. The observed pattern of cellular skin infiltration suggests an immune-mediated tissue injury including T-cell-mediated cytotoxicity and delayed hypersensitivity reactions in addition to direct parasitic action.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1432-1440
    Keywords: Kidney ; Glomerulus ; Mesangium ; Mesangial failure ; Electron microscopy ; Animal models
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary We present a structural analysis of the ability of the biomechanical unit consisting of mesangium and glomerular basement membrane to maintain normal capillary architecture in the face of mechanical challenges due to high intraglomerular pressures. Capillary support function may be considered in terms of the stabilization of local form (development of wall tension against capillary dilation) and global form (centripetal fixation of capillary loops to maintain higher order form). The pathologic consequences of the loss of this support are illustrated by way of experimental models of mechanical mesangial failure. Such failure may express itself as mesangial widening, increased transmesangial macromolecule “traffic,” ballooning of capillary segments, and unfolding of capillary loops. Mechanisms are described by which these structural changes may lead to segmental glomerular sclerosis.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    International journal of legal medicine 105 (1992), S. 173-175 
    ISSN: 1437-1596
    Keywords: Human brain tissue ; Natural mummification ; Histology ; Histochemistry ; Electron microscopy ; Elemetal analysis ; Gehirn ; Mensch ; Naturaliche Mumifikation ; Histologie ; Histochemie ; Elektronenmikroskopie ; Atmospektralanalyse
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine , Law
    Description / Table of Contents: Zusammenfassung Bei Ausgrabungen in Bulgarien wurden Schädel und Knochen von 39 Individuen im Alter zwischen 35 und 60 Jahren, die vor ca. 45–50 Jahren begraben wurden, gefunden. Bei der nachfolgenden gerichtsmedizinischen Experitse wurden in zwei intakten Schädeln und zwischen den Knochen anderer Schädel sieben harte Gebilde (zwei ganze und fünf Fragmente), die wie geschrumpfte menschliche Gehirne aussahen, identifiziert. Entsprechende Proben von diesem Material wurden für 3–4 Tage mit 15% wässriger Lösung von Glycerol weicher gemacht und danach lichtmikroskopisch und elektronenmikroskopisch untersucht. An entsprechenden Stückchen von frischem menschlichem Gehirn und den gefundenen Proben wurde eine Atomspektral-analyse zur Bestimmung des chemischen Bestandes an Elementen durchgeführt. Die komplexe Untersuchung des Materials ergab, daß es sich bei diesem Fund um einen Sonderfall von natürlich mumifizierten menschlichen Gehirnen handelt, die durch sonderbare Bedingungen nur im Schädel der begrabenen Individuen entstanden sind.
    Notes: Summary When skulls and bones were exhumed from a mass grave in Bulgaria and subjected to medicolegal examination they were found to originate from 39 humans aged 36–60 years old who had been buried approximately 45–50 years ago. Solid structures which strongly resembled shrunken human brain tissue were found inside 2 intact skulls. Among other bones 5 similar structures were found one of which was an almost entirely preserved human brain, and the others were fragments from different regions of the human brain. Samples of these structures were immersed in 15% aqueous glycerol solution to soften and were examined by light and electron microscopy. Sampels of this material and of fresh human brain were subjected to elementary atomic spectral analysis. These complex studies indicated the samples to be naturally mummified human brain tissue and that this process had occurred due to specific conditions within the cranial cavities after burial.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1432-2307
    Keywords: Carnitine-palmityl-transferase deficiency ; Acute vascular lesions ; Acute myofibrillar lesions ; Ischaemia ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary A case of severe exercise-induced myoglobinuria in a 14-year-old boy suffering from a carnitine-palmityl-transferase (CPT) defect is reported. Biopsies of the forearm muscle were examined using light and electron microscopy in the acute and recovery phases of the illness. The first biopsy showed the presence of scattered foci of necrosis where necrotic fibres with occasional disruptions of the basal lamina were seen around injured capillaries. Various degrees of damage and different stages of evolution were found in these foci, which also contained regenerating muscle fibres. In the second biopsy, performed 2 weeks later, most of the fibres displayed a normal structure. Necrosis was no longer present. However, in some areas perivascular fibrosis was prominent, the fibres were small and irregularly shaped, and their nuclei often centrally located. These data strongly suggest that circulatory disorders and ischaemia, brought about by premature acute metabolic imbalance, could be involved in the development of exerciseinduced myolysis observed in CPT deficiency. The risk of fibrous cardiomyopathy in these patients is pointed out.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Virchows Archiv 421 (1992), S. 105-113 
    ISSN: 1432-2307
    Keywords: Parotid gland ; ras ; Transgenic mouse ; Electron microscopy ; Immunocytochemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary In the transgenic TG.SH (mouse mammary tumour virus/v-Ha-ras) mouse, designed to develop mammary tumours, occasional spontaneous salivary gland tumours have been reported, predominantly in males. The incidence and histomorphology of salivary gland tumours in 73 TG.SH mice were surveyed and in total, 21.9% developed both overt and microscopic parotid tumours. The majority developed between 73 and 150 days of age. In 31.5% of the TG.SH mice, occasional unilateral, but more frequently bilateral exophthalmos due to hyperplasia of the intraorbital (Harderian) lacrimal gland was observed. In 70% of these animals, parotid tumours developed later. Since Harderian gland hyperplasia, occurring as early as 5 weeks of age, preceded the development of palpable salivary gland lesions, this stigma is useful for the early selection of animals likely to progress to tumour formation. Before tumour-bearing transgenic mice are considered to be suitable models of human neoplastic disease, morphological characterization is necessary to ensure that the tumours are histologically representative of the human lesions for which they are potential models. In this study, all parotid tumours consisted of acinar-like glandular structures with central lumina discernible by electron microscopy. Ultrastructurally, secretory granules evident in the apical cytoplasm of the tumour cells resembled the zymogen granules of the normal parotid acinar cell, and some cells had a prominent complement of rough endoplasmic reticulum. These features, along with focal amylase expression detected immunohistochemically in some parotid tumours, identified these neoplasms as acinic cell carcinomas that mimic the human salivary gland acinic cell carcinoma faithfully.
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  • 6
    ISSN: 1432-2307
    Keywords: Silver staining ; Paired helical filaments ; Cerebral amyloid ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary A one step en bloc silver staining method which was originally established to study nucleolar organizer regions has been applied for the demonstration of both paired helical filaments (PHF) and extracellular cerebral amyloids in semi-thin sections and at the electron microscopic level. The three forms of PHF can be visualized: (1) neurofibrillary tangles are shown in all stages from first appearance in form of intracellular patches of PHF to severely degenerated shadow-like “ghost” tangles; (2) neuropil threads are distinctly stained in great numbers; and (3) PHF are easily detected as neuritic components in amyloid plaques. All forms of fibrillar extracellular amyloid structures, i.e. “diffuse”, “classical” and “burnt out” plaques, are well demonstrated; congophilic angiopathy reveals amyloid preferentially in arteries and arterioles of the leptomeninges and cortex ranging from small circumscribed patches to large circumferential amounts with occasional plaque-like condensations or broad loose accumulations of amyloid; perivascular cuffs and laminar subpial deposits of amyloid are stained as well. At the electron microscopic level all lesions are clearly visible in non uranyl/lead-stained specimens, characterized by varying numbers of silver grains on a pale background. The detailed demonstration of structures in archival material, which had been stored in paraffin and re-embedded for electron microscopy, is due to the demonstration of argyrophilic structures by the protective colloidal developer of gelatin and formic acid and to the proteolytic resistance of insoluble PHF and extracellular amyloids in plaques and congophilic angiopathy.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Virchows Archiv 420 (1992), S. 453-457 
    ISSN: 1432-2307
    Keywords: Uterus ; Paraganglioma ; Intracytoplasmic hyaline globules ; Immunohistochemistry ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary We report a malignant uterine paraganglioma in a 40-year-old female, who died 7 months after the initial diagnosis. On light microscopy the tumour showed a typicalzellballen pattern as well as a pronounced cellular pleomorphism. In many tumour cells hyaline globules were demonstrated within the cytoplasm. Immunohistochemically the lesion was characterized by the presence of neuron-specific enolase, protein gene product 9.5 and synaptophysin, and electron microscopically by the occurrence of neurosecretory granules.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 1432-0533
    Keywords: Peripheral neuropathy ; Cryoglobulinemia ; Immunohistochemistry ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Histological, immunohistochemical and ultrastructural sural nerve and skin biopsy findings in a case of cryoglobulinemia secondary to an IgM-kappa-producing non-Hodgkin lymphoma are described. The main finding was an occlusive microangiopathy present in both the sural nerve and the skin. Widespread cryoglobulin deposits of the proliferated vasa nervorum were associated with pronounced changes probably evoked by ischemia. Moderate perivascular inflammation, but no florid vasculitis was additionally present. Our observations indicate that occlusive microangiopathy by precipitated cryoglobulins may be a relevant pathogenetic factor in cryoglobulinemic peripheral neuropathy.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 1432-0533
    Keywords: Progressive supranuclear palsy ; Neurofibrillary tangles ; Pick body ; Immunocytochemistry ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Degeneration of heterogeneous systems in the central nervous system, with widespread distribution of argyrophilic neuronal fibrillary inclusions, was found in a patient with presenile dementia. Atrophy was circumscribed in the frontal and temporal lobes. Neuronal loss was severe in the basal ganglia, subthalamic nucleus, and substantia nigra. Immunocytochemical study using anti-phosphorylated tau and anti-ubiquitin antibodies in conjunction with ultrastructural observations revealed two types of inclusions: neurofibrillary tangles (NFTs) of progressive supranuclear palsy (PSP) in the Edinger-Westphal nucleus, locus coeruleus, cerebellar dentate nucleus, inferior olivary nucleus, and posterior horn of the spinal cord; and Pick bodies (PBs) in the atrophied cerebral cortex and red nucleus. PSP-type NFTs and PBs have been demonstrated in a single case for the first time. Despite their pathognomonic significance in certain disorders, we suggest that these inclusions may reflect a form of cytoskeletal disorganization, which is not entirely restricted to a single disease entity.
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  • 10
    ISSN: 1432-0533
    Keywords: Localized hypertrophic neuropathy ; Electron microscopy ; Immunohistochemistry ; Nerve growth factor receptor ; Schwann cells
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Immunoreactivity for nerve growth factor receptor (NGFR) was examined using a monoclonal antibody against human NGFR in the sural nerve of a 24-year-old woman, affected by localized hypertrophic neuropathy (LHN). NGFR expression was correlated with electron microscopy and with immunoreactivity for S-100 protein, laminin, HLA-DR, HNK-1, P0 glycoprotein and neurofilament peptides. Our results indicate that in LHN most of whorl-forming cells are NGFR positive and S-100 protein or HLA-DR negative. These data along with the ultrastructural features suggest their origin from perineurium.
    Type of Medium: Electronic Resource
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 186 (1992), S. 407-429 
    ISSN: 1432-0568
    Keywords: Acetylcholine receptors ; Immunocytochemistry ; Electron microscopy ; Human motor endplate ; Human cerebral cortex ; Neurodegenerative disorders
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Acetylcholine and its receptors are involved in a variety of important signal transduction processes. As shown here paradigmatically for the human neuromuscular junction and the cerebral cortex, acetylcholine receptors can be visualized immunohistochemically at the cellular and subcellular level under physiological and pathological conditions. At normal motor endplates nicotinic cholinoceptors are localized at the surface of the postsynaptic junctional folds. In myasthenic syndromes investigation of muscle biopsies enables the diagnosis of receptor deficiencies at the ultrastructural level. In normal cerebral cortex pyramidal neurons are equipped with both nicotinic and muscarinic acetylcholine receptors localized to postsynaptic densities. In neuropsychiatric diseases cholinoceptor expression can be monitored at the cellular level by quantititative assessment of immunolabeled cortical neurons.
    Type of Medium: Electronic Resource
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 185 (1992), S. 547-557 
    ISSN: 1432-0568
    Keywords: Dorsal tegmental nucleus of Gudden ; Laterodorsal tegmental nucleus ; Synaptic organization ; Anterograde tracing study ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary We examined the synaptic organization of ascending projections from the pars ventralis of the dorsal tegmental nucleus of Gudden (TDV) and the laterodorsal tegmental nucleus to the lateral mammillary nucleus (LM). The LM neuropil consists of terminals containing pleomorphic synaptic vesicles and forming symmetric synaptic contact, and terminals containing round synaptic vesicles and forming asymmetric synaptic contact. They make up 63% and 37%, respectively, of all axodendritic terminals. All axosomatic terminals contain pleomorphic vesicles and make symmetric contact. Following injection of WGA-HRP into the TDV, many anterogradely labeled terminals and retrogradely labeled cells are found in the LM. Labeled terminals contact mainly proximal (more than 2 μm diameter) and intermediate (1–2 μm diameter) dendrites. Serial ultrathin sections of the LM show that 55% of axosomatic terminals are labeled anterogradely. Following injection of WGA-HRP into the laterodorsal tegmental nucleus, many anterogradely labeled terminals are found in the LM, but no retrogradely labeled cells are present. Labeled terminals contact mainly distal (less than 1 μm diameter) and intermediate dendrites as well as somata. In the LM neurons, 46% of axosomatic terminals are labeled anterogradely. All labeled terminals from these nuclei contain pleomorphic vesicles and make symmetric synaptic contact. These results indicate that almost all axosomatic terminals come from the TDV and the laterodorsal tegmental nucleus, which send inhibitory inputs to the lateral mammillary nucleus.
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 83 (1992), S. 134-139 
    ISSN: 1432-0533
    Keywords: Scrapie ; Creutzfeldt-Jakob disease ; Neuronal autophagy ; Neuropathology ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary We report the presence of autophagic vacuoles (AV) in neuronal perikarya and neuronal processes of rodents with experimental scrapie and Creutzfeldt-Jakob disease. AV were composed of sequestrated cytoplasmic areas containing ribosomes and occasionally mitochondria and small secondary vacuoles. The formation of AV may contribute to neuronal degeneration and ultimately to neuronal loss.
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  • 14
    ISSN: 1432-0533
    Keywords: Alzheimer's disease ; Astrocytes ; Electron microscopy ; Immunohistochemistry ; Paired helical filaments
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary A 54-year-old man who had cerebellar ataxia and pseudobulbar palsy at the age of 29 years, and soon developed dementia, myoclonus and convulsions, died after about 20 years in a vegetative state. Histological examination of the extensively atrophic and devastated brain (680 g) revealed the almost total loss of cerebral cortical neurons associated with numerous β-protein amyloid plaques, many extracellular tangles and a large number of hypertrophic astrocytes, and prominent amyloid angiopathy. The astrocytes were frequently immunopositive for anti-human tau antibody (anti-htau) and anti-ubiquitin antibody (anti-ubi). Double immunostaining with anti-htau and anti-glial fibrillary acidic protein (GFAP) antibody clearly demonstrated htau-positive domains within the GFAP-positive perikarya/and processes of several astrocytes. Electron microscopy of the hippocampal CA1, which was completely devoid of pyramidal neurons, revealed, in astrocytes, abnormal filaments indistinguishable from the paired helical filaments (PHFs) seen in neurons. On immunoelectron microscopy, the filaments were observed to be labeled with anti-htau and anti-ubi, exhibiting the same immunohistochemical features as neuronal PHFs. This is the first demonstration of clearly constricted and both tau- and ubiquitin-positive PHFs in astrocytes, indicating that, in some special conditions like in our case, processes similar to those that attack neurons also affect astrocytes and ultimately make the latter form PHFs.
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  • 15
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 186 (1992), S. 363-370 
    ISSN: 1432-0568
    Keywords: Retinal photoreceptors ; Electron microscopy ; Teleost ; Astronatus ocellatus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The structure and arrangement of the retinal photoreceptors of the velvet cichlid fish (Astronotus ocellatus) have been studied by light and electron microscopy. Rods, single cones and double (twin) cones are present. In the light-adapted state, rods are very tall cells that reach deep into the retinal epithelial (RPE) layer. The long outer segment is composed of discs of uniform diameter displaying one or two incisures. The rod inner segment shows a distal ellipsoid of mitochondria, and then narrows dramatically in the myoid region. Rod nuclei are electron dense and located deep in the outer nuclear layer. Rod synaptic spherules are small and show two to three invaginated synaptic sites as well as superficial synapses. Single cones are similar to the individual members of a double cone and all display a short tapering outer segment, a large ellipsoid of mitochondria and a myoid rich in rough endoplasmic reticulum, polysomes, Golgi zones and autophagic vacuoles. Double cones have extensive subsurface cisternae along their entire contiguous surfaces. Cone nuclei are large and vesicular and located close to or through the external limiting membrane. The synaptic pedicles of cones are larger, more electron lucent, and display more invaginated (ribbon) synapses as well as conventional (superficial) synaptic sites than do the rod spherules. Rod photoreceptors certainly undergo retinomotor movements and it is probable that cones do as well. In the light-adapted state the cone photoreceptors are arranged in a repeating square mosaic pattern with one single cone surrounded by four double (twin) cones.
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  • 16
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 84 (1992), S. 630-637 
    ISSN: 1432-0533
    Keywords: Dentrites ; Excitotoxicity ; Glutamate ; N-Methyl-d-aspartate ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary This study documents the ultrastructural features of acute neuronal injury following N-methyl-d-aspartate (NMDA) receptor activation. NMDA (100 nmol/μl) or vehicle was infused over a 15-min period into the lateral ventricle of adult rats. After perfusion fixation, specimens demonstrating normal and abnormal patterns of vascular permeability to horserdish peroxidase were sampled for ultrastructural analysis. In NMDA-infused rats, brain regions exhibiting protein extravasation contained swollen dendritic profiles and abnormal neuronal perikarya. Although periventricular regions were most severely affected, parenchymal abnormalities were also detected in the cerebral cortex, septum, striatum, thalamus, hypothalamus and cerebellum. Mildly affected dendrites contained dark compact mitochondria, while in severely swollen dendrites mitochrondia were enlarged with ruptured cristae. Focal sites of plasma membrane disruption were also detected within swollen dendrites. Swollen neurons commonly displayed peripheral pallor and increased numbers of cytoplasmic vacuoles. Other neurons appeared dark and shrunken, some containing disrupted mitochrondria and pyknotic nuclei. Pretreatment with the NMDA antagonist MK-801 (2 mg/kg) attenuated the neuronal and dendritic alterations. In conditions where cerebrospinal fluid levels of glutamate are abnormally elevated, excessive NMDA receptor activation may lead to early vascular and neuronal complications which could work in concert to promote brain injury.
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  • 17
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 84 (1992), S. 621-629 
    ISSN: 1432-0533
    Keywords: Blood-brain barrier ; Endothelium ; Excitotoxicity ; N-Methyl-d-aspartate ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The purpose of this study was to document the early cerebrovascular consequences of excessive N-methyl-d-aspartate (NMDA) receptor activation. Five microliters of NMDA (100 nmol/μl) or vehicle was infused over a 15-min period into the lateral ventricle of adult rats. The protein tracer horseradisch peroxidase (HRP) was injected intravenously for blood-brain bartier (BBB) studies. The intraventricular infusion of vehicle (n=5) caused no alterations in arterial blood pressure or microvascular damage away from the intraventicular probe tract. In contrast, NMDA infusion (n=8) led to a gradual increase in arterial blood pressure (mean 36 mm Hg). Multifocal regions of HRP extravasation were observed bilaterally throughout the neuraxis following NMDA infusion. Sites of BBB disruption and hemorrhage included brain regions bordering ventricular spaces. In addition, isolated foci of protein extravasation were commonly detected in the cerebral cortex, thalamus, basal forebrain, septum and cerebellum. Pretreatment with the noncompetitive NMDA antagonist MK-801 (2 mg/kg) substantially reduced the BBB responses to NMDA. However, microvascular abnormalities were seen in NMDA-infused rats where blood pressure elevations were inhibited by blood removal. In addition to neurons, cerebral blood vessels are also acutely affected by NMDA receptor activation. Blockage of NMDA receptor channels following brain injury may potentially provide protection by attenuating BBB breakdown and subsequent brain edema.
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  • 18
    ISSN: 1432-0533
    Keywords: Striatonigral degeneration ; Putaminal pigment ; Iron ; Atomic absorption spectroscopy ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary We measured the total content of iron, cooper, zinc and manganese in the putamen of four patients with striatonigral degeneration (SND) and age-and gender-matched normal controls. The iron content in the SND patients was five times greater than in the controls. Electron microscopic histochemistry revealed the iron reaction products in the pigments showing a triphasic pattern of coarse, electron-dense globules, fine granular and fibrillary materials, and lamellated structures. These findings suggest that increased iron deposition may be related to pigment formation in the putament of SND.
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  • 19
    ISSN: 1432-0533
    Keywords: Histiocytic markers ; Astrocytoma ; Electron microscopy ; Glial fibrillary acidic protein ; Granular cell tumor
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary A case of cerebral granular cell tumor (GCT) is reported. Histologically, the growth was composed of benign astrocytes, granular cells and transitional forms between both elements. Glial fibrillary acidic protein was detected in the glial component and, to a lesser extent, in the granular cells. Alpha-1-antichymotrypsin was demonstrated in the latter component only. Ultrastructural study also supported the evidence that neoplastic astrocytes became granular cells. The survey of the literature and our own results suggest that GCTs in this particular location, even when histologically benign, seem to have a worse prognosis than the low-grade supratentorial astrocytomas.
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  • 20
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 186 (1992), S. 371-377 
    ISSN: 1432-0568
    Keywords: Retinal pigment epithelium (RPE) ; Electron microscopy ; Teleost ; Astronatus ocellatus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The morphology of the retinal pigment epithelium (RPE), choriocapillaris and Bruch's membrane (complexus basalis) have been studied by light and electron microscopy in the velvet cichlid (Astronotus ocellatus). The RPE is composed of a single layer of large columnar cells. The basal (scleral) border of these cells is minimally infolded, whereas the apical (vitreal) surface displays numerous pigment-laden processes which in light-adaptation surround both rod and cone outer segments. Laterally the RPE cells are joined by a series of basally located tight junctions. Wandering phagocytes are a constant feature within this epithelial membrane. The RPE cells display a large, vesicular nucleus, numerous mitochondria, much smooth endoplasmic reticulum, polysomes, myeloid bodies, phagosomes and melanosomes. Rough endoplasmic reticulum is relatively scarce within these cells. Although only light-adapted specimens were examined, it is thought that the melanosomes are capable of extensive retinomotor movement. The endothelium of the choriocapillaris facing Bruch's membrane is typically very thin but shows few fenestrations. Bruch's membrane is typical of other teleost species in that it is composed of only three layers.
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  • 21
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 186 (1992), S. 519-527 
    ISSN: 1432-0568
    Keywords: Intestine ; Interstitial cells ; Innervation ; Electron microscopy ; Guinea pig
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Systematic examination using electron microscopic montages and serial sections has demonstrated that three types of interstitial cell, namely gap junction-rich cells, glycogen-rich cells and fibroblast-like cells, are densely located along the whole extent of the deep muscular plexus of the guinea pig small intestine. They tend to be distributed in an alternating fashion in the cellular network, connected with muscle cells of the outer, circular layer by means of gap junctions. These three types of interstitial cell show close relations to two types of nerve varicosity: one type is characterized by clear round vesicles with diameters of about 50 nm, and the other by flattened vesicles measuring about 35 nm by 70 nm. Electron-dense patches have been observed at the cytoplasmic side of the axonal membranes. Muscle cells of both inner and outer circular layers also show close relations to these two types of nerve varicosity. These morphological features are discussed with the implication that they may have some regulatory role in intestinal movement.
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  • 22
    Electronic Resource
    Electronic Resource
    Springer
    Archives of dermatological research 284 (1992), S. 290-296 
    ISSN: 1432-069X
    Keywords: Cepharanthine ; Minoxidil ; Culture ; Hair cells ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The effects of cepharanthine and minoxidil on proliferation, differentiation and keratinization of cultured cells from the murine hair apparatus were examined electron microscopically. Both cepharanthine and minoxidil stimulated cell proliferation and delayed initiation of differentiation and keratinization of the cultured cells. On day 6, most control cells (87%) cultured in a 0.03 mM calcium medium without cepharanthine and minoxidil were differentiated into several subpopulations corresponding to those of in vivo cell layers of the hair apparatus, while most of the cells cultured with cepharanthine (71%) or minoxidil (70%) were still immature. On day 13, the number of degenerated cells increased (63%) in the control culture, whereas in the culture treated with cepharanthine or minoxidil, cell degeneration scarcely occurred (5% and 8%, respectively). Differentiated cells having tonofilaments were often observed in the cepharanthine- and minoxidil-treated cultures (76% and 72%, respectively). Elevation of extracellular calcium up to 1.0 mM induced keratinization (34%) in the control culture on day 6, while no keratinized cells were observed in the cepharanthine- or minoxidil-treated culture. On day 13 keratinization similarly occurred in the cultures with cepharanthine (30%) or minoxidil (48%). These results show that both cepharanthine and minoxidil may directly influence proliferation, differentiation and keratinization of cultured cells from the hair apparatus.
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  • 23
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    Archives of dermatological research 284 (1992), S. 242-245 
    ISSN: 1432-069X
    Keywords: Immunogold ; Electron microscopy ; Human skin ; Actin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Normal human skin was embedded in Lowicryl K4M. Actin microfilaments were localized by applyinga postembedding immunogold technique using the monoclonal anti-actin antibody HHF35. Actin microfilaments are part of the cytoskeleton in muscle and nonmuscle cells. Together with myosin they produce contraction. The antibody labelled myofilaments in smooth muscle arrector pili cells, myoepithelial cells and pericytes. In sweat gland cells the microvilli system, a zone beneath the cytoplasma membrane correponding to the adhesion belt region, and apocrine decapitation formations showed labelling.
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  • 24
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    Archives of dermatological research 284 (1992), S. 303-306 
    ISSN: 1432-069X
    Keywords: Hair follicle ; Basal lamina ; Dermal papilla cells ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
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  • 25
    ISSN: 1432-1238
    Keywords: Catheter ; Electron microscopy ; Infection ; Adherence ; Candida albicans
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Objective The purpose of the study was do describe the architecture of accretions occurring on the tips of central venous catheters (CVC). Design A conservative procedure was used followed by two different techniques of electron microscopy Setting and patients the study included 19 catheters which have been used on intensive cared adults, and which were chosen among those of parallel 300 CVC study. Measurements and results CVC were considered sterile, contaminated, colonized or infected according to microbiological and clinical criteria. CVC were found to remain much cleaner than in past clescriptions. When present, accretions were located on the olive-shaped end, and displayed stratified structures with three types of material: amorphous material, thrombus components and inflammatory cells. Bacteria were not seen, even on culture positive CVC. Candida albicans was found on one CVC in the cytoplasm of ganulocytes, and made xio direct contact with the plastic surface. Conclusion This technique should contribute to the understanding of the pathobiology of CVC infection and provide information proving or precluding the involvement of microbial adherence to polymers in vivo.
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  • 26
    ISSN: 1432-1106
    Keywords: Immunocytochemistry ; Visual pathways ; Electron microscopy ; Hamster
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The expression of specific calcium binding proteins is being used increasingly as a potential neuroanatomical marker for neurons with similar functions. In this study, the distribution of calbindin D28k in the superior colliculus (SC) of adult hamsters was examined by light and electron microscopy. Calbindin immunoreactivity was prominent in specific regions and laminae of the SC throughout its rostrocaudal extent, and was found to label horizontal, vertical and stellate cell types. In addition, calbindin label highlighted “bridges” of neuronal processes in the intermediate layers. The most frequent calbindin-immunoreactive profiles seen in the electron microscope were dendrites, some of which were post-synaptic to apparent retinal ganglion cell axon terminals. Labelled axons and axon terminals were less frequently encountered. There was considerable overlap between the size distribution of calbindin D28k-immunoreactive neurons and that of GABA-immunoreactive or Nissl stained neurons in the SC. However, using a double fluorescent labelling technique, and examination of the tissue with confocal laser microscopy, no neurons were observed in the hamster SC that showed immunoreactivity for both calbindin and GABA. In this regard, the SC is similar to the mammalian lateral geniculate nucleus and the pretectum, but differs from the neocortex, where calbindin and GABA are colocalized. The demonstration in the SC, as well as other parts of the nervous system, of sub-populations of neurons that contain distinct calcium-binding proteins suggests that these neurons have different functional properties. Correlative studies may clarify the relevance of these cytoplasmic components as cell markers, as well as their different patterns of association with neurotransmitters and peptides.
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  • 27
    ISSN: 1432-2048
    Keywords: Bradyrhizobium ; Electron microscopy ; Glycine (root nodules) ; High-pressure freezing ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract High-pressure freezing of chemically untreated nodules of soybean (Glycine max (L.) Merr.), in sharp contrast to chemical fixation and prefixation, appears to preserve the ultrastructure close to the native state. This is supported by the observation that the peribacteroid membrane of high-pressure-frozen samples is tightly wrapped around the bacteroids, a finding that is fully consistent with the current views on the physiology of oxygen and metabolite transport between plant cytosol and bacteroids. In soybean root nodules, the plant tissue and the enclosed bacteria are so dissimilar that conventional aldehyde-fixation procedures are unable to preserve the overall native ultrastructure. This was demonstrated by high-pressure freezing of nodules that had been pre-fixed in glutaraldehyde at various buffer molalities: no buffer strength tested preserved all ultrastructural aspects that could be seen after high-pressure freezing of chemically untreated nodules.
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  • 28
    ISSN: 1432-0738
    Keywords: Bis(tributyltin) oxide ; Liver ; Electron microscopy ; X-ray microanalysis ; Biochemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The toxic effects of bis (tributyltin) oxide (TBTO) on the rat liver were studied with an electron microscope and the accumulation sites of tin were determined with an X-ray microanalyzer. The activities of serum enzymes and the concentration of serum bilirubin were also analyzed. Male Wistar rats received an intramuscular injection of 0.5 ml/kg of TBTO. Marked swelling of the mitochondria appeared in the hepatocytes 4 h after injection of TBTO. Cytoplasmic vacuoles, which contained degenerated mitochondria, gradually increased in number in these hepatocytes. This in turn may have caused a decrease in the volume of hepatic cell cords and an enlargement of sinusoids in the entire hepatic lobule. However, fine structures of intrahepatic bile ducts were not altered. By X-ray microanalysis, tin peaks were preferentially obtained from swollen mitochondria of the hepatocytes. By polarographic analysis of the respiratory responses of mitochondria, it was demonstrated that rates of state 4 respiration and respiratory control ratio were significantly disturbed in TBTO-treated rats in comparison with those of controls. The activities of AST (aspartate aminotransferase) and ALT (alanine aminotransferase) were significantly increased after TBTO treatment, but those of ALP (alkaline phosphatase), LAP (leucine aminopeptidase) and total bilirubin were not changed. These results indicated that parenterally administered TBTO accumulated in the liver cell mitochondria and disturbed oxidative phosphorylation. Mitochondrial dysfunction might induce severe damage of the hepatocytes. Four days after injection of TBTO, hepatic structures and chemical indices were almost restored by the regeneration of hepatocytes.
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  • 29
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    Archives of microbiology 157 (1992), S. 381-388 
    ISSN: 1432-072X
    Keywords: PhiX174 ; Bacterial lysis ; Escherichia coli ; Electron microscopy ; Membranes ; Cell envelope
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Expression of cloned gene E of bacteriophage PhiX174 induces lysis by formation of a transmembrane tunnel structure in the cell envelope of Escherichia coli. Ultrastructural studies of the location of the lysis tunnel indicate that it is preferentially located at the septum or at polar regions of the cell. Furthermore, the diameter and shape of individual tunnel structures vary greatly indicating that its structure is not rigid. Apparently, the contours of individual lysis tunnels are determined by enlarged meshes in the peptidoglycan net and the force produced at its orifice, by the outflow of cytoplasmic content. Once the tunnel is formed the driving force for the lysis process is the osmotic pressure difference between cytoplasm and medium. During the lysis process areas of the cytoplasmic membrane which are not tightly attached to the envelope are extended inward by the negative pressure produced during lysis. After cell lysis external medium can diffuse through the lysis tunnel filling the inner cell space of the still rigid bacterial ghosts.
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  • 30
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    Child's nervous system 8 (1992), S. 326-331 
    ISSN: 1433-0350
    Keywords: Medulloblastomas ; Immunohistochemistry ; Cytokeratins ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Thirty-five paraffin-embedded medulloblastomas (19 from children and 16 from adults; 24 classic medulloblastomas, 10 desmoplastic medulloblastomas, 1 tumor with neuronal differentiation) were examined for reactions with antibodies against glial fibrillary acidic protein (GFAP), cytokeratins KL1 and MNF116, desmin, and vimentin. Only the tumor from the youngest patient, a 152-day-old boy, showed a positive immunoreaction for cytokeratins. Because of this age-related expression of cytokeratins in medulloblastomas primarily in very young children, cytokeratin positivity was interpreted as a sign of tumor immaturity. Five medulloblastomas showed scattered GFAP-positive reactive astrocytes and/or other positive, probably neoplastic, cells. Only two tumors showed GFAP immunoreactivity in unequivocally neoplastic cells. Of six tumors that reacted with vimentin, three showed strong reactivity throughout, one being the tumor from the 152-day-old boy. The remaining three demonstrated nests of vimentin-positive cells with weak or intense somatic immunoreactivity for vimentin. None of the 35 cases showed positivity for desmin, indicating that mesenchymal differentiation is restricted to the rare so-called medullomyoblastomas.
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  • 31
    ISSN: 1573-4935
    Keywords: Transferrin ; Receptor ; Isolation ; Reconstitution ; Liposomes ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Human transferrin receptor was isolated from Triton X-100 solubilized placental plasma membranes by a rapid one-step chromatographic procedure based on immunoadsorption of the receptortransferrin complex on anti-transferrin Sepharose and lectin-affinity on wheat germ agglutinin. Following exchange of Triton X-100 with CHAPS or n-octylglucoside, the purified receptor was incorporated into egg phosphatidylcholine liposomes upon, detergent removal by dialysis (lipid/protein ratio 15:1 to 45:1 (w/w) Reconstitution of the receptor was confirmed by trypsin cleavage to dissociate the large extracellular receptor domain from the liposomal membranes. Electron micrographs of the receptor-lipid recombinants negatively stained with sodium sillicotungstate, showed ographs of the receptor-lipid recombinants negatively stained with sodium sillicotungstate, showed that the receptor molecules distributed very inhomogeneously on the liposomes, most receptors being clustered. Single copies of the receptor were seen as elongate structures (5×10 nm) oriented with their long axis parallel to the liposome surface and separated from this by a 2–3 nm gap. This result provides evidence for a narrow connecting link between the globular extracellular receptor domain and the membrane spanning segment.
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  • 32
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    Bioscience reports 12 (1992), S. 495-501 
    ISSN: 1573-4935
    Keywords: Electron microscopy ; secretion ; neuropeptides ; exocytosis ; endocytosis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Exo- and endocytotic processes induced by depolarization of isolated neurosecretory nerve terminals show a close temporal correlation, which suggests a short time of integration of the neurosecretory granule membrane with the plasma membrane. In order to determine minimal time requirements for exocytosis-coupled endocytosis to occur, we have analyzed by electron microscopy uptake of horserdish peroxidase (HRP) as a fluid phase marker at the onset of depolarization. We have applied rapid mixing and sampling (quenched flow) to assess events in subsecond time peroids after stimulation. A significant number of labelled endocytotic vacuoles was observed during the first second of depolarization. This number then further increased by a factor of about 2 (within 5 s) and 4 (within 50s). Thus, as for exocytosis, the rate of endocytosis decreased considerably during prolonged stimulation. These data indicate i) that a substantial proportion of secretory granules undergoes exocytosis very shortly after stimulation, and ii) that, following exocytosis, the minimal time required for consecutive membrane retrieval is in the sub-second range.
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  • 33
    ISSN: 1432-2072
    Keywords: Haloperidol ; Clozapine ; Perforated synapses ; Electron microscopy ; Tardive dyskinesia ; Extrapyramidal syndrome
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Perforated synapses, which contain a discontinuous density along the postsynaptic membrane, can increase or decrease in numbers following various behavioral and biochemical manipulations. We have previously established that 14-day treatment with haloperidol causes an increase in the number of perforated synapses within the caudate nucleus (dorsolateral region) but not the nucleus accumbens (Meshul and Casey 1989). This effect was reversed if the animals were withdrawn from the drug for an equivalent period of time. We have now further examined the effects of haloperidol administration, which is associated with a high incidence of extrapyramidal side effects (EPS) and tardive dyskinesia (TD), and assessed the effects of clozapine, which appears to have a lower potential for inducing EPS and TD. Administration of haloperidol for 2 weeks significantly increased the percentage of perforated synapses in the caudate, but not in the nucleus accumbens or layer VI of medial prefrontal cortex (MPCx). There was an increase in specific [125I]epidepride binding to D-2 receptors in the caudate nucleus and MPCx following haloperidol. Administration of clozapine for 2 weeks did not affect the percentage of perforated synapses in any of the three dopamine (DA)-rich regions that were examined. There was an increase in specific [3H]SCH 23390 binding to D-1 receptors and in specific [125I]epidepride binding to D-2 receptors only within MPCx following clozapine. The absence of any change in the density of perforated synapses within the dorsolateral caudate nucleus following clozapine correlates with: 1) the lack of effect on specific DA receptor binding or down regulation of serotonin (5-HT2) receptors (as reported by others), or 2) the inability in clozapine-treated animals to depolarize block substantia nigra (A9) DA neurons. These results may be related to the low incidence of EPS and TD observed with clozapine.
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  • 34
    ISSN: 1432-0878
    Keywords: Chordotonal organ ; Scolopidium ; Homology ; Electron microscopy ; Sensilla ; Evolution ; Actias luna (Insecta)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The structure of a simple chordotonal organ, the presumed homologue of the noctuoid moth tympanal organ, is described in the atympanate moth, Actias luna. The organ consists of a proximal scolopidial region and a distal strand, which attaches peripherally to the membranous cuticle ventral to the hindwing alula. The strand is composed of elongate, microtubule-rich cells encased in an extracellular connective tissue sheath. The scolopidial region houses three mononematic, monodynal scolopidia, each comprised of a sensory cell, scolopale cell, and attachment cell. The dendritic apex is octagonally shaped in transverse section, its inner membrane lined by a laminated structure reminiscent of the noctuoid tympanal organ ‘collar’. A 9+0-type cilium emerges from the dendritic apex, passes through both the scolopale lumen and cap, and terminates in an extracellular space distal to the latter. Proximal extensions of the attachment cell and distal prolongations of the scolopale cell surrounding the cap are joined by an elaborate desmosome, with which is associated an extensive electron-dense fibrillar plaque. Within the scolopale cell, this plaque constitutes the scolopale ‘rod’ material. The data are discussed in terms of both the organ's potential function, and its significance as the evolutionary proto-type of the noctuoid moth ear.
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  • 35
    ISSN: 1432-0878
    Keywords: Retina ; Dopaminergic neurons ; Synapses ; Inner plexiform layer ; Immunocytochemistry ; Electron microscopy ; Bufo marinus (Anura)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Tyrosine hydroxylase (TH) immunocytochemistry was utilized to quantify dopaminergic synapses in the inner plexiform layer of the retina of Bufo marinus. Since dopaminergic cells have bistratified dendritic arborisation in the inner plexiform layer, attention was given to the segregation of synapses between the scleral and the vitreal sublaminae. Light-microscopically, a more elaborate dendritic branching was observed in the scleral than in the vitreal sublamina. In contrast, about 55% of synapses occurred in the vitreal one fifth of the inner plexiform layer, 30% in the scleral fifth, and 15% in the intermediate laminae. Input sources and output targets showed only minor quantitative differences between sublaminae 1 and 5. TH-immunoreactive processes were found in presynaptic (62.8%) and postsynaptic (37.2%) positions. Synapses to the stained dendrites derived from bipolar (40.4%) and amacrine (59.6%) cells, whereas outputs from the TH-positive processes were directed to amacrine cells (56.8%) and to small and medium-sized dendrites (35.4%); at least some of these can be considered as ganglion cell dendrites. TH-positive profiles neither formed synapses with each other nor were presynaptic to bipolar cell terminals. Junctional appositions of the immunoreactive profiles were occasionally seen on non-stained amacrine and ganglion cell dendrites in the scleral sublamina of the inner plexiform layer and on optic axons in the optic fibre layer. Although dopaminergic cells are mainly involved in amacrine-amacrine interactions, inputs from bipolar terminals and outputs to ganglion cell dendrites were also substantial, suggestive of a role also in vertical information processing.
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  • 36
    ISSN: 1432-0878
    Keywords: Regeneration ; Skeletal muscle ; Injury ; Autoradiography ; Morphometry ; Electron microscopy ; Mouse (SJL/J BALB/c)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Skeletal muscle regeneration in SJL/J and BALB/c mice subjected to identical crush injuries is markedly different: in SJL/J mice myotubes almost completely replace damaged myofibres, whereas BALB/c mice develop fibrotic scar tissue and few myotubes. To determine the cellular changes which contribute to these differential responses to injury, samples of crushed tibialis anterior muscles taken from SJL/J and BALB/c mice between 1 and 10 days after injury were analysed by light and electron microscopy, and by autoradiography. Longitudinal muscle sections revealed about a 2-fold greater total mononuclear cell density in SJL/J than BALB/c mice at 2 to 3 days after injury. Electron micrographs identified a similar proportion of cell types at 3 days after injury. Autoradiographic studies showed that the proportions of replicating mononuclear cells in both strains were similar: therefore greater absolute numbers of cells (including muscle precursors and macrophages) were proliferating in SJL/J muscle. Removal of necrotic muscle debris in SJL/J mice was rapid and extensive, and by 6 to 8 days multinucleated myotubes occupied a large part of the lesion. By contrast, phagocytosis was less effective in BALB/c mice, myotube formation was minimal, and fibrotic tissue conspicuous. These data indicate that the increased mononuclear cell density, more efficient removal of necrotic muscle, together with a greater capacity for myotube formation in SJL/J mice, contribute to the more successful muscle regeneration seen after injury.
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  • 37
    ISSN: 1432-0878
    Keywords: Enkephalins ; Neuropeptides ; Neurohemal organ ; Immunogold ; Electron microscopy ; Carcinus maenas, Uca pugilator, Eriocheir sinensis (Crustacea)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Leu-enkephalin containing secretory granules were demonstrated in axon terminals of immunogoldlabeled electron-microscopic sections of the sinus gland of three brachyuran crustaceans. These granules have a diameter of 120+-15 nm and differ in electron density from those located in adjacent terminals containing hyperglycemic or molt-inhibiting hormone. These neurohormones do not show co-localization with leu-enkephalin. The cross-reactivity of leu-enkephalin antiserum with met-enkephalin is less than 1%. The sinus glands of the three species examined show no immunoreactivity for FMRF-amide. A modulatory activity of endogenous enkephalin by paracrine mechanisms is suggested.
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  • 38
    ISSN: 1432-0878
    Keywords: Basic fibroblast growth factor ; Regeneration ; Degeneration ; Immunohistochemistry ; Electron microscopy ; Masseter muscle ; Myoneural junction ; Mouse (dystrophic mdx)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The localization of basic fibroblast growth factor (bFGF)-like immunoreactivity in the masseter muscle of dystrophic mdx mice on postnatal day 28 was investigated by immunoblot analysis and electron microscopy. Crude homogenate of the masseter muscle, when subjected to immunoblotting with a bFGF antiserum, exhibited a main band with the same molecular weight (18 kDa) as bovine bFGF. By electron microscopy, bFGF immunoreactivity was detected in small regenerating myocytes; the smaller cells were the premature myocytes, the most intense staining was the immunoreactivity within the cytoplasm. Putative precursors of the muscle cells with a few myofilaments, which were most intensely labeled with anti-bFGF, contacted each other and possibly developed into multinucleated myocytes through cell fusion. Mature myocytes with densely packed myofilaments and peripherally located nuclei did not exhibit bFGF immunoreactivity; they formed myoneural junctions with motor nerve endings immunoreactive for bFGF. Early differentiating myocytes with intense bFGF-like immunoreactivity did not make contact with immunoreactive nerve terminals. Degenerating large myocytes with a limited number of distorted and/or disrupted myofilaments exhibited electron-dense deposits in the cristae of mitochondria; these deposits were not abolished by immunoadsorption control experiments. Thus, the cell-size-dependent decrease in bFGF immunoreactivity in regenerating but not in degenerating myocytes provides a morphological basis for an autoregulatory role of bFGF in muscle regeneration. This study suggests that neuronal bFGF is not involved in initial muscle regeneration in the dystrophic mdx mouse.
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  • 39
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    Cell & tissue research 270 (1992), S. 87-93 
    ISSN: 1432-0878
    Keywords: Ovarian nerves ; Development ; Folliculogenesis ; Tyrosine hydroxylase ; Immunohistochemistry ; Electron microscopy ; Rat (Sprague Dawley)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Sympathetic neurotransmitters have been shown to be present in the ovary of the rat during early postnatal development and to affect steroidogenesis before the ovary becomes responsive to gonadotropins, and before the first primordial follicles are formed. This study was undertaken to determine if development of the ovarian innervation is an event that antedates the initiation of folliculogenesis in the rat, Rattus norvegicus. Serial sections of postnatal ovaries revealed a negligible frequency of follicles 24 h after birth (about 1 primordial follicle per ovary). Twelve hours later there were about 500 follicles per ovary, a number that more than doubled to about 1300 during the subsequent 12 h, indicating that an explosive period of follicular differentiation occurs between the end of postnatal days 1 and 2. Electron microscopy demonstrated that before birth the ovaries are already innervated by fibers containing clear and dense-core vesicles. Immunohistochemistry performed on either fetal (day 19) or newborn (less than 15h after birth) ovaries showed the presence of catecholaminergic nerves, identified by their content of immunoreactive tyrosine hydroxylase (TH), the rate-limiting enzyme in catecholamine biosynthesis. While some of these fibers innervate blood vessels, others are associated with primordial ovarian cells, thereby suggesting their participation in non-vascular functions. Since prefollicular ovaries are insensitive to gonadotropins, the results suggest that the developing ovary becomes subjected to direct neurogenic influences before it acquires responsiveness to gonadotropins.
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  • 40
    ISSN: 1432-0878
    Keywords: Adrenal cortex ; Ageing ; Steroidogenesis ; Electron microscopy ; Morphometry ; Rat (Wistar)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The morphological counterpart of the well-known age-dependent marked impairment of glucocorticoid secretion of rat adrenals was investigated by use of morphometric techniques. For this purpose 4-, 8-, 16- and 24-month-old rats were studied. Despite the notable lowering of both basal and ACTH-stimulated production of corticosterone by collagenase-dispersed inner adrenocortical cells, ACTH and corticosterone plasma concentrations displayed significant increases with ageing. Zona fasciculata (ZF) and zona reticularis (ZR) showed a notable hypertrophy in aged rats, which was due to rises in both the average volume and number of their parenchymal cells. The hypertrophy of ZF and ZR cells was in turn associated with increase in the volume of the mitochondrial compartment and proliferation of smooth endoplasmic reticulum, i.e., the two organelles involved in steroid-hormone synthesis. All these morphologic changes, conceivably due to the chronic exposure to high levels of circulating ACTH, are interpreted as a response enabling ZF and ZR to compensate for their age-dependent lowering in glucocorticoid secretion. Stereology also demonstrated that ZF and ZR cells underwent a striking age-related lipid-droplet repletion. Lipid droplets are the intracellular stores of cholesterol esters, the obligate precursors of steroid hormones in rats. This finding is in keeping with the contention that the mechanism underlying the age-dependent decline in rat-adrenal glucocorticoid secretion mainly involves impairments of the utilization of intracellular cholesterol previous to its intramitochondrial transformation to pregnenolone.
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  • 41
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    Cell & tissue research 270 (1992), S. 273-279 
    ISSN: 1432-0878
    Keywords: Macrophages ; Small intestine ; Large intestine ; External muscle layer ; Immunohistochemistry ; Histochemistry ; Electron microscopy ; Man
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary In the external layers of human small and large intestine macrophage-like cells were characterized by immunohistochemical, histochemical and electronmicroscopical methods. Using immunohistochemistry and a number of monoclonal antibodies, the presence and distribution of phenotypic subpopulations of macrophages were evaluated. In all locations macrophage-like cells were identified with antibody EBM11, which recognizes CD68 antigen, C3bi which recognizes CD11b, and partly with an antibody which recognizes protein 150,95 (CD11c). Macrophage-like cells in the external muscle layer were HLA-DR-positive (expressing the MHC class-II antigen), in contrast to macrophage-like cells in the subserosa and submucosa. Macrophage-like cells in the external muscle layer were mostly acid phosphatase-negative, and at the electron-microscopic level they were found to have features of macrophages: primary lysosomes, coated vesicles and pits. However, very few secondary lysosomes were present. Birbeck granules were not observed. It is concluded that in the external muscle layer of human small and large intestine numerous macrophages of a special type are present. It is discussed whether this cell type plays a role in gastrointestinal motility and/or has an immunological function.
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  • 42
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    Cell & tissue research 267 (1992), S. 321-335 
    ISSN: 1432-0878
    Keywords: Teeth ; Cementum ; Cementoblasts ; Matrix production ; Electron microscopy ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The present study describes the formative process of the initiation of cellular intrinsic fiber cementum (CIFC) in still growing human teeth. From 29 premolars and molars with incomplete roots developed to 60–90% of their final length, 8 premolars (with roots formed to three quarters of their final length) were selected for electron-microscopic investigation. All teeth were clinically intact and prefixed in Karnovsky's fixative immediately after extraction. Most of them were decalcified in ethylene diaminetetraacetic acid (EDTA), and the apical part of the roots was divided axially into mesial and distal portions that were subdivided in about 5 slices each. Following osmication and embedding in Epon, these blocks were cut for light- and electron-microscopic examination. In addition, 5 teeth with incomplete roots were freed from organic material and processed for scanning electron microscopy. It was found that CIFC-initiation commenced very close to the advancing root edge and resulted in a rapid cementum thickening. Thereafter, appositional growth continued on the already established cementum surface. Large, basophilic and rough endoplasmic reticulum-rich cementoblasts, some of which became cementocytes, were responsible for both fast and slow CIFC-formation. The CIFC-matrix was free of Sharpey's fibers and composed of more or less organized intrinsic collagen fibrils, in part fibril bundles, that ran roughly parallel to the root surface. Initially, the cementum fibrils intermingled with those of the dentinal collagen fibrils, which were not yet mineralized. This boundary subsequently underwent calcification. The development of collagen fibril bundles and their extracellular arrangement were associated with cytoplasmic processes probably involved in fibril formation and fibril assembly. Many cementoblasts contained intracytoplasmic, membrane-bounded collagen fibrils, which probably were related to fibril formation rather than degradation.
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  • 43
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    Cell & tissue research 267 (1992), S. 385-389 
    ISSN: 1432-0878
    Keywords: Leydig cells ; Macrophages ; Development, ontogenic ; Electron microscopy ; Testis ; (Rat Wistar)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Testicular macrophages and Leydig cells from adult animals are known to be functionally coupled. For example, secreted products from macrophages stimulate testosterone secretion by Leydig cells. In adult rat testes, structural coupling also exists between these cells. This coupling consists of cytoplasmic projections from Leydig cells located within cytoplasmic invaginations of macrophages. Although macrophages are known to exist in the testis in immature animals, it is not known when these digitations develop. The purpose of the present study was to determine whether the time of their development coincides with known maturational events that occur in Leydig cells, particularly during the peripubertal period. Testes from rats at 20, 30 and 40-days-of-age as well as testes from mature rats weighing more than 500 gm were prepared for ultrastructural analysis. It was found that digitations form between 20 and 30-days-of-age. These structures varied from simple tubular projections to complicated branched structures, suggesting that digitations are more than simple invaginations of microvilli into coated vesicles as previously described. Subplasmalemmal linear densities were also observed within macrophages juxtaposed to Leydig cells. Collagen was commonly observed between macrophages and Leydig cells in animals 20 days old. These studies demonstrate that although macrophages are present in the testis in maximal numbers at 20 days-of-age, they do not form junctions with Leydig cells until day 30. This is just prior to the major increase in secretory activity of rat Leydig cells that occurs during puberty.
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  • 44
    ISSN: 1432-0878
    Keywords: Intestine ; Interstitial cells ; Pacemaker ; Electron microscopy ; Guinea-pig
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Interstitial cells associated with the deep muscular plexus of the guinea-pig small intestine were studied by electron microscopy, and three-dimensional cell models were reconstructed from serial ultrathin sections with a computer graphic system. Three types of cells were recognized. The first type was similar in shape to smooth muscle cells, but did not contain an organized contractile apparatus. Many large gap junctions comprising about 4% of the cell surface were present; they connected cells of the first type to each other, to the second type of cell and to smooth muscle cells of the outer circular layer. The second type of cell had a welldemarcated cell body with long slender processes and was characterized by a large amount of glycogen comprising about 9% of the cell volume. The third type of cell was similar to fibroblasts, and contained well-developed Golgi apparatus and rough endoplasmic retiulum. Some of these fibroblast-like cells (a possible subtype) formed small gap junctions. All three types of cells showed close relationships with nerve varicosities. This cellular network consisting of gap-junction-rich cells, glycogen-rich cells and smooth muscle cells may be involved in the pacemaking activity of intestinal movement.
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  • 45
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    Cell & tissue research 268 (1992), S. 239-245 
    ISSN: 1432-0878
    Keywords: Urinary bladder ; Epithelial desquamation ; TPA ; Electron microscopy ; Rat (Donryu)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary 12-O-tetradecanoylphorbol-13-acetate (TPA) is known to affect the proliferation and/or differentiation of several types of cells. We injected TPA directly into the lumen of rat bladder to determine, using scanning and transmission electron microscopy, its effects on the bladder epithelium in vivo. At 1 h after TPA injection (1μg/ml), the superficial cells of the epithelium had changed their morphology, and large spherical vacuoles occupied their cytoplasm. In some areas, the underlying intermediate cells were exposed by the desquamation of the superficial cells. During the next few hours, TPA was excreted from the bladder lumen by voluntary micturition, but the desquamation of the superficial cells proceeded further. All the superficial cells were lost from the luminal surface by 24 h after TPA injection. The changes noted were specific for the superficial cells and were not observed in the intermediate or basal cells. After 24h, part of the epithelium had a three-layer structure, indicating that regeneration was taking place. These results demonstrate that TPA selectively affects and desquamates superficial cells in a short period of time. This experimental system may be useful for studying in vivo cell proliferation and/or differentiation.
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  • 46
    ISSN: 1615-6102
    Keywords: ATPase ; UTPase ; Electron microscopy ; Energy-dispersive X-ray microanalysis ; Gomphrena globosa ; Histochemistry ; Hordeum distichon ; Monstera deliciosa ; Phloem
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary For the histochemical localization of nucleoside triphosphatases at the electron microscopic level, prefixed tissues were incubated with lead nitrate in addition to substrate (GOMORI reaction). While ATP and UTP as substrates gave electron-dense reaction products at the plasmalemma of sieve tubes, companion cells and phloem parenchyma cells, and at plasmodesmata in primary pitfields, AMP gave reaction products only at the tonoplast of parenchyma cells. Since electron-dense deposits also occur in cell walls and vacuoles, energy dispersive X-ray microanalysis was used to distinguish between lead deposits and lead-phosphate deposits. The latter were restricted to the symplast. Among the three plant species used, the leaf bundle phloem ofHordeum distichon showed ATPase activity largely restricted to the phloem cells, except for the thickwalled sieve tubes. Some activity also bordered the chloroplasts of the bundle sheath cells. In the C4 plantGomphrena globosa, ATPase and UTPase activities appeared to be the greater in phloem parenchyma cells than in sieve tubes. In the phloem of youngMonstera deliciosa roots, ATPase occurred not only at the plasmalemma of sieve tubes, but also around sieve-tube plastids. When compared with AMP as substrate, it appears that nucleoside triphosphates are the natural substrates of the enzyme(s) in the plasmalemma of sieve tubes and phloem parenchyma cells.
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  • 47
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    European archives of oto-rhino-laryngology and head & neck 249 (1992), S. 168-171 
    ISSN: 1434-4726
    Keywords: Cochlea-Stria vascularis ; Electron microscopy ; Endocochlear potential ; Loop diuretics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The purpose of this study was to compare the effects of several organic acids (probenecid, sodium salicylate and penicillin G) on the endocochlear potential (EP) and the ultrastructure of the stria vascularis of the chinchilla with the effects of furosemide on these parameters. chinchillas received 50 mg/kg i.v. doses of probenecid, sodium salicylate or penicillin G, or 25 mg/kg i.v. furosemide. The EP was monitored continuously before and for 60 min afterwards. The stria vascularis was removed at 10-min intervals from animals and from 10 to 60 min after the injection of these agents. Specimens were then processed for transmission electron microscopy. Only furosemide had an effect on the EP, causing a reversible reduction. The reduction of the EP was accompanied by the appearance of edema in the intercellular spaces of the stria vascularis. No significant edema was found after probenecid, sodium salicylate or penicillin G. This was consistent with the finding that none of these latter three agents affected the endocochlear potential.
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  • 48
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    European archives of oto-rhino-laryngology and head & neck 249 (1992), S. 216-223 
    ISSN: 1434-4726
    Keywords: Cricopharyngeal dysphagia ; Muscle biopsy ; Electron microscopy ; Enzyme histochemistry ; Myositis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The structural changes in the cricopharyngeal muscle (CM) were examined ultrastructurally and by enzyme histochemistry in five patients suffering from idiopathic cricopharyngeal dysphagia (ICD). Diagnosis was established by fiberoptic esophagoscopy, esophageal manometry and cineradiography. Cricopharyngeal myotomy was performed with marked improvement in all patients. Intraoperatively, a biopsy was taken from the CM. Additionally, all patients underwent neurological examination for possible generalized muscle disease, and a biopsy was taken from a limb muscle. CM from nine cadavers without known history of dysphagia served as control. The control samples disclosed structural changes which were considered to be pathological in other skeletal muscles, and required that the criteria for CM pathology we modified accordingly. In three patients changes in CM histology suggested specific pathogenesis: one patient had evidence for a generalized myositis but was only symptomatic for dysphagia. Another patient had muscle fiber atrophy and slight inflammation in her CM, possibly due to alcohol abuse. The third patient had loss of CM fibers with replacement by connective tissue enough to cause functional disturbances. In two patients no cause for dysphagia was found in either immunohistochemistry or electron microscopic studies. These results demonstrate the special structural features of the CM and indicate that ICD can have multiple etiologies.
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  • 49
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    European archives of oto-rhino-laryngology and head & neck 249 (1992), S. 224-230 
    ISSN: 1434-4726
    Keywords: Inner ear ; Rat spiral limbus ; Intercellular matrix ; Electron microscopy ; Immunomorphology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The matrix of the spiral limbus is obviously a special form of the intercellular substance. In the present study, the rat's spiral limbus was investigated by electron microscopy after fixation with ruthenium red and tannic acid and immunofluorescence to demonstrate matrix components. Collagen types I, II, V, VI, VII, IX and XI and fibronectin were not observed. Collagen type II and cartilage-specific proteoglycans, however, occurred in large quantities. The basal lamina of interdental cells and inner sulcus cells did not contain any collagen type IV. while the basal lamina of the capillaries had only minor amounts. Laminin and nidogen appeared in large amounts in the basal lamina. After fixation with tannic acid, the matrix between the interdental cells and the capillaries contained 20- to 22-nm-thick single and irregularly running fibrils as well as plaques of a fine granular material. After fixation with ruthenium red, 30-to 60-nm-thick, electron-dense granules occurred and most probably consisted of proteoglycans. These findings indicate that the composition of the matrix of the spiral limbus is similar to that of cartilage but not identical.
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  • 50
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    European archives of oto-rhino-laryngology and head & neck 249 (1992), S. 287-292 
    ISSN: 1434-4726
    Keywords: Nerve endings ; Outer hair cells ; Acoustic exposure ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Rabbits were exposed to 100 dB pure-tone sound at 2 kHz for 2 h. Electron microscopy was used to study the relationship between changes in the outer hair cells, afferent nerve endings and efferent nerve endings. There was no relationship found between the degree of changes produced in the afferent nerve endings and that the outer hair cells. However, there was a relationship demonstrable between the degree of changes seen in the efferent nerve endings and the infranuclear region of the outer hair cells. These findings show that acoustic trauma will damage most the infranuclear region of the outer hair cells, while efferent nerve endings are injured next and least affected are afferent nerve endings.
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  • 51
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    The @Anatomical Record 234 (1992), S. 255-262 
    ISSN: 0003-276X
    Keywords: Corticotropin releasing hormone ; Adrenal gland ; Mitochondria ; Sprague-Dawley rat ; Electron microscopy ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The mitochondria of rat adrenals were investigated qualitatively and quantitatively in different functional states of the adrenal cortex. Following stimulation of the animals with corticotropin releasing hormone (CRH), the corticosterone serum levels reached a maximum 1 hour after stimulation with CRH. The amount of inner mitochondrial membrane within the zona fasciculata increased showing a biphasic time course, with a first maximum 2 hours and a second maximum 8 hours after stimulation. In contrast, a significant rise of mitochondrial volume occurred only 24 hours after CRH stimulation. Therefore, the dense vesicularization of mitochondrial cristae may constitute an early process to enhance the steroidogenic capacity of these cells. Within cells of the transition zone between zona glomerulosa and zona fasciculata, we could depict a special type of mitochondria with characteristic crescent-like cristae only seen after stimulation with CRH. This type of mitochondria may represent an intermediate form between mitochondria of zona glomerulosa and zona fasciculata underlining the impressive transformational capacity of adrenocortical mitochondria. After hypophysectomy, zona fasciculata cells contained mitochondria with tubular inner membranes, representing a hypofunctional state. In contrast, the hypofunctional state after hypophysectomy and the hyperfunctional state after stimulation of the adrenal cortex via CRH injection did not appear to correlate with the morphology of mitochondria from the zona reticularis and adrenal medulla.© Willey-Liss, Inc.
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  • 52
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    The @Anatomical Record 234 (1992), S. 335-347 
    ISSN: 0003-276X
    Keywords: Anatomy and histology ; Basement membrane ; Collagen ; Connective tissue ; Elastic tissue ; Electron microscopy ; Rats ; Submandibular gland ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The submandibular salivary gland originates from the floor of the mouth whose mucosa contains elastic fibers. Therefore, such fibers were sought in the duct system of the derivative organ. In adult rats, light microscopy has indeed revealed fine, circumferential, elastic fibers near the basement membrane of the duct epithelium. In the larger extralobular ducts, they were separated from several layers of longitudinal elastic fibers by a capillary-rich zone sparse in elastic fibers except for fine angular ones. More peripherally, larger angular-appearing fibers were frequently present near the submandibular parasympathetic ganglia in the duct wall. As duct diameter decreased, elastic fiber size and number diminished. Intralobularly, the smaller striated ducts, granular and intercalated ducts, and acini generally lacked such fibers. Electron microscopy of the extraglandular portion of the main duct revealed fibrils extending from both fibroblasts and elastic fibers that were close to the epithelium. Microfibrils coursed from them toward the lamina densa. Anchoring filaments joined the lamina densa to the basal plasma membrane of the epithelium. Elastic fibers also appeared to connect to both capillaries and collagen via finer intermediate structures. These associations might permit dynamic interactions of fibroblasts, fibers, smaller fibrillar components, vasa, and the duct epithelium. This interplay could occur during feeding and grooming when tongue protrusion and neck extension stretch the submandibular duct and the gland itself. As a result, the tensile forces engendered could modify cell geometry and the calibers of the larger ducts' lumens and intercellular spaces, thus affecting the flow and composition of salivary secretion.© Willey-Liss, Inc.
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  • 53
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    The @Anatomical Record 234 (1992), S. 161-171 
    ISSN: 0003-276X
    Keywords: Blood cells ; Teleosts ; Gilthead seabream ; Sparus aurata ; Light microscopy ; Electron microscopy ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The peripheral blood cells of the gilthead seabream (Sparus aurata L.) were studied by light and transmission and scanning electron microscopic methods. Acidophilic erythroblasts and mature erythrocytes, round, oval, and fusiform thrombocytes, neutrophils, acidophils and basophils, lymphocytes, plasma cells, and monocyte-macrophages were characterized. A comparison of our light and electron microscopic results was carried out. The results were discussed with those for other fish species and the main modifications from the common vertebrate haematological pattern observed being considered.© Willey-Liss, Inc.
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  • 54
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    Journal of Physical Organic Chemistry 5 (1992), S. 244-252 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The protonation of diphenyl sulfoxide and several substituted diphenyl sulfoxides was probed by the MNDO-PM3 method to gain a theoretical insight into the experimentally observed preference for stable diphenyl sulfoxonium ion formation (O-protonation) in 1:1 FSO3H - SbF5 (Magic Acid) - SO2. In agreement with solution studies, O- protonation is uniformly favored (by ca 17 kcal mol -1) over S-protonation. The differences in the heats of formation of protonated and unprotonated diphenyl sulfoxides are increased by electron-withdrawing substituents (F, CF3) and decreased by electron-donating groups (Me, OMe). Variations in the SO bond length and bond order in the onium ions are compatible with simple resonance arguments and the oxonium/sulfonium character of both the O- and S-protonated onium ions. Surprisingly, the O- and S-protonated dibenzothiophene S-oxides are predicted to have identical energetics as compared with the corresponding protonated diphenyl sulfoxides. On structure optimization dibenzothiophene S-oxide itself, if the initial geometry is somewhat twisted, rearranges by ring expansion to give a new heterocycle with lower energy. A rotational barrier study on the parent O-protonated diphenyl sulfoxide showed two minima, separated by 1.3 kcal mol-1, at HOSC dihedral angles of 60° and 240°. The two conformations correspond to syn and anti orientations of the OH proton relative to the aromatic rings, and support the lowtemperature solution observations of the presence of two distinct sulfoxonium ions in solution. The rotational barriers for diphenyl sulfoxonium cation are compared with those of O-protonated dimethyl sulfoxide.
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  • 55
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The base-promoted nitrile-forming elimination reactions of YCH=CHCβH=NOCH=CHZ (Y=OCH3, H or Cl and Z=H or NO2) were studied by the AM1 MO theoretical method with Cl- as a base. The reaction is found to proceed by an E1cB-like E2 mechanism in which Cβ - H bond cleavage is more advanced than N - O bond breaking. The syn-elimination has a more E1cB-like transition state (TS) than the anti elimination, which is attributed to the structurally favourable nN - ó * (Cβ - H) charge-transfer interaction. An electron-withdrawing Y substituent lowers the activation barrier by stabilizing negative charge developed on Cβ in the TS. An electron-withdrawing substituent in the leaving group (Z = NO2) tends to enhance the anti relative to the syn elimination process by depressing the δ*(N - O) level, which in turn makes the nć - δ*(N - O) interaction more effective. The YCH=CH -  and  - CβH=N fragments are perpendicular in the TS, which is stabilized by delocalization of negative charge developed on the Cβ atom.
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  • 56
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    Journal of Physical Organic Chemistry 5 (1992), S. 253-258 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An AM1/PM3 study of several tetrahalomethane-arene molecular complexes is presented. The results indicate the existence of weak attractive non-dispersion interactions in some of these complexes, which can be rationalized in terms of multipole - multipole and multipole - induced dipole interactions. No evidence was found for the occurrence of charge transfer in the ground states of these complexes.
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  • 57
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    Journal of Physical Organic Chemistry 5 (1992) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 58
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    Journal of Physical Organic Chemistry 5 (1992), S. 285-286 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The first direct determination of a 1,2-chlorine atom shift in a chlorobenzylcarbene was achieved by nanosecond laser flash photolysis. Arrhenius activation parameters of Eact = 3.39 ± 0.14 kcal mol-1 and log [A(s-1)] = 10.98 ± 0.14 were obtained for 1,2-chlorine migration in α-methyl-α-chlorobenzyl(ch1oro)carbene. The lifetime of this carbene is considerably longer than previously estimated and the measured Eact, is in excellent agreement with that determined by product analysis.
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  • 59
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    Journal of Physical Organic Chemistry 5 (1992), S. 275-284 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rate constants of the pseudo-first-order methylation reaction of seven substituted pyridinium-N-phenoxide betaine dyes by iodomethane, were determined by UV-visible spectrophotometry in nine different solvents. The influence of substituents on the position of the long-wavelength, intramolecular charge-transfer absorption band of the unsubstituted betaine dye can be described by a modified Hammett equation. The solvent-dependent absorption constant ρA correlates satisfactorily with the acceptor properties of the nine solvents used. The substituent-dependent alkylation rate constants (In k) correlate linearly with the Hammett substituent constants, whereas the solventdependence of in k follows a more complicated pattern. Temperature-dependent measurements of the rate of alkylation exhibit an isoenthalpic behaviour for all the betaines in all the solvents investigated, i.e. the Arrhenius activation energy is almost constant for all differently substituted betaines in a given solvent. Temperature-dependent measurements of the alkylation rate of the unsubstituted betaine in different solvents led to an isosolvent relationship, i.e. the corresponding Arrhenius plots show a common point of intersection. According to the theory of isokinetic relationships, this isosolvent behaviour is interpreted in terms of a resonant energy exchange between the reacting species and the surrounding heat-bath system, which in this particular case seems to be the betaine molecule itself.
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  • 60
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    Journal of Physical Organic Chemistry 5 (1992), S. 295-298 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: To study molecular features connected with chirality, a procedure for the quantitative estimation of the chirality level of compounds of different classes is needed. A procedure for estimating the molecular asymmetry level relative to mirror-reflection axes of symmetry, S1, S2, S4 and S6, has been developed. The geometrical mean of these parameters is the disymmetry function (DF). To calculate the DF, the molecule must be fixed in the coordinate system, transferred to the main axes of inertia.
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  • 61
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The efficiency of the developed method of dissymmetry functions was studied using various model systems. The alteration of the dissymmetry function was analysed with systematic variations of the bond lengths, valence angles and masses of atoms in model tetrahedra. The behaviour of the dissymmetry function was studied for conformationally labile systems and chiral polyhedra. In general, it was found that in all cases the alteration of the dissymmetry function is in agreement with the speculative representations of the changes in degree of chirality.
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  • 62
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    Journal of Physical Organic Chemistry 5 (1992), S. 287-294 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Based on analysis of recently reported measurements, it is suggested that, provided a sufficiently large set of specific rate measurements in a wide variety of solvent types is available, the negligible to moderate improvements in the correlations of other types of benzylic chlorides, which are gained by use of a benzylic chloride (in place of 1-adamantyl chloride) as the standard substrate, do not justify the development of new specialized scales of solvent ionizing power. A similar conclusion is reached concerning solvent ionizing power scales developed for use with benzylic p-nitrobenzoates. However, such scales could be helpful when specific rates of solvolysis in only a limited variety of solvents are available, e.g. when a change in mechanism severely limits the range of operation of one of the pathways. Contrary to a previous claim, variations in ion-pair return could be the cause of deviations from Grunwald-Winstein plots for solvolyses of benzhydryl chloride in fluorinated alcohol solvents; such effects could be coupled, at least in part, with variations in aromatic ring solvation.
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  • 63
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    Journal of Physical Organic Chemistry 5 (1992), S. 317-321 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The differences between charge-transfer transition energies calculated for donor-acceptor pairs at infinite separation and values determined experimentally for the charge-transfer complex geometry vary according to the charge type of the pairs and within a group of fixed charge type. It is argued that these differences provide a guide to the slope of the state-correlation curves for the product configuration in electrophile-nucleophile reactions of the corresponding charge type and that the observed variation invalidates the use of the simple expression ΔE=fΛ-β with constant f, derived from the curve-crossing model, to estimate energy barriers to reaction.
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  • 64
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: For a number of chiral α,β-unsaturated carbonyl compounds, cyclohexanone and cyclohexenone derivatives, existing essentially in the form of single molecular conformation, the correlation dependences were established between the values of the calculated dissymmetry functions (DF) with respect to atomic masses and atom refractions, and the induction effectiveness of helical ordering in the nematic mesophase (twisting power). Such correlative dependencies, as the examples show, allow one to predict safely enough the twisting power of new substances with the ‘fixed’ molecular conformation. Types of dissymmetry functions and kinds of correlative dependences, the most acceptable for these reasons, were revealed. Dissymmetry functions formed on the basis of atom refractions (polarizabilities) describe the influence of the molecular structures of chiral compounds on the twisting power with higher accuracy than those that characterize the dissymmetry of the atomic masses distribution, according to the important role of the dispersion forces in the formation of helical ordering in liquid crystalline systems. The components characterizing the distribution dissymmetry of atomic refractions and masses with respect to the long and two shorter axes as the peculiar characteristics of biaxiality of chiral molecules describe the influence of the molecular structure on the twisting power with the same accuracy as the general DF do. Thus influence of chiral dopant molecules on the interactions between molecules in the uniaxial mesophases is negligible within the limits of the DF method. Based on the calculations for model systems it is established that the presence of the non-linear cinnamoyl fragment has a decisive influence on the molecular dissymmetry of the chiral α,β-unsaturated ketones. The alkyl groups influence the molecular dissymmetry only slightly, but it is important that their presence ensures the stabilization of the chiral conformer with the defined helicity of the cinnamoyl fragment.
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  • 65
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    Journal of Physical Organic Chemistry 5 (1992), S. 322-326 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The enol of acetophenone was generated flash photolytically in aqueous solution by photosolvolysis of PhCBr=CH2 and photohydration of PhC≡CH and PhC≡CD, and rates of its ketonization were measured in dilute perchloric acid solutions in H2O and D2O at 25°C. The rate constants so obtained provide the solvent isotope effects, kH+/kD+ = 5.02 ± 0.08, and the secondary isotope effect for deuterium substitution at the β-position of the enol double bond, (kH/kD)β = 0.999 ± 0.014. Arguments are presented which show that these isotope effects requre a stepwise rather than a concerted mechanism for the ketonization reaction.
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  • 66
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    Journal of Physical Organic Chemistry 5 (1992), S. 334-340 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The use of an assistant reagent to monitor spectroscopically the concentration of compounds that lack chromophores is described. It is demonstrated, for example, that the concentration of an aliphatic alcohol (present during acidcatalyzed hydrolysis or esterification reactions) can be monitored continuously by addition of a small amount of chromium trioxide. From a knowledge of the rate law and the rate constants for chromic acid oxidations, - d [CrO3]/dt = k [alcohol] [CrO3], the concentration of alcohol can be determined at any time by monitoring the absorbance of chromic acid at 363 nm. The rate at which the concentration of the alcohol is changing can then be used to calculate rate constants for the corresponding esterification or hydrolysis reactions. Rate constants obtained in this way are compared with those previously obtained by use of direct methods, and the application of this approach to the study of kinetics under conditions not accessible by other methods is illustrated.
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  • 67
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    Journal of Physical Organic Chemistry 5 (1992), S. 349-354 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The ionization constants of sixteen 5-furylmethylenehydantoins and 5-thienylmethylenehydantoins were measured in 80% (w/w) dimethyl sulphoxide-water solvent at 25°C. The effects of the 2-/3-furyl and 2-/-3-thienyl rings and the effects of configuration and conformation on acidity are discussed. The very low acidity of (Z)-5-(2-furyl)methylene-3-methylhydantoin suggests the possibility of some weak intramolecular interaction between the proton at N-1 and the 2-furyl oxygen in the s-cis conformation.
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  • 68
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The substitution reactions of Br(CH2)nBr(1, n = 3-5) with KCN in methanol were studied in detail. Second-order rate constants k1 [formation of the mononitrile (2) from 1] and k2 (formation of the dinitrile (3) from 2) were determined, as were the rates for the reaction of H(CH2)nBr (4, n = 3-5) with KCN under the same conditions. The ratios k2/k1 ( = x) of the three homologs of 1 were found to be 1.15, 0.77 and 0.61 for n = 3, 4 and 5, respectively; a x value of 0.5 indicates that the functional groups behave independently. The second-order rate constants k1 (statistically corrected) and k2 exhibit modest enhancements compared with model compound 4 when any of the following substituents are present: δ or ∊-bromo, γ-, δ-, or ∊-cyano. By contrast, a γ-bromo substituent slightly retards the rate. These results indicate that the functional groups do influence each other to a modest degree by field effects which accelerate the reactions. Steric effects do not appear to play a significant role.
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  • 69
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    Journal of Physical Organic Chemistry 5 (1992), S. 429-434 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reaction between 1-fluoro-2,4-dinitrobenzene and n-butylamine in toluene shows a two-step plot of kobs, values vs the initial values of the concentration of the amine. The usual base-catalysis mechanism for HF elimination from the zwitterionic intermediate hardly explains this kinetic behaviour and the kinetic effect of addition of salts (and of 2-hydroxypyridine) to the reaction mixtures at different initial values of the concentration of n-butylamine. In contrast, the kinetic behaviours are easily explained by the presence of substrate-amine (or catalyst) interactions on the pathway of the substitution reaction.
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  • 70
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    Journal of Physical Organic Chemistry 5 (1992), S. 74-82 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Owing to the importance of the concept of aromaticity, different indices have been developed to try to quantify this property. The possible π delocalization through an X—SOn—X group (X = C, N; n = 0, 1 or 2) could explain heteroaromaticity in rings containing the moiety. For that reason, the aromaticity of five-membered sulphurcontaining rings with different oxidation numbers (S, SO and SO2) and including no (thiophene), one (isothiazole) or two (1,2,5-thiadiazole) adjacent atoms was investigated. Ab initio calculations were carried out to determine geometrical parameters (planarity of the ring, bond length and bond order), electronic structure (charge distribution and dipolar moment) and the participation of d-orbitals of sulphur. According to these calculations, only compounds with S(II) can be considered to be aromatic, whereas compounds bearing S(IV) or S(VI) are better described as ylides.
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  • 71
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    Journal of Physical Organic Chemistry 5 (1992), S. 83-92 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hydrolysis of geranyl diphosphate (GPP) at pH 7 in water gives largely linalool (LOH) + geraniol (GOH) in the ratio of 3:1. Added N-3 generates mixed acylic allylic azides and increases the LOH GOH ratio to 15:1 in 2 M NaN3, but does not speed up the overall reaction. Hydrolysis of neryl diphosphate (NPP) gives largely α-terpineol (TOH) +p LOH, but their ratio is not very sensitive to NaN3 concentration although acyclic azide and small amounts of α-terpinyl azide (TN3) are formed. Hydrolysis of α-terpinyl diphosphate (TPP) gives large amounts of the cyclic alkenes, limonene and terpinolene. Added N-3 does not change the amount of elimination, but increases the ratio of limonene to terpinolene, and diverts some substitution product to TN3. Trapping of carbocationic species from GPP by N-3 is sharply increased by addition of Mn2+, which also catalyzes the overall reaction. Products of reaction of GPP are derived from acyclic intermediates and of NPP from acyclic and cyclic intermediates, and ionizations of the three substrates do not generate common carbocationic species.
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  • 72
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    Journal of Physical Organic Chemistry 5 (1992), S. 104-107 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cyclopropylmethoxycarbene undergoes ambiphilic-nucleophilic intermolecular reaction with alkenes and methanol, but its intramolecular chemistry (1,2-carbon migration) is suppressed (k 〈 3 × 103 s-1) by the α-methoxy substituent.
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  • 73
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    Journal of Physical Organic Chemistry 5 (1992) 
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    Keywords: Organic Chemistry ; Physical Chemistry
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  • 74
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    Journal of Physical Organic Chemistry 5 (1992), S. 101-103 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dewar-anthraquinone (1a) and 1,2,3-tri-tert-butyl-5,8-Dewar-anthraquinone (1b) were synthesized. Thermodynamic parameters for their cycloreversion to the corresponding anthraquinones indicate that thermal population of the excited states of the products via non-adiabatic valence isomerization is energetically feasible. On thermolysis of 1b, the formation of a detectable amount of 1,2,3-tri-tert-butyl-1,4-Dewar-anthraquinone (3) was observed. The excited singlet state of 1,2,3-tri-tert-butylanthraquinone (2b) produced via the non-adiabatic process is responsible for the formation of 3.
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  • 75
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    Journal of Physical Organic Chemistry 5 (1992), S. 109-118 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A molecular mechanics study on some organophosphorus podands, with both rigid and flexible terminal groups, and on their complexes with Li+ and Na+ was carried out. Na+ causes smaller deformations of the ligands than Li+, but its complexes are less stable, as the interaction energy with the podands is weaker. The ligands with rigid terminal groups are, in general, more pre-organized for complex formation. The cation-ligand interaction energies, including also the changes in steric energies, are always higher in complexes of flexible molecules than in those containing rigid ligands. The lower entropy losses which accompany the formation of complexes of rigid molecules with alkali metal cations probably account for the observed higher stabilities of the complexes.
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  • 76
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    Journal of Physical Organic Chemistry 5 (1992), S. 119-122 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polarographic half-wave potentials for the electrochemical reduction of a series of para-substituted iodobenzenes in acetonitrile, acetone, benzonitrile, dimethylformamide, dimethyl sulphoxide and methanol obey Hammett equations and the reaction constant found, ρ = 0·36 ± 0·02, is independent of the solvent used. The results obtained are discussed on the basis of a mechanism of the electrode process.
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  • 77
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The application of cavity theories of solution and linear solvation energy relationships to the interpretation of enthalpy of solution values of tert-butyl halides in hydroxylic media, measured at 25 °C and infinite dilution, is deserted, in order to define the intermolecular forces acting between solutes and solvents. It is concluded that solvent dipolarity and solvent HBD acidity effects dominate the solution process. An empirical equation relating the enthalpies of solution with selected properties of both solvents and solutes is proposed. New experimental Δ Hs∞ values for tert-butyl iodide in 13 alcohols are reported.
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  • 78
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    Journal of Physical Organic Chemistry 5 (1992), S. 123-128 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 10, 10-Dimethyl-9-anthrylidene (DMA) was studied by laser flash photolysis (LFP) techniques. LFP of the requisite diazo precursor in pentane or carbon tetrachioride produced transient spectra attributed to the hydrocarbon and monochlorinated diarylmethyl radicals, respectively. In the presence of pyridine and oxygen, ylides were formed upon LFP of 10, 10-dimethyl-9-diazoanthrone. However, ylides are not formed in acetonifrile or acetone. The carbene itself was not detected by transient absorption spectroscopy. The absolute rate constants for reaction of DMA with pyridine, methanol and triethylsilane are 1·96 × 109, 1·8 × 1010, and 1·0 × 108 I mol-1 s-1, respectively. It is concluded that the singlet and triplet states of DMA are essentially degenerate.
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  • 79
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    Journal of Physical Organic Chemistry 5 (1992), S. 142-154 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Some transimination processes were studied using an intermolecular model formed by pyridoxal-5′ -phosphate (PLP) an amino acid and dodecylamine (DOD) in an aqueous medium. All the kinetic constants for the reversible reaction were determined. The results show that in these cases transimination proceeds through an addition-elimination by forming a diamine geminal intermediate. Equilibria are always shifted to dodecylamine-PLP Schiff base formation. Differences between the stability of this Schiff base and the ∊-aminocaproic Schiff base cannot be explained only on the basis of the different nucleophicities of amine groups and therefore differences in the imine double bond environment must be taken into account to explain this behaviour.
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  • 80
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    Notes: The cycloaddition reactions of 4-methylphenylthio-, methoxy-, 4-methoxyphenyl-, phenyl-, chloro- and cyanoallene with tert-butylthioacrylonitrile (BTA) in toluene-d8 solution were investigated. The relative reactivity sequence of these substituted allenes is 4-methylphenylthio ∼ methoxy- 〉 4-methoxyphenyl- 〉 phenyl- 〉 chloro- 〉 cyanoallene. Activation parameters were measured for diradical intermediate formation of BTA with 4-methylphenylthio-, methoxy- and 4-methoxyphenylallene, giving average values of Ea and ΔS± of 14.2-16.8 kcal mol-1 and ca. -33 eu, respectively. The relative reactivity sequence is consistent with a FMO allene-HOMO, BTA-LUMO dominant interaction for diradical intermediate formation. However, the regioselectivity of attack on the substituted allene appears to be thermodynamically controlled. The formation of the diradical intermediates in these cycloaddition processes appears to be irreversible. However, the ring closure of the diradical intermediates formed from 4-methylphenylthio-, methoxy- and 4-methoxyphenylallene is reversible under the conditions of the kinetic experiments. The kinetically controlled ring closure of the diradical intermediates is allyl radical SOMO controlled, while the final cycloadduct distribution is thermodynamically controlled.
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  • 81
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    Journal of Physical Organic Chemistry 5 (1992) 
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 82
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    Journal of Physical Organic Chemistry 5 (1992), S. 201-208 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relative stabilities of gaseous protonated propylene oxide and its isomers, protonated propanal, oxetane and acetone, were reinvestigated in a Fourier transform ion cyclotron resonance mass spectrometer by using multiple-stage tandem mass spectrometri experiments. The dependence of ion structure on internal energy was examined by generating the ions in proton transfer reactions with different exothermicities and then probing their structures by using energy-resolved mass spectrometry (collision-activated dissociation as a function of collision energy). In contrast to results obtained in several recent investigations, protonated propylene oxide was found to be distinct from its more stable isomers when generated with only a small amount of internal energy. When the exothermicity of the proton transfer reaction was higher than 6 kcal mol-1 (1 kcal = 4·184 kJ) or when the epoxide ion was subjected to multiple activating collisions, rapid isomerization to protonated propanal occurred. The energy required for opening of the epoxide ring estimated to be similar to that measured earlier for protonated cyclohexene oxide (5-10 kcal mol-1).
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  • 83
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    Journal of Physical Organic Chemistry 5 (1992), S. 218-224 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The ESR spectra of 2-arylindan-1,3-dionyl radicals in various solvents at 343 K were obtained and assignments of the hyperfine structures were made. The hyperfine coupling constant (hfcc) of the dimethylamino nitrogen increases whereas the 2',6'-hydrogen hfcc decreases as the ET value, a solvent polarity parameter, increases. MO calculations were made according to the semi-empirical procedure of Rieger and Fraenkel; the nitrogen and oxygen Coulomb integrals were adjusted so that the calculated spin density on the nitrogen atom agrees with that estimated from its hfcc. It is found that the π-moment of the radicals increases from 9·13 D in toluene to 9·85 D in acetic acid. The solvent dependence of the equilibrium between the radicals and its dimer has been explained in terms of the solventinduced π-moment in polar solvents.
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  • 84
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    Journal of Physical Organic Chemistry 5 (1992), S. 225-229 
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A bond and group equivalent scheme that allows the calculation of heats of formation for aldehydes and ketones from ab initio 6-31G* energies has been developed. For a group of 24 aldehydes and ketones, the RMS error for the calculated heat of formation was 0 · 46 kcal mol-1. Heats of formation have been predicted for an additional seven compounds for which the experimental values are believed to be either in error or unknown. There are some problems with the norbornanones.
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  • 85
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    Journal of Physical Organic Chemistry 5 (1992), S. 239-243 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The pK values of some arylthiomethylbenzoic acids and the corresponding sulphones were determined spectrophotometerically. The role of substituent and the position of the carboxylic group are discussed.
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  • 86
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rate, endo/exo and diastereofacial selectivities of the Diels-Alder reaction between cyclopentadiene and ( - )-menthyl acrylate were measured in a series of organic solvents and organic-aqueous mixtures. Regression analyses show that a model with the α empirical solvent parameter accounts for most of the changes in rates and diastereofacial selectivities, whereas in the case of the endo/exo selectivity, inclusion of the π* and δ parameters is needed. Theoretical calculations carried out on the model reaction between methyl acrylate and cyclopentadiene using dielectric continuum and supermolecule models do not clearly show the effect of the different solvation mechanisms on rate. However, they agree with the above-mentioned influence of α and π* on the endo/exo and diastereofacial selectivities.
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  • 87
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The enhancement factors of the 1H polarization induced in radical pairs generated by α-cleavage of 12C=O- and C=O-labelled ketones deviate from the ratios expected on the basis of the relative abundances of the respective carbon isotopomers. For dibenzyl ketone, the ratio of absolute CIDNP intensities of the 1H(13C) doublet (90% 13C=O) to the 1H(12C) singlet (10% 12C=O) was found to be 〉9:1 at 58·3 kG and 〈9:1 at 21 kG. Similar deviations were observed for other 13C labelled ketones, viz. deoxybenzoin (13C=O) and acetophenone (13C=O or 13CH3). This novel enhancement or suppression effect on the CIDNP enhancement can be ascribed to the presence of a second hyperfine coupled nucleus in the intermediate radical pair. The individual contributions of the g factor difference (Δg), the external magnetic field strength (Ho), and the hfc constants of the observed (aA) and the interacting nucleus (ax) in the enhancement-suppression are exemplified. The experimental results are consistent with theoretical calculations of the mutual effect of Δg, H0, aA and ax on the CIDNP enhancement factor of the observed nucleus.
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  • 88
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    Journal of Physical Organic Chemistry 5 (1992), S. 269-274 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rate constants (k2) were determined for the reduction of 1-benzyl-3-cyanoquinolinium ion by phosphonate dianion in mixed solvents consisting of propan-2-ol and water. The reduction product was mostly 1-benzyl-3-cyano-1,4-dihydroquinoline with a trace of the 1,2-isomer. The solvent properties were varied by increasing the fraction of water in the mixed solvent, which increases the polarity of the solvent. Increasing the proportion of alcohol makes the solvent a better electron pair donor. The higher fraction of propan-2-ol in the mixed solvent gives rise to a substantial increase in k2. A quantitative comparison of the solvent effect on this reaction with the solvent effects on related reactions suggests a solvent Brønsted α value of 0·45. This suggests that the PO3- unit of the transition state interacts only weakly with the solvent although the final oxidized product is phosphate.
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  • 89
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    Journal of Physical Organic Chemistry 5 (1992), S. 609-613 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The visible spectrum of di-tert-butylstilbazolium betaine (DTBSB) was recorded in eight simple amides. The appearance of a ‘coarse’ structure in the main absorption band is due to the shielding effect of the tert-butyl groups, which hinder the approach of the solvent. Since this structure disappears in formamide, it is concluded that this solvent associates through its NH to the carbonyl group of DTBSB. For the other amides, there is a clear relationship between the steric effect, for both the N- and C-substituents, of the solvent-solute hydrogen bond association and the structure of the visible band.
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  • 90
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The title compounds (1 and 3, respectively) were studied by X-ray crystal structure analysis. Both are trigonal, space group R3, with lattice parameters a = 27.718(6), c = 8.161(2) Å, Z = 3 and a = 31.267(7), c = 6.560(2), Z = 18, respectively. The dodecamethyl compound 1 is isomorphous with its parent hexakis(4-benzylphenoxy)benzene (2), a known host. However, ‘collapse’ along the c-axial direction has occurred such that the appreciable clathrate cavity of 2 has been replaced by only a very small residual void for 1. Phenol 3 does not pack in discrete [OH]6 hydrogenbonded hexamers; instead, molecules are assembled in infinite chains, linked by OH…O hydrogen bonds of length 2.735(3) Å, which are propagated along threefold screw axes. A variable-temperature CPMAS NMR study of sidechain aryl group rotation in 1 gives a value ΔG≠ of 14.0 ± 0.7 kcal mol-1 (at 42 °C) for the (crystallographically unique) para -disubstituted ring, a similar 14 kcal mol-1 free energy barrier being found hindering rotation of this ring, and of the outer phenyl ring of 1, at 9°C.
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  • 91
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A transition structure for the syn and anti attack of formonitrile oxide on both cis-3,4-dichlorocyclobutene and norbornene was obtained using HF/3-21G method. These calculations correctly predict dominance of the syn attack in the reaction of dichlorocyclobutene and 100% syn selectivity, with respect to the methano bridge, in the reaction of norbornene. Analysis of the activation energy shows that the inherent facial bias of dichlorocyclobutene is reflected, at the transition state, in a complex way in the deformation energy of both dichlorocyclobutene and formonitrile oxide and in the interaction energy between them. With norbornene the out-of-plane deformation energy of the olefinic hydrogens clearly emerges as the major factor in controlling facial selectivity.
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  • 92
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    Journal of Physical Organic Chemistry 5 (1992) 
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    Keywords: Organic Chemistry ; Physical Chemistry
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  • 93
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    Journal of Physical Organic Chemistry 5 (1992), S. 341-348 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two amphiphilic oximes, 10-phenyl-10-hydroxyiminodecanoic acid (oxime II) and 4-(9-carboxynonanyl)-1-(9-carboxy-1-hydroxyimino nonanyl)benzene (oxime III) were synthesized. The pKa values of oximes II and III and acetophenoxime (oxime I) and the rates of oximolysis of p-nitrophenyl acetate (NPA) and p-nitrophenyl octanoate (NPO) were determined in the presence and absence of micellar hexadecyltrimethylammonium bromide (CTAB). The rates of oximolysis increased by up to 3 × 104-fold in the presence of CTAB. Quantitative analysis of micellar effects, using an ion-exchange pseudo-phase model, allowed the determination of the second-order rate constants for the reactions of oximes I-III with NPA and NPO in the micellar pseudo-phase. The calculated rate constants in the micellar pseudo-phase were lower than those in water, demonstrating that the rate enhancements were due to substrate concentration in the micelles. Comparison of the rate constants in micelles and water suggests that the sites of reaction of oximes I-III with NPO and NPA are similar to those in bulk aqueous solution. Micellar incorporation of the hydrophobic oximes II and III does not lead to a major change in the nucleophilicity of the oximate anion.
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    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 5 (1992), S. 355-360 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 2,2′-Furil (di-2-furyl diketone) undergoes photoreduction to give furoin on irradiation at 366 nm in triethylamine-containing benzene and ethers. On the other hand, in ethanol the photoirradiation leads to the formation of an enediol type of compound, 1,2-di(2-furan)ethene-1,2-diol. The results of quenching and sensitization both for the photoreactions and the phosphorescence demonstrate that furoin and the enediol are formed via the lowest excited singlet and the triplet states of 2,2′-furil, respectively.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 95
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 5 (1992) 
    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
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  • 96
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 5 (1992), S. 361-366 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The alkaline hydrolysis reaction of methyl nitrate was simulated by quantum mechanical and molecular mechanical methods. The gas-phase reaction was calculated to proceed with no barrier when ab initio calculations at the STO-3G level were utilized, and with a very small barrier (5.70 kJ mol-1) when the MINDO/3 method was applied. In solution, the solvation energy was estimated to be 70.33 kJ mol-1 by molecular mechanical calculations. Thus the activation energy (76.03 kJ mol-1) of alkaline hydrolysis of methyl nitrate was found to be in good agreement with the available experimental value (82.42 kJ mol-1). The results indicated that the substantial activation barrier in alkaline hydrolysis was essentially solvent-induced.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 97
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solvolysis of 1,1-diphenyl-1-X-ethane (1-X) [X = 4-nitrobenzoate (PNB), 3,5-dinitrobenzoate (DNB), AcO, MeOH+, EtOH+ or H2O+] was studied in 20 vol% dimethyl sulphoxide in water, in which specific salt effects are very small, and in 25 vol% acetonitrile in water. Substrates with negatively charged leaving groups yield more elimination product 1,1-diphenylethene (3) than those with uncharged groups, indicating the intermedicacy of ion pairs. Thus, three times more alkene is formed in the reactions of the substrates 1-OAc and 1-PNB than in the acid-catalysed hydrolysis of 1-OMe and 1-OAc. The substitution products may be formed via the solvent-equilibrated carbocation since the measured nucleophilic selectivities are very similar with different leaving groups.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 98
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 5 (1992), S. 373-381 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of oxidation of indole (In) and 5-substituted indoles (OCH3, Br and Cl) by chloramine-B (CAB) were studied in alkaline medium with Os(VIII) as catalyst at 303 K. At low [In]0 the rate law rate = k [CAB] [Os(VIII)] [In]0 is obeyed, which changes to rate = k [CAB] [Os(VIII)] [OH-]-1 at higher substrate concentrations. Variation of ionic strength has no effect on the rate and the dielectric effect is negative. The reaction was studied at different temperatures and activation parameters were evaluated. Hammett correlation of substituent effects indicated a linear free energy relationship with ρ+ = - 1.0, showing the formation of an electrondeficient transition state. From enthalpy-entropy relationships and Exner correlations, the isokinetic temperature β was found to be 330 K, indicating enthalpy as a controlling factor. The mechanism assumes the formation of a complex between oxidant and Os(VIII) at high and low [In]0. Proton inventory studies in H2O-D2O mixtures showed the involvement of a single exchangeable proton of OH- ion in the transition state.
    Additional Material: 3 Ill.
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  • 99
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 5 (1992), S. 382-394 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A molecular mechanical model is presented which allows computational interpretation of stereodynamics in ferrocenophanes by using a simple form of bending potential for angles involving the central iron atom and extended to carbon atoms of different cyclopentadienyl rings. Potential energy surfaces of [3] -, [4] - and [45] ferrocenophanes were studied in detail. For [3] ferrocenophane, the calculated energy barrier of the bridge reversal process agrees well with the experimental value. The previous interpretation of a rigid bridge in [4] ferrocenophane is questioned on the basis of the calculated low barriers. The predominance of experimentally indistinguishable enantiomeric pairs may be responsible for the misinterpretation. [45] Ferrocenophane is estimated to interconvert into D5-symmetric global energy minima over barriers of 13-15 kcal mol-1 through one-by-one flipping of five tetramethylene bridges.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 100
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 5 (1992), S. 395-408 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The application of computational techniques to biology, chemistry and physics is growing rapidly. Quantitative structure-activity relationships (QSAR) have been used widely to relate biological activities and physicochemical properties to molecular structural features. A difficulty in this approach has been non-uniformity of parameter sets resulting in the inability to examine contributions across properties and data sets. Linear solvation energy relationships (LSER) developed by Kamlet and Taft successfully utilize a single set of parameters to correlate a wide range of biological, chemical and physical properties. The empirical LSER solvatochromic parameters have been replaced with theoretically determined parameters to permit greater ease in a priori property prediction. These TLSER descriptors have given good correlations and interpretations for some biological activities. This paper discusses the application of these descriptors to six physicochemical properties involving equilibria, kinetics and spectra. The results show good correlation and physical interpretation.
    Additional Material: 12 Tab.
    Type of Medium: Electronic Resource
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