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  • Electronic Resource  (327)
  • 2010-2014
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  • 1986  (164)
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  • Electronic Resource  (327)
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  • 2010-2014
  • 1985-1989  (164)
  • 1970-1974  (163)
  • 1880-1889
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  • 1
    Electronic Resource
    Electronic Resource
    Histopathology of otitis media with effusion (1986)
    Springer
    European archives of oto-rhino-laryngology and head & neck 243 (1986), S. 269-273 
    Details
    ISSN: 1434-4726
    Keywords: Otitis media with effusion ; Electron microscopy ; Human temporal bones
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Ultrastructural studies of the middle ear mucosa appear to be of significant value in better understanding the pathology of otitis media with effusion (OME). Our present study was undertaken in order to take advantage of the use of electron microscopy in investigating all areas of the middle ear mucosa. Tissues studied were obtained from the fresh postmortem temporal bones of three patients with OME and terminal head and neck malignancies. In the mucoid type of effusion (cases 1 and 2), goblet cells were seen to proliferate and secretory activity was greatly enhanced. In contrast, there was no evidence of secretory cell proliferation in the serous type of effusion. It was noteworthy that accumulated fluid was not homogeneous in the same ear, as exemplified by case 1, in which both mucoid and serous effusions were present. This occurrence was possibly the result of topographic diversity involving the secretory activity of the middle ear.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00464444
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  • 2
    Electronic Resource
    Electronic Resource
    Experimental tympanosclerosis following infection with Streptococcus pyogenes and vitamin D3 intoxication (1986)
    Springer
    European archives of oto-rhino-laryngology and head & neck 243 (1986), S. 296-303 
    Details
    ISSN: 1434-4726
    Keywords: Experimental tympanosclerosis ; Induced calcifications ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary A rat animal model was used to study the ultrastructure of submucosal calcifications induced in the middle ear following inoculation with Streptococcus pyogenes and high doses of parenteral vitamin D3. The morphological changes present in affected animals resembled the classical picture of tympanosclerosis. While calcification occurred about bacterial remnants and myelin structures, the most important calcification centers were lysosomal and non-lysosomal matrix vesicles in the extracellular spaces. These formed band-like calcifications close to the basal membrane without affecting the epithelial layer. This animal model offers the possibility of studying the effect of various therapeutic regimens in the treatment of the dynamic tympanosclerotic process.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00460205
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  • 3
    Electronic Resource
    Electronic Resource
    Heterogeneity of circular mitochondrial DNA molecules from sugar beet with normal and male sterile cytoplasms (1986)
    Springer
    Current genetics 10 (1986), S. 695-700 
    Details
    ISSN: 1432-0983
    Keywords: Sugar beet ; Cytoplasmic male sterility ; Mitochondrial DNA ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Mitochondrial (mt) DNAs from normal (N) and male sterile (S) cytoplasms of sugar been have been isolated and investigated by electron microscopy. The results showed that mtDNA was composed of a heterogeneous population of circular molecules. Their contour lengths varied from 0.28 to 51 μm, but unlike in the case of maize, a large difference was not observed in the distribution of molecular classes greater than 1.0 μm between N and S cytoplasms of sugar beet. On the other hand, N and S cytoplasms were shown to contain their own characteristic combinations of small circular mtDNA species with lengths between 0.28 μm and 0.6 μm. Mitochondrial DNAs from various sources of male-sterile cytoplasms were analyzed by agarose gel electrophoresis to determine the extent of cytoplasmic variation. Additional low molecular weight DNA bands appeared in all male-sterile lines examined, and as a result, three distinctive banding patterns were recognized. These data are in general agreement with those based upon restriction endonuclease digestion of mt and chloroplast DNAs and the genetic analysis of fertility restoration in test crosses.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00410918
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  • 4
    Electronic Resource
    Electronic Resource
    Alpha-subunit-producing pituitary adenomas (1986)
    Springer
    Virchows Archiv 409 (1986), S. 417-431 
    Details
    ISSN: 1432-2307
    Keywords: Pituitary neoplasms ; Pituitary hormones ; Immunocytochemistry ; Electron microscopy ; Alpha-subunit ; Acromegaly
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Immunohistological techniques demonstrate the alpha-subunit of glycoprotein hormones in the majority of endocrine-inactive, undifferentiated pituitary adenomas and pituitary oncocytomas. In about one-fifth of endocrine-active adenomas, the alpha-subunit is produced in combination with either adrenocorticotropic hormone or prolactin, and it is found in combination with growth hormone in about half of those adenomas causing acromegaly. Pure alpha-subunit-producing, endocrine-inactive adenomas characteristically have small secretory granules that are destroyed by direct osmium fixation, but are well preserved after prefixation with glutaraldehyde. As only a few atypical prolactinomas show similar secretory granules, and as they display a positive reaction for the alpha-subunit only exceptionally, this ultrastructural feature can serve as a guide to differentiate such adenomas.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00705414
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  • 5
    Electronic Resource
    Electronic Resource
    Frequency and diagnostic value of the virus-like filamentous intranuclear inclusions in giant cell tumor of bone, not associated with Paget's disease (1986)
    Springer
    Virchows Archiv 410 (1986), S. 65-68 
    Details
    ISSN: 1432-2307
    Keywords: Giant-cell ; Virus-like inclusion ; Intranuclear inclusion ; Giant cell tumour of bone ; Paget's disease of bone ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary This paper deals with the paramyxovirus-like intranuclear inclusions observed in giant cells tumours of bone (GCTB). Twenty-one (49%) of 43 cases of GCTB (1977–1985), either fresh and/ or cultured, show these ultrastructural inclusions. Fifty samples of various bone lesions in which giant cell lesions occurred, including aneurysmal cysts, hyperparathyroidism, osteoblastoma, human and rat osteopetrosis, GCT of tendon sheaths, and non skeletal granuloma were used as controls. These, together with 20 samples of normal bone (osteoclasts) did not contain intranuclear or intracytoplasmic viral inclusions.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00710907
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  • 6
    Electronic Resource
    Electronic Resource
    Effects of experimental torsion of the spermatic cord on Leydig cell function in the guinea pig testis: An ultrastructural stereological analysis (1986)
    Springer
    Urological research 14 (1986), S. 253-256 
    Details
    ISSN: 1434-0879
    Keywords: Guinea pig ; Spermatic cord torsion ; Stereology ; Electron microscopy ; Leydig cell
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary An ultrastructural stereological analysis of Leydig cells of the guinea pig testis was carried out following surgically induced testicular torsion. Morphometric analyses of the Leydig cells of the experimental group of animals revealed an increase in the nucelar and mitochondrial volume and a decrease in the lipid volume, in comparison to those in the Leydig cells of the control group of animals. We believe that these changes in the Leydig cells of the experimental group of animals are indicative of cellular hypertrophy. The possible mechanisms of the Leydig cell hypertrophy in the guinea pig testis following the induction of spermatic cord torsion are discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00256568
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  • 7
    Electronic Resource
    Electronic Resource
    Ultrastructural abnormalities in muscular vessels of hyperthyroid patients (1986)
    Springer
    Acta neuropathologica 71 (1986), S. 64-69 
    Details
    ISSN: 1432-0533
    Keywords: Muscular diseases ; Capillar pathology ; Grave's disease ; Hyperthyroidism ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary an electron microscope study of needle biopsies from the quadriceps muscle was carried out in 11 non=selected patients (ten females and one male), with clinically and laboratory-diagnosed hyperthyroid disease. Alterations of the normal structure of muscle fibres were found in all cases. Changes in capillaries were found in ten patients, and ranged from an increase in basement membrane thickness with reduplication, to total destruction of the capillaries. The importance of the vascular involvement in the muscles of patients with Graves-Basedow disease is stressed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00687963
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  • 8
    Electronic Resource
    Electronic Resource
    Proliferating potential of folliculo-stellate cells in human pituitary adenomas (1986)
    Springer
    Acta neuropathologica 71 (1986), S. 233-242 
    Details
    ISSN: 1432-0533
    Keywords: Folliculo-stellate cell ; Pituitary adenoma ; Glial fibrillary acidic protein ; S-100 protein ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Folliculo-stellate cells (FS cells) in 40 pituitary adenomas and portions of anterior pituitary adjacent to the tumor in 26 cases were investigated immunohistochemically, using polyclonal antisera to S-100 protein (S-100) and glial fibrillary acidic protein (GFAP). The objective was to clarify the histological behavior of the FS cells. In most pituitary adenomas there were few or no S-100-or GFAP-positive cell, in comparison with numerous positive cells in the parts of the adenohypophyses compressed by adenomas. However, positive FS cells were observed in some types of pituitary adenomas. Growth hormone and prolactin producing adenomas frequently contained significant amounts of FS cells. In non-functioning adenomas, an unique case of FS cell adenoma was present. The adenoma was composed mainly of FS cells and immature glandular cells. The FS cells were sometimes located around follicles containing Periodic acid Schiff-positive material. Therefore, the FS cell adenoma is characterized by S-100- and GFAP-positive FS cells and PAS-positive follicles. In this type of adenoma, FS cells seemed to be the main proliferating component. In parts of the adenohypophyses adjacent to the adenomas, GFAP0-positive FS cells were numerous. In the pathological conditions FS cells may possess the potential of reactive proliferation.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00688045
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  • 9
    Electronic Resource
    Electronic Resource
    The distribution of Ia antigen in the lesions of rat acute experimental allergic encephalomyelitis (1986)
    Springer
    Acta neuropathologica 70 (1986), S. 149-160 
    Details
    ISSN: 1432-0533
    Keywords: Ia antigen ; Central nervous system ; Experimental allergic encephalitis ; Immunohistochemistry ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Ia antigen, encoded within the major histocompatibility complex, plays an important role in the activation of T lymphocytes. Since experimental allergic encephalitis is an essentially T cell-mediated disease, Ia antigen in the central nervous system (CNS) may be pathogenetically relevant. The occurrence of Ia antigen in the CNS of normal rats and of rats with experimental allergic encephalitis was studied by light and electron microscope immunocytochemistry using the monoclonal anti-Ia antibodies Ox 4 and Ox 6. In normal, unsensitized animals a distict population of stellate cells in the meninges and some perivascular mononuclear cells in the nervous tissue carried Ia antigen. In rats with experimental allergic encephalitis a dramatic increase of Ia-positive cells was found. In addition to the positive cells found in normal animals, monocytes, macrophages and many lymphocytes in the meningeal perivascular and parenchymal inflammatory infiltrates as well as “activated microglia” stained for Ia antigen. We did not find evidence for Ia expression on endothelial cells, astrocytes or other components of the CNS in either normal or diseased rats.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00691433
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  • 10
    Electronic Resource
    Electronic Resource
    Transplantation of Pacinian corpuscles of the rat into the brain (1986)
    Springer
    Acta neuropathologica 69 (1986), S. 314-321 
    Details
    ISSN: 1432-0533
    Keywords: Pacinian corpuscles ; Transplantation to the brain ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary In adult inbred rats of the AVN strain, branches of the crural interosseous nerve were dissected out from donors and transplanted into the brain of recipients, together with a cluster of Pacinian corpuscles, (either into a suction cavity or the cerebral cortex) into a slit 1–2 mm deep. The grafts were fixed and processed for electron microscopy 10 days to 6 months after the operation, and their ultrastructure was examined. Sporadic axons of small diameter grew into the nerve branches of some of the grafts from 11 days onward, and became myelinated during the 2nd month after the operation, but none of the transplanted Pacinian corpuscles became reinnervated. The corpuscles, however, survived denervation and grafting. Most of them retained a well-preserved inner core and an intact capsule, consisting of a normal complement of 29.2±1.0 (mean ±SE) capsular layers (n=8), as did the corpuscles previously examined after denervation in situ. Some of the corpuscles underwent degenerative changes, presumably due to a delayed or restricted revascularization. In this group of corpuscles, the inner core underwent disintegration and was gradually replaced by collagen fibrils, whereas the capsule remained preserved but the number of its layers eventually reduced by 40%. It is assumed that the lack of reinnervation of the grafted Pacinian corpuscles was due to the paucity of regenerating axons, and their failure to form correct projections along those Schwann cell columns connected with the corpuscles.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00688310
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  • 11
    Electronic Resource
    Electronic Resource
    Intercellular deposits of basement membrane material in active human pituitary adenomas detected by immunostaining for laminin and electron microscopy (1986)
    Springer
    Acta neuropathologica 71 (1986), S. 326-331 
    Details
    ISSN: 1432-0533
    Keywords: Pituitary adenoma ; Basement membrane ; Laminin ; Immunohistochemistry ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Thirty-eight human pituitary adenomas (24 endocrine active and 14 endocrine inactive tumors) were studied immunohistochemically for the presence of the basement membrane component, laminin, and ultrastructurally for the presence of basement membrane. Immunoreactivity of laminin delineated staining of epithelial and endothelial basement membranes, the reaction product being confined mostly to the perivascular zones. Moreover, a hitherto undescribed presence of intercellular laminin-positive droplets was observed in ten of the active adenomas (nine patients with hyperprolactinemia and/or acromegalia and one patient with Cushing's syndrome). Concurrently, at the ultrastructural level, bunches of basement membrane-like material intermingled between the adenoma cells were demonstrated in seven of these ten active adenomas. Furthermore, secretory granules were entrapped occasionally in this intercellular matrix, indicating a mutual dependence between excessive hormone extrusion and an increase of “misplaced” deposits of basement membrane components, e.g., laminin.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00688057
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  • 12
    Electronic Resource
    Electronic Resource
    Astroblastoma revisited: A report of three cases (1986)
    Springer
    Acta neuropathologica 70 (1986), S. 10-16 
    Details
    ISSN: 1432-0533
    Keywords: Astroblastoma ; Immunohistopathology ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The very existence of astroblastoma has been a question of considerable controversy, although there appears now to be sufficient documentation to establish it as a tenable entity. Due to the rarity of this tumor, little information exists in the literature as to its natural history, efficacy of therapy and its pathological and radiological appearance. We report three cases of astroblastoma, describing their natural history, the response to therapeutic interventions and their light microscopic, ultrastructural and immunohistochemical characteristics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00689508
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  • 13
    Electronic Resource
    Electronic Resource
    Ultrastructural localization of S-100 protein in neurofibroma (1986)
    Springer
    Acta neuropathologica 69 (1986), S. 103-110 
    Details
    ISSN: 1432-0533
    Keywords: Neurofibroma ; von Recklinghausen's disease ; S-100 protein ; Electron microscopy ; Immunoelectron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The nature of the cells in neurofibromas was studied by electron microscopy and immunoelectron-microscopic examination of S-100 protein. Ultrastructurally, all five neurofibromas studied were found to be composed of Schwann cells, perineurial cells, and intermediate cells, which had features of both perineurial cells and fibroblasts. The Schwann cells had complex, branched cytoplasmic processes and a continuous basal lamina. The perineurial cells were distinguishable from Schwann cells by the presence of numerous pinocytotic vesicles, unbranched slender cytoplasmic processes and a discontinuous basal lamina. The intermediate cells had no basal lamina, but were topographically related to Schwann cells and had a similar fine structure to that of perineurial cells. Thus, they seemed to be modified neoplastic perineurial cells. Immunoelectron-microscopic studies showed the presence of cells with and without S-100 protein in the neurofibromas: cells with S-100 protein resembled Schwann cells ultrastructurally, and those without S-100 protein were perineurial and intermediate cells. Some Schwann cells with S-100 protein in one neurofibroma had numerous pinocytotic vesicles characteristic of perineurial cells, suggesting that Schwann cells and perineurial cells, are functional variants of the same cell type. Thus this study showed that neurofibromas were composed of Schwann cells with S-100 protein and perineurial and intermediate cells, including socalled endoneurial fibroblasts, without S-100 protein. Morphological and functional transition seems to occur between Schwann cells and perineurial cells, and between perineurial cells and intermediate cells.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00687045
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  • 14
    Electronic Resource
    Electronic Resource
    Farber's disease in two siblings, sural nerve and subcutaneous biopsies by light and electron microscopy (1986)
    Springer
    Acta neuropathologica 72 (1986), S. 178-188 
    Details
    ISSN: 1432-0533
    Keywords: Farber's disease ; Peripheral nerve ; Subcutaneous nodules ; Electron microscopy ; Ceramidase deficiency
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Two siblings born from consanguineous tunisian parents are reported. They showed a severe form of Farber's disease with prominent involvement of the central and peripheral nervous system: low conduction velocity was noticed in both children. Macular cherry red spots were observed in one of them. The diagnosis for the girl investigated was confirmed by evidence of ceramidase deficiency in cultured fibroblasts. Here we report the pathological findings in the subcutaneous nodules using light and electron microscopy (one case), and in sural nerves using morphometric studies (both cases). Varying morphological aspects of intracellular inclusions, depending on the tissues involved, are described and discussed. A review of all cases reported since Farber's first paper in 1952 is given.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00685981
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  • 15
    Electronic Resource
    Electronic Resource
    Minisegments of newborn rat optic nerves in vitro: gliogenesis and myelination (1986)
    Springer
    Experimental brain research 65 (1986), S. 189-199 
    Details
    ISSN: 1432-1106
    Keywords: Rat optic nerve ; Gliogenesis ; Myelination ; In vitro ; In vivo ; Electron microscopy ; Immunocytochemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The question of whether the development of CNS glial cells requires the presence of axons or not can be studied with in vitro systems. In order to compare the differentiation of glial cells during development in vitro with that in situ, we have selected the optic nerve, which is anatomically as well as histotypically a well defined structure. For the in vitro investigations, small explants, called minisegments, of newborn rat optic nerves were cultivated taking four major conditions into account: (1) the regular size of the minisegments should guarantee a permanent exchange of the culture medium in order to avoid cell death, (2) neither mechanical nor enzymatic dissociation of the tissue were applied, (3) the minisegments were explanted into flasks without substrate for cell adhesion and (4) the minisegments were under constant gyratory agitation. The following in situ results were obtained: optic nerves of newborn rats are morphologically characterized by the presence of naked axons, astrocytes, glial precursors, and the absence of both differentiated oligodendrocytes and myelin. At postnatal day 5 myelin sheaths are still absent. Two weeks after birth, differentiated oligodendrocytes and microglial cells are present and numerous axons are surrounded by compact myelin. The in vitro experiments show the following main results, which were obtained after 14 h, 2 d, 5 d and 14 d in culture: during time in culture, the shape of minisegment of newborn rat optic nerves undergoes drastic changes, which indicate high cellular dynamics. After 14 h in vitro, axonal profiles, cells with pyknotic nuclei as well as clusters of astrocytes and glial precursors are present. After 2 days in culture the axonal profiles disappeared and the number of degenerating cells decreased drastically. Many large cells, probably phagocytes containing inclusions and more cells are differentiated. At the stage of 5 d in vitro 4 major types of cells can be distinguished: differentiated oligodendrocytes, which form compact and loose myelin, astrocytes, large and small glioblasts and phagocytes. Immunoprecipitates for myelin basic protein and/or myelin associated glycoprotein were found in oligodendrocytes, in their processes and associated to the myelin. Processes of some astrocytes showed immunoreactive products of glial fibrillary acidic protein. After two weeks in culture, the minisegments were mostly composed of astrocytes, whereas oligodendrocytes became rare and phagocytes disappeared. It can be concluded that CNS glial cells can attain their structural and immunocytochemical characteristics in the total absence of neuronal cell bodies and axons. However, it can be speculated that neurons (or neuronal factors) could regulate the number of astrocytes and oligodendrocytes and keep these glial cells in a physiological equilibrium.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00243842
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  • 16
    Electronic Resource
    Electronic Resource
    A paediatric case of sideroblastic anaemia (1986)
    Springer
    European journal of pediatrics 145 (1986), S. 422-427 
    Details
    ISSN: 1432-1076
    Keywords: CFU-E ; BFU-E ; Electron microscopy ; Sideroblastic anaemia ; Dyserythropoiesis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract We examined the morphological and functional characteristics of erythroblasts derived from marrow erythroid progenitor cells grown in a methylcellulose microculture, which were taken from a female child with rate atypical sideroblastic anaemia (SA) partially responsive to pyridoxine. Colony formation was within the normal range in three successive cultures (median values: 82.25 CFU-E and 16.4 BFU-E derived colonies/6.6×104 cells) compared to growth by normal cells (65-315 CFU-E and 9-40 BFU-E). We evaluated in vitro differentiation by biochemical microassay of a cytosol enzyme involved in the haeme pathway: uroporphyrinogen I synthase (UROS). The UROS values in the erythroid colonies from SA marrow were at the lower end of the normal range (median values: 6.7±0.3 and 14.4±3.8 pmol uroporphyrinogen/h in CFU-E and BFU-E-derived colonies respectively versus 17.4±7.3 and 25±7.2 pmol/h in CFU-E and BFU-E colonies from normal subjects. Ultrastructural examination of the SA erythroblasts from non-cultured bone marrow or derived from cultured BFU-E revealed the characteristic deposition of iron in mitochondria around the nucleus of most cells (ringed sideroblasts). However, the majority of cultured cells had marked dyserythropoietic featuress, with a large number of bilobulated or trilobulated crythroblasts, multiple cytoplasmic vacuoles, numerous abnormalities of the nucleus, and excessive membrane material beneath the plasma membrane, all features difficult to observe in non-cultured marrows.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00439253
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  • 17
    Electronic Resource
    Electronic Resource
    Cytomorphological changes in liver cells exposed to allyl and benzyl isothiocyanate and their cysteine and glutathione conjugates (1986)
    Springer
    Archives of toxicology 59 (1986), S. 103-110 
    Details
    ISSN: 1432-0738
    Keywords: Cytotoxicity ; Cell morphology ; RL-4 hepatocyte ; Electron microscopy ; In vitro study ; Allyl isothiocyanate ; Benzyl isothiocyanate ; Tert-butylhydroperoxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Since allyl isothiocyanate has been reported to be a bladder carcinogen and benzyl isothiocyanate is a known anti-carcinogen, it is important to know the mode of their cytotoxic action. This was investigated in a RL-4 hepatocyte cell line by studying the morphological effects of increasing concentrations of the isothiocyanates and their glutathione and cysteine conjugates. These effects were compared with those induced by tert-butylhydroperoxide which supposedly has its primary effect upon the cytosolic glutathione status and thus upon the integrity of Ca2+-sequestrating mitochondria. The results agree with the previously postulated role of conjugation in the exposure of cells to isothiocyanates: Conjugates show effects similar to those produced by the free parent compounds because conjugates release free isothiocyanates in aqueous solution. The cytomorphological effects increase in a more or less dose-dependent manner with increasing concentrations of isothiocyanate or exposure time. Probably due to increased exposure, suspended RL-4 cells are more sensitive to the toxic action than cells growing on a substrate. No qualitative differences were found between the effects of allyl and benzyl isothiocyanate, indicating that their different effects in vivo are perhaps related to organ-specific differences in equilibrium between the conjugated and unconjugated forms of the test substances. The first cytomorphological effects of isothiocyanates consist of surface blebbing (zeiosis) and swelling of dictyosomal cisternae. At higher concentrations swelling extends to vesicles of endoplasmic reticulum. Mitochondria are not affected until the cells reach the necrotic phase of injury. In contrast, tert-butylhydroperoxide causes mitochondrial damage in an early pase of toxic injury. The cellular symptoms suggest that the primary target of isothiocyanates is in the plasma membrane and the cellular membrane system, affecting the monovalent cation and water balance of the cell organelles rather than the Ca2+ homeostasis as in cells exposed to tert-butylhydroperoxide. Differences in lipophilicity may be at the basis of this differenc in primary action.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00286732
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  • 18
    Electronic Resource
    Electronic Resource
    An electron microscopic study of cerebral vasospasm with resultant myonecrosis in cases of subarachnoid haemorrhage, meningitis and trans-sylvian surgery (1986)
    Springer
    Journal of neurology 233 (1986), S. 348-357 
    Details
    ISSN: 1432-1459
    Keywords: Cerebral vasospasm ; Myonecrosis ; Myofilament ; Calcium ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Electron microscopic data on the development of myonecrosis following cerebral vasospasm associated with subarachnoid haemorrhage, meningitis and trans-sylvian surgery are presented. The basic feature of myonecrosis was dissolution of myofilaments with resultant fine granular or filamentous material. The disintegrating cytoplasm often contained numerous glycogen granules, dense bodies, autophagic vacuoles and myelin-like membranous bodies. A well-developed sarcoplasmic reticulum was preserved despite myofilament dissolution, while mitochondria showed marked sweling. The nuclei showed either dilution of chromatin or pyknotic change. The basal lamina was remarkably thickened and maintained an irregular outline of the necrotic smooth muscle cells. Enlarged intercellular space contained abundant cellular debris, vesicular structures and connective tissue fibres. The pathogenesis of these changes is discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00313921
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  • 19
    Electronic Resource
    Electronic Resource
    A three dimensional model of the photosynthetic membranes of Ectothiorhodospira halochloris (1986)
    Springer
    Archives of microbiology 146 (1986), S. 267-274 
    Details
    ISSN: 1432-072X
    Keywords: Photosynthesis ; Membrane structure ; Electron microscopy ; Ectothiorhodospira ; Serial thin sectioning ; Three dimensional reconstruction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The three dimensional organization of the complete photosynthetic apparatus of the extremely halophilic, bacteriochlorophyll b containing Ectothiorhodospira halochloris has been elaborated by several techniques of electron microscopy. Essentially all thylakoidal sacs are disc shaped and connected to the cytoplasmic membrane by small membraneous “bridges”. In sum, the lumina of all thylakoids (intrathylakoidal space) form one common periplasmic space. Thin sections confirm a paracrystalline arrangement of the photosynthetic complexes in situ. The ontogenic development of the photosynthetic apparatus is discussed based on a structural model derived from serial thin sections.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00403228
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  • 20
    Electronic Resource
    Electronic Resource
    Role of relA mutation in the survival of amino acid-starved Escherichia coli (1986)
    Springer
    Archives of microbiology 143 (1986), S. 400-402 
    Details
    ISSN: 1432-072X
    Keywords: E. coli relA +/relA ; Starvation survival ; Guanosine tetraphosphate ; Electron microscopy ; Glycogen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Amino acid-starved cells of Escherichia coli relA +, which contain a large number of glycogen particles, are able to survive in phosphate buffer for a longer time period than their relaxed counterparts. With regard to NH 4 + starvation differences in the survival of both strains were not found. NH 4 + starved cells of E. coli relA are able to synthesize glycogen but amino acid-starved cells of the relA strain are not. We suggest that the synthesis of glycogen triggered by guanosine tetraphosphate during amino acid starvation is responsible for the prolonged viability of the E. coli relA + strain.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00412809
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  • 21
    Electronic Resource
    Electronic Resource
    Bradyrhizobium japonicum mutants defective in root-nodule bacteroid development and nitrogen fixation (1986)
    Springer
    Archives of microbiology 144 (1986), S. 355-366 
    Details
    ISSN: 1432-072X
    Keywords: Bradyrhizobium ; Electron microscopy ; Mutants ; Nitrogen fixation ; Nodulation ; Soybean ; Symbiosis ; Transposon Tn5
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The genome of the slow-growing Bradyrhizobium japonicum (strain 110) was mutagenized with transposon Tn5. A total of 1623 kanamycin/streptomycin resistant derivatives were screened in soybean infection tests for nodulation (Nod) and symbiotic nitrogen fixation (Fix). In this report we describe 14 strains possessing a stable, reproducible Nod+Fix- phenotype. These strains were also grown under microaerobic culture conditions to test them for free-living nitrogen fixation activity (Nif). In addition to strains having reduced Fix and Nif activities, there were also strains that had reduced symbiotic Fix activity but were Nif+ ex planta. Analysis of the genomic structure revealed that the majority of the strains had a single Tn5 insertion without any further apparent physical alteration. A few strains had additional insertions (by Tn5 or IS50), or a deletion, or had cointegrated part of the vector used for Tn5 mutagenesis. One of the insertions was found in a known nif gene (nifD) whereas all other mutations seem to affect different, hitherto unknown genes or operons. Several mutant strains had an altered nodulation phenotype, inducing numerous, small, widely distributed nodules. Light and electron microscopy revealed that most of these mutants were defective in different stages of bacteroid development and/or bacteroid persistence. The protein patterns of the mutants were inspected by two-dimensional gel electrophoresis after labelling microaerobic cultures with l-(35S)methionine. Of particular interest were mutants lacking a group of proteins the synthesis of which was known to be under oxygen control. Such strains can be regarded as potential regulatory mutants.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00409885
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  • 22
    Electronic Resource
    Electronic Resource
    Pathogenesis of pulmonary fibrosis induced by chrysotile asbestos (1986)
    Springer
    Virchows Archiv 408 (1986), S. 329-346 
    Details
    ISSN: 1432-2307
    Keywords: Pulmonary fibrosis ; Asbestosis ; Chrysotile ; Macrophages ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary A single instillation of 1 mg chrysotile B with a fiber length between 0.05 and 0.2 µm in 0.1 ml tricaprylin was made via a polyvinyl catheter into the lower lobe of the right lung of 120 six-week-old Wistar rats under anesthesia. The animals were killed at intervals between five minutes and two years. The lower lobes of the right lung were investigated by light and electron microscopy. The process of pulmonary fibrosis induced by asbestos can be subdivided into four phases: these are the phase of phagocytosis (five to 15 min), the phase of granuloma formation (between one and two weeks), the phase of septal fibrosis (between two and six months) and finally the scar stage (after one year). After instillation of small asbestos fibers into the alveoli, a major proportion of these fibers is phagocytosed by alveolar macrophages after five minutes and leaves the lungs via the airways. A proportion of the fibers penetrates through the alveolar wall (mostly conveyed by type I pneumocytes) and reaches the interstitium of the lungs. There, the fibers are taken up by pulmonary tissue macrophages and giant cells. Within the phagolysosomes, the fibers are broken down into fragments less than 0.01 µm in length. Type II pneumocytes produce surfactant in excess. These cells become necrotic, tubular myelin and lamellar bodies pass into the alveoli and into the interstitium. Surfactant is phagocytosed by resident macrophages. These macrophages phages can break down. Besides asbestos and surfactant, mediators of fibrillogenesis are released. Macrophages following up from blood monocytes ingest surfactant and asbestos. This process is perpetuated up to complete scarring. After two years, small asbestos fibers less than 0.01 µm long are present in fibroblasts and pleural mesothelia.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00707692
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  • 23
    Electronic Resource
    Electronic Resource
    Diversity of Vicia faba circular mtDNA in whole plants and suspension cultures (1986)
    Springer
    Theoretical and applied genetics 72 (1986), S. 541-547 
    Details
    ISSN: 1432-2242
    Keywords: Mitochondrial DNA of plants ; Electron microscopy ; Suspension culture ; Vicia faba
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary A comparative analysis of the Vicia faba mitochondrial genome in whole plants and in longterm suspension culture has been conducted. Restriction fragment patterns of the mtDNA isolated from these two sources were notably different. Electronmicroscopic analysis also revealed significant differences. Large circular mtDNA patterns shifted from a 37–80 kb subpopulation, which was predominant in whole plants, to 18–34 kb subpopulations although in both classes notable quantities of circular molecules of 80 to 120 kb and more were also found. Both in whole plant and suspension culture cells very large circular DNAs were observed. Some of them had lengths nearly 290 kb and could be considered as evidence of the existence of master chromosomes. The minicircular DNA population was also altered. In the suspension culture we observed a notable increase of percentage of minicircles with sizes near 1 kb. Simultaneously, the percentage of minicircles with sizes near 3.5–10 kb significantly increased in suspension culture cells. In addition, a new peak (10–12 kb) of minicircles appeared. Copy number alterations for some sequences homologous to CCC1A, CCC1B and CCC2 (Negruk et al. 1982, 1985) were shown. Southern hybridization revealed the existence of a family of minicircles having sizes 1.4–2 kb with predominance of CCC1A, CCC1B and CCC2. The copy numbers of CCC1B and some minor minicircles was changed in the suspension culture when compared with the whole plants.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00289538
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  • 24
    Electronic Resource
    Electronic Resource
    Lipokeratinocytes of the epidermis of a cetacean (Phocena phocena) (1986)
    Springer
    Cell & tissue research 244 (1986), S. 385-394 
    Details
    ISSN: 1432-0878
    Keywords: Cetaceans ; Lamellar bodies ; Epidermal lipids ; Permeability barrier ; Electron microscopy ; Phocena phocena
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Biochemical and ultrastructural analysis of epidermis from the porpoise, Phocena phocena, revealed certain similarities and differences between cetaceans and terrestrial mammals. The predominant cell of cetacean epidermis, not found in normal terrestrial mammals, is a lipoker-atinocyte, which elaborates not only keratin filaments, but also two types of lipid organelles: first, lamellar bodies, morphologically identical to those of terrestrial mammals, are elaborated in great abundance in all suprabasal epidermal layers, forming intercellular lipid bilayers in the stratum corneum interstices: and second, non-membrane-bounded droplets appear and persist in all epidermal layers. Although the porpoise lipokeratinocyte morpologically resembles the sebokeratocyte of avians in certain respects, nonmembrane-bounded lipid droplets are not released into the intercorneocyte space as they are in avian stratum corneum. Whereas phospholipid/neutral lipid gradients are similar in porpoise and terrestrial mammals, PAS-positive glycoconjugates, specifically glycosphingolipids, are retained in porpoise stratum corneum, but lost from these layers in terrestrials. The novel, non-polar acylglucosyl-ceramides, which also are lost during cornification in terrestrial mammals, are retained in porpoise stratum corneum. The lipid components of porpoise lipokeratinocytes appear to subserve not only barrier function in a hypertonic milieu, but also underlie the unique buoyancy, streamlining, insulatory, and caloric properties exhibited as adaptations to the cetacean habitat.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00219214
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  • 25
    Electronic Resource
    Electronic Resource
    Collagen remodeling during decidualization in the mouse (1986)
    Springer
    Cell & tissue research 244 (1986), S. 443-448 
    Details
    ISSN: 1432-0878
    Keywords: Collagen ; Uterus ; Decidua ; Mouse ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary An ultrastructural study of the features and distribution of collagen fibrils was performed in the endometrium of virgin and pregnant (2nd to 11th day) mice. Collagen-containing structures were observed in the cytoplasm of fibroblasts on the 2nd day of pregnancy. Treatment of tissues with lanthanum nitrate established that these structures were intracytoplasmic. Their association with lysosome-like bodies suggested the occurrence of intracellular digestion of collagen, probably connected with remodeling of the endometrial stroma prior to decidualization. On the 4th day of pregnancy, very few collagen fibrils were present in the intercellular space. From the 6th day of pregnancy onwards, “thick” collagen fibrils were observed between decidual cells. The diameter of these fibrils measured up to 300 nm whereas the fibrils present in the endometrium of virgin mice measured 40–68 nm.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00219220
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  • 26
    Electronic Resource
    Electronic Resource
    Culture of intramural cardiac ganglia of the newborn guinea-pig (1986)
    Springer
    Cell & tissue research 244 (1986), S. 605-612 
    Details
    ISSN: 1432-0878
    Keywords: Heart innervation ; Tissue culture ; Autonomic ganglia ; Non-neuronal cells ; Cell interrelationships ; Electron microscopy ; Guinea-pig
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The present study describes the ultrastructure of non-neuronal cells and their interrelationships with intracardiac neurones present in cultures dissociated atria and interatrial septum from newborn guinea-pig. When compared with the in situ preparation, most of these features in culture were similar to those observed in situ, but some differences were also apparent. Both mature and immature Schwann cells were observed in culture, and as in situ, the latter were closely associated with intracardiac neurones, whilst the former were more widely separated. The ultrastructure of satellite cells was more variable in culture than in situ: three general types were distinguished on the basis of their 10-nm filament content. This variation could be due to conditions of culture. Interstitial cells were present in culture and closely resembled those described in situ, although there was less space between cultured interstitial cells and their associated cells. Many fibroblasts, some myoblasts and a few mast cells were also found in the culture preparations.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00212540
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  • 27
    Electronic Resource
    Electronic Resource
    Culture of intramural cardiac ganglia of the newborn guinea-pig (1986)
    Springer
    Cell & tissue research 244 (1986), S. 595-604 
    Details
    ISSN: 1432-0878
    Keywords: Heart innervation ; Tissue culture ; Autonomic ganglia ; Neurones ; Small granule-containing cells ; Electron microscopy ; Guinea-pig
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The ultrastructure of cultured intrinsic neurones and SIF (small intensely fluorescent) cells dissociated from the atria and interatrial septum of newborn guinea-pig heart has been studied for the first time and compared with these cells in situ. Mononucleate and binucleate neuronal somata and their processes were observed in the culture preparation; their ultrastructure was similar to that of neurones in intracardiac ganglia observed in situ. The number of neurites associated with neuronal cell bodies increased after the first week in culture. A subpopulation of intracardiac neurones showed abnormalities in culture, comparable to the changes previously described in neurones of the monkey heart after unilateral vagotomy in situ. Small granule-containing cells were observed in culture, corresponding to those described in the heart in situ. One type of large process in the culture preparation containing densely packed mitochondria has not been seen in situ, suggesting that changes in cell ultrastructure due to the conditions of culture cannot be discounted. However, the ultrastructure of the cultured cells was, for the most part, consistent with that of the same cell type in situ, indicating that the culture preparation may be a useful model for investigation of the roles and interactions of intramural neurones in the heart, which are inaccessible for such studies in situ.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00212539
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  • 28
    Electronic Resource
    Electronic Resource
    Morphological evidence for the existence of a more complex cytoskeleton in Amoeba proteus (1986)
    Springer
    Cell & tissue research 246 (1986), S. 163-168 
    Details
    ISSN: 1432-0878
    Keywords: Cytoskeletal organization ; Filaments ; Triton extraction ; Replica technique ; Electron microscopy ; Amoeba proteus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Various stabilization and extraction procedures were tested to demonstrate the ultrastructural organization of the cytoskeleton in normal, locomoting Amoeba proteus. Most reliable results were obtained after careful fixation in glutaraldehyde/lysine followed by prolonged extraction in a polyethylene glycol/Triton X-100 solution. Before dehydration in a graded series of ethanol and critical-point drying, the amoebae were split by the sandwich-technique, i.e., by mechanical cleavage of cells mounted between two poly-L-lysine-coated glass slides. Platinum-carbon replicas as well as thin sections prepared from such cell fragments revealed a cytoskeleton composed of at least four different types of filaments: (1) 5–7-nm filaments organized as a more or less ordered cortical network at the internal face of the plasma membrane and probably representing F-actin; (2) 10–12-nm filaments running separately or slightly aggregated through the cytoplasm and probably representing intermediate filaments; (3) 24–26-nm filaments forming a loose network and probably representing microtubules; and (4) 2–4-nm filaments as connecting elements between the other cytoskeleton constituents. Whereas microfilaments are responsible for protoplasmic streaming and other motile phenomena, the function of intermediate filaments and cytoplasmic microtubules in amoebae is still obscure.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00219013
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  • 29
    Electronic Resource
    Electronic Resource
    Structure and development of the surface coat of erythrocytic merozoites of Plasmodium knowlesi (1986)
    Springer
    Cell & tissue research 245 (1986), S. 281-290 
    Details
    ISSN: 1432-0878
    Keywords: Electron microscopy ; Malaria parasites ; Merozoites ; Surface coat ; Maturation ; Plasmodium knowlesi
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The surface of extracellular merozoites of P. knowlesi is covered with a coat 15–20 nm thick, made up of clusters of filaments standing erect on the plasma membrane. Filaments have stems 2 nm thick, the peripheral ends of which are complex, branching or ending in long trailing threads. Coat filaments occur on the surface of the parasite in regular rows at an early schizont stage, and persist until well after merozoite release. They are sensitive to trypsin and papain, and bind ethanolic phosphotungstate, indicating a proteinaceous nature. They are also removed by exposure to phosphate-buffered saline. Filaments bear negative charges, binding cationised ferritin throughout the depth of the coat and staining with ruthenium red. They cover the whole merozoite surface and mediate intercellular adhesion at distances of 15–150 nm, membrane to membrane. It is suggested that these filaments correspond to a major merozoite surface protein, and are important in the initial capture of red cells.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00213933
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  • 30
    Electronic Resource
    Electronic Resource
    Nephridial innervation in the leech Hirudo medicinalis L. (1986)
    Springer
    Cell & tissue research 245 (1986), S. 397-404 
    Details
    ISSN: 1432-0878
    Keywords: Leech ; Nephridium ; Innervation ; Electron microscopy ; Cobalt filling ; Hirudo medicinalis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The main organs for salt and water homeostasis in the medicinal leech, the nephridia, were found to be densely innervated by a single branch of the corresponding median anterior segmental nerve. The projections of two different neurons into the nephridia are described: 1. Dendritic projections of the previously identified, afferent ‘nephridial nerve cell’, a possible salt receptor, lie between the urine forming cells and the blood vessels supplying the nephridium without making any contact. 2. Projections of an unidentified neuron which contains dense-core vesicles (85 nm) as well as smaller clear vesicles (45 nm) contact the primary urine forming canaliculus cells. The neurosecretory role of these neurons is considered.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00213947
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  • 31
    Electronic Resource
    Electronic Resource
    The coxo-trochanteral muscle receptor organ of locusts (1986)
    Springer
    Cell & tissue research 243 (1986), S. 517-524 
    Details
    ISSN: 1432-0878
    Keywords: Muscle receptor organ ; Electron microscopy ; Tubular body ; Mechanosensory transduction ; Locust, Locusta migratoria migratorioides (R.&F.)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The coxo-trochanteral muscle receptor organ of the hind leg of the locust Locusta migratoria migratorioides (R.&F.) has been investigated by use of scanning and transmission electron microscopy with special emphasis on its distal attachment site. The overall morphology of the receptor muscle, the sensory neuron and its dendrites was found to share many common features with other arthropod sense organs of that type with two important differences: (1) the connective tissue segment (= intercalated tendon) is extremely short compared to that of other muscle receptor organs; (2) the naked dendritic terminals of the non-ciliated, multipolar sensory neuron of the organ contain clusters of microtubules, interconnected by an amorphous matrix, that resemble the tubular bodies of ciliated, epithelial receptor cells.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00218058
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  • 32
    Electronic Resource
    Electronic Resource
    The hypothalamo-hypophysial system of the frog Rana temporaria (1986)
    Springer
    Cell & tissue research 243 (1986), S. 649-654 
    Details
    ISSN: 1432-0878
    Keywords: Median eminence ; Peptidergic projections ; Aminergic projections ; Electron microscopy ; Autoradiography ; Frog (Rana temporaria)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The median eminence (ME) of the adult frog, Rana temporaria, was studied by means of electron microscopy including quantitative electron-microscopic autoradiography. In frogs captured in May and June numerous peptidergic neurosecretory fibres extending via the internal zone to the pars nervosa display large swellings containing few granules, mitochondria, neurotubules and cisternae of the smooth endoplasmic reticulum. In addition, few secretory globules up to 1.5 μm in diameter occur in these varicosities. In animals collected during the autumn period many of these neurosecretory swellings filled with neurosecretory granules and polymorphic inclusions resemble Herring bodies. Three types of granule-containing neurosecretory fibres were observed in the external zone (EZ) of the ME of adult R. temporaria. Peptidergic A1- and A2-type fibres are characterized by granules 150–220 nm and 100–160 nm in diameter, respectively. Monoaminergic fibres of type B with granules approximately 100 nm in diameter represent ∼ 50% of all neurosecretory elements in the EZ of the frog ME; ∼12% of the total number of granule-bearing axons in the EZ actively taking up radiolabelled 5-hydroxytryptophan are thought to be serotoninergic terminals. Neurosecretory terminals of all types and glial vascular endfeet establish direct contacts with the perivascular space of the primary portal capillaries. Some neurosecretory terminals are separated from the lumen of the third ventricle by a thin cytoplasmic lamella of tanycytes. The possible physiological significance of this structural pattern is discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00218074
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  • 33
    Electronic Resource
    Electronic Resource
    An ultrastructural study of embryonic chick retinal neurons in culture (1986)
    Springer
    Cell & tissue research 245 (1986), S. 563-577 
    Details
    ISSN: 1432-0878
    Keywords: Chick retina ; Tissue culture ; Electron microscopy ; Development, ontogenetic ; Differentiation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The differentiation of cells and synapses in explants of 9-day-old chick embryo retina has been studied by light and electron microscopy over a period of 35 days in vitro, and samples of retina from the 9-day chick foetus were directly fixed and prepared for study. At the time of explantation the retinae were poorly differentiated and no lamination was apparent. From day 14 onwards, (i) outer and inner nuclear layers (ONL, INL) separated by a layer of neuropil corresponding to the outer plexiform layer (OPL) and (ii) a layer of scattered large ganglion cells separated from the INL by a zone of neuropil resembling the inner plexiform layer (IPL) were apparent, and (iii) a well-differentiated outer limiting membrane was established close to the surface of the explants. In the oldest cultures some development of photoreceptor outer segments occurred but a distinct optic nerve fibre layer did not form. Although cell identification presented problems even in the oldest cultures, the major retinal cell types described in vivo could be identified. Photoreceptor cells developed pedicles in the OPL which became filled with synaptic vesicles and synaptic ribbons and established ribbon synapses (including triads) with and were commonly invaginated by processes from horizontal and bipolar cells. Processes of bipolar cells in the IPL formed simple and dyad synapses. At least two types of presynaptic amacrine cells were also identified in the INL, one of which contained large numbers of dense-core vesicles. The ganglion cells, though sparse, were large and well differentiated. These findings show that all the major neuronal types of the retina are capable of developing and differentiating in vitro, lagging behind the time-table of development and differentiation in vivo by approximately 7 days, but resulting in a histotypically organised retina with synaptic neuropil showing many similarities to the corresponding neuropil in vivo.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00218558
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  • 34
    Electronic Resource
    Electronic Resource
    Embryonic cholinesterase activity during morphogenesis of the mouse genital tract (1986)
    Springer
    Cell & tissue research 244 (1986), S. 153-164 
    Details
    ISSN: 1432-0878
    Keywords: Cholinesterase ; Genital tract ; Mesenchyme ; Histochemistry ; Electron microscopy ; Mouse embryo
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary In the genital tract of male and female mouse embryos cholinesterase activity is described that is independent from innervation. The enzyme activity is localized in the mesenchyme at the junction of Wolffian and Müllerian ducts with the urogenital sinus. During male development prostate buds and vesicular glands grow out into the cholinesterase-active mesenchyme. During female development the active mesenchyme participates in the downgrowth of the vaginal anlage. Ultrastructurally the cholinesterase activity is localized in the perinuclear cisterna and in smooth endoplasmic reticulum of the mesenchymal cells. The enzyme activity disappears with definitive differentiation of the tissue. The embryonic cholinesterase is a component of a primitive muscarinic system. Its relation to the morphogenetic action of testosterone and its possible general functions are discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00218393
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  • 35
    Electronic Resource
    Electronic Resource
    Cytoplasmic virus-like particles associated with the nucleolus in wheat, similar to “S bodies” and retroposon particles (1986)
    Springer
    Protoplasma 133 (1986), S. 160-164 
    Details
    ISSN: 1615-6102
    Keywords: Cytoplasm ; Electron microscopy ; Nucleolus ; Virus-like particles ; Wheat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Wheat roots from germinating seedlings of Chinese spring wheatTriticum aestivum grown for 36 hours at 20°C were examined by conventional thin-section electron microscopy. Virus-like particles were seen inside a large cytoplasmic intrusion into the nucleus having the appearence of a nucleolar vacuole. The particles were isometric and about 50 nm in diameter with a membrane-like coat and a small core. The cytoplasmic intrusion was bounded by nuclear envelope with pores apparent where it abutted nucleoplasm. The particles are similar to previously reported solitary particles “S bodies” from a range of plants but are also similar in size and morphology to the retroposon particles associated with copia like elements in other organisms. The position of the virus-like particles in the young wheat roots is discussed in relation to interactions with components of the cell skeleton.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01304631
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  • 36
    Electronic Resource
    Electronic Resource
    Influence of culture medium pH on charasome development and chloride transport inChara corallina (1986)
    Springer
    Protoplasma 130 (1986), S. 5-11 
    Details
    ISSN: 1615-6102
    Keywords: Chara corallina ; Charasome development ; Chloride transport ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Internodal cells ofChara, grown in culture either at pH 5.7, 6.5 or 7.5, were studied to determine their chloride influx capability, the quantitative aspects of charasome morphology and the degree to which these two parameters could be correlated. In cells grown at pH 5.7 the charasomes were relatively small, were widely spaced on the plasma membrane, and contributed only a 0.6% increase to the surface area of the plasma membrane in the acid region of the cell. In contrast, the charasome membrane surface area of cells grown at pH 7.5 had increased × 19, the density of charasomes on the cell surface increased × 42, thus producing a × 3.57 increase in the acid region plasma membrane surface area. Chloride influx in cells grown at pH 7.5 was × 8.7–12.7 greater than in cells grown at pH 5.7. Cells that had been starved of chloride exhibited a × 2.4 average increase in the rate of chloride influx. Our observations establish the existence of a positive correlation between the rate of chloride influx and the increase in membrane surface area due to charasomes, although other factors, such as the effect of pH on transport-related enzymes, and the effect of charasome structure on chemical equilibria, may also be of importance.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01283326
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  • 37
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    Electronic Resource
    The effects of raised phosphate level on the energy metabolism, contractile function, and fine structure of oxygenated and oxygen-deficient myocardium (1986)
    Springer
    Heart and vessels 2 (1986), S. 6-14 
    Details
    ISSN: 1615-2573
    Keywords: Inorganic phosphate ; Normoxia/anoxia ; ATP ; Glycogen ; Cardiac function ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The possible role of inorganic phosphate (Pi) in depressing the contractility of oxygen-deficient myocardium was investigated by examining the effects of 30 mM Pi on the cardiac function and myocardial biochemistry and fine structure in normoxic and anoxic Langendorff-perfused isolated rat hearts. In normoxia, the intracellular Pi level increased three-fold, the ATP content remained normal, and there was moderate loss of glycogen only. Contractile performance (as assessed from systolic pressure recordings) was significantly depressed, as was the heart rate for the first 10 min. The myocardial fine structure showed persistent glycogen, marked relaxation of myofibrils, and a higher incidence of vacuolation than in hearts with normal Pi. In anoxia, the intracellular Pi level was comparable with that of the perfusate and both ATP and glycogen were severely depleted. Contractile performance and heart beat ceased completely at 15 min, although in anoxic controls both persisted at low levels for at least 25 min. In anoxia, Pi also depressed coronary flow rate. In the inner half of the ventricular wall of oxygen-depleted hearts, where flow became reduced after 15 or more min, Pi markedly reduced the formation of intramitochondrial densities and augmented mitochondrial swelling and ischaemic contracture, which extended out through the mid-myocardium. In the outer half of the wall, where flow remained high, it promoted severe dilatation of the sarcoplasmic reticulum vesicles and undifferentiated regions of the intercalated discs. The observed effects in normoxia are probably attributable at least in part to the lowering of the free Ca2+ concentration of the perfusate by the increased Pi level. The effects in anoxia may be related chiefly to the critical reduction of available intracellular Ca2+ and the more rapid and extensive development of ischaemic contracture.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02060238
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  • 38
    Electronic Resource
    Electronic Resource
    In vivo homologous recombination intermediates of yeast mitochondrial DNA analyzed by electron microscopy (1986)
    Springer
    Molecular genetics and genomics 202 (1986), S. 421-428 
    Details
    ISSN: 1617-4623
    Keywords: Recombination intermediates ; Mitochondrial DNA ; Electron microscopy ; Saccharomyces cerevisiae
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary To study the structure of in vivo mitochondrial DNA recombination intermediates in Saccharomyces cerevisiae, we used a deletion mutant of the wild type mitochondrial genome. The mtDNA of this petite is composed of a direct tandem repetition of an ∼4,600 pb monomer repeat unit with a unique HhaI restriction enzyme site per repeat. The structure of native mtDNA isolated from log phase cells, and mtDNA crosslinked in vivo with trioxsalen plus UVA irradiation, was studied by electron microscopy. Both populations contained crossed strand “Holliday” type recombination intermediates. Digestion of both non-crosslinked and crosslinked and mtDNA with the enzyme HhaI released X and H shaped structures composed of two monomers. Electron microscopic analysis revealed that these structures had pairs of equal length arms as required for homologous recombination intermediates and that junctions could occur at points along the entire monomer length. The percentage of recombining monomers in both non-crosslinked and trioxsalen crosslinked mtDNA was calculated by quantitative analysis of all the structures present in an HhaI digest. The relationship between these values and the apparent dispersive replication of mtDNA in density-shift experiments and mtDNA fragility during isolation is discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00333272
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  • 39
    Electronic Resource
    Electronic Resource
    Electron microscopic localization of hydrogenase genes on the megaplasmid pHG 1 in Alcaligenes eutrophus (1986)
    Springer
    Molecular genetics and genomics 202 (1986), S. 476-480 
    Details
    ISSN: 1617-4623
    Keywords: Hydrogen bacterium ; Hydrogenase genes ; Megaplasmid pHG1 ; Localization ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Plasmids carrying hydrogenase genes in Alcaligenes eutrophus wild type H 16 and in two transposon Tn5 —induced mutants have been investigated by electron microscopy. Besides the pHG1 megaplasmid (458±27 kb) carrying genes coding for structural and regulatory properties of hydrogenases, small plasmids of unknown significance have been detected. The sizes of EcoRI fragments obtained from pHG1 were measured from electron micrographs. They were significantly different from sizes determined previously by agarose gel electrophoresis. Plasmid pHG1 isolated from the wild type H 16 was shown to contain two inverted repeats (IR 16-1 and IR 16-2) with sizes similar to known transposons. From electron microscopic hybridization studies, it was deduced that the sites of insertion of Tn5 into a regulation gene on pHG1 for both soluble and membrane-bound hydrogenase, and of Tn5-Mob into the gene coding for structural properties of the soluble hydrogenase, are about 67.2 kb apart. One of the inverted repeats (IR 16-1) was localized in between these sites.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00333280
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  • 40
    Electronic Resource
    Electronic Resource
    Abnormal mucociliary function in a mucocoele of the maxillary antrum (1986)
    Springer
    European archives of oto-rhino-laryngology and head & neck 243 (1986), S. 207-210 
    Details
    ISSN: 1434-4726
    Keywords: Maxillary sinus mucocoele ; Mucociliary system ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary We have examined the mucociliary function present in a mucocoele of the maxillary antrum and have found certain abnormalities in the tissues studied. Our findings also indicate that the mucocoele's intrinsic pathology is too complex to be improved by any conservative treatment and justifies its surgical removal.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00470623
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  • 41
    Electronic Resource
    Electronic Resource
    An experimental study of auditory dysfunction associated with hyperlipoproteinemia (1986)
    Springer
    European archives of oto-rhino-laryngology and head & neck 243 (1986), S. 242-245 
    Details
    ISSN: 1434-4726
    Keywords: Hyperlipoproteinemia ; Auditory dysfunction ; Cochlea ; Histochemistry ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary We sought to clarify whether or not hyperlipoproteinemia induces auditory dysfunction. In so doing, we studied the general states and cochlear pathologies of guinea pigs after the administration of a hyperlipid diet for 3 months. Serum biochemistries indicated marked elevations of cholesterol, high density lipoprotein (HDL)-cholesterol and low density lipoprotein (LDL) levels. An increased auditory threshold varying from 10 to 20 dB was observed in 40% of the guinea pigs using auditory brainstem responses. Histochemical study of the inner ear revealed variations in lipid metabolism and partial disorders of the outer hair cells. Electron microscopic observations showed vacuolar and parenchymal protrusions on the surfaces of the stria vascularis and Corti's organ, and vacuolar degeneration was seen around the capillary vessels of the vascular stria. Our data has shown that the auditory dysfunction present in the inner ear was less marked than were the morphological changes seen. Our findings suggest that other factors besides hyperlipoproteinemia are involved in the development of severe auditory damage.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00464438
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  • 42
    Electronic Resource
    Electronic Resource
    Italian multicenter study of dementia: a pathologically verified case of Alzheimer disease (1986)
    Springer
    Neurological sciences 7 (1986), S. 161-163 
    Details
    ISSN: 1590-3478
    Keywords: Alzheimer disease ; Electron microscopy ; Epidemiological study
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Sommario Viene descritto lo studio neuropatologico di un caso incluso nello Studio Multicentrico Italiano sulla Demenza sulla base di dati clinici. L'esame istologico ed ultrastrutturale conferma la diagnosi di malattia di Alzheimer avvalorando quindi il protocollo clinico.
    Notes: Abstract The pathological findings in a case included in the Italian multicenter study of dementia on clinical grounds are reported. The histological and ultrastructural examination confirms the diagnosis of Alzheimer disease, evidence for the validity of the clinical protocol.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02230435
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  • 43
    Electronic Resource
    Electronic Resource
    Masthead (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180101
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  • 44
    Electronic Resource
    Electronic Resource
    Hydrogen abstraction by hydrocarbon radicals. I. Interactions between 1-phenyl ethyl radicals and 1-phenyl ethanol as well as benzyl alcohol (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 31-40 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hydrogen abstraction by 1-phenylethyl radicals (ṘH) from phenylmethyl-carbinol (HROH) and benzyl alcohol (H2R′OH) has been studied in the liquid phase at 120°C. 1-Phenylethyl radicals have been generated by thermal decomposition of azo-bis-1-phenyl ethane and the formation of ethylbenzene (RH2), acetophenone (RO), and 2,3-di-phenyl butane (R2H2) has been monitored during the reaction.In order to optimize the experimental conditions, a mechanism has been assumed for the various pathways of the disappearance of ṘH and by using estimated rate parameters a presimulation was performed.The relative rate constants obtained are: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {\frac{{k_{\rm H} }}{{\sqrt {{\rm 2}k_t } }} = 1.4{\rm } \times {\rm }10^{ - 4} {\rm L}^{1/2} {\rm mol}^{ - 1/2} {\rm s}^{ - 1/2} } & {{\rm for}} & {{\rm HROH}} \\ \end{array} $$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {\frac{{k_{\rm H} }}{{\sqrt {{\rm 2}k_t } }} = 1.0{\rm } \times {\rm }10^{ - 4} {\rm L}^{1/2} {\rm mol}^{ - 1/2} {\rm s}^{ - 1/2} } & {{\rm for}} & {{\rm H}_{\rm 2} {\rm R'OH}} \\ \end{array} $$\end{document} where kH refers to the hydrogen abstraction while kt is the combination rate coefficient of the radicals ṘH.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550180104
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  • 45
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    Electronic Resource
    A reevaluation of low temperature experimental rate data for the reactions of O atoms with methane, ethane, and neopentane (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 59-82 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The experimental data for the reactions of oxygen atoms with methane, ethane, and neopentane at temperatures below ca. 600 K have been reexamined. In the case of CH4 and C2H6 reactions, detailed computer models have been assembled to test the assumptions regarding stoichiometries that were made in the original studies in order to derive elementary rate coefficients from the experimentally observed reaction rates. It was found in both cases that the measurements are especially sensitive to secondary reactions not taken into account and impurities in the reagent alkane. Because the original reports did not include sufficient experimental details, it is not now possible to correct their results quantitatively. However, it appears, qualitatively, that the values for the O + CH4 and O + C2H6 rate coefficients were overestimated by factors of approximately 2 to 3 in the 250-400 K temperature range, with the error increasing as T decreases. Although the experimental results for the O + neopentane reaction are not as sensitive to the same kinds of complications, a comparison of the low-temperature measurements with those for the O + ethane reaction suggests that the previously recommended rate coefficients, based on the data of Herron and Huie, are probably also too high by a factor of 2 to 3.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550180107
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  • 46
    Electronic Resource
    Electronic Resource
    Determination of absolute rate data for the reactions of atomic sodium, Na(32S1/2), with CH3F, CH3Cl, CH3Br, HCl, and HBr as a function of temperature by time-resolved atomic resonance spectroscopy (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 83-98 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We present a kinetic study of the reactions of ground-state sodium atoms with the molecules CH3F, CH3Cl, CH3Br, HCl, and HBr at elevated temperatures (537-966 K). Na(32S1/2) was generated by the pulsed irradiation of various sodium halide vapors and monitored by time-resolved atomic resonance absorption of the unresolved D-lines at λ = 589 nm [Na(32PJ) ← Na(32S1/2)] in the “single-shot mode.” The photoelectric signals were amplified without distortion, captured, and digitized in a transient recorder interfaced to a microcomputer for data analysis. Absolute second-order rate constants were measured at various temperatures in each case, yielding the following Arrhenius parameters (kRX = A exp(-E/RT), errors 1σ): which constitute, to the best of our knowledge, the first direct measurements of these quantities. The reaction between Na and HBr demonstrated anomalous behaviour which is discussed in terms of potential surfaces that have been calculated previously for this type of collisional process. The data are compared with analogous results for Na + CF4, CF3Cl, and CF3Br and with single-temperature measurements on diffusion flames.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180108
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  • 47
    Electronic Resource
    Electronic Resource
    Rate constants for the decarboxylation of the t-butoxicarbonyl radical and concurring radical terminations directly obtained by kinetic ESR (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 145-158 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants of various simultaneous reactions of t-butoxicarbonyl and t-butyl radicals generated by photolysis of t-butylpivalate in n-heptane are directly determined by kinetic electron spin resonance. The temperature dependence of the decarboxylation reaction t-BuOĊO → t-Bu. + CO2 obeys log )K/S-1( = 13.8-49.0/θ where θ = 2.303 RT/kJ . mol-1. The self- and cross-termination of the radicals are diffusion limited.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180202
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  • 48
    Electronic Resource
    Electronic Resource
    Masthead (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180301
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  • 49
    Electronic Resource
    Electronic Resource
    Linearization of second-order reaction data (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 281-286 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction data described by the second-order growth function A(t) = A∞(αt) (1 + αt)-1, where A∞ is the ultimate value of the product concentration A(t), can be linearized by plotting a suitable function F(t) against the time (t). The slope of the straight line obtained is (2α), where α is the product of the rate constant (k2) and the initial concentration of either reactant, with the result that k2 can be determined without knowledge of Aϰ. Optimal determination of the parameter α requires that data taking be limited to the interval 0 ≤ t ≤ T, where (αT) is approximately 4.0. Numerical data derived from an experiment on the exchange of lead by zinc ions in the enzyme carbonic anhydrase are analyzed to illustrate the method. The effects of small errors in the initial concentrations and of small deviations from second-order kinetics are briefly discussed.
    Additional Material: 3 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550180302
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  • 50
    Electronic Resource
    Electronic Resource
    Effects of nonionic, cationic, and anionic micelles on the kinetics of the complexation reaction of nickel (II) with pyridine-2-azo-p-dimethylaniline (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 609-621 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The stopped-flow technique has been used to study the effect of cationic (CTAN), nonionic (Triton X-100), andanionic (SDS) micelles on the rate of the reaction between nickel(II) ion and the ligand pyridine-2-azo-p-dimethylaniline (PADA) at 20.0°C and ionic strength 0.03 mol dm-3. The complex formation reaction is markedly inhibited by both CTAN and Triton X-100 micelles. The kinetic dataare found to conform to a reaction mechanism which implies only partitioning of the ligand between water and the micellar phase, the estimated bindingconstant of PADA being significantly larger in the presence of CTAN aggregates. Anionic micelles strongly speed the complexation reaction, Which occurs in the micellar phase with the same rate and the same mechanism as in water. The extent of binding of PADA to anionic micelles is similar to that found for the cationic micellar aggregates.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180602
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  • 51
    Electronic Resource
    Electronic Resource
    Erratum (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 719-720 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180609
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  • 52
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of the oxidation of primary alcohols by sodium N-chloroethylcarbamate (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 689-699 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidation of primary alcohols by sodium N-chloroethylcarbamate in acid solution, results in the formation of corresponding aldehydes. The reaction is first order with respect to the oxidant and alcohol. The rate increases with an increase in acidity. The oxidation of α,α-dideuterioethanol exhibited a primary kinetic isotope, kH/kD = 2.11 at 298 K. The value of solvent isotope effect k(H2O)/k(D2O) = 2.23 at 298 K. Addition of ethyl carbamate does not affect the rate. (EtOC(OH)NHCl)+ has been postulated as the reactive species. Plots of (log k2 + Ho) against (Ho + log[H+]) are linear with the slope, φ, having values from 1.78-1.87. This suggested a proton abstraction by water in the rate-determining step. The rates of oxidation of alcohols bearing both electron-withdrawing and electron-donating groups are more than that of methanol. A concerted mechanism involving transfer of a hydride ion from the C—H bond of the alcohol tothe oxidant and removal of a proton from the O—H group by a water molecule has been proposed.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550180607
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  • 53
    Electronic Resource
    Electronic Resource
    Theory of fast multiple bond-switching reactions: NO + NH2 (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 721-737 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A theoretical treatment is given for fast, multiple bond-switching reactions, such as NO + NH2 → N2 + H2O. These reactions are characterized by all or most of the bonds being broken. The collision complex involved (whether long or short lived) is shown to be extremely anharmonic. Consideration of the master equation describing the competing processes of complex formation, internal rearrangement and collisional deactivation yields easily applied sufficient conditions for the recombination rate coefficient being independent of pressure.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550180702
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  • 54
    Electronic Resource
    Electronic Resource
    Kinetic analysis of the disproportionation of aqueous glyoxal (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 757-773 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rates of disproportionation of 0.015-0.4 mM aqueous glyoxal toglycolic acid were measured at 0.24-75 mM NaOH and constant ionic strength, leading to the empirical rate expression r = (a1[OH-] + a2[OH-]2) [GT]/(1 + a3[OH-]), where [GT] is the total glyoxal concentration. These results were confirmed in bicarbonate/carbonate buffer and at 2-20 mM [GT]. The rate form is in contradiction to earlier work on glyoxal, which suggested a second-order dependence on [OH-], but agrees with the rate equation for phenylglyoxal disproportionation. The kinetic data can be explained by a mechanism postulating the presence of monohydrated and dihydrated forms of glyoxal in equilibrium, with the rate-limiting steps being intramolecular hydride ion transfers to the unhydrated carbonyl carbon of the mono- and divalent anions of glyoxal monohydrate.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550180704
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  • 55
    Electronic Resource
    Electronic Resource
    Stopped-flow investigations of the reaction kinetics of carbon dioxide with some primary and secondary alkanolamines in aqueous solutions (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 445-457 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction kinetics of carbon dioxide with four alkanolamines of industrial importance (MEA, DGA, DEA, and DIPA) have been investigated with the aid of the stopped-flow technique, allowing the determination of rate constants for carbamates formation. The constants obtained for MEA at 20°C and 25°C are in good agreement with recent literature data. The kinetic behavior of DGA was found to be almost identical to that of MEA.The rate constants obtained for DIPA at 25°C (54 M-1 s-1) is half as large as that for DEA (110 M-1 s-1). The former one is satisfactorily compared with the recent values proposed by Blauwhoff et al. Activation energies have also been obtained for DEA (23.2 kJ mol-1) and for DIPA (58.7 kJ mol-1) and their mechanistic implications are discussed in relation with the relevanceof a rate-determining proton transfer step in the process of carbamate formation.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550180404
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  • 56
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    Electronic Resource
    Kinetics and mechanism of the pyrolysis of 1-Chloro-1, 1-difluoroethane in the presence of chlorine (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 497-504 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The first stage thermal reactions of CF2CICH3 in the presence of chlorine have been studied between 554 and 614 K. These are and \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CF}_{\rm 2} {\rm CICH}_{\rm 3} {\rm + CI}_{\rm 2} \to {\rm CF}_{\rm 2} {\rm CICH}_{\rm 2} {\rm CI + HCI} $$\end{document} Rate equations derived from a radical mechanism are shown to fit the experimental results. Values of Arrhenius parameters for the decomposition of the CF2ClCH2. radical and its reactions with Cl2 and Cl are given.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550180408
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  • 57
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    Electronic Resource
    Radical steps in diethyl ether decomposition (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 829-836 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of diethyl ether was studied in the temperature range 697.2-760.5 K. The rate constant of reaction (1), and the ratio of the rate constant of reaction (2) to that of (12): were calculated from the amounts of products: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_1 ({\rm s}^{{\rm - 1}}) = (17.2 \pm 0.6) - (82.4 \pm 2.0{\rm kcal mol}^{{\rm - 1}})/2.3RT $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_2 /k_{12^{1/2} } ({\rm dm}^{{\rm 3/2}} {\rm mol}^{{\rm - 1/2}}) = (4.1 \pm 0.4) - (11.9 \pm 1.3{\rm kcal mol}^{{\rm - 1}})/2.3RT $$\end{document}
    Additional Material: 3 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550180803
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  • 58
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    The chromatographic retention of H and D atoms on quartz (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 861-869 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chromatographic retention of H and D atoms has been observed in a quartz tube using argon as a carrier gas for D and six different gases for H. The results give equilibrium constants for the reversible adsorption of H and D on quartz as well as the rates of desorption. Self-consistent conclusions can be drawn from the data. The adsorption energy appears to be ca. 50 kJ mol-1 indicating weak chemisorption. The observations are consistent with vibration frequencies on the surface of around 700-900 cm-1 for D. and around 1000-1300 cm-1 for H. It appears that only a fraction of the surface atoms (ca. 10-2) act as adsorption sites.
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    Measurements of the bimolecular rate constants for S + O2 → SO + O and CS2 + O2 → CS + SO2 at high temperatures (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 871-884 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The bimolecular reactions in the title were measured behind shock waves by monitoring the O-atom production in COS—O2—Ar and CS2—O2—Ar mixtures over the temperature range between 1400 and 2200 K. A value of the rate constant for S + O2 → SO + O was evaluated to be (3.8 ± 0.7) × 1012 cm3 mol-1 s-1 between 1900 and 2200 K. This was connected with the data at lower temperatures to give an expression k2 = 1010.85 T0.52 cm3 mol-1 s-1 between 250 and 2200 K. An expression of the rate constant for CS2 + O2 → CS + SO2 was obtained to be k21 = 1012.0 exp(-32 kcal mol-1/RT) cm3 mol-1 s-1 with an error factor of 2 between 1500 and 2100 K.
    Additional Material: 8 Ill.
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    Electronic Resource
    Masthead (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180901
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    Preface (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. vi 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180902
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  • 62
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    The kinetics and the mechanism of the thermal gas-phase reaction between NO2 and 1,1-dichlorodifluoroethylene, CF2CCl2 (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 907-917 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gas phase reaction between NO2 and CF2CCl2 has been investigated in the temperature range from 50 to 80°C. The reaction is homogeneous. Three products are formed: O2NCF2CCl2NO2 and equimolecular amounts of CINO and of O2NCF2C(O)Cl. The rate of consumption of the reactants is independent of the total pressure, the reaction products, and added inert gases and can be represented by a second-order reaction: \documentclass{article}\pagestyle{empty}\begin{document}$$ - \frac{{d[{\rm NO}_{\rm 2}]}}{{dt}} = - 2\frac{{d[{\rm CF}_{\rm 2} {\rm CCI}_{\rm 2}]}}{{dt}} = k[{\rm NO}_{\rm 2}][{\rm CF}_{\rm 2} {\rm CCI}_{\rm 2}] $$\end{document}However, the distribution of the products is influenced by the pressure of the present gases, which favor the formation of the dinitro-compound in a specific way. The effect of CF2CCl2 is the greatest. In the absence of added gases, the ratio of O2NCF2CCl2NO2 to that of O2NCF2C(O)Cl is proportional to (CF2CCl2 + γP products).The experimental results can be explaned by the following mechanism: P and X represent the products and the added gases: \documentclass{article}\pagestyle{empty}\begin{document}$$ - \frac{{d[{\rm NO}_{\rm 2}]}}{{dt}} = - 2\frac{{d[{\rm CF}_{\rm 2} {\rm CCI}_{\rm 2}]}}{{dt}} = k_1 [{\rm NO}_{\rm 2}][{\rm CF}_{\rm 2} {\rm CCI}_{\rm 2}] $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 = 3.16 \pm 0.5 \times 10^6 \exp ( - 10500 \pm 1000{\rm cal/}RT){\rm M}^{{\rm - 1}} {\rm s}^{{\rm - 1}} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm \gamma }_{{\rm CF}_{\rm 2} {\rm CCI}_{\rm 2} } :{\rm \gamma }_P :{\rm \gamma }_{{\rm C}_{\rm 2} {\rm F}_{\rm 5} {\rm CI}} :{\rm \gamma }_{{\rm CCL}_{\rm 3} } :{\rm \gamma }_{{\rm CF}_{\rm 4} } :{\rm \gamma }_{{\rm N}_{\rm 2} } = 1:0.22:0.15:0.14:0.054:0.015 $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm \gamma }_{{\rm NO}_{\rm 2} } 〈 0.01 $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_3 = 1.4 \pm 0.3 \times 10^8 {\rm s}^{{\rm - 1}} $$\end{document}
    Additional Material: 2 Ill.
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    Masthead (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180701
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  • 64
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    Base-catalyzed tritium exchange between tritium-containing heavy water and deuterated chloroform-kinetics and equilibrium (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 739-755 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We develop a kinetic model for the exchange of tritium and deuteriumbetween tritium-containing heavy water and deuterated chloroform in a two-phase liquid system, catalyzed by hydroxide ion (sodium hydroxide). For the exchange reaction yielding tritiated chloroform andheavy water, the measured equilibrium constant is 0.518 at 25-45°C, independent of temperature. The rate constant (for the controlling step, deuteron abstraction from chloroform) is 0.22 L/mol s at 25°C, 0.72 at 35°C, and 2.0 at 45°C, corresponding to an activation energy of 87 kJ/mol. Comparison is made with literature data, and effects of mass transfer on the apparent rate constant are discussed.
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  • 65
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    Thermodynamic and kinetic analysis of the dimerization of aqueous glyoxal (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 775-789 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Equilibria and rates of interconversion between monomeric and dimeric glyoxal were measured in aqueous solution. The equilibrium constant [G2]/[G1]2 was 0.56 M-1 at 25°C, and was hardly affected by changes of ionic strength and pH but increased rapidly with increase of temperature. The rate of depolymerization was first-order in dimer, with the pseudo first-order rate coefficient in the pH range 1.3-7.8being of the form b1[H3O+] + b2 + b3[OH-]/(1 + b4[OH-]) + b5[OH-]. Coefficients b1 and b2 were more strongly affected by changes of temperature, though [OH-] was much the more effective catalyst. This rate form has not previously been observed for monomer-dimer inter-conversion of α-hydroxycarbonyls and α-dicarbonyls or for related reactions such as mutarotations and hydrations. Equivalent rate forms arisefrom reactions where an intermediate at steady state and low concentration is produced.
    Additional Material: 6 Ill.
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  • 66
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    Masthead (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/kin.550180801
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    Reaction of the NO3 radical with CO: Determination of an upper limit for the rate constant using FTIR spectroscopy (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 819-827 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An upper limit for the reaction rate of CO with the nitrate radical NO3 has been determined equal to 4 × 10-19 cm+3 molec-1 s-1 at 295 ± 2 K. In the experiment the isotopic species C13O16 and C13O18 mixed at 1-2 ppmv level in synthetic air have been reacted with NO3 and the reaction followed using long path infrared absorption FT spectroscopy. The result is of interest in the studies on the role played by NO3 in nighttime tropospheric chemistry.
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  • 68
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    The reaction of OH radicals with dimethyl sulfide (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 837-846 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gas phase reaction of OH radicals with dimethyl sulfide (CH3SCH3) have been studied at various temperatures and total pressures using two relative rate methods and a flash photolysis technique. For the relative rate methods, rate constants were measured at 296 ± 2 K as a function of the O2 pressure at a total pressure of ca. 740 torr. Data from these three experimental techniques were not in agreement. It is concluded that the relative rate techniques are subject to secondary reactions, possibly involving CH3S radicals. A rate constant of (2.5-0.6+0.9) × 10-12 e(130 = 102)/T cm3 molecule-1 s-1 obtained using the flash photolysis-resonance fluorescence data in the absence of O2, and which is in agreement with the lower range of values previously reported in the literature, is recommended.
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  • 69
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    Kinetics and mechanism of the OH + CIO2reaction (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 847-859 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constant k1 for the reaction of OH radicals with CIO2 molecules was measured in a discharge flow system over the temperature range 293 ≤ T ≤ 473 K and at low pressures, 0.5 ≤ P ≤ 1.4 torr, using electron paramagnetic resonance or laser-induced fluorescence to monitor the pseudo first-order decay of OH concentrations. At 293 K, the value obtained for k1 was (7.2 ± 0.5) × 10-12 cm3 molecule-1 s-1. Within the temperature range of this study, a negative temperature dependence was observed: k1 = (4.50 ± 0.75) × 10-13 exp[(804 ± 114)/T] cm3 molecule-1 s-1. HOCl was detected by mass spectrometry as a product of the reaction and was titrated using OH + Cl2 as a source in the calibration experiments. A simulation of the mechanism of the OH + ClO2 reaction indicated that HOCl was mainly produced in the first reaction step. Both this result and the observed T dependence of k1 suggest that this reaction proceeds via an intermediate adduct with a cyclic geometry.
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    Dynamical stereochemistry of the hydrogen exchange reaction: A computational study (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1023-1045 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The barrier for the hydrogen exchange reaction increases with the bend angle of H3. The implications for the dynamics of the reaction are explored on two levels. The static one uses the concept of a relaxed potential. This provides for a convenient, yet realistic representation. Itallows for the response of the molecule to the approaching atom. Among features made very evident by the relaxed potential is the possibility that hotH atoms can react by insertion. It also shows the widening of the cone of acceptance upon reagent vibrational excitation. On the dynamical level, classical trajectory computations are used to illustrate the dependence of the reactivity on the angle of attack and on the translational and vibrational excitation of the reagents. Detailed product distributions are generally not sensitive to the attack angle. An exception is the HD/H2 branching ratio in H + HD reactive collisions.
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    Oxidation of benzyl alcohols by nitrous and nitric acids in strong sulfuric acid media (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1277-1288 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have studied the oxidation of benzyl alcohols by nitrous and nitric acid in sulfuric acid media. The oxidation by nitrous acid is rapid and has an activation energy of 10.6 ± 0.8 kcal mol-1. A Hammett plot of logk2 vs. σ+ is linear with a ρ value of -1.4. The oxidation by nitric acid in sulfuric acid media is autocatalytic. From the kinetic and product analyses, it is concluded that a common oxidant, the nitrosonium ion is involved when either nitrous or nitric acid is used. A mechanism is proposed which involves the abstraction of hydride from the alcohols as the rate determining step. It is demonstrated that the autoxidation of the alcohols is catalyzed by nitrous acid or nitric oxide.
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  • 72
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    Rate constant of OH + OCS reaction over the temperature range 255-483 K (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1303-1314 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constant of the reaction between OH and OCS in helium over the temperature range 255-483 K has been determined using the discharge flow-resonance fluorescence technique. The OCS has been carefully purified to avoid interference from H2S and CO impurities. An FTIR with a multireflection cell was used to determine the impurity concentrations and the purified sample was found to contain less than 0.005% of H2S. At 300 K, the rate constant was determined to be (2.0 ±0.40.8) × 10-15 cm3 molecule-1 s-1. Although the rate constants showed slight positive deviation at lower temperatures, thev can be satisfactorily fitted by the Arrhenius equation, k = 1.13 × 10-13 exp(-1200/T) cm3 molecule-1 s-1. No pressure dependence was observed at all temperatures, nor was O2 enhancement observed under our experimental conditions.
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    Gas phase thermal isomerization of 4-acetyl-5-methyl-isoxazole (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1333-1340 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase thermal isomerization of 4-acetyl-5-methyl-isoxazole affords 3-cyano-2,4-pentanedione as the only product in good agreement with previous proposed isomerization mechanism for isoxazoles. On the other hand, kinetic parameters and MO theoretical calculations do not agree with those previously reported. An alternative reaction mechanism which explains this fact is discussed.
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  • 74
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    Infrared laser-induced decomposition of 2,2-dimethyloxetane (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1215-1234 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The unimolecular decomposition of 2,2 dimethyloxetance to give either isobutence and formaldehyde or ethene and acetone induced by a pulsed CO2 laser has been investigated. Absorption characteristics and fractional decomposition have been studied as a function of laser fluence, irradiation frequency, reactant pressure, and added inert bath gas. Both absorption cross section and fractional decomposition are approximately independent of pressure of 2,2-dimethyloxetane below 50 times; 10-3 torr and increase with pressure at higher pressures of 2,2-dimethyloxetane. At pressures sufficiently low that collisions are negligible during the laser pulse, added inert gases reduce the amount of decomposition. Calculations of the fractional decomposition have been carried out based on RRKM theory and assuming either a Boltzmann or a Poisson intermolecular energy distribution. Master equation calculations of both absorption and decomposition for 10R20 irradiation have also been performed. Agreement between observed and calculated results for 10R20 irradiation could be obtained only by assuming that most, but not all, of the molecules in the irradiated volume absorb the laser radiation. Differences between the absorptions of the 10R20 and 9P20 lines and in the resulting extents of decomposition indicate that the fraction of irradiated molecules which absorbs 9P20 radiation is smaller than the fraction which absorbs 10R20 radiation.
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    Masthead (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550181201
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  • 76
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    Kinetics of the oxidation of nitric oxide by chlorine and oxygen in nonaqueous media (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1289-1302 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reaction between nitric oxide and chlorine have been investigated in both carbon tetrachloride and glacial acetic acid. The nitric oxide-oxygen reaction has been investigated in carbon tetrachloride.The appearance of product, NOCl or NO2, was monitored spectrophotometrically at a wavelength of 475 nm for NOCl and 343 nm for NO2. These measurements were performed using an Amino-Morrow stopped-flow apparatus equipped with a Beckman D U monochromator.The data for both the NO—Cl2 and NO—O2 systems could be fitted to the third-order integrated equation and the calculated rate constants were 2.75 × 103 M-2 s-1 and 2.79 × 106 M2 s-1, respectively, at 25.1°C.There was a noted increase in rate constants on changing the solvent from carbon tetrachloride to acetic acid.The likelihood of a termolecular encounter is inherent in the mechanism, however, no real evidence to substantiate either a direct termolecular or a series of two bimolecular steps has been obtained, although a -7 kcal for ΔH0 would support the latter.
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  • 77
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    Rates and mechanisms of oxidation of ZnTPP by CCI3O2 radicals in various solvents (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1315-1321 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Trichloromethylperoxyl radicals were produced by pulse radiolysis of air saturated solutions containing CCl4. The rate constants for the reaction of CCl3O2 radicals with zinc tetraphenylporphyrin (ZnTPP) were determined in various solvents. They were found to vary between 3 × 107 and 3 × 109 M-1 s-1. The changes in rate constants result from complexation of ZnTPP with the different solvents, but did not correspond to changes in redox potential of ZnTPP. The rate constants were found to depend on the strength of the axial complexation, indicating an inner sphere mechanism whereby the radical binds to the metal prior to electron transfer.
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  • 78
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    The kinetics and the mechanism of the thermal gas-phase reaction between bis(trifluoromethyl)trioxide, CF3O3CF3 and 1,1-dichlorodifluoroethylene, CF2CCI2 (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1323-1331 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal addition of CF3O3CF3(T) to CF2CCl2(E) has been investigated between 49.6 and 69.5°C. The initial pressure of CF3O3CF3 was varied between 7 and 240 torr and that of CF2CCl2 between 4 and 600 torr. Four products of formula CF3O(E)j OOCF3, where j = 1 → 4 are formed. The sum of the products Σi = 14 CF3O(E)jOOCF3 is equal to the amount of trioxide decomposed.The reaction is homogeneous. Its rate is not affected by the total pressure and the presence of inert gas. It is a free radical telomerization with four basic steps: thermal decomposition of CF3O3CF3 into CF3O. and CF3O2., chain initiation by addition of CF3O. to olefin incorporated in, and telomeric radicals termination.The consumption of alkene is well represented by the equation: \documentclass{article}\pagestyle{empty}\begin{document}$$ - d[E]/dt = k_1 [T]\left\{ {1 + \sum\limits_{j = 1}^3 {\prod\limits_{i = 1}^j {[1 + (k_{t_1 } k_1^{1/2} /k_{gi} } k_t^{1/2})([T]^{1/2} /[E])]^{ - 1} } } \right\} $$\end{document} where (d[E]/d[T]) = \documentclass{article}\pagestyle{empty}\begin{document}$$ \bar n $$\end{document} is the mean chain length of telomerization. \documentclass{article}\pagestyle{empty}\begin{document}$$ \bar n $$\end{document} varies from 1.45 at 1.5 torr of E to 3.3 at 400 torr of E. Above this pressure E has no influence on \documentclass{article}\pagestyle{empty}\begin{document}$$ \bar n $$\end{document}.The estimated value of the constant for the addition of telomeric radicals to alkene is:\documentclass{article}\pagestyle{empty}\begin{document}$$ k_g \simeq 8.6 \pm 6.0 \times 10^4 \exp ( - 2300 \pm 200{\rm col mol}^{{\rm - 1}} /RT){\rm M}^{{\rm - 1}} {\rm s}^{{\rm - 1}} $$\end{document}
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  • 79
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    Effect of olefins on the thermal decomposition of propane part I. The model reaction (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 227-239 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Study of the thermal decomposition of propane at very low conversions in the temperature range 760-830 K led to refinement of the mechanism of the reaction.The quotient VCH4 + C2H4/VH2 + C3H6 characterizing the two decomposition routes connected with the 1- and 2-propyl radicals proved to depend linearly on the initial propane concentration. This suggested the occurrence of intermolecular radical isomerization: in competition with decomposition of the 2-propyl radical: The linearity led to the conclusion that the selectivity of H-abstraction from the methyl and methylene groups by the methyl radical is practically the same as that by the H atom. The temperature-dependence of this selectivity ( μ = kCH3/kCH2) was given by\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm \mu = }\frac{{k_3 }}{{k_4 }} = \frac{{k_1 }}{{k_2 }} = 10^{0.26 \pm 0.03} \exp ( - 7.24 \pm 0.45{\rm kJ mol}^{{\rm - 1}} /RT). $$\end{document} Further evaluation of the dependence gave the Arrhenius representation \documentclass{article}\pagestyle{empty}\begin{document}$$ \frac{{k_7 }}{{k_6 }} = 10^{ - 5.97 \pm 0.03} \exp (115 \pm 5.1{\rm kJ mol}^{{\rm - 1}} /RT){\rm mol}^{{\rm - 1}} {\rm dm}^{\rm 3} $$\end{document} for the ratio of the rate coefficients of the above isomerization and decomposition reactions.Steady-state treatment resulted in the rate equation of the process, comparison of which with measurements gave further Arrhenius dependences.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550180208
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    Effects of olefins on the thermal decomposition of propane part III. Some remarks on the kinetics of decomposition (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 255-265 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conditions of applicability of quasi-steady-state kinetic treatment have been investigated with respect to the explanation of the decomposition of propane and the influence of ethylene on this.From the measured rate of accumulation of ethane and from the relations between the kinetic equations describing product formation, the rate parameters of the initiation reactions were determined, for which the temperature-dependences \documentclass{article}\pagestyle{empty}\begin{document}$$ k_i = 10^{17,05 \pm 0.99} \exp ( - 356 \pm 11{\rm kJmol}^{{\rm - 1}} /RT)s^{ - 1} $$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{ie} = 10^{12.0 \pm 0.99} \exp ( - 225 \pm 15{\rm kJmol}^{{\rm - 1}} /RT){\rm mol}^{{\rm - 1}} {\rm dm}^{\rm 3} s^{ - 1} $$\end{document} were found.In the decomposition of propane under the examined conditions, the chain length exceeds 500. In response to ethylene the chain length significantly decreases, but even in this case the decomposition chains are long enough for it to be assumed that the ratios of radical concentrations are governed by the propagation steps.Calculations demonstrated that the actual radical concentration during a sufficiently short induction period approximates to the stationary concentration, so that it does not seriously affect the accuracy of the kinetic treatment.
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    URL: http://dx.doi.org/10.1002/kin.550180210
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  • 81
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    Reaction of CF3 radicals with C2H6 (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 437-443 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The hydrogen transfer reaction between C2H6 and CF3 radicals, generated by the photolysis of CF3I, has been studied in the temperature range 298-617 K. The rate constant, based on the value of 1013.36 cm3 mol-1 s-1 for the recombination of CF3 radicals, is given by \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_2 = (11.90 \pm 0.09) - (33230 \pm 740)/19.145T $$\end{document} where k2 is in cm3 mol-1 s-1 and E is in J mol-1. These results are compared with those previously reported, and the following best value for k2 is recommended: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_2 = (11.94 \pm 0.07) - (33670 \pm 540)/19.145T $$\end{document}
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    URL: http://dx.doi.org/10.1002/kin.550180403
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  • 82
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    The influence of the effective potential on the strong collision limiting low-pressure rate coefficients (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 459-472 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The influence of the effective potential energy curves on the calculation of the strong collision limiting low-pressure rate coefficients of thermal dissociation-recombination reactions was analyzed in terms of the factorized formalism of Troe. An analysis of 26 reactions employing a Morse potential coupled with a quasitriatomic molecular model and an explicit account of the adiabatic zero-point barriers, as originallyproposed by Troe, was performed. A comparison between calculations realizedwith an exactly fitted looseness parameter, α, and with a standard value of α = 1.0 Å-1, indicates that the use of this last value is satisfactorily justified in the evaluation of thestrong collision limiting low-pressure rate coefficients. A study interms of restrictive relationships between the looseness and Morse parameters and ab initio, radial potentials (for CH4, CH3O2, and HO2) was also realized. The uncertainties in the evaluation of termolecular rate coefficients due to the lack of a complete knowledge of the long-range potentials are also briefly discussed.
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    URL: http://dx.doi.org/10.1002/kin.550180405
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  • 83
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    Kinetics of the gas phase reaction of OH radicals with pyrrole and thiophene (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 487-496 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute rate constants for the gas phase reaction of OH radicals with pyrrole (k1) and thiophene (k2) have been measured over the temperature ranges 298-440 and 274-382 K, respectively, using the flash photolysis-resonance fluorescence technique. The rate constants obtained were independent of the total pressure of argon diluent over the range 25-100 torr andwere fit by the Arrhenius expressions \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 = (2.7 \pm _{0.6} ^{0.8}) \times 10^{ - 11} \exp [(403 \pm 93)/T]{\rm cm}^{\rm 3} {\rm molecule}^{{\rm - 1}} {\rm s}^{{\rm - 1}} $$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$$ k_2 = (1.2_{ - 0.6} ^{ + 1.0}) \times 10^{ - 12} \exp [(584 \pm 217)/]{\rm cm}^{\rm 3} {\rm molecule}^{{\rm - 1}} {\rm s}^{{\rm - 1}} $$\end{document} with rate constants at 298 ± 2 K of k1 = (1.03 ± 0.06) × 10-10 cm3 molecule-1 s-1 and k2 = (8.9 ± 0.7) × 10-12 cm3 molecule-1 s-1. [These errors represent two standard deviations (systematic errors could constitute an additional ca. 10% uncertainty)]. These results are discussed with respect to the previous literature data and the atmospheric lifetimes of pyrrole and thiophene.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550180407
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  • 84
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    Kinetics of the solvolysis of the trans-dichlorobis(1,2-diaminoethane)-cobalt(III) Ion in water + urea mixtures (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 529-536 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Following the kinetic investigation of the solvolysis of a range of cobalt(III) complexes in mixtures of water + cosolvent wherethe cosolvent enhances the solvent structure and decreases the dielectric constant, kinetic data are now reported for such a solvolysis in water + urea where urea acts as a structure breaker and enhances the dielectric constant. A plot of log (rate constant) against reciprocal of the dielectric constant shows that differential effects of changes in solvent structure occur between the initial and the transition states and, as in theinvestigations using structure-enhancing cosolvents, the principal effect of change in solvent structure on the cobalt(III) cation occurs on the penta-coordinated ion in the transition state.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550180503
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  • 85
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    Rate constants and kinetic isotope effects for hydrogen/deuterium abstraction by chlorine atoms from the chloromethyl group in CH2ClCH2Cl, CD2ClCD2Cl, CH2ClCHCl2, and CH2ClCDCl2 (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 513-527 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The abstraction of hydrogen and deuterium from 1,2-dichloroethane, 1,1,2-trichloroethane, and two of their deuterated analogs by photochemically generated ground state chlorine atoms has been investigatedin the temperature range 0-95°C using methane as a competitor. Rate constants and their temperature coefficients are reported for the following reactions Over the temperature range of this investigation an Arrhenius law temperature dependence was observed in all cases. Based on the adopted rate coefficient for the chlorination of methane [L.F. Keyser, J. Chem. Phys., 69, 214 (1978)] \documentclass{article}\pagestyle{empty}\begin{document}$$ k_r /{\rm cm}^{\rm 3} {\rm s}^{{\rm - 1}} = (1.65 \pm 0.32) \times 10^{ - 11} \exp [ - (1530 \pm 68)/T] $$\end{document} which is commensurate with the present temperature range, the following rate constant values (cm3 s-1) are obtained: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 = (4.93 \pm 0.96) \times 10^{ - 11} \exp [ - (1087 \pm 68)/T] $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_2 = (2.92 \pm 0.57) \times 10^{ - 11} \exp [ - (1362 \pm 68)/T] $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_3 = (2.39 \pm 0.57) \times 10^{ - 11} \exp [ - (1750 \pm 68)/T] $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_4 = (1.68 \pm 0.33) \times 10^{ - 11} \exp [ - (1965 \pm 68)/T] $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_5 = (1.22 \pm 0.24) \times 10^{ - 11} \exp [ - (1948 \pm 68)/T] $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_6 = (1.47 \pm 0.28) \times 10^{ - 11} \exp [ - (1910 \pm 68)/T] $$\end{document} The observed pure primary, and mixed primary plus α- and β3-secondary kinetic isotope effects at 298 K are k3/k6 = 2.73 ± 0.08, and k1/k2 = 4.26 ± 0.12, respectively. Both show a normal temperature dependence decreasing to k3/k6 = 2.39 ± 0.06 and k1/k2 = 3.56 ± 0.09 at 370 K. Contrary to some simple theoretical expectations, the kinetic isotope effect for H/D abstraction decreases with increasing number of chlorine substituents in the geminal group in a parallel manner to the trend established previously for C1-substitution in the adjacent group. The occurrence of a β-secondary isotope effect, k4/k5, is established; this effect suggests a slight inverse temperature dependence.
    Additional Material: 7 Tab.
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  • 86
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    High temperature kinetics of the thermal decomposition of the lower alkanoic acids (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 575-596 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of propanoic acid dilute in argon has beenstudied in a single-pulse shock tube over the temperature range of 1100-1500 K and over the pressure range of 14-18 atm. The decomposition kinetics have been satisfactorily computer modelled by means of afree radical mechanism involving H and OH chains.Recent single-pulse shock tube product analyses of acetic acid decomposition have been computer modelled using a free radical mechanism for decarboxylation coupled to a unimolecular dehydration reaction.A comparison between the thermal decomposition kinetics of the C1—C3 alkanoic acids is made. The present studies do notprovide evidence for the participation of transition states involving a pentavalent carbon atom in the pyrolyses of the lower alkanoic acids.
    Additional Material: 7 Ill.
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  • 87
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    Masthead (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180601
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  • 88
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    Mutual isomerization of cyclopentyl and 1-Penten-5-y1 radicals (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 623-637 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Unimolecular reactions of mutual isomerization of cyclopentyl and 1-penten-5-yl radicals have been investigated by chemical activation. The radicals were generated by adding energized hydrogen atoms (EH about 23 kcal mol-1) to the double bond of either cyclopentane or 1,4-pentadiene. Based on the extensive steady-state RRKM calculations employing the experimental data from this work as well as from the literature, the threshold energies for the cyclopentyl ring opening and closure are 32 ± 0.3 and 16.2 ± 0.3 kcal mol-1, respectively. The entropy of activation for the ring opening is close to zero.
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  • 89
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    Acetaldehyde oxidation in the negative temperature coefficient regime: Experimental and modeling results (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 655-688 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acetaldehyde oxidation has been studied in experiments at temperatures of 553 and 713 K carried out in a low pressure, static reactor and in numerical modeling calculations using a detailed chemical kinetic reaction mechanism. The results of the experimental study were used to construct and validate the reaction mechanism, which was then used to examine acetaldehydeoxidation in the negative temperature coefficient regime between 550 and 900 K. This mechanism was also tested against independent measurements of acetaldehyde oxidation carried out by Baldwin, Matchan, and Walker. The overall rate of reaction and the properties of the negative temperature coefficient regime were found to be sensitive to the competition between radical decomposition reactions and the addition of molecular oxygen to acetyl and methyl radicals, including particularly \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 3} + {\rm O}_2 + {\rm M = CH}_{\rm 3} {\rm O}_{\rm 2} + {\rm M} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 3} {\rm CO} + {\rm M = CH}_{\rm 3} {\rm + CO} + {\rm M} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 3} {\rm CO} + {\rm O}_{\rm 2} {\rm = CH}_{\rm 3} {\rm CO}_{\rm 3} $$\end{document} During these experiments, an upper limit to the rate of decomposition ofCH3O2H was measured at 553 K. Implications of the results for future kinetic modeling of engine knock are discussed.
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    URL: http://dx.doi.org/10.1002/kin.550180606
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    The thermodynamic state of the hot gas behind reflected shock waves: Implication to chemical kineticsThis research was supported by the Division of Chemical Sciences, United StatesDepartment of Energy, Washington, D.C., under Contract No. DE-AC02-76CH00016 (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 409-436 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Procedures are discussed to correct for nonideality in a shock tube used in the reflected mode in conjunction with flash photolysis and atomic resonance absorption to measure chemical kinetics of atoms at high temperatures. Experimentally, pressure time profiles for the incident and reflectedshock regions are made close to the location of the observation windows through which absorbance is measured. The corresponding temperatures are calculated from the adiabatic equation of state. Justification for this procedure is provided by extending Mirels' boundary layer theory to take intoaccount interaction of the reflected wave with the flowing gas in the free stream and in the boundary layer. These theoretical methods are described for calculating the thermodynamic and hydrodynamic states behind the reflected wave from initial values of pressure and temperature and the measured velocity of the incident wave. The implication of these results to kinetic measurements at high temperature is discussed.
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    URL: http://dx.doi.org/10.1002/kin.550180402
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  • 91
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    An Ab initio determination of the rate constant for H2 + CN → H + HCNWork performed under the auspices of the Office of Basic Energy Sciences, Division of Chemical Sciences, US Department of Energy, under Contract W-31-109-Eng-38 (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 473-486 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactants, products, and saddle point for the reaction H2 + CN → H + HCN have been studied by ab initio calculations. The computed structures, frequencies, and energetics are compared directly to available measurements and, indirectly, to experimental rateconstants. The theoretical rate constants used in the comparison are calculated with conventional transition state theory. By reduction of the computed reaction barrier to 4.1 kcal mol,-1 good agreement with experimental rate constants is obtained over a 3250-K temperature range. This computed rate constant is well represented by the form 4.9 × 10-18 T2.45 e-1, 126/T over the temperature range of 250 K-3500 K. Substantial reaction rate curvature is found due to low-frequency bending modes at the saddle point. The results for this reaction are compared to other abstraction reactions involving H atom transfer to identify correlations between reaction exothermicity and both abstraction barriers and reaction rate curvature.
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    URL: http://dx.doi.org/10.1002/kin.550180406
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  • 92
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    Rate constants of O2(1Δg) (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 505-512 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constants of O2(1Δg) with aliphatic alcohols, terpenes, unsaturated hydrocarbons, chlorinated hydrocarbons, oxygen, and diamines have been studied in thepresence of NO2. The rate constants for oxygen, 1,2-ethane diamine, and 1,2-propane diamine are (9.9 ± 0.4) × 102, (8.7 ± 0.7) × 104, and (1.4 ± 0.3) × 104 1/mol/s, respectively. The rate constants for all other compounds are less than the oxygen rate constant.
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    URL: http://dx.doi.org/10.1002/kin.550180409
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  • 93
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    Gas phase kinetic and thermochemical data for endo- and exo-5-monosubstituted bicyclo[2.2.2]Oct-2-Enes (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 537-545 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal reactions of endo- and exo-5-Y bicyclo[2.2.2]oct-2-enes (NYBO and XYBO) where Y = methyl, ethyl, and isopropyl have been studied in the gas phase between 567 and 695 K. For both isomers they are parallel first-order retro-Diels-Alder reactions with elimination of ethene (E) and monosubstituted ethene (YE).The observed Arrhenius parameters are used to discuss the mechanism and to estimate the heats of formation and the entropies of NYBO and XYBO. Group values are proposed for estimation of these thermochemical data for compounds of the same type by means of the methods of Benson.
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  • 94
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    Estimations of OH radical rate constants from H-atom abstraction from C—H and O—H bonds over the temperature range 250-1000 K (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 555-568 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for overall H-atom abstraction by hydroxyl radicals from C—H and O—H bonds are estimated for alkanes, haloalkanes, aldehydes, ketones, ethers, alcohols, nitriles, and nitrates over thetemperature range 250-1000 K. These estimated rate constants utilize the modified Arrhenius expression K = A'T2e-E'/T in combination with the recommendations given in the recent review and evaluation of OH radical kinetics of Atkinson [1]. This estimation procedure gives good agreement, generally to within better than a factor of 2, of the estimated rate constants with theserecommendations.
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    URL: http://dx.doi.org/10.1002/kin.550180506
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  • 95
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    Effects of Olefins on the Thermal Decomposition of Propane Part IV. Influence of Propylene (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 301-312 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On the basis of the thermal decomposition of mixtures of propylene and propane with molar ratios of 0.0-0.33 in the temperature range 779-812K, the influencing functions describing the inhibition by propylene of the decomposition of propane were determined. The rate-reducing effect is explained mainly by the reactions \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm C}_{\rm 3} {\rm H}_{\rm 6} + {}^.{\rm R} \longrightarrow {}^.{\rm C}_{\rm 3} {\rm H}_{\rm 5} + RH $$\end{document} (in which .R = .H, .CH3 and 2-Ċ3H7) and also by the addition reactions \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm C}_{\rm 3} {\rm H}_{\rm 6} + {}^.{\rm H} \to 1 - {\rm \dot C}_{\rm 3} {\rm H}_{\rm 7} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ \to 2 - {\rm \dot C}_{\rm 3} {\rm H}_{\rm 7}. $$\end{document} It was established that the bulk of the allyl radicals formed \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm C}_{\rm 3} {\rm H}_{\rm 8} + {}^.{\rm C}_{\rm 3} {\rm H}_{\rm 5} \to 1 - {\rm \dot C}_{\rm 3} {\rm H}_{\rm 7} + {\rm C}_{\rm 3} {\rm H}_{\rm 6} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ \to 2 - {\rm \dot C}_{\rm 3} {\rm H}_{\rm 7} + {\rm C}_{\rm 3} {\rm H}_{\rm 6} $$\end{document} participate in the chain step, but, due to their lower reactivity, they restore the decomposition chain more slowly than the original radicals do.From the characteristic change in the ratio υCH4/υH2, the rate ratios of hydrogenabstraction reaction by radicals from propylene and propane could be determined. In these reactions there was no significant difference between the selectivities of the radicals. For an interpretation of the changes, the decomposition mechanism must be completed with the reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm C}_{\rm 3} {\rm H}_{\rm 6} + 2 - {\rm \dot C}_{\rm 3} {\rm H}_{\rm 7} \to 1 - {\rm \dot C}_{\rm 3} {\rm H}_{\rm 7} + {\rm C}_{\rm 3} {\rm H}_{\rm 6}. $$\end{document}Evaluation of the influencing curves revealed that the initiation reactions \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm C}_{\rm 3} {\rm H}_{\rm 6} + {\rm C}_{\rm 3} {\rm H}_{\rm 6} \to {}^.{\rm C}_{\rm 3} {\rm H}_{\rm 5} + {}^.{\rm C}_{\rm 3} {\rm H}_{\rm 7} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm C}_{\rm 3} {\rm H}_{\rm 8} + {\rm C}_{\rm 3} {\rm H}_{\rm 6} \to {}^.{\rm C}_{\rm 3} {\rm H}_{\rm 7} + {}^.{\rm C}_{\rm 3} {\rm H}_{\rm 7} $$\end{document} must be taken into account.By parameter estimation we have determined the rate ratios characterizing the above initiation reactions, the unimolecular decomposition of propane, hydrogen abstraction by radicals from propane and propylene, intermolecular isomerization of the 2-propyl radical via propane and propylene, and abstraction of propane hydrogens by the ethyl and methyl radicals; these are given in Tables II.
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    URL: http://dx.doi.org/10.1002/kin.550180304
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  • 96
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    Gas-phase thermolysis of sulfur compounds. Part VIII. Chloromethyl allyl, cyanomethyl allyl, 1-cyanoethyl allyl and neopentyl allyl sulfides (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 355-362 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolyses of four alkyl allyl sulfides with substituents on the α—C atom of the alkyl moiety have been studied in a stirred-flow system over the temperature range 340-400°C and pressures between 2 and 12 torr. The only products formed are propene and thioaldehydes. The reactions showed first-order kinetics with the rate coefficients following the Arrhenius equations: Chloromethyl allyl sulfide: \documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{{\rm - 1}}) = 10^{10.74 \pm 0.23} \exp ( - 144 \pm 3){\rm kJ/mol}RT $$\end{document} Cyanomethyl allyl sulfide: \documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{{\rm - 1}}) = 10^{10.20 \pm 0.19} \exp ( - 129 \pm 2){\rm kJ/mol}RT $$\end{document} 1-cyanoethyl allyl sulfide: \documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{{\rm - 1}}) = 10^{11.09 \pm 0.18} \exp ( - 141.5 \pm 2.2){\rm kJ/mol}RT $$\end{document} Neopentyl allyl sulfide: \documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{{\rm - 1}}) = 10^{10.54 \pm 0.24} \exp ( - 144 \pm 3){\rm kJ/mol}RT $$\end{document}The effects of these and other substituents on the reactivity is discussed in relation with the stabilization of a polar six-centered transition state. The results support a non-concerted mechanism where the 1-5 α—H atom shift is assisted by its acidic character.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180308
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  • 97
    Electronic Resource
    Electronic Resource
    Competing Channels in Infrared Multiple Photon Decomposition (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 379-398 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Infrared multiple photon decompositions (IRMPD) with more than one reactive pathway can provide significantly more kinetic information than can single-channel photolyses. The rates of the competing unimolecular reactions and the rate of photon absorption are interrelated, so that knowledge of one yields information about the others. The goals and pitfalls of IRMPD experiments on several well-studied classes of reactants are reviewed.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180310
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  • 98
    Electronic Resource
    Electronic Resource
    Masthead (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180401
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  • 99
    Electronic Resource
    Electronic Resource
    On the rates of decarbonylation of hydroxyacetyl and other acyl radicals (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 791-800 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of decarbonylation of the hydroxyacetyl radical in acetonitrile is measured by effect modulated ESR spectroscopy and found to be log (KD/s-1) = (11.0 ± 1.5)-(2.3RT)-1 (37 ± 8)kJ/mol. The result is shown to be reasonably well connected with a variety of decarbonylation data known for other acyl species by asimple Evans-Polanyi relation.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180706
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  • 100
    Electronic Resource
    Electronic Resource
    The explosive reaction of carbon monoxide and oxygen at 973 and 1048 K (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 801-817 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conditions leading to an explosive reaction of carbon monoxide and oxygen in the presence of small amounts of water have been examined at temperatures of 973 and 1048 K. Carbon monoxide and water were formed in the presence of oxygen by reaction with a thin film of carbon deposited on a quartz vessel. The carbon provided a reactive and reproducible surface, giving aconsistent rate of termination and thus allowing a quantitative descriptionof the conditions at the explosion in the region of the first limit. Calculations of the rates of the various branching and termination reactions at the onset of the explosion showed that the simple mechanism described earlier was still adequate to explain the reaction at temperatures up to 1050 K. From experiments with inert gases the transition from the first explosion limit to the region of the second explosion limit was demonstrated.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180707
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