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  • 1985-1989
  • 1975-1979  (127)
  • 1930-1934
  • 1975  (127)
  • Physical Chemistry  (82)
  • Rat
  • 1
    ISSN: 1432-2307
    Keywords: Lathyrism ; Capillaries ; Rat ; Ultrastructure ; Flavonoids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The ultrastructure of rat myocardial capillaries was studied in the course of experimental lathyrism. Endothelial cells were hypertrophic, with a sinuous profile of the plasma membrane facing the lumen and with a consistent increase of pinocytotic vesicles; the nuclei were irregular in shape; ATPase activity was no more demonstrable. Therefore, various and well distinct structural endothelial mechanisms seem to be primarily involved, causing an alteration of the dynamics of transcellular exchanges and of the permeability of the vascular wall. Simultaneous treatment with certain flavonoids, (O-(β-hydroxyethyl)-rutosides and Na(+)-epicatechin-2-sulfonate), resulted in a less pronounced alteration and a more rapid recovery. The possibility of the existence of a common site of action of lathyrogens and flavonoids is raised in the discussion.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Research in experimental medicine 165 (1975), S. 213-217 
    ISSN: 1433-8580
    Keywords: Rat ; Lymph nodes ; lymphography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Most the lymphatic system in the rat was directly observed in our experiment by radiological means. The lymphatics of the limbs were firstly revealed by subcutaneous injection of Patent Blue V. Lipiodol was used as radio-opaque compound injected by a micro-technique fully described by the authors.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Mycopathologia 55 (1975), S. 53-55 
    ISSN: 1573-0832
    Keywords: Rubratoxine B ; Mitochondria ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract The in vitro effect of rubratoxin B on the electron transport system of rat liver mitochondria was investigated. This mycotoxin depressed oxygen consumption in ADP-lacking mitochondria and in ADP-coupled mitochondria, using succinate or β-hydroxybutyrate as substrats. Rubratoxin B is neither an oxidative-phosphorylation inhibitor nor uncoupling agent. Its effect is compared with aflatoxin B1.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 148 (1975), S. 73-87 
    ISSN: 1432-0568
    Keywords: Rat ; Temporal cortex ; Synaptogenesis ; Retzius-Cajal cells ; Poly morphous cells
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The onset of synaptogenesis was studied in the temporal cortex of rat fetuses whose age ranged between 15 and 19 days of gestation. First synapses were found at a surprisingly early stage of cortical development: on day 16. These contacts showed relatively few vesicles and very inconspicuous membrane-thickenings. They were located in the marginal layer, above as well as below the narrow band formed by the newly arrived first neuroblasts of the prospective cortical plate. The postsynaptic structures were probably dendrites of the horizontally or obliquely orientated neurons scattered throughout the marginal layer (such neurons were seen even within the cell-dense band). On day 17, the cortical plate separated the differentiated cells definitely into a superficial and a deep population. As on the following days, synapses were found above and below the cortical plate but not within it. In addition to contacts showing the same features as those described on day 16, there were already synapses with numerous vesicles and clearly asymmetric membrane thickenings. On days 18 and 19 the borders of the cortical plate became more clear-cut. The well-differentiated neurons situated above and below this plate could now be identified as Retzius-Cajal cells of the prospective molecular layer and as polymorphous cells of the layer VI b respectively. The presence of axo-somatic contacts on these neurons provided direct evidence that both cell types are targets for synapses. Desmosome-like junctions were found even in the youngest fetuses studied. Their roughly symmetric membrane thickenings were clearly more conspicuous than those of earliest synapses. Desmosome-like junctions occurred very frequently between structures which subsequently were never seen to become synaptically linked. During the entire period studied, numerous coated vesicles fused with cell membranes were noted. Such “open” vesicles were seen on neurons (sometimes in the immediate vicinity of synapses) but also on non-nervous, extracortical as well as intracortical structures. Thus there does not seem to be a specific relationship between desmosome-like junctions and coated vesicles on the one hand and synapse formation on the other.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 148 (1975), S. 47-58 
    ISSN: 1432-0568
    Keywords: Rat ; Endometrium ; Ultrastructure ; Progesterone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The effects of various dosages and of various time periods of treatment with progesterone have been studied in the spayed, mature rat. Test objects were the cells of the luminal epithelium and of the endometrial stroma which were examined by qualitative and quantitative electron microscopy. No significant response was observed in epithelial or stromal cells until after 12 hrs of progesterone treatment. The nuclei of both cell types were then more circular than earlier with reduced long diameters. The functional significance of this change in configuration is unclear since only in the stromal cells was it followed by nuclear growth. Further, after 12 hrs of treatment the relative amounts of mitochondria and granular endoplasmic reticulum of stromal cells were reduced while the volume of the stromal cell cytoplasm appeared enlarged. This is taken as evidence that progesterone causes an intracellular oedema probably by decreasing cell membrane permeability. This response is probably not specific for the stroma but also includes the luminal epithelium, although the volume of the epithelial cell cytoplasm could not be determined here. Nucleolar enlargement did occur in stromal cells and was observed after 12 hrs of treatment but was not significant until after 24 hrs. At this point of time the net amount of granular endoplasmic reticulum in stromal and epithelial cells was increased indicating an increased protein synthesis in both cell types. However, only in the stromal cells was this associated with nucleolar enlargement, which supports the idea that progesterone stimulates protein synthesis through different mechanisms in the two cell types. Testing various dosages of progesterone showed that 0.5 mg had an effect similar to 5 mg of progesterone. When 0.05 mg progesterone was injected the only effect observed was an increase in the amount of apical vesicles of the luminal epithelium, showing that the epithelium is more sensitive to progesterone than the stroma.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 148 (1975), S. 89-97 
    ISSN: 1432-0568
    Keywords: Superior cervical ganglion ; Paraganglionic cells ; Rat ; Guanethidine ; Catecholamines
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Paraganglionic cells in the rat superior cervical ganglion were investigated by fluorescence and electron microscopy following treatment with guanethidine for 5–30 days. Control animals received saline and guanidine. Fluorescence cytophotometric measurements revealed a general decrease in the catecholamine content of paraganglionic cells in guanethidine-treated animals. However a few cell clusters showed focal increases. Similarly by electron microscopy there was a general decrease in the number of dense core vesicles in the majority of paraganglionic cells with a minority of cell clusters showing increases.—guanethidine—as well as guanidine—treated animals showed non-specific cytological alterations such as mitochondrial swelling and increase of cytoplasmic glycogen. However no changes of catecholamine contents and of dense core vesicles were noted in control animals. These results confirm the conception that in rat paraganglionic cells the dense core vesicles are the main storage site of catecholamines. The marked difference in the response of some cell clusters to the experimental treatment can be considered as evidence of functional heterogeneity of this cell population in the rat superior cervical ganglion.
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  • 7
    ISSN: 1432-0568
    Keywords: Corticotropin releasing factor ; Neurosecretion ; Hypophysis ; X-irradiation ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary In 195 female Wistar rats the influence of adrenalectomy, total body X-irradiation and dexamethasone treatment on the amount of CRF-granules in the external zone of the median eminence and “classical” neurosecretory material (NSM) in the internal zone of the median and in the posterior lobe of the hypophysis has been studied. In the normal rat only very few CRF-granules occur. 15 days after adrenalectomy increased amounts of CRF-granules but normal amounts of “classical” NSM are found. X-irradiation leads to a slight diminishment of “classical” NSM in normal rats. In adrenalectomized animals X-irradiation causes no changes in the amount of “classical” NSM but a marked decrease in the amount of CRF-granules. Application of dexamethasone from the 15th to 18th day after adrenalectomy enhances the augmentation of CRF-granules in irradiated and non-irradiated rats but does not influence the amount of “classical” NSM. The findings show that no correlation exists between the quantitative changes of CRF-granules and “classical” NSM under the experimental conditions used. Therefore it is to be assumed that the release of the two substances is regulated by different control mechanisms and that the substances have a different functional significance. The observations do not exclude the possibility that CRF-granules and “classical” NSM are biochemically identical.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Inflammation research 5 (1975), S. 57-61 
    ISSN: 1420-908X
    Keywords: Rat ; Lymphostatic encephalopathy ; Harmine ; Tremor ; Antiphlogistics ; Blood-brain barrier ; Permeability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Injection of the tremorigenic alkaloid harmine into lymphostatic encephalopathic rats leads to a longer duration of tremor and higher brain concentrations than in shamoperated controls. In lymphostatic encephalopathic as well as in normal rats different antiphlogistics shorten the tremor duration and decrease harmine concentraion in brain. The antiphlogistics do not influence the plasma concentration of harmine, its protein binding and its tremorend concentration in brain. The effect of antiphlogistics in lymphostatic encephalopathic rats is considered as a consequence of the reduced blood-brain barrier permeability. Obviously in sick animals the blood-brain barrier permeability for harmine is not increased; the prolonged harmine tremor and the increased alkaloid concentration in the brain are consequences of the impaired cerebral lymphatic drainage only.
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  • 9
    ISSN: 1432-0533
    Keywords: Experimental CNS tumours ; Methylnitrosourea ; Ethylnitrosourea ; Clonal growth ; Serum-free culture ; db cAMP treatment ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Six clones from methylnitrosourea (MNU) or ethylnitrosourea (ENU) induced tumours obtained in the nervous system of the rat were cultured in serum-free medium or treated with dibutyryl cyclic AMP (db cAMP) in vitro. All clones originated from longterm cultures. Three clones forming sarcomas after syngeneic transplantation showed only very slight changes following treatment, whereas the three glioma clones showed striking alterations. They formed long processes or showed rounding of their perikarya. In serum-free medium the cellular shape is intermediate between that seen in normal conditions and that seen in db cAMP treated cultures. The altered cultures resemble the primary cultures of the respective tumours. The relationship of these alterations to tumour types are discussed.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 11 (1975), S. 49-55 
    ISSN: 1432-0428
    Keywords: Rat ; blood glucose ; plasma insulin ; pancreas perfusion ; insulin secretion ; thyroxine ; glucose ; tolbutamide ; pyruvate ; isoprenaline
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Thyroxine treatment increases blood glucose and plasma insulin levels in the rat. The hypoglycemic effect of tolbutamide is more pronounced in treated animals. The immediate insulin secretory response of the isolated perfused pancreas to maximal, but not to submaximal, glucose stimuli was increased after thyroxine treatment, especially in the lower dose range. However, as thyroxine treatment reduces insulin release during the prolonged late phase, the total amount of insulin released from the pancreas is reduced. Both the early response to tolbutamide and the subsequent basal secretion were increased after thyroxine treatment. When the pancreas of treated rats was exposed to glucose plus pyruvate the inhibition of the late phase was reversed. Isoprenaline did not overcome the inhibitory effect of thyroxine treatment on the late phase of glucose-induced insulin release. Thyroxine induces a selective inhibition of glucose induced insulin release which is reversed by pyruvate; this indicates that thyroxine interferes with the glycolysis in the beta cell.
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  • 11
    ISSN: 1432-0428
    Keywords: Rat ; ammonium infusion ; blood ammonia ; glucose metabolism ; plasma immunoreactive insulin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary In order to explain the abnormalities of glucose metabolism previously observed in patients with blood ammonia elevation, the effect of a transitory hyperammonemia on I. V. glucose tolerance was investigated in rats. An I. V. glucose tolerance test was performed in 3 groups of 15 rats 60 min after the beginning of a 95 min infusion of either a 2 ml isotonic NaCl solution (control group) or ammonium acetate solutions at low (0.50 μmol/kg/min. NH4+) or high doses (1.70 μmol/kg/min NH4+). The “high” NH4+infusion produced an increase of blood ammonia to levels near 1000 μg/100 ml, a significant decrease in the K coefficient for glucose disappearance (2.53 × 10−2±0.20 compared to 4.92 × 10−2±0.13 in control group) and a suppression of the radioimmunological plasma insulin (I.R.I.) response to glucose. With the “low” NH4 + infusion the hyperammonemia was less pronounced (200–300 μg/100 ml), but the decrease in K(3.02 × 10−2±0.15) and in the first phase of I.R.I, release remained significant. The decrease in glucose disappearance rate could be accounted for by the proportional decrease in insulin secretion. Thus glucose intolerance induced by ammonium acetate infusions may be due to a direct effect of NH4 + on the pancreas. These abnormalities in glucose metabolism depend on the quantity of infused ammonium.
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 23 (1975), S. 157-166 
    ISSN: 1432-1106
    Keywords: Ventrobasal thalamus complex ; Thermosensitivity ; Burstactivity ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Recordings were made of spike-trains from 163 neurons of the rostral part of the ventrobasal thalamus complex of the rat while the temperature of the scrotal skin was altered. The following results were obtained: 55 neurons were nonthermosensitive, 7 neurons cold-sensitive and 101 neurons warm-sensitive. In the case of the warm-sensitive cells a definite discrimination was possible: 61.4% of the neurons altered their firing behavior during peripheral cooling, changing from relatively even spike frequency to burst firing. This change could be induced repeatedly by altering the temperature. 38.6% of the neurons, on the other hand, reacted to cooling by slowing down their frequency. By way of statistical methods the firing patterns of the two response-types were analyzed more precisely and the differences in response to temperature stimuli more exactly defined. Likewise, the spatial distribution of the two response-types of warm-sensitive cells exhibited differences; whereas the cells devoid of burst activity occured rather uniformly in the region of the thalamus studied, the cells with bursting activity were confined more to the mediocaudal region. These findings are discussed with regard to the phenomenon of peripheral bursts and to the projection of thermoafferent pathways onto the ventrobasal thalamus complex. The functional interpretation of the various cell reactions and their role in the central processing of thermoafferent signals still remains unexplained and requires comparative studies of peripheral and central parts of the thermoafferent system.
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 22 (1975), S. 175-183 
    ISSN: 1432-1106
    Keywords: Rat ; Hypoglossal nucleus ; Axotomy ; Subsurface cisterns
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary A quantitative ultrastructural survey was made of subsurface cisterns and their association with overlying structures in the left hypoglossal nucleus of normal rats, and rats which had received left hypoglossal axotomies 7–84 days previously. Subsurface cisterns in normal rats occurred in some hypoglossal neurones, and, sporadically, in proximal dendrites. They were mostly subsynaptic, and often associated with Nissl substance. From 7–14 days postoperatively, when many somatic boutons temporarily lost contact with the perikaryal surface, and were replaced by a microglial sheath, the percentage of perikaryon with underlying cistern was significantly reduced. The Nissl substance was also dispersed at this stage, and not restored until 28 days postoperatively. At 21 days normal percentages of subsurface cistern were restored, but the cisterns were now mostly subastrocytic, an astrocytic sheath having replaced the microglial sheath. From 63 days onwards the cisterns were mostly subsynaptic again as boutons returned to the regenerating perikarya and the temporary astrocytic sheath disappeared. It is suggested that subsurface cisterns might alter the overlying perikaryal surface in some way during neuronal regeneration, causing certain boutons to adhere there.
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  • 14
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 22 (1975), S. 525-540 
    ISSN: 1432-1106
    Keywords: Supraoptic nucleus ; Quantitative electron microscopy ; Afferent fiber connections ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary A quantitative electron microscopic study of synaptic terminal degeneration was performed in the supraoptic nucleus (NSO) after a variety of major transections or ablations, destroying or interrupting in different combinations the afferent pathways known from earlier and own light microscopic degeneration studies. Solutions of a set of equations, expressing the percentage degenerations in synaptic profiles after different combinations in which the several pathways are interrupted by the various interferences, enabled the authors to give the following percentage numbers for afferent synapses from different sources. 32.7% of supraoptic afferents originate from the brain stem probably representing the monoaminergic innervation of this nucleus. The medial basal hypothalamus (21.0%), amygdala (13.5%), septum (13.5%), hippocampus (8.5%) and olfactory tubercle and further rostral cortical region (17.0%) are the other main sites of origin of supraoptic nucleus afferents. There are no supraoptic afferents from the optic nerve, superior cervical ganglion or fimbria hippocampi.
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  • 15
    Electronic Resource
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    Springer
    International archives of occupational and environmental health 34 (1975), S. 167-175 
    ISSN: 1432-1246
    Keywords: N,N-Dimethylformamide ; Embryotoxicity ; Rat ; Inhalation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The purpose of this study, which was conducted for industrial toxicological reasons, was to investigate the possible embryotoxic and teratogenic effects after inhalation of dimethylformamide in rats. In a dynamic inhalation apparatus groups of 22–23 rats were subjected to approx. 18 ppm (maximum allowable concentration in the working area, MAC=20 ppm) and 172 ppm in the air for 6 hrs/day on 10 consecutive days, i.e. from the 6th to 15th day of gestation. The dimethylformamide inhalation did not cause any visible impairment to female rats as regards general behaviour, appearance or weight development during the treatment or the entire gestation period. The gestation rate was unchanged. The development of the fetuses was not influenced in any way by the exposure of the pregnant animals to approx. 18 ppm. In contrast the fetuses taken by caesarean section from the dams exposed to 172 ppm weighed significantly less than the fetuses of the control animals. Skeletal development of these fetuses, however, was normal. All other reproduction parameters were within the normal range for this strain. The study showed that the inhalation of dimethylformamide in concentration up to approx. 10 times the MAC had no teratogenic effect on rats.
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  • 16
    Electronic Resource
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    Springer
    Psychopharmacology 44 (1975), S. 287-289 
    ISSN: 1432-2072
    Keywords: Delta-9-tetrahydrocannabinol ; Social behaviour ; Mouse ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The behavioural effects of delta-9-tetrahydrocannabinol in mice and rats have been studied by an ethological analysis of encounters between animals injected with the drug and partners injected with the solvent (Tween-saline). In both species, Immobility was increased and Non-Social Activity reduced after injections of 5 mg/kg of delta-9-tetrahydrocannabinol. Flight was increased in treated mice but not in treated rats. Aggression was not significantly altered in either species. Thus, in the mouse, the qualitative behavioural effects of delta-9-tetrahydrocannabinol were similar to those previously reported for crude cannabis resin. Comparison of the dose-response data indicated that some other constituents of cannabis may reduce the Flight reaction from delta-9-tetrahydrocannabinol although not interfering with Immobility.
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  • 17
    ISSN: 1432-2013
    Keywords: High Altitude ; Coronary Blood Flow ; Cardiac Output ; Cardiac Hypertrophy ; Rat ; TissueP O 2
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary In rats exposed to a simulated high altitude of 3500 m for their whole prenatal and postnatal life a severe cardiac hypertrophy develops. In rats born and first staying 5 weeks at sea level and then being exposed to simulated high altitude, only a unilateral right cardiac hypertrophy occurs. In both groups nutritional coronary blood flow was estimated in left ventricle, right ventricle, and septum and was compared with control animals of similar age. Coronary blood flow was measured at hypoxia in all groups. At first cardiac output was determined by the Fick principle, then86Rb was applied and the animals were killed after 55 sec. Activity of86Rb was measured in both cardiac ventricles and septum and the fractional uptake was calculated. According to Sapirstein (1956, 1958) the distribution of86Rb follows the distribution of cardiac output and from both these data the nutritional blood flow to the parts of the heart may be estimated. Cardiac output was similar in rats exposed to simulated high altitude later in life (“newcomers”) and in control animals, but it was significantly lower in rats born in the low pressure chamber (“natives”). Fractions of cardiac output supplying cardiac ventricles and septum in rats from both hypoxic groups were significantly higher than in control animals. In the “natives” they were significantly higher than in the “newcomers”. The fractions of cardiac output in both “newcomers” and “natives” remained significantly higher than those of the control animals, also when calculated per gram of heart tissue. Nutritional coronary blood flow (in ml/min) was higher in both ventricles and septum of the “newcomers” and in the right ventricle of the “natives”, and lower in the septum of the “natives”, when compared with control animals. Coronary blood flow per gram of heart tissue (in ml/min·g) was significantly higher in all cardiac parts of the “newcomers”, but it was about the same in all cardiac parts of the “natives” when compared with controls. The importance of observed changes concerning myocardial tissue oxygenation is analyzed by using Krogh's cylindrical tissue model.
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  • 18
    Electronic Resource
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    Pflügers Archiv 357 (1975), S. 201-207 
    ISSN: 1432-2013
    Keywords: Allantoin ; Uricase ; Kidney ; Clearance ; Micropuncture ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Renal excretion of allantoin was measured by tracer techniques. After injection of 2-C14 urate and H3 inulin, clearances of allantoin and inulin were measured and both proximal and distal tubules were micropunctured. In confirmation of earlier results 2-C14 urate injected into an intact animal is very rapidly converted to C14 allantoin: after 15 min more than 90% of urinary tracer is present as allantoin. It was further observed that 1) allantoin clearance is essentially identical with inulin clearance over a wide range of urine flows; 2) no net transport of allantoin occurs in either proximal or distal tubules. Clearly allantoin is handled by the rat kidney like inulin. The total excretion of filtered allantoin unlike that of filtered urate provides an easy and effective mechanism for animals possessing the enzyme uricase to dispose of their purine loads.
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  • 19
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    Pflügers Archiv 353 (1975), S. 171-189 
    ISSN: 1432-2013
    Keywords: Enzyme Secretion ; Hormonal Stimulation ; Narcosis ; Pancreas ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary 1. A method for collecting duodenal juice and gastric content separately, in conscious rats, is described. Metal cannulas were implanted into the stomach fundus. For the main experiment a double lumen tube was inserted through the cannula via the pylorus into the duodenum. 2. The following secretion patterns were observed: a) In the resting state there was a constant flow rate of duodenal volume, bicarbonate, trypsin and amylase. b) Cholinergic stimuli were capable of increasing enzyme secretion as much as fourfold for a period of 30 to 40 min when administered as a single subcutaneous injection. This effect was annulled by atropine. c) Secretin and cholecystokinin-pancreozymin given together in a single injection s. c. or i. v., elicited a similarly strong response. d) Identical ranges of the secretion maxima were found with a tendency to decrease after the first hour, when the hormones were infused either s. c. or i. v. e) Doses from 0.5 to 25 U/100 g b. w./hr showed identical responses. Doses below 0.2 U/100 g/hr were without effect. 3. Narcosis (pentobarbital) inhibited markedly the resting and stimulated enzyme secretion. 4. The method is suitable for examination of physiological and pharmacological effects on resting and stimulated enzyme secretion of the rat pancreas.
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  • 20
    Electronic Resource
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    Pflügers Archiv 353 (1975), S. 215-225 
    ISSN: 1432-2013
    Keywords: Muscle Regeneration ; Muscle Transplantation ; Contractile Properties of Muscle Transplants ; Denervation of Muscle ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The soleus or extensor digitorum longus muscles of young rats were freely grafted into the bed of the corresponding contralateral muscle. The grafts were of normal muscle or muscles which had been denervated for 14 days. Grafts of normal muscle were characterized by little or no contractile activity for the first 2–4 days after transplantation. In contrast, denervated grafts contracted weakly, but consistently, throughout this early period. The patterns of contraction were complex. In early transplants, the contractions were due entirely to surviving muscle fibers in the graft, and the contractile characteristics were those of denervated muscle fibers. After the first week, contractions of newly regenerating muscle fibers within the grafts were superimposed upon and later took over those from the fibers that survived the original transplantation. The contraction time approached those of the normal soleus or extensor muscles during the second month after grafting, and the grafts contracted like fast or slow muscles.
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  • 21
    Electronic Resource
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    Experimental brain research 23 (1975), S. 463-470 
    ISSN: 1432-1106
    Keywords: Rat ; Hypoglossal nucleus ; Axotomy ; Horseradish peroxidase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The left hypoglossal nuclei of normal rats, and rats which had received left hypoglossal nerve axotomies 7–21 days previously, were studied by electron microscopy after injection of horseradish peroxidase as a marker of extracellular space and pinocytosis. Quantitative analysis showed that the number of pinocytotically-derived structures in presynaptic boutons was significantly increased in rats at 7, 14, and 21 days after axotomy when compared with normal rats. It was suggested that presynaptic boutons which became detached from injured neurones retracted by a membrane cycling mechanism involving pinocytotic uptake of bouton plasmalemma, without compensatory membrane production elsewhere. It was confirmed that the channels in the microglial cells communicated with the extracellular space.
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  • 22
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    Archives of toxicology 34 (1975), S. 309-314 
    ISSN: 1432-0738
    Keywords: Glafenine ; Chloroquine ; 4-Amino-7-chloroquinoline ; Rat ; Glafenin ; Chloroquin ; 4-Amino-7-chlorchinolin ; Ratte
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Bei oraler Zufuhr in einer Dosierung von 150 bis 450 mg/kg 2 Tage hintereinander an etwa 100 g schweren Ratten bewirkt Glafenin eine vorübergehende Nephritis mit Steigerung von Blutharnstoff, Hypertrophie der Nebennieren und Veränderungen des Serumproteinogramms. An die 4-Amino-7-chlorochinolin-Struktur scheinen diese toxischen Wirkungen nicht gebunden zu sein, denn die ähnlichen Derivate, Chloroquin und Amodiaquin, rufen sie in äquimolekulären Dosen nicht hervor. Glycerol, ein im Organismus entstehendes Hydrolysisprodukt des Glafenins, zeigte sich auch wirkungslos. Die Toxicität ist wahrscheinlich auf das Glafenin selbst oder sein saures Abbauprodukt 4-(0-carboxyphenylammo-7-chlorochinolin, zurückzuführen.
    Notes: Abstract When given orally in elevated but nonlethal doses (150 to 450 mg/kg, on 2 consecutive days), glafenine induces in rats (body weight 100 g) a transient nephritis with an increase in blood urea, hypertrophy of adrenals, and some changes in the serum proteinogram. These effects do not appear to be due to the 4-amino-7-chloroquinoline structure from which glafenine is derived, as they are not observed with the structural analogue chloroquine given at equimolar doses under the same conditions. Further, they do not appear to be due to glycerol, the by-product of metabolic glafenine hydrolysis. The responsible molecule appears to be either glafenine itself or its acid metabolite 4-(0-carboxyphenylamino) 7-chloroquinoline.
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  • 23
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    Archives of toxicology 34 (1975), S. 213-225 
    ISSN: 1432-0738
    Keywords: Lead ; Chelating agents ; Toxicity ; Rat ; Blei ; Chelatbildner ; Toxicität ; Ratte
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Die intraperitoneale Verabfolgung von Pb-Acetat führt zu einer mäßigen und vorübergehenden hypochromen Anämie, zu einer lang dauernden erhöhten Ausscheidung der δ-Aminolävulinsäure mit dem Urin, während die Ausscheidung der alkalischen Phosphatase überhaupt nicht und die von Lactatdehydrogenase nur geringfügig beeinflußtwird. Es wird gefolgert, daß weder die hamatologische Reaktion noch die angedeutete Nephrotoxicität für die letale Wirkung von Pb verantwortlich sind. Die Chelattherapie begann 3 Tage nach der letzten Pb-Dosis und erstreckte sich auf 7 Wochen, wobei die intraperitoneale Tages-dosis 25, 50 bzw. 100 μmol/kg betrug. Die Wirksamkeit in bezug auf die Erhöhung der Pb-Ausscheidung mit dem Urin nahm in der Reihenfolge ab: Ca-Diäthylentriaminpentaacetat 〉 2,3-Dimercaptopropan-1-sulfonat 〉 Zn-Diäthylentriaminpentaacetat 〉 D-Penicillamin. Das vermehrt ausgeschiedene Pb stammt im wesentlichen aus dem Skelett. Die Chelatbildner erniedrigten ebenfalls die Ausscheidung der δ-Aminolävulinsäure, erwiesen sich aber als unwirksam, die hämatologische Reaktion und die letale Wirkung von Pb günstig zu beeinflussen. Durch diese negativen Ergebnisse wird der Wert der Chelatbehandlung von Fällen akuter Pb-Vergiftung in Frage gestellt.
    Notes: Abstract The intraperitoneal administration of Pb acetate (5 × 20 mg Pb/kg per day) evokes a moderate and transient hypochromic anemia, a long-lasting enhanced urinary excretion of δ-aminolevulinic acid whereas the urinary excretion of alkaline phosphatase is not affected and that of lactic debyhrogenase only marginally. It is concluded that neither the hematologic response nor the slight nephrotoxicity are responsible for the lethal action of Pb. Chelate treatment started 3 days after the last Pb dose and was continued over 7 weeks. The daily intraperitoneal dose was 25, 50, and 100 μmol/kg, respectively. The efficacy in promoting the urinary excretion of Pb decreased in the following order: Ca diethylenetriaminepentaacetate 〉 2,3-dimercaptopropane-1-sulfonate 〉 Zn diethylenetriaminepentaacetate 〉 D-penicillamine. This effect was mainly due to the mobilization of skeletal Pb. The chelating agents also lowered the excretion of δ-aminolevulinic acid but failed to exert a beneficial influence on the anemia and the lethal action of Pb. These negative results raise questions about the usefulness of chelation therapy in cases of acute Pb poisoning.
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  • 24
    ISSN: 1432-0738
    Keywords: Acrylonitrile ; Phenobarbital ; SKF 525-A ; Dimercaprol (BAL) ; Thiosulfate ; Cyanide-Thiocyanate ; Route of Administration ; Drug Biotransformation ; Rat ; Mouse ; Chinese Hamster ; Acrylonitril ; Phenobarbital ; SKF 525-A ; Dimercaprol (BAL) ; Thiosulfat ; Cyanid ; Thiocyanat ; Applikationsart ; Biotransformation ; Ratte ; Maus ; Chinesischer Hamster
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Wistar Ratten, Standard-Albinomäuse und chinesische Hamster (Weibchen) erhielten eine einmalige Dosis von Acrylonitril, 0,5 oder 0,75 mmol/kg Gewicht. Die Ausscheidung des Thiocyanats, Hauptmetaboliten des Acrylonitrils, wies bei Ratten nach einer oralen (20 %), intraperitonealen und subcutanen (2 bis 5%) und intravenösen (1 %) Applikation einen sinkenden Umwandlungsanteil auf. Auch bei Hamstern und Mäusen rief die orale Verabreichung eine höhere Umwandlung hervor als bei der intraperitonealen Zufuhr. Die Vorbehandlung von Ratten mit Phenobarbital, SKF 525-A, Cystein oder Dimercaptopropanol, hatte keinen signifikanten Einfluß auf die Ausscheidung von Thiocyanat im Harn. Hingegen erhöhte die gleichzeitige Applikation von Thiosulfat bedeutend den Anteil von Thiocyanat, und zwar bei Ratten fast zweifach, bei Mäusen mehr als dreifach. Die Studie bestätigt den ausgeprägten Einfluß der Verteilung (first pass metabolic phenomenon) auf das metabolische Schicksal von Acrylonitril. Anscheinend ist die starke Bindung von Acrylonitril und die Cyanoethylierung für den so markanten Einfluß der Applikationsart verantwortlich. Nach oraler, intraperitonealer und intravenöser Applikation von Acrylonitril wurde dieser bei Mäusen effektiver in Thiocyanat metabolisiert als bei Ratten. Die größere Umwandlung von Acrylonitril in Thiocyanat und die stärkere Senkung seiner akuten Toxicität nach Thiosulfat deuten auf eventuelle Unterschiede im Mechanismus der toxischen Wirkung von Acrylonitril bei Mäusen und Ratten hin. In der Toxicität des Acrylonitrils für Ratten spielt Cyanid anscheinend eine kleine Rolle, wohl aber für Mäuse.
    Notes: Abstract Female Wistar rats, conventional albino mice, and Chinese hamsters were given a single dose of acrylonitrile, 0.5 or 0.75 mM/kg body weight. The elimination in the urine of thiocyanate, which is the main metabolite of acrylonitrile, indicated a decreasing proportion of biotransformation after oral (over 20 %), intraperitoneal, or subcutaneous (2 to 5 %), and intravenous (1 %) administration in rats. Oral administration of acrylonitrile in hamsters and mice was also followed by higher biotransformation than intraperitoneal administration. Pretreatment of rats with phenobarbital, SKF 525 A, cysteine, or dimercaprol did not significantly influence elimination of thiocyanate in the urine after the administration of acrylonitrile, but simultaneous administration of thiosulfate significantly increased the metabolized portion of acrylonitrile given intraperitoneally in rats (almost twice) and mice (more than three times). Acrylonitrile was found to be strongly bound in blood. The study confirmed the marked effect of distribution (first-pass metabolic phenomenon) on the metabolic fate of foreign compounds. The strong acrylonitrile binding and cyanoethylation are apparently responsible for the unusually high influence of the different routes of administration on the metabolic fate of acrylonitrile. Acrylonitrile was more effectively metabolized to thiocyanate in mice than in rats after oral, intraperitoneal, and intravenous administration. A greater response of acrylonitrile to thiocyanate metabolism and a larger decrease in its acute toxicity after thiosulfate in mice than in rats indicate possible differences in the mechanism of acrylonitrile toxicity in these animals. Cyanide apparently plays a minor role in the acrylonitrile toxicity in rats, but may play quite an important one in mice.
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  • 25
    ISSN: 1432-1750
    Keywords: Lung fibrosis ; Rat ; Paraquat ; Lungenfibrose ; Ratte ; Paraquatlunge
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Es wird die Erzeugung einer Lungenfibrose bei Spraque-Dawley-Ratten mittels mehrfacher Injektion von Paraquat intraperitoneal beschrieben. Notwendige Dosierungen, Intervalle zwischen den Injektionen sowie der zeitliche Ablauf der histologischen Veränderungen werden dargelegt.
    Notes: Summary An experimental model of lung fibrosis by multiple i.p. injections of the herbicide Paraquat is described. The schedules, intervals between injections and histological changes are described.
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  • 26
    ISSN: 1432-2072
    Keywords: LSD-25 ; UML ; Acute ; Chronic ; Behaviour ; 5-HT ; Brain ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Successive daily injections of LSD-25 and UML (1-methyl-d-lysergic acid butanolamide) caused progressive depression of brain 5-HT levels in the rat. On the fourth day, the decrease was significant with respect to the highly significant fall observed after a single administration, whereas it had been shown earlier that conditioned behaviour is no longer affected by LSD-25 after 3 days and that simultaneous administration of a single dose of LSD-25 and UML is equally ineffective in this respect. Its depression of 5-HT levels, however, has now been shown to be equal to that of LSD-25 alone at doses that influence conditioned behaviour. The findings indicate that changes in such behaviour are not dependent on brain 5-HT levels and that no link exists between such levels and the psychotomimetic effect of LSD-25 in man.
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  • 27
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    Psychopharmacology 41 (1975), S. 301-304 
    ISSN: 1432-2072
    Keywords: Mescaline ; Anti-Drug Antibody ; Hapten ; Immunopharmacology ; Rabbit ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Antibodies with mescaline binding specificity were raised in rabbits by immunization with conjugates of bovine serum albumin with mescaline or its analogue 3,4,5-trimethoxyphenylacetic acid. Immunized rats were given mescaline and their behavior was compared to that of non-immunized controls.
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  • 28
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    Psychopharmacology 42 (1975), S. 147-152 
    ISSN: 1432-2072
    Keywords: Nicotine ; Selection ; Avoidance Conditioning ; Rat ; Latency ; Freezing
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Rats of both sexes from the genetically selected Roman High Avoidance (RHA), the Roman Low Avoidance (RLA) and the Roman Control (RCA) strains were given one 30-min session of two-way escape-avoidance conditioning (30 trials) in a shuttle box with a buzzer as the conditioned stimulus and shock as the unconditioned stimulus in a factorial design involving three time intervals (0,15 and 30 min) following one subcutaneous injection of saline or of nicotine in five doses (0.05, 0.1, 0.2, 0.4, or 0.8 mg/kg of body weight). Six measures relating to performance were analysed in whole or part. While the number of avoidance responses showed the expected strain differences, no effect of dose or delay interval could be detected. Avoidance and escape latencies and intertriai activity showed some effects of these variables, especially in interaction with sex and strain. Dose determined pre-sessional activity, but its effect was strain dependent. The failure to confirm previous findings is discussed in the context of other instances in the literature, and the results of an operant experiment confirming the continuing sensitivity of the Roman strains to the effects of nicotine are reported.
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  • 29
    ISSN: 1432-2072
    Keywords: p-CPA ; Ethanol ; Pentobarbital ; Tolerance ; Brain 5-HT ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Rats were rendered tolerant to ethanol or pentobarbital by daily oral administration. Motor impairments after test doses of ethanol or pentobarbital were measured prior to and at various times during chronic treatment in order to assess the degree of tolerance development. Chronic administration of p-chlorophenylalanine (p-CPA) in a dosage regimen which produced and maintained approximately 95% depletion of brain serotonin (5-HT) did not alter motor impairment after initial acute administration of ethanol or pentobarbital. However, the rate of tolerance development to the motor-impairing effects of both drugs was slowed down in p-CPA-treated rats. p-CPA did not appear to exert this effect by altering the disposition of ethanol or pentobarbital, since blood levels determined 20 min after administration of the test doses were similar in animals treated with p-CPA and in controls. These findings suggest that brain 5-HT may have a role in tolerance development to ethanol and pentobarbital.
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  • 30
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    Psychopharmacology 42 (1975), S. 231-234 
    ISSN: 1432-2072
    Keywords: Heroin ; Self-Stimulation ; Water Intake ; Food Intake ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Male rats maintained with continuous access to levers for intracranial self-stimulation (ICSS), water, and food were subjected to five consecutive daily injections of heroin (5 mg/kg). Rates of lever pressing for ICSS were increased in 8 rats, 2–6 hrs after administration of heroin. Rates of lever pressing for water and food were not significantly changed during this period. Naloxone (5 mg/kg) pretreatment attenuated by 82% the facilitative effect of heroin on ICSS. A second group of 8 rats maintained at reduced ICSS rates failed to show an increase in lever pressing for ICSS with heroin. The facilitative effect of heroin described in this study is consistent with previously reported studies describing the effects of morphine on ICSS.
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  • 31
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    Psychopharmacology 42 (1975), S. 255-261 
    ISSN: 1432-2072
    Keywords: Methadone ; Mode of Withdrawal ; Body Weight ; Relapse ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Physical dependence on methadone was induced in rats by an initial “forced drinking” procedure and subsequently by i.p. administration of the drug. In a subsequent Experimental Phase of the study the physical dependence of one group was sustained by a “methadone maintenance” treatment, while two other groups were withdrawn from the drug, one gradually and one abruptly. When relapse trials were carried out during a Readdiction Phase it was found that the maintained group voluntarily consumed significantly greater amounts of methadone than did the two withdrawal groups. These groups did not differ between themselves but did in turn ingest significantly more methadone than a control group with no prior exposure to the drug. The characteristic loss of body weight reliably found during withdrawal from morphine was not demonstrated. This may have been due to the unexpected weight loss which occurred during the last stage of the initial Addiction Phase. The dependent variables of amount of methadone solution and the percentage of fluid consumed as methadone solution correlated highly. However the amount of methadone solution ingested was a better indicator of addiction liability as it was not influenced by fluctuations in the amount of water consumed by the animals.
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  • 32
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    Naunyn-Schmiedeberg's archives of pharmacology 288 (1975), S. 109-121 
    ISSN: 1432-1912
    Keywords: Halothane and Nitrous Oxide Anaesthesia ; 5-HT Turn-Over ; Brain ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The effects of anaesthesia with halothane and nitrous oxide on the turn-over of 5-HT in the rat brain were analysed. The rate of 5-HT synthesis was estimated on the basis of 5-HTP accumulation following 5-HTP decarboxylase inhibition. Inhalation anaesthetics reduced the rate of 5-HT synthesis in the whole brain, this effect being particularly marked in the forebrain. In addition, the reduction of the rate of 5-HT synthesis was still detected after a large tryptophan loading indicating that halothane and nitrous oxide anaesthesia reduced the activity of tryptophan hydroxylase in vivo. The utilization of 5-HT was also delayed during anaesthesia since the rate of 5-HT disappearance following the inhibition of its synthesis at the decarboxylation step was decreased in the whole brain. In spite of this reduced turnover of 5-HT in the brain of rats exposed to inhalation anaesthetics, the 5-HIAA levels were permanently elevated. This was the result of a partial inhibition of the active elimination of the acidic metabolite from the brain during this kind of anaesthesia.
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  • 33
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    Naunyn-Schmiedeberg's archives of pharmacology 287 (1975), S. 1-10 
    ISSN: 1432-1912
    Keywords: Dopamine ; Adrenomedullary Hormones ; Synthesis ; Rat ; Adrenals ; Subcellular Distribution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Rats received intravenous injections of3H-tyrosine and were killed at various time intervals thereafter.3H-dopamine (DA) in the adrenals reached a maximum within 1.5 min after the administration of3H-tyrosine. From the 15th min it disappeared with an apparent half life of 90 min.3H-Adrenaline (A) +3H-noradrenaline(NA) increased much more slowly and reached a plateau 120–240 min after the injection. The approximate synthesis rate of adrenal A+NA, calculated from the specific activity curves, ranged from 9.3 to 2.2 nmoles/h per kg b.w. The highest value was noted the first few minutes, the lowest 1–2 hrs after the administration of3H-tyrosine. In some experiments subcellular fractionation of the adrenals was performed. In untreated animals the amount of DA and A+NA recovered from the supernatant fraction was about 10 and 8 per cent, respectively, of the total amount recovered from the supernatant and particulate fractions. In the adrenals of animals receiving3H-tyrosine 3.75 or 60 min beforehand these figures were significantly elevated whereas the DA and A+NA of the particulate fraction did not deviate significantly from control values. The specific activities of3H-DA were the same in the supernatant and particulate fractions within 3.75 min after the injection of3H-tyrosine.
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  • 34
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    Naunyn-Schmiedeberg's archives of pharmacology 288 (1975), S. 147-153 
    ISSN: 1432-1912
    Keywords: Adenylate Cyclase ; Phosphodiesterase ; cAMP ; Gastric Mucosa ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The effects of starvation, feeding and pentagastrin on gastric mucosal adenylate cyclase (AC) and phosphodiesterase (PDE) activity were studied in the rat. 1. Starvation for 24 hrs and 48 hrs reduced both NaF stimulated and basal AC activities. 2. Feeding of starved rats slowly raised the AC activity up to 430% within 4 hrs after feeding. This effect was more pronounced under basal conditions than with NaF stimulation. 3. A single i.p. injection of pentagastrin (125 μg/kg) caused a stimulation of basal AC lasting 45 min, which was followed by a subsequent decrease in the basal and NaF stimulated enzyme activity. 4. PDE activity was not influenced by starvation and feeding but underwent a transient inhibition by pentagastrin. Accordingly gastric mucosal cAMP levels after starvation, feeding and pentagastrin are regulated by changes in AC and not in PDE activity. The rise in AC activity after feeding appears to be related to functions other than H+ and pepsin secretion.
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  • 35
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    Naunyn-Schmiedeberg's archives of pharmacology 288 (1975), S. 185-193 
    ISSN: 1432-1912
    Keywords: Avoidance Acquisition ; Development ; Pimozide ; d-Amphetamine ; Catecholamines ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The acquisition of a conditioned avoidance response (CAR) was investigated in rats of nursing mothers given pimozide 0.5 mg/kg on days 1, 2, 3, 4, 5, 6, and 7 after delivery. Four weeks after birth, the male litter-mates were tested for CAR acquisition in a two-way avoidance situation or for correct CAR acquisition in a brightness discrimination situation. Offspring of mothers treated with pimozide were markedly inferior in the CAR acquisition in both behavioural situations as compared to those of mothers given glucose. The administration of d-amphetamine 15 min prior to the training session specifically counteracted the behavioural impairment obtained in the offspring of pimozide-treated mothers. The results obtained in the present investigation lend further support to the contention that the behavioural deficits in offspring of nursing mothers treated with neuroleptic agents are due to a developmental disturbance in central catecholamine neurones.
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  • 36
    ISSN: 1432-0878
    Keywords: Median eminence ; Rat ; Populations of axonal granules ; Electron microscopy, morphometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung In Fortsetzung einer früheren Arbeit wurde die Eminentia mediana von männlichen und weiblichen Ratten, sowie die trächtiger und durstender Tiere auf die Fragestellung hin untersucht, ob 1. die Eminentia mediana der erste Ort ist, wo die beiden Neurohormone Oxytocin und Vasopressin freigesetzt werden, und 2. ob sich die Axone in der externen Schicht der Eminentia mediana aufgrund der mittleren Durchmesser ihrer Granula in verschiedene Populationen differenzieren lassen. Bei männlichen und weiblichen Kontrolltieren haben die Oxytocin-bzw. Vasopressin-granula in der Eminentia mediana bereits ihre endgültige Größe erreicht; ihr mittlerer Durchmesser ändert sich nicht mehr wesentlich bis zum Hypophysenhinterlappen. Allerdings gibt der unterschiedliche prozentuale Anteil beider Populationen in der Eminentia mediana, in Zusammenhang mit den früher bestimmten Werten für die jeweiligen Kerne und die Neurohypophyse, Hinweise auf gewisse Unterschiede im turnover beider Hormone bei männlichen und weiblichen Tieren. Bei graviden und durstenden Ratten findet sich eine scheinbare Abnahme der Granula Durchmesser in den oxytocin-bzw. vasopressinführenden Axonen. In Verbindung mit sehr charakteristischen morphologischen Befunden, besonders bei langdurstenden Tieren, sprechen die morphometrischen Ergebnisse dafür, daß in der Eminentia mediana bereits Neurohormon freigesetzt wird, wenn eine schnelle Deckung des peripheren Bedarfes notwendig ist. Die Axone mit Granula, die kleiner sind als 115 nm, lassen sich in der internen Schicht der Eminentia mediana aufgrund der mittleren Durchmesser ihrer Granula in vier Populationen aufteilen. Ihre mittleren Granula-Durchmesser liegen bei etwa 84 nm, 96 nm, 103 nm und 110 nm. Dieselben vier Populationen finden sich sowohl in der Zona palisadica als auch in der perikapillären Schicht der Eminentia mediana. Im Unterschied zur Zona interna findet sich aber in diesen beiden Schichten noch eine fünfte Population von Axonen mit einem mittleren Granula-Durchmesser von etwa 70–75 nm. Der mengenmäßige Anteil dieser fünf Populationen aber ist unterschiedlich in der Zona palisadica und in der perikapillären Schicht einerseits und in den verschiedenen Tiergruppen andererseits. Einige morphologische Befunde an den Tanycyten werden im Zusammenhang mit der neueren Literatur diskutiert.
    Notes: Summary In connection with previous studies (Krisch, 1974), a morphologic analysis of the median eminence of male, female, pregnant, and thirsting rats has been made, in order to evaluate: 1. whether the median eminence is an additional area where oxytocin and vasopressin may be released from neurosecretory axons in the zona interna; 2. whether it is possible to distinguish different populations of axons according to the mean diameters of their granules in the external zone of the median eminence. In the zona interna of the male and the female control animals, the oxytocin-and vasopressin-containing granules have already reached their final diameters, i.e. their size remains constant until they reach and are stored in the neurohypophysis. However, the relative proportions of these populations in the fibre layer of the median eminence indicate certain differences between male and female animals, concerning the turnover of oxytocin and vasopressin. In pregnant, as well as in thirsting animals, there is an apparent decrease of the mean granule diameters in oxytocin and vasopressin-containing axons. In particular in the latter group, ballooned axons in the fibre layer of the median eminence, containing disintegrating granules, tubular structures filled with electron dense material, and fine-flocculent material in the axoplasm, together with the morphometric results, support our concept that in case of highly increased peripheral demand the contents of the mature, large granules are released into the axoplasm of the fibre layer in the median eminence. In addition, axons containing granules smaller than 115 nm may be classified into four populations with mean diameters of 84 nm, 96 nm, 103 nm, and 110 nm. The same populations are found in the palisade zone of the median eminence as well as in the pericapillary zone, but in contrast to the zona interna there is a fifth population of axons containing very small granules with a mean diameter of about 70–75 nm. The relative proportions of these five populations differ between the zona palisadica and the pericapillary zone on the one hand and between the experimental groups on the other hand. Some morphological findings concerning the tanycytes are discussed with respect to previously published data.
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  • 37
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    Cell & tissue research 164 (1975), S. 447-456 
    ISSN: 1432-0878
    Keywords: Protein secretion ; Protein synthesis ; Salivary glands ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The effect of pilocarpine and food uptake on the rate of incorporation of [3H]-leucine in vivo was measured by means of quantitative radioautography in three exocrine cells of the rat: the acinar and the granular duct cells of the submandibular and the acinar cells of the parotid gland. The three cell types react differently. The submandibular acinar cells showed a decrease in incorporation rate after pilocarpine administration but not after feeding. The incorporation rate of the granular duct cells of the submandibular gland remains constant after both stimulations. The acinar cells of the parotid gland show an increase in incorporation rate of [3H]-leucine in response to both. The contrast between the submandibular and the parotid gland could also be demonstrated radiobiochemically, the results reflecting the incorporation rates of the acinar cells of both glands, giving no information on the contribution of other cell types. The decrease in incorporation rate of the submandibular gland acinar cells is accompanied by a shift of polyribosomes towards monomers.
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  • 38
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    Cell & tissue research 164 (1975), S. 457-466 
    ISSN: 1432-0878
    Keywords: Protein secretion ; Protein synthesis ; Salivary glands ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary After stimulation of the protein secretion by pilocarpine or feeding the rate of incorporation of [3H]-leucine increases in the acinar cells of the parotid gland of the rat while the secretory cells of the submandibular gland show a moderate decrease (Kuijper et al., 1975b). Since the rate of labelled amino acid incorporation depends on the specific radioactivity of the amino acid used, which is not easy to determine in vivo, experiments in vitro were performed to get an idea of the influence of this factor on the measured changes in [3H]-leucine incorporation. In vitro both cell types showed a more pronounced but essentially identical reaction as in vivo. Since in these experiments the specific radioactivity of the extracellular leucine is the same whether fragments of stimulated or unstimulated glands incorporate the radioactive amino acid, the increase of incorporation in the parotid and the decrease in the submandibular cells cannot be ascribed to differences in specific radioactivity of leucine, unless the intracellular leucine pool should show great differences between secreting and non-secreting cells. However, in vitro the submandibular gland cells under both conditions appear to use the extracellular leucine for their protein synthesis (or a small compartmentalized pool in rapid exchange with the extracellular pool). In the parotid cells the whole intracellular pool showed such a rapid exchange with the extracellular one that for practical reasons one may say that these cells, too, rely on the extracellular specific radioactivity of leucine in their protein synthesis. We conclude that the rat parotid gland cells show a rapid and substantial increase of protein synthesis after stimulation of their enzyme secretion, while the submandibular gland cells do not.
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  • 39
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    Cell & tissue research 164 (1975), S. 435-446 
    ISSN: 1432-0878
    Keywords: Protein secretion ; Protein synthesis ; Salivary glands ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary In untreated, fasting animals the cells of the serous demilunes of the sublingual gland incorporate [3H]-leucine at a higher rate than any other of the 5 main cell types of the 3 major salivary glands. The acinar cells of the submandibular and the mucous cells of the sublingual gland show intermediate values, while the cells of the granular ducts of the submandibular and the acini of the parotid gland have a low rate of incorporation. In fasting animals extrusion of newly synthesized protein starts early in the cells of the serous demilunes. It starts between 4 and 7 hrs after [3H]-leucine injection in the acinar cells of the submandibular gland, while the other cell types did not lose substantial amounts of labelled (glyco)protein within 7 hrs. The secretion of protein is stimulated by the cholinergic drug pilocarpine in all but one of the 5 types of salivary gland cells studied. The acinar cells of the submandibular gland react strongly, the granular duct cells less strongly. Still less are the reactions of the acinar cells of the parotid and of the mucous cells of the sublingual gland. The cells of the serous demilunes of the latter appear to be insensible to pilocarpine. The effect of food uptake on secretion does not differ from pilocarpine stimulation, with one exception: the acinar cells of the parotid gland react more strongly on food uptake than on cholinergic stimulation.
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  • 40
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    Cell & tissue research 163 (1975), S. 249-262 
    ISSN: 1432-0878
    Keywords: Superior cervical ganglion ; Rat ; Catecholamines ; p-Chlorophenylalanine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Ganglion cells and paraganglionic (PG) cells in the developing rat superior cervical ganglion were studied following postnatal treatment with p-chlorophenylalanine (pCPA) for 5 to 8 days. Litter mates, injected with saline solution, served as controls. Ganglion cells of control animals were differentiated ultrastructurally according to L. Eränkö (1972 a) into late sympathicoblasts and young sympathetic nerve cells. In both maturation stages treatment with pCPA caused marked swelling of mitochondria, concomitant with minor changes of other cell organelles. Parallel to the ultrastructural alterations, fluorescence microscopy and cytophotometry revealed a slight diminution of diffuse fluorescence intensity in sympathetic neurons as the expression of a mainly extragranular amine depletion. In distinction from ganglion blocking agents the alterations are regarded as a general toxic effect of pCPA upon maturing sympathetic neurons, which secondarily influences catecholamine storage sites. Following treatment with pCPA, in PG-cells an alteration of mitochondria was scarcely to recognize. Specific granules were distinctly decreased in number, in some cases to an almost complete degree. Concordant to ultrastructural observations a marked diminution of fluorescence intensity was demonstrable in SIF-cells. In addition in these elements the fluorescence spectrum shifted towards the green field. Fluorescence cytophotometric evaluations confirmed the optical impression. Provided, that PG-cells, demonstrated with electron microscopy, are identical with SIF-cells in fluorescence microscopy, the results are discussed on the basis of a specific decrease of primary catecholamines due to an enzyme inhibition involved in catecholamine synthesis.
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  • 41
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    Cell & tissue research 161 (1975), S. 183-191 
    ISSN: 1432-0878
    Keywords: Hypothalamus ; Pituitary ; Rat ; Localization of 3H-dexamethasone ; Radioautography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The central nervous system and the pituitary of adrenalectomized male rats injected with 3H-dexamethasone were examined by radioautography. At 1 hr after the injection, radioactivity concentration was high in the medial basal hypothalamus, the pituitary and the pineal gland. In the hypothalamus, radioactive material was found to be selectively concentrated in neurons in the ventral part of nucleus arcuatus and in the infundibular region. In the anterior pituitary, a large proportion of cells showed silver grains both in the cytoplasm and over the cell nuclei. However, in a small number of cells, the radioactive material was associated with the cell nuclei. Less radioactivity was present in the intermediate and posterior lobes. The pineal gland contained more silver grains than did other regions of the brain. The results obtained in the present study suggest essentially an action of dexamethasone in the medial basal hypothalamus and at the level of the pituitary.
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  • 42
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    Cell & tissue research 158 (1975), S. 281-283 
    ISSN: 1432-0878
    Keywords: Glycocalyx ; Urinary bladder ; Ruthenium red ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Earlier statements to the contrary, the present study demonstrates the presence of a cell surface coat (glycocalyx) on the luminal plasma membrane of the super ficial transitional epithelial cells lining the urinary bladder of male Buffalo rats. This coat was demonstrated with ruthenium red, an electron dense stain, which revealed a surface layer, 60–80 Å thick, separated from the outer leaflet of the plasma membrane by an electron lucent layer, approximately 30 Å thick. The structure of the glycocalyx was not affected by 12 weeks of treatment with dibutylnitrosamine, a known bladder carcinogen.
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  • 43
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    Cell & tissue research 159 (1975), S. 49-62 
    ISSN: 1432-0878
    Keywords: Autonomic ganglia ; Pelvic plexus ; SIF cells ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary To further evaluate the role of autonomic ganglia in the regulation of pelvic visceral activity, the neural elements in the major pelvic ganglion of the male rat have been studied with histochemical and electron microscopic techniques. The principal findings are that the ganglion is composed of cholinergic and adrenergic ganglion cells as well as small intensely fluorescent (SIF) cells. Polarity in the ganglion is indicated by clustering of small ganglion cells which stain intensely for acetylcholinesterase (AChE) along the pelvic nerve while larger cells, with weak to moderate AChE activity, collect near small branches of the hypogastric nerve. Some cholinergic ganglion cells are enclosed by a plexus of adrenergic terminals. SIF cells appear to be in contact with both cholinergic and adrenergic cells, although many of the fluorescent beads around adrenergic neurons may be short dendrites of ganglion cells, rather than processes of SIF cells. Two types of SIF cells may be distinguished on the basis of size and morphology of their granulated vesicles. Afferent synapses of the cholinergic type were common on SIF cells of the large granule and small granule type. Portions of SIF cells with large granules occur within the capsule of ganglion cells. Contacts seen here were interpreted as efferent synapses from SIF cells to the dendrites of ganglion cells.
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  • 44
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    Cell & tissue research 156 (1975), S. 377-380 
    ISSN: 1432-0878
    Keywords: Vasopressin-neurophysin neurons ; Suprachiasmatic nuclei ; Immunoenzyme histochemistry ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Immuno-enzyme histochemical investigations on the hypothalamus of the normal rat showed (1) that the Suprachiasmatic nuclei produce vasopressin; (2) that it is highly probable that these nuclei do not produce oxytocin. From the present and previous investigations it may be concluded that the Suprachiasmatic neurons produce a vasopressin-neurophysin complex.
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  • 45
    ISSN: 1432-0878
    Keywords: Adenohypophysis ; Rat ; L-dopa ; Fluorescence histochemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The uptake of L-dopa into the cells of the adenohypophysis of the rat was studied during the postnatal development and at adult age using the formaldehyde-induced fluorescence method (FIF). The cells taking up L-dopa were classified by Alcian blue-PAS-Orange G staining. The correlation between the cells taking up L-dopa and those containing tryptophyl-peptide was estimated during the postnatal period and in adult rats. The cells containing tryptophyl-peptide were demonstrated using fluorescence induced by treatment with combined formaldehyde and acetyl chloride vapour. The following observations were made: 1) Great majority of the cells taking up L-dopa did not contain tryptophyl-peptide. Thus the accumulation of L-dopa into the cells of pars distalis is not due to accumulation of L-dopa into the cells by the same transport mechanism as the amino acids for tryptophyl-peptide. 2) Of the cells taking up L-dopa in the adult rats 96% were chromophobes, 2.0% acidophilic cells (somatotrophs and cells producing prolactin), 0.9% R-mucoid cells (corticotrophs), and 1.2% S1- and S2-mucoid cells (gonadotrophs and thyrotrophs). At 10 and 25 days' age the relative numbers of the cells taking up L-dopa were about the same. 3) Pretreatment with nialamide caused only a slight increase in the number of the cells taking up L-dopa. The decrease in the number of the cells uptaking L-dopa of the pars distalis, which takes place after 5 weeks' age is thus not caused by the increased MAO-activity. 4) Strongly chromophilic cells did not take up L-dopa. At the light of our results it seems evident that L-dopa is taken up by the chromophobic cells when these differentiate into chromophilic cells. The accumulation of L-dopa may be a sign of an active transport of amino acids into the cells. The accumulation of L-dopa into the chromophobic stellate and follicular cells may reflect their metabolic activity. These cells probably have an important role in the production of the hormones of the pars distalis.
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  • 46
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    International Journal of Chemical Kinetics 7 (1975), S. 1-13 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The temperature dependence of the vibration-vibration energy transfer between the v3 mode of N2O and the first vibrational level of CO was determined over a range of 780 to 1400°K using a shock tube. Several mixtures of CO-N2O were tested, diluted in 95% Ar. The Landau-Teller plot of the vibration-vibration relaxation times has a least squares line of \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{{\rm 10}} p\tau _{{\rm VV}} = 2.69T^{ - 1/3} - 1.70 $$\end{document} where pτvv is in atm ·μsec and T in °K. The measured kinetic reaction was determined to be \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm N}_{\rm 2} {\rm O(001) + CO(O)} \to {\rm N}_{\rm 2} {\rm O}(000) + {\rm CO(1) + 81cm}^{{\rm - 1}} $$\end{document} The transfer probabilities for this process were found to vary directly with temperature.
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  • 47
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The activation energy parameters for the reaction of PdX42- (X=Cl-, Br-) in aqueous halide acid solution with thiourea (tu) and selenourea (seu) have been determined. High rates of reaction parallel low enthalpies and appreciable negative entropy of activation. The rate law in each case simplifies to kobs=k[L] where L=tu or seu, and only ligand-dependent rate constants are observed at 25°C. The ligand-dependent rate constants for the first identifiable step in the PdCl42- + X system is (9.1±0.1) × 103 M-1 sec-1 and (4.5±0.1) × 104 M-1 sec-1 for X=tu and seu, respectively, while for the PdBr42- + X system it is (2.0±0.1) × 104 M-1 sec-1 and (9.0±0.1) × 104 M-1 sec-1 for X=tu and seu, respectively.
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  • 48
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    International Journal of Chemical Kinetics 7 (1975), S. 125-142 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A detailed shock-tube investigation of the ignition in H2 + Cl2 + Ar mixtures in a shock tube is presented, and the mechanism of the reaction is discussed. Ignition delay times were determined from pressure and heat flux measurements behind reflected shock waves. The induction times measured ranged between 35 and 2100 μsec over the temperature range of 830-1260°K. The experimental results of close to seventy tests can be correlated by the relationship \documentclass{article}\pagestyle{empty}\begin{document}$$ t_{{\rm ig}} = 10^{ - 12.73} \exp (18.75 \times 10^3 /RT) \cdot [{\rm Cl}_{\rm 2}]^{ - 0.66} [{\rm H}_{\rm 2}]^{ - 0.60} [{\rm Ar]}^{{\rm 0}{\rm .40 }} \,\sec. $$\end{document} where the concentrations are expressed in mole/cm3. The above relationship served as a basis for a computer modeling of the ignition delay times. Ten calculations, simulating typical laboratory experiments, were run by the computer for each reaction scheme and the obtained temperature and composition dependence of the induction times were compared with the ones observed experimentally. A reaction scheme based on a simple exothermal chain propagation could not reproduce the experimental relationship. When the energy branching reaction HCl*(ν) + Cl2 → (HCl3) → HCl + Cl + Cl was added to the reaction scheme, a much better agreement with the experiment was obtained. It is believed that the above reaction does take place and that it is the main supplier of atoms to the system.
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  • 49
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    International Journal of Chemical Kinetics 7 (1975), S. 205-214 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Spectrophotometric methods have been used to obtain rate laws and rate parameters for the following reactions: with ka, kb, Ea, Eb having the values 85±5 l./mole · s, 5.7±0.2 s-1 (both at 298.2°K), and 56±4 and 66±2 kJ/mole, respectively. with kc=0.106±0.004 l./mole ·s at 298.2°K and Ec=67±2 kJ/mole. with kd=(3.06 ±; 0.15) × 10-3 l./mole ·s at 298.2°K and Ed=66±2 kJ/mole.Mechanisms for these reactions are discussed and compared with previous work.
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  • 50
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    International Journal of Chemical Kinetics 7 (1975), S. 249-272 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of decarbonylation of [Ir(CO)(dp)2]Cl and [IrCl(CO)2(Ph3P)2] has been studied in different solvents, at temperatures between -25° and +70°C, by means of reactors of defined fluid dynamics which allow a separation to be made between “physical” and “chemical” rate constants. Chemical rate constants have been found to depend markedly on the diffusion coefficients of carbon monoxide in the various solvents. The process of decarbonylation has been described, for both reactions, by the sequence: structural isomerization, characterized by a very low preexponential factor, decomposition of the less stable isomer against the solvent's barrier, and diffusion of carbon monoxide to the gas-liquid interface. The kinetic problems involved in the determination of rate constants and their implications have been emphasized.
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  • 51
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    International Journal of Chemical Kinetics 7 (1975), S. 287-300 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The overall photobromination reactions \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm Br}_{\rm 2} + {\rm R}_{\rm F} {\rm I} \to {\rm IBr} + {\rm R}_{\rm F} {\rm Br} $$\end{document} have been studied using a competitive technique. Relative Arrhenius parameters were obtained for the rate-determining step These were placed on an absolute basis using previous-absolute values of A and E for RFI=CF3I. The activation energies were used to calculate bond dissociation energies D(R—I) with the following results: TextRF-E16D(RF-I)(kcal/mole)CF3I10.852.6C2F5I8.850.6n-C3F7I7.449.2i-C3F7I7.549.2n-C4F9I6.748.4E16 from [1]The D(RF-I) are compared with related D(R—I) and it is concluded that for a given alkyl group RH and the corresponding perfuloroalkyl group RF, D(RH-I) 〉 D(RF-I) whereas it has previously been found that D(RH-X;) 〈 D(RF-X) where X is not iodine.
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  • 52
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    International Journal of Chemical Kinetics 7 (1975), S. 341-349 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rates of reaction of t-BuOOK, t-BuOK, n-BuOOK, and p-MeC6H4OKwith p-nitrophenyl diphenylphosphinate 1 and with p-nitrophenyl benzoate 2 have been measured in toluene both in the absence and in the presence of crown polyether dicyclohexyl-18-crown-6 3a. The rates of nucleophilic displacementon 1 by HOO-, t-BuOO-, and some “nonalpha” oxyanions in water have also been determined. Solvent transfer from water to toluene results in increasing the nucleophilic reactivity of the t-butyl hydroperoxide anion. Rate ratios QQa are given which allow one to estimate the enhanced reactivity of t-BuOO- (an α-nucleophile) compared to oxygen nucleophiles of comparable base strength toward 1 and 2. These are for substrate 1, Qα (water) ≃ 6.5 and Qα (toluene) ≃ 2.7; for substrate 2, Qα (water) ≃ 5.5 and Qα (toluene) ≃ 5. The hypothesis is advanced that solvation is not a major factor in determining the α-effect of the t-butylhydroperoxide anion.
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  • 53
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    International Journal of Chemical Kinetics 7 (1975), S. 633-636 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 54
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    International Journal of Chemical Kinetics 7 (1975) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 55
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    International Journal of Chemical Kinetics 7 (1975), S. 463-471 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A consecutive single-route reaction is considered. When two (groups of) steps compete in controlling the overall reaction rate, there exists a general rule that the earlier step in the flow of the overall reaction tends to be rate-determining with the increase of the reaction affinity. The latter may, however, be distributed more or less evenly to both steps.
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  • 56
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    International Journal of Chemical Kinetics 7 (1975), S. 479-507 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanisms of the pyrolyses of the n-alkanes C3H8, n-C4H10, and n-C5H12 at temperatures between 390 and 560°C have been studied by the construction and evaluation of sets of several hundred reactions. Rate parameter values were assigned using literature data and calculated estimates. Time-dependent numerical solutions were computed for the experimental conditions of several rate and product studies reported in the literature. The comparisons of these a priori computations with experiment show excellent agreement for propane and agreement for butane and pentane within the estimated error limits of the assigned rate parameters. These results demonstrate that the general “state of knowledge” of the mechanism of alkane pyrolysis, namely, the reactions and their rate parameters, is such that reasonable a priori predictions of experimental results can be made. Discussions of the major stepwise processes in the pyrolyses are presented, and the importance of allyl radicals in termination is demonstrated.
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  • 57
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    International Journal of Chemical Kinetics 7 (1975), S. 547-555 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition rate of chemically activated ethyltrimethylgermane from the reaction 1CH2 + (CH3)4Ge, where 1CH2 was produced from diazomethane photolysis at 3660 Å, is 8.6 × 105 sec-1. This result combined with RRKM theory and critical energy estimates yields an Arrhenius A factor of log[A (sec-1)/methyl] = 14.7 ± 0.8 for methyl rupture from germanium.Log A values for methyl rupture from carbon, silicon, and germanium linearly correlate with the vibrational-rotational entropies of the corresponding tetramethyls. Extrapolation predicts log[A (sec-1)/methyl] = 14.4 and 14.3 for methyl rupture from tin and lead, respectively.
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  • 58
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    International Journal of Chemical Kinetics 7 (1975), S. 625-631 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The addition of methoxy radicals to several olefins has been studied by a competitive method at 127°C in gas phase. The thermal decomposition of dimethyl peroxide was used as methoxy radical source. The rate of addition to the double bond was measured relative to the oxidation of carbon monoxide. For the addition to ethylene it was obtained that \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{{\rm add}} = \left({3.7 \pm 0.8} \right) \times 10^4 M^{ - 1} \cdot {\rm s}^{{\rm - 1}} $$\end{document} This rate constant is similar to the one shown by methyl radicals under similar conditions. From the relative rate of addition to several chlorinated and fluorinated olefins it can be concluded that methoxy radicals show very little “electrophilic” character.
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  • 59
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    International Journal of Chemical Kinetics 7 (1975) 
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 60
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    International Journal of Chemical Kinetics 7 (1975), S. 33-37 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The present study reports the measurement of the V-V energy transfer rates for the CO*—COS system in the temperature range of 195 to 370°K. The measured rates exhibit a slight inverse temperature dependence. The experimental results are compared to prediction based on a model of long-range dipole-dipole interactions between colliding molecules. The effect of single quantum rotational transitions is compared to that of multiquantum rotational transitions.
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  • 61
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    International Journal of Chemical Kinetics 7 (1975), S. 77-86 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Electronically excited tin atoms Sn(51D2), 1.068 eV above the 53P0 ground state, have been generated by the pulsed irradiation of tin tetramethyl and monitored photoelectrically in absorption by time-resolved attenuation of atomic resonance radiation at λ=285.06 nm [Sn((5d3F20) ← (5p2 1D2))]. Deactivation rate constants are reported for the quenching of Sn(51D2) with a range of collision partners and the resulting data are compared with those for analogous states within group IV, namely, C(21D2) and Pb(61D2). The data are discussed in terms of correlations based on both the weak and strong spin orbit coupling approximations.
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  • 62
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    International Journal of Chemical Kinetics 7 (1975), S. 661-677 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidation of acetylene by water vapor was studied behind the reflected shock in a single-pulse shock tube. Computer simulation experiments reproduced the experimental results in the temperature range of 1500 to 2000°K. The kinetic scheme suggested here involves three major processes, (1) production of hydrogen atoms by the sequence of reactions which lead from acetylene to carbon; (2) production of OH radicals, mainly by the reaction H + H2O → H2 + OH, and (3) fast oxidation of the acetylene and other C/H species by the available oxidants in the system. The experimental results of methane oxidation suggest that methane is converted to acetylene prior to its oxidation. The implication of the experimental results to processes occurring in planetary atmospheres as a result of thunder shock waves is briefly discussed.
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  • 63
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    International Journal of Chemical Kinetics 7 (1975), S. 443-451 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The equilibrium quotients for the formation of Co(NH3)5Cl2+ from Co(NH3)5OH23+ and Cl- were 3.74±0.25 M-1 and 6.07±0.54 M-1 at 45.0°C in 10:1 mole ratio water: dimethyl sulfoxide and in 25 w/w % aqueous ethanol, respectively, and those forthe formation of the ion pair Co(NH3)5OH23+ . Cl- were 1.21±0.20 M-1 and 1.58±0.17 M-1, respectively, in the same solvents. The aquation and anation rateconstants were determined at 45.0°C for these two solvents over the range of chloride-ion concentrations 0.0 ≤ [Cl-] ≤ 0.9 M. The aquation rate constant was essentially independent of chloride-ion concentration in each solvent over this range. The inverse of the pseudo-first-order anation rate constant was linearly dependent on the inverse of the chloride-ion concentration in each solvent. The least squares relationships between (1/kan) and (1/[Cl-]) gave intercepts and ratios of intercept to slope which were analyzed interms of Id and D mechanisms. It was concluded that the data were not satisfied by a D mechanism, but that they were consistent with an Id mechanism.
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  • 64
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    International Journal of Chemical Kinetics 7 (1975), S. 535-546 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction between a hydroquinone aqueous solution and manganese dioxide has been investigated by electron paramagnetic resonance spectroscopy. A very stable p-benzosemiquinone anion is formed when an aqueous solution of hydroquinone is passed through a column of manganese dioxide. The kinetics for the reaction between hydroquinone and manganese dioxide follow the equation \documentclass{article}\pagestyle{empty}\begin{document}$$ \frac{{dC}}{{d\left({W/F} \right)}} = k_1 ^0 \left({A_0 - C} \right) - k_2 ^0 C $$\end{document} where A0 is the initial concentration of hydroquinone, C is the concentration of p-benzosemiquinone anions, W is the amount of manganese dioxide, F is the feed rate of a hydroquinone aqueous solution, and k10 and k20 are constants; k10 = 3.1 × 10-2 (cm3/g MnO2· min), k20 = 3.2 (cm3/g MnO2·min).A mechanism for the reaction is proposed such that Mn(IV) in manganese dioxide is reduced to Mn(II) with hydroquinone from which the semiquinone anion is formed via a neutral semiquinone. The formation of semiquinone anions from several substituted hydroquinones is also discussed.
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  • 65
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    International Journal of Chemical Kinetics 7 (1975), S. 575-587 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Solvent-solute interactions in the peroxyacid oxidations are believed to be specific rather than electrostatic in nature. The kinetic solvent effects reported for the oxidations of organic sulfides, olefins, acetylenes, nitrosobenzenes, thioketones, and aryl sulfines reveal that in each case the rates are fast in nonbasic solvents (e.g., benzene, nitrobenzene, and halogenated hydrocarbons) relative to those in basic solvents such as DMF, dioxane, and alcohols. The rates in CF3CH2OH and aqueous or partially aqueous media are again higher than those in the basic solvents. This remakably similar pattern of sensitivity of rates to changes in the solvent nature appears to be characteristic of these oxidations as demonstrated by the existence of linear free-energy relationship. The behavior is best understood in terms of cyclic transition states for these oxidations in which charge separation is avoided by intra- or intermolecular hydrogen bonding depending on the nature of the solvent. Solvent effects on sulfoxide oxidation and on oxidations by hydrogen peroxide and t-butylhydroperoxide are also briefly discussed.
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  • 66
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    International Journal of Chemical Kinetics 7 (1975), S. 637-638 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 67
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    International Journal of Chemical Kinetics 7 (1975), S. 679-688 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of tetrafluorohydrazine has been studied from 578 to 791°K. The stoichiometry has been established as \documentclass{article}\pagestyle{empty}\begin{document}$$ 6{\rm NF}_{\rm 2} \to 4{\rm NF}_{\rm 3} + {\rm N}_{\rm 2} $$\end{document} Reaction rates have been measured and the effects of surface area, inert gas pressure, and nitric oxide have been examined. The rate-determining step proposed is \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm 2NF}_{\rm 2} \to {\rm NF}_{\rm 3} + {\rm NF} $$\end{document} and the general rate expression obtained for this is \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 = 10^{9.0 \pm 0.4} \exp {{ - 36,950 \pm 500} \mathord{\left/ {\vphantom {{ - 36,950 \pm 500} {RTM^{ - 1} \cdot \sec ^{ - 1} }}} \right. \kern-\nulldelimiterspace} {RTM^{ - 1} \cdot \sec ^{ - 1} }} $$\end{document}
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  • 68
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The high-pressure absolute rate constants for the decomposition of nitrosobenzene and pentafluoronitrosobenzene were determined using the very-low-pressure pyrolysis (VLPP) technique.Bond dissociation energies of DH0(C6H5—NO) = 51.5 ± 1 kcal/mole and DH0 (C6F5—NO) = 50.5 ± 1 kcal/mole could be deduced if the radical combination rate constant is set at log kr(M-1·sec-1) = 10.0 ± 0.5 for both systems and the activation energy for combination is taken as 0 kcal/mole at 298°K. δHf0(C6H5NO), δHf0(C6F5NO), and δHf0(C6F5) could be estimated from our kinetic data and group additivity. The values are 48.1 ± 1, -160 ± 2, and - 130.9 ± 2 kcal/mole, respectively. C-X bond dissociation energies of several perfluorinated phenyl compounds, DH0(C6F5-X), were obtained from the reported values of δHf0(C6F5X) and our estimated δHf0(C6F5) [X = H, CH3, NO, Cl, F, CF3, I, and OH].
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  • 69
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    International Journal of Chemical Kinetics 7 (1975), S. 785-795 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of chlorine atom abstraction from trichloromethyl groups of the haloethanes (XCCl3), CF3CCl3, CH3CCl3, C2Cl6, C2Cl5H, and CH2ClCCl3, by radiolytically generated cyclohexyl radicals was studied in the liquid phase by a competitive method. The chlorine atom abstraction data were put on an absolute basis by comparing the rates of the metathetical reactions with the known rate of addition of cyclohexyl radicals to C2Cl4.The following Arrhenius parameters were obtained: The error limits are the standard deviations from least mean square Arrhenius plots. It is shown that the neighboring group effect on the rate of chlorine atom abstraction from the trichloromethyl groups can be correlated with Taft polar substituent constants.
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  • 70
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    International Journal of Chemical Kinetics 7 (1975) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 71
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The homogeneous exchange reaction between tetradeutero methane and ammonia was studied behind reflected shocks in a single-pulse shock tube over the temperature range of 1300-1800°K. The rate of production of CD3H at the early stages of the reaction in mixtures ranging between 1-4.5% NH3 and 1-4.3% CD4 in argon is given by d[CD3H]/dt=kb [CD4]0[NH3]0, where kb=8 × 1016 exp (-65.3 × 103/RT) cm3/mole·sec. This activation energy is considerably lower than the one that may be expected on the basis of a pure free radical mechanism. It is rationalized by C2D6 impurities in the methane. No clear answer can be obtained regarding the role of a four-center intermediate in this reaction.
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  • 72
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    International Journal of Chemical Kinetics 7 (1975), S. 879-894 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The specific decomposition rates of chemically activated methylcyclobutane produced from CH2(1A1) reaction with cyclobutane have been determined. CH2(1A1)was produced from ketene photolyses at 3340 and 3130 Å and from diazomethane photolyses at 4358 and 3660 Å. Comparisons of the excitation energies of the methylcyclobutane, determined by RRKM theory calculations, and the experimental results for the ketene systems, with thermochemically predicted maximum excitation energies, favor an Arrhenius A factor in the range of 5 × 1015 to 1 × 1016 sec-1 for methylcyclobutane. This result is consistent with (1) the comparison of RRKM theory calculations and the experimental unimolecular falloff for methylcyclobutane, (2) the comparison of experimental A factors for cyclobutane and other alkylcyclobutane decompositions, and (3) two out of three reported experimental A factors for methylcyclobutane. An analysis of these and previous results leads to a value of the CH2(1A1) ↔ CH2(3B1) energy splitting of 9±3 kcal/mole.
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  • 73
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    International Journal of Chemical Kinetics 7 (1975), S. 973-979 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decompositions of ethyl chloride, iso propyl chloride, and tertiary butyl chloride were studied in a static system in the pressure range of 0.1-300 torr. The following Arrhenius equations for the high-pressure limit were obtained: The pressure dependence of the first-order rate constant (falloff) for these three unimolecular dehydrochlorination reactions, starting with approximately equal kω values, by proper choice of temperature, is shifted to lower pressures with increasing molecular size:
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  • 74
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    International Journal of Chemical Kinetics 7 (1975), S. 23-31 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The high-temperature oxidation of formaldehyde in the presence of carbon monoxide was investigated to determine the rate constant of the reaction HO2 + CO = CO2 + OH (10). In the temperature range of 878-952°K from the initial parts of the kinetic curves of the HO2 radicals and CO2 accumulation at small extents of the reaction, when the quantity of the reacted formaldehyde does not exceed 10%, it was determined that the rate constant k10 is \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{10} = (1.7 \pm 0.5) \times 10^{ - 10} \exp [ - (23,000 \pm 3000/RT)]\,{\rm cm}^{\rm 3} /{\rm molec}{\rm.sec} $$\end{document} A computer program was used to solve the system of differential equations which correspond to the high-temperature oxidation of formaldehyde in the presence of carbon monoxide. The computation confirmed the experimental results. Also discussed are existing experimental data related to the reaction of HO2 with CO.
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  • 75
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Modified nuclear recoil techniques have been used to obtain accurate relative bimolecular rate coefficients for thermally induced hydrogen abstraction reactions by atomic fluorine. New results are reported for 12 hydrocarbons and partially fluorinated hydrocarbons studied at 303°K.
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  • 76
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    International Journal of Chemical Kinetics 7 (1975), S. 45-62 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of the electronically excited sulfur-dioxide sensitized isomerization of cis-2-butene has been studied through the measurement of the initial quantum yields of trans-2-butene formation in 3130-A irradiated gaseous binary mixtures of SO2 and cis-2-butene and ternary mixtures of SO2, cis-2-butene, and CO2. The kinetic treatment of the present data from the SO2—C4H8 mixtures and those of recent similar studies of Penzhorn and Güsten [3] and Cox [4] are all consistent with the involvement of only the long-lived fluorescent 1B1 and phosphorescent 3B1 states of SO2 in the isomerization mechanism. The data give (k2a + k2b)=0.21±0.04; SO2(1B1) + SO2 → SO2(3B1) + SO2(2a); SO2(1B1) + SO2 → (2SO2) (2b). The analogous intersystem crossing ratio for the SO2(1B1)-cis-2-butene quenching collisions is the largest observed among the many quencher molecules studied; the value lies in the range of 0.85 to 0.37, with the extremes representing different choices of alternative data and possible mechanisms. From the present data the ratio of the SO2(3B1) quenching rate constant with SO2 to that with cis-2-butene as quencher is estimated to be (2.7±1.2) × 10-3, in good agreement with our directly measured ratio from lifetime studies (2.91±0.23) × 10-3 [30-32], and the value found in isomerization studies by Cox (2.40±0.09) × 10-3 [4]. The simple two-excited state mechanism, which is seemingly applicable to the relatively low-pressure binary SO2-butene mixture results, is not adequate to explain the data obtained in experiments with large quantities of added CO2 gas. Here an “excess” quantum yield of isomerization is observed. Several alternative mechanisms can be used to rationalize these results, but all alternatives must incorporate some other excited SO2 species (X) as well as SO2(3B1) and SO2(1B1). The kinetics suggest that the ill-defined state is unreactive toward the olefin and decays nonradiatively to SO2 largely in experiments at the lower pressures, X → SO2 (11); it may generate SO2(3B1) in a collisionally induced process at high added inert gas (CO2) pressures, X + CO2 → SO2(3B1) + CO2 (10a) and X + CO2 → SO2 + CO2 (10b). The data give k11/(k10a + k10b)=0.026 mole/l.
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  • 77
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    International Journal of Chemical Kinetics 7 (1975), S. 143-157 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reactions of O(3P) and D atoms with cyclohexane have been investigated using fast-flow techniques. The rates of reaction were computed by monitoring changes in both atom and cyclohexane concentrations using electron spin resonance and mass spectrometric methods, respectively. The O(3P) + C6H12 reaction was studied over a temperature range of 344 to 513°K and we obtain a specific rate constant of (3.2±0.6) × 1014 exp (-4400±400/RT) cm3/mole·sec for this reaction. The only reaction product detectable mass spectrometrically under flow conditions of excess oxygen atoms is formaldehyde.The D + C6H12 reaction was studied over a temperature range of 297 to 596°K. A specific rate constant of (4.1±1.0) × 1013 exp (-4000±300/RT) cm3/mole·sec was obtained for this reaction. On the basis of the results obtained in these studies, the important primary process in both the O(3P) and D atom reactions is concluded to be abstraction of a hydrogen atom from the cyclohexane molecule.
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  • 78
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    International Journal of Chemical Kinetics 7 (1975), S. 161-182 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The quantum yields of SO3 formation have been determined in pure SO2 and in SO2 mixtures with NO, CO2, and O2 using both flow and static systems. In separate series of experiments excitation of SO2 was effected within the forbidden band, SO2(3B1) ← \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm SO}_2 (\tilde X,^1 A_1 ) $$\end{document}, and within the first allowed singlet band at 3130 Å. The values of ΦSO3 were found to be sensitive to the flow rate of the reactants. These results and the apparently divergent quantum yield results of Cox [10], Allen and coworkers [24, 26, 29], and Okuda and coworkers [11] were rationalized quantitatively in terms of the significant occurrence of the reactions SO + SO3 → 2SO2 (2), and 2SO → SO2 + S [or (SO)2] (3), in experiments of long residence time. From the present rate data, values of the rate constants were estimated, k2=(1.2±0.7) × 106; k3=(5±4) × 105 l·/mole · sec. ΦSO3 values from triplet excitation experiments at high flow rates of NO—SO2 and CO2—SO2 mixtures showed the sole reactant with SO2 leading to SO3 formation in this system to be SO2(3B1); SO2(3B1) + SO2 → SO3 + SO(3Σ-) (la); k1a=(4.2±0.4) × 107 l./mole · sec. With excitation of SO2 at 3130 Å both singlet and triplet excited states play a role in SO3 formation. If the reactive singlet state is 1B1, the long-lived fluorescent state, SO2(1B1) + SO2 → SO3 + SO (1 Δ or 3Σ-) (lb), then k1b=(2.2±0.5) × 109 l./mole · sec. From the observed inhibition of SO3- formation by added nitric oxide, it was found that the SO3-forming triplet state, generated in this singlet excited SO2 system, had a relative reactivity toward SO2 and NO which was equal within the experimental error to that observed here for the SO2(3B1) species. Either SO2(3B1) molecules were created with an unexpectedly high efficiency in 3130 Å excited SO2(1B1) quenching collisions, or another reactive triplet (presumably 3A2 or 3B2) of almost identical reactivity to SO2(3B1) was important here.
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  • 79
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    International Journal of Chemical Kinetics 7 (1975), S. 273-285 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the thermal bromination reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm Br + CF}_{\rm 3} {\rm I} \to {\rm IBr + CF}_{\rm 3} {\rm Br} $$\end{document} have been studied in the range of 173-321°C. For the step we obtain \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}\,k_{11} \,({\rm cm}^{\rm 3} /{\rm mole} \cdot {\rm sec) = (13}{\rm .19) - (10840} \pm {\rm 460)/}\theta $$\end{document} where θ=2.303RT cal/mole. From the activation energy for reaction (11), we calculate that \documentclass{article}\pagestyle{empty}\begin{document}$$ D({\rm CF}_{{\rm 3}^{\rm - } } {\rm I) = 52}{\rm .6} \pm {\rm 1}{\rm .1}\,{\rm kcal/mole}\,{\rm at 25}{}^{\rm 0}{\rm C} $$\end{document} This is compared with previously published values of D(CF3-I). The relevance of the result to published work on kc for a combination of CF3 radicals is discussed.
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  • 80
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    International Journal of Chemical Kinetics 7 (1975), S. 331-339 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of the inhibited pyrolysis of pentachloroethane was studiedover the temperature range of 820 to 865°K using the toluene-carrier technique in a stirred-flow reactor. The pyrolysis rate was found to be first order in reactant, and the rate constant is described by k=1011.6±0.7 exp [(-48,200±2600)/RT] sec-1. An increase by a factor of 6.6 in the surface/volume of the reactor had a negligible effect on the rate. This observation, in addition to a reevaluation of earlier kinetic data for the pyrolysis of pentachloroethane, lead to the following conclusions concerning the pyrolysis mechanism. The initiation and termination as well as the propagation reactions were homogeneous, the termination involved both Cl and C2Cl5 radicals (crosstermination), and autocatalysis was caused by interaction between chlorine and pentachloroethane rather than by dissociation of molecular chlorine.
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  • 81
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    International Journal of Chemical Kinetics 7 (1975), S. 399-415 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidation of CFClCFCl and CF2CCl2 were studied at room temperature by chlorine- and oxygen-atom initiation. The chlorine-atom initiated oxidation of CFClCFCl yields CCl2FCF(O) as the exclusive product. Its quantum yield is ∼420, which gives k3a/k3b=210 where reactions (3a) and (3b) are The O(3P)—CFClCFCl reaction gives CClFO with a quantum yield of 0.80, polymer, and small amounts of an unidentified product which is probably cyclo-(CFCl)3. Thereaction paths are with k9a/k9=0.80. The overall reaction of O(3P) with CFClCFCl proceed one fifth as fast as the O(3P)-C2F4 reaction. When O2 is also present, the same free-radical chain oxidation occurs by O(3P)initiation as by chlorine-atom initiation.The chlorine-atom initiated oxidation of CF2CCl2 gives CF2ClCCl(O) as the major product, with quantum yields ranging from 42 to 85. Smaller amounts of CF2O and CCl2O are produced in equal amounts with quantum yields of ∼3.5. The reactions responsible for the products are The O(3P)-CF2CCl2interaction yields CF2O and with quantum yields of 1.0 and ∼0.85, respectively. In thepresence of O2 the radical chain products are observed, but the mechanism is different than that for other chloroolefins.
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  • 82
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    International Journal of Chemical Kinetics 7 (1975), S. 639-648 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the combination of methyl radicals with NO and O2 have been measured by flash photolysis of azomethane coupled with product analysis by gas chromatography. Values of the rate constants have been obtained over the pressure region from 50 to 700 torr with He, N2, and Ar as quenching molecules.The high-pressure limits were obtained through an RRKM model calculation and were found to be \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{\rm CH}_{\rm 3} + {\rm NO} + {\rm M} \to {\rm CH}_{\rm 3} {\rm NO} + {\rm M}} \hfill & {k_\infty = 3.2 \times 10^{ - 11} {{{\rm cm}^{\rm 3} } \mathord{\left/ {\vphantom {{{\rm cm}^{\rm 3} } {{\rm molec} \cdot {\rm sec}}}} \right. \kern-\nulldelimiterspace} {{\rm molec} \cdot {\rm sec}}}} \hfill \\ {{\rm CH}_{\rm 3} + {\rm O}_{\rm 2} + {\rm M} \to {\rm CH}_{\rm 3} {\rm O}_{\rm 2} + {\rm M}} \hfill & {k_\infty = 1.7 \times 10^{ - 12} {{{\rm cm}^{\rm 3} } \mathord{\left/ {\vphantom {{{\rm cm}^{\rm 3} } {{\rm molec} \cdot {\rm sec}}}} \right. \kern-\nulldelimiterspace} {{\rm molec} \cdot {\rm sec}}}} \hfill \\ \end{array} $$\end{document} The rate constants were measured relative to the methyl combination reaction k1 with k1 = 9.5 × 10-11 cm3/molec · sec. The RRKM model suggests D0(CH3—O2) = 32 ± 3 kcal/mole.
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  • 83
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    International Journal of Chemical Kinetics 7 (1975), S. 907-917 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism and kinetics of the reaction of O(3P) atoms with propane were investigated using molecular modulation spectroscopy, with the O(3P) atoms being generated by the Hg photosensitized decomposition of N2O. The absorption spectrum of the X2II3/2 state of OH was observed in the ultraviolet between 307 and 309 nm, and it was confirmed that OH was the product of the O(3P) reaction with propane. The rate constants for the reactions of O(3P) and OH with propane were determined to be 3.9±0.7±1010 and 1.19±0.05±1012 cm3/mole·sec, respectively, at T=56±5°C.
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  • 84
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    International Journal of Chemical Kinetics 7 (1975), S. 919-926 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetics of protonation of Li+, Na+, K+, and Cs+ salts of anthracene radical anions (A-·,Cat+) and dianions (A2-, 2Cat+) by MeOH and MeOD in tetrahydrofuran (THF) and dimethoxyethane (DME) led to the determination of the isotope effect (kH/kD) in the following reactions: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm MeOH(MeOD) + A}\bar \cdot {\rm,Cat}^{\rm + } \to MeO^ - {\rm,Cat}^{\rm + } {\rm + AH} \cdot {\rm (D)} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm (MeOH)}_{\rm 2} {\rm or (MeOD)}_{\rm 2} {\rm + A}\bar \cdot {\rm,Cat}^{\rm + } \to {\rm MeOH,MeO}^ - {\rm,Cat}^{\rm + } {\rm + AH} \cdot {\rm (D)} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm MeOH (MeOD) + A}^{{\rm 2 - }} {\rm,2Cat}^{\rm + } \to {\rm MeO}^ - {\rm,Cat}^{\rm + } {\rm + AH(D)}^{{\rm - 1}},{\rm Cat}^{\rm +} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm MeOH (MeOD) + (A,Cat}^{\rm + } {\rm,A}^{{\rm 2 - }} {\rm,Cat}^{\rm + }) \to {\rm MeO}^ - {\rm,Cat}^{\rm + } {\rm + A + AH(D)}^{\rm - },{\rm Cat}^{\rm +} $$\end{document}Studies of cation and solvent influence on the rate constants of these reactions and on the magnitude of the isotope effect permitted us to draw some conclusions about the structure of the pertinent transition states. It seems that only the tight A-·,Na+ pairs participate in the protonation, and on this basis the fraction of tight ion paris of A-·,Na+ in DME was estimated. Our results have been compared with data reported in the literature.
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  • 85
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    International Journal of Chemical Kinetics 7 (1975), S. 109-123 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A very low-pressure pyrolysis (VLPP) apparatus has been constructed and shown to yield kinetic data consistent with other VLPP systems. The technique has been applied to the pyrolysis of cyclobutyl cyanide over the temperature range of 833-1203°K. The reaction was found to proceed via a single pathway to yield ethylene and vinyl cyanide. If A∞ is based on previous high-pressure data for this reaction and for cyclobutane pyrolysis, then RRKM theory calculations show that the experimental unimolecular rate constants are consistent with the high-pressure Arrhenius parameters given by \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}\,k_\infty ({\rm sec}^{{\rm - 1}}) = 15.0 - (57.0 \pm 1.0)/\theta $$\end{document} where θ=2.303 RT in kcal/mole. If A∞ is adjusted relative to the more recent parameters for cyclobutane pyrolysis suggested by VLPP studies, then the Arrhenius expression becomes \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log }\,k_\infty ({\rm sec}^{{\rm - 1}}) = 15.9 - (59.1 \pm 1.0)/\theta $$\end{document} The cyano group reduces the activation energy for cyclobutane pyrolysis by 6±1 kcal/mole, and on the basis of a biradical mechanism this value may be attributed to the cyano stabilization energy.
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  • 86
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    International Journal of Chemical Kinetics 7 (1975), S. 183-194 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of chlorine atom abstraction from the chloromethanes (CM)CCl4, CHCl3, and CH2Cl2 by radiolytically generated cyclohexyl radicals has been studied in the liquid phase by a competitive method. The halogen abstraction data have been put on an absolute basis by comparing the rates of the metathetical reactions with the known rate of addition of cyclohexyl radicals to C2Cl4.The following Arrhenius parameters were obtained: TextCMlog A(CM)/A(C2Cl4)E(CM)—E(C2Cl4)(kcal/mole)log A(CM)(1./mole·sec)E(CM) (kcal/mole)Temperaure Range(°K)CCl40.72±0.02-1.42±0.059.40±0.085.88±0.15333-453CHCl30.77±0.062.86±0.019.45±0.1210.16±0.11392-492CH2Cl20.56±0.126.37±0.279.42±0.1813.67 ± 0.37463-543The error limits are the standard deviations from least mean square Arrhenius plots.The possible application of the Evans-Polanyi relationship to chlorine atom abstraction reaction from CM is considered.
    Additional Material: 2 Ill.
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  • 87
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    International Journal of Chemical Kinetics 7 (1975), S. 223-247 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High-temperature (〉1000°K) pyrolysis of acetaldehyde (∼1% in an atmosphere of pure nitrogen) was examined in a turbulent flow reactor which permits accurate determination of the spatial distribution of the stable species. Results show that the products in order of decreasing importance are CO, CH4, H2, C2H6, and C2H4. Rates of formation were consistent with the Rice-Herzfeld mechanism by including reactions to explain C2H4 formation and the possible presence of ketene. A steady-state treatment of the complete mechanism indicates that the overall reaction order decreases from \documentclass{article}\pagestyle{empty}\begin{document}$ \frac{3}{2} $\end{document} to 1, which is supported by the new experimental data. Using earlier low-temperature results, the rate constant for the reaction CH3CHO → CH3 + CHO (1) was found as k1=1015.85±0.21 exp (-81,775±1000/RT) sec-1. Also, data for the ratio of rate constants for reactions CH3CHO + CH3 → CH4 + CH3CO (4) and 2CH3 → C2H6(6) were fitted to the empirical expression k4/k61/2=10-13.89±0.03T6.1 exp(-1720±70/RT) (cm3/mole·sec)1/2 and causes for the curvature are discussed. The noncatalytic effect of oxygen on acetaldehyde pyrolysis at high temperature is explained.
    Additional Material: 11 Ill.
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  • 88
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    International Journal of Chemical Kinetics 7 (1975), S. 15-22 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase photolysis of perfluoroacetone in the presence of ethane has been shown to result in the production of significant amounts of 1, 1-bis(trifluoromethyl)propanol-1, (CF3)2(C2H5)COH, and 1, 1, 4, 4-tetrakis(trifluoromethyl)butane-1, 4-diol, (CF3)2C(OH)-CH2CH2C(OH)(CF3)2. A mechanism is presented which accounts for the relative rates of formation of these products at room temperature.
    Additional Material: 1 Ill.
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  • 89
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    International Journal of Chemical Kinetics 7 (1975), S. 63-76 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A kinetic investigation of electronically excited arsenic atoms in the low-lying states, As(4p3 2DJ) and As(4p3 2PJ), ca. 1.33 and 2.28 eV, respectively, above the 44S3/2 ground state, has been carried out by atomic absorption spectroscopy. Atoms in these optically metastable states were generated by the pulsed irradiation of suitable arsenic compounds (AsMe3 for 2D and AsCl3 for 2P) in different spectral regions and monitored photoelectrically by time-resolved attenuation of atomic resonance radiation. Rate constants for the deactivation of these two states are reported for a range of collision partners. The data are compared with those of the analogous states of lighter atoms in group V, namely, P(32DJ, 32PJ) and N(22DJ, 22PJ), and discussed in terms of spin and orbital symmetry considerations.
    Additional Material: 4 Ill.
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  • 90
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 7 (1975), S. 99-107 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photochemistry of azoisopropane is reinvestigated at 366 nm over an extended pressure range by using n-butane as an added bath gas, and over a range of temperature from 277° to 180°C. The Stern-Volmer type plot of the N2 product quantum yield is interpreted in terms of the decomposition of the vibrationally excited upper singlet and triplet states, with the onset of the dissociation of the vibrationally equilibrated triplet state as the temperature is increased. The energy barrier for the dissociation of the vibrationally equilibrated first triplet state is found to be 8.8 kcal/mole. Triplet sensitization experiments with biacetyl correlate with our observations, and it is suggested that the proposed mechanism is generally applicable to the photodissociation of acyclic azoalkanes at 366 nm, based on a comparison of our data with those of Wu and Rice on hexafluoroazomethane.
    Additional Material: 2 Ill.
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  • 91
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 7 (1975) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 92
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 7 (1975), S. 195-203 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The π*←n excited state kinetics of hexafluoroacetone are reinvestigated in the presence of a vibrational relaxer and sufficient triplet state quencher so that only the reactions of the electronically excited upper singlet state are examined. From a Stern-Volmer type analysis it is concluded that vibrational relaxation of the initially formed vibrationally and electronically excited upper singlet state is via a multistage collisional mechanism. An activation energy of about 6 kcal/mole is reported for the unimolecular decomposition of the upper singlet state.
    Additional Material: 2 Ill.
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  • 93
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    International Journal of Chemical Kinetics 7 (1975), S. 215-222 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate equations have been deduced for two possible mechanisms for the reactions of N-methyl-N-nitrosoaniline in acid solution, namely, (1) for the generally accepted intermolecular mechanism which involves denitrosation followed by C-nitrosation and (2) a mechanism involving intramolecular rearrangement which takes place concurrently with denitrosation. The observed rate constants obtained under various experimental conditions are consistent only with mechanism (2). In particular the question of halide ion catalysis differentiates clearly between the two mechanisms. Mechanism (1) predicts a first-order dependence upon chloride (or other halide) ion under all conditions, whereas (2) allows a first-order chloride ion dependence only in the presence of a large excess of a “nitrite trap” such as sulphamic acid, urea, hydrazoic acid, hydroxylamine, etc., whereas at the other limit of high concentration of added N-methylaniline, the rate constants should be independent of the halide ion concentration. The predictions based on mechanism (2) are all borne out by experiment.
    Additional Material: 1 Tab.
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  • 94
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    International Journal of Chemical Kinetics 7 (1975), S. 301-315 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A flow tube method has been used to determine rate constants for the elementary reactions: Oxygen atoms were produced by adding a small excess of NO to a stream of partially dissociated nitrogen, and their reaction with hydrogen halide was monitored by observing the intensity of the NO + O afterglow. Experiments were carried out at temperatures from 293 to 440°K with HCl, and from 267 to 430°K with HBr. The role of secondary reactions was minimised and the residual effects were allowed for. The rate constants for the primary reactions could be matched by Arrhenius expressions: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{1a} = 2.5\left({_ - ^ + } \right.\left. {{}_{0.8}^{1.2} } \right) \times 10^{ - 12} \,{\rm exp}\frac{{{\rm ( - 5}{\rm .9} \pm {\rm 0}{\rm .3}\,{\rm kcal/mole)}}}{{RT}} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ k_{1b} = 4.0( \pm 0.7) \times 10^{ - 12} \,{\rm exp}\frac{{{\rm ( - 2}{\rm .7} \pm {\rm 0}{\rm .1}\,{\rm kcal/mole)}}}{{RT}} $$\end{document} where the units are cm3/molec·sec and the errors correspond to a standard deviation.
    Additional Material: 3 Ill.
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  • 95
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    International Journal of Chemical Kinetics 7 (1975), S. 351-362 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the thermal hydrocracking of indan were investigatedin a high-pressure flow reactor at temperatures from 470 to 530°C, total pressures of up to 300 atm, and molar ratios from 3 to 40. The effect of the hydrogen pressure was reflected especially in a change of the experimental rate equations for the formation of toluene from rT=k [indan]0.5 [hydrogen] to rT=k′ [indan] 0.75[hydrogen]0.75 with hydrogen partial pressureincreasing from 73 to 230 atm. The rate equation of n-propylbenzene remained constant at rPr=k″ [indan] [hydrogen]1.5. Simultaneously the Arrheniusparameters of toluene changed significantly, while those of n-propylbenzene remained unchanged.The observed effect of the hydrogen pressure is explained as a change inthe rates of the intermediate reactions; it provides an excellent agreementbetween the theoretical and experimental data. It was found that the steady-state concentration of the hydrogen atoms, which act as chain carriers in the thermal hydrocracking, was much smaller than the thermodynamic equilibrium concentrations
    Additional Material: 7 Ill.
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  • 96
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    International Journal of Chemical Kinetics 7 (1975), S. 417-432 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A detailed chemical mechanism for the cerium catalyzed bromination and oxidation of malonic acid by bromate has been developed, and complete numerical solutions have been obtained for the temporal behavior of the concentrations of the intermediate species. The many points of similarity with the experimentally observed initial decay, long quiescence, and abrupt transition to sustained oscillation establish confidence in the essential validity of the proposed mechanism. Close examination of the time dependence of these species concentrations as well as the magnitude of the several reaction channels permits the clarification of the switching mechanism causing theoscillatory behavior of this system. The results appear to exhibit limit cycle behavior, in accordance with theoretical predictions.
    Additional Material: 7 Ill.
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  • 97
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    International Journal of Chemical Kinetics 7 (1975), S. 473-477 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No. Abstract.
    Additional Material: 1 Ill.
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  • 98
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    International Journal of Chemical Kinetics 7 (1975), S. 531-534 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Disproportionation-combination rate ratios have been measured for a number of pairs of thermalized radicals (298°K) generated by thermalization of chemically activated cycloalkyl radicals, their ring-opened products, and ethyl radicals. These ratios are reported and briefly discussed. The rate of isomerization of the chemically activated pent-2-en-5-yl radical via H-atom transfer to the allylic pent-1-en-3-yl radical is also given.
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  • 99
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 7 (1975), S. 557-574 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of hydrogenation of cyclohexene, catalyzed by CoH3(PPh3)3, has been measured under various conditions and, based on these data, a mechanism has been postulated. For the individual steps of the mechanism enthalpy and entropy differences have been determined. The interpretation of these parameters gives evidence for a more detailed mechanism, in which solvent molecules play an important part as “stand-in” for ligands, dissociated from the catalyst species.
    Additional Material: 8 Ill.
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  • 100
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    International Journal of Chemical Kinetics 7 (1975), S. 363-379 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The modified semi-ion pair model for four-center reactions initially developed to treat the addition of hydrogen halides to olefins, including polar olefins, has been extensively applied to these systems. In addition, the restriction that the species added be a hydrogen halide has been relaxed and addition of HOH to olefins is treated within the same frame-work. Input parameters, transition state properties, and calculated activation energies are presented for 111 such reactions. Calculated activation energies for the elimination reactions agree to better than ±2 kcal/mole, on the average, with experimental values where these areknown.
    Additional Material: 1 Ill.
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