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  • 1965-1969  (118)
  • 1920-1924
  • Physical Chemistry  (56)
  • Psychopharmacology  (37)
  • Ultrastructure
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 4 (1969), S. 84-90 
    ISSN: 1432-0827
    Keywords: Ultrastructure ; Inorganic salts ; Atherosclerosis ; Diffraction ; Aorta
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé La diffraction à rayons X, la diffraction électrique et le microscope électronique suggérent qu'en dehors des composants usuels de calcium phosphate (apatite), un nombre d'autres éléments et radicaux sont également présents dans l'arteriosclérose aortique, lesquels sont capables de jouer un rôle dans le développement de la plaque «calcifiée» et dans celui de la lésion anorganique, caractéristique pour l'artériosclerose juvenile. Selon les cas étudies, l'artériosclerose aortique peut se présenter déjà au cours de la troisième decade de la vie et sa composition anorganique est presq'identique à celle de la plaque développée.
    Abstract: Zusammenfassung Sowohl die Befunde der Röntgendiffraktion als auch jene der Elektronendiffraktion und der Elektronenmikroskopie lassen vermuten, daß bei der Aortenatherosklerose zusätzlich zu den üblichen Komponenten von Calciumphosphat (Apatit) eine Reihe anderer Elemente und Radikale vorhanden sind; diese können eine Rolle spielen bei der Entwicklung der “verkalkten” Plaque und bei anorganischen Läsionen juveniler Atherosklerosen. Bei den untersuchten Fällen kann die Aortenatherosklerose bereits im 30. Lebensjahr auftreten; die anorganische Zusammensetzung der Plaque ist nahezu identisch mit jener der bereits entwickelten.
    Notes: Abstract X-ray diffraction, electron diffraction and electron microscopy suggest that in aortic atherosclerosis, in addition to the usual components of calcium phosphate (apatite), a number of other elements and radicals are present which may play a role in the development of the “calcified” plaque and in juvenile atherosclerotic inorganic lesion. In the cases studied, aortic atherosclerosis may appear as early as in the third decade and its inorganic composition is almost identical with the developed plaque.
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  • 2
    ISSN: 1432-0428
    Keywords: Microaneurysms (conjunctival) ; Ultrastructure ; Epinephrine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé La réponse des dilatations vasculaires conjonctivales à l'application locale d'adrénaline a été testée chez 25 sujets. Les dilatations veinulaires irrégulières disparaissaient, les microanévrysmes veinulaires subissaient une contraction partielle, tandis que les microanévrysmes capillaires ne se contractaient pas après application d'adrénaline. Des spécimens de biopsie de la conjonctive ont été examinés au microscope à lumière et au microscope électronique chez quatre sujets diabétiques, chez lesquels les microanévrysmes avaient été mis en évidence par biomicroscopie. On a noté un épaississement marqué de la membrane basale et un agrandissement du cytoplasme endothélial dans les capillaires dilatés. Les péricytes étaient normaux en nombre et en apparence. Chez trois non-diabétiques les dilatations capillaires conjonctivales n'ont pas subi ces modifications. On a observé un degré plus faible d'épaississement de la membrane basale chez un diabétique plus jeune. La découverte de microanévrysmes capillaires conjonctivaux chez un diabétique semblerait donc indiquer la présence de microangiopathie.
    Abstract: Zusammenfassung Das Ansprechen von Bindehautgefäß-Aneurysmen auf lokale Adrenalinapplikation wurde bei 25 Vp. überprüft. Darunter verschwanden unregelmäßige venöse Erweiterungen und die venösen Mikroaneurysmen kontrahierten sich teilweise, während sich die kapillären Mikroaneurysmen unter Adrenalin nicht verkleinerten. Biopsiepräparate aus der Bindehaut von 4 Diabetikern, bei denen sich durch Biomikroskopie Mikroaneurysmen hatten nachweisen lassen, wurden licht- und elektronenmikroskopisch untersucht. In den erweiterten Kapillaren fielen dabei eine deutliche Verdickung der Basalmembran und eine Vermehrung des endothelialen Cytoplasma auf. Die Pericyten erschienen nach Zahl und Aussehen normal. Erweiterungen von Bindehautkapillaren bei 3 Nichtdiabetikern zeigten diese Veränderungen nicht. Bei einem jüngeren Diabetiker ließ sich eine weniger ausgeprägte Verdickung der Basalmembran beobachten. Der Nachweis von Mikroaneurysmen in den Bindehautkapillaren eines Diabetikers spricht also für das Vorliegen einer Mikroangiopathie.
    Notes: Summary The response of conjunctival vascular dilatations to topical epinephrine was tested in 25 subjects. Irregular venular dilatations disappeared, venular microaneurysms underwent partial contraction, while capillary microaneurysms did not contract following application of epinephrine. Biopsy specimens of the conjunctiva were examined by light and electron microscopy in four diabetic patients in whom microaneurysms had been demonstrated by biomicroscopy. Marked thickening of the basement membrane and enlargement of the endothelial cytoplasm were noted in the dilated capillaries. Pericytes were normal in number and appearance. Conjunctival capillary dilatations in three nondiabetics failed to show these changes. A milder degree of basement membrane thickening was observed in a younger diabetic. The finding of conjunctival capillary microaneurysms in a diabetic would thus appear to indicate the presence of microangiopathy.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 12 (1969), S. 116-140 
    ISSN: 1432-0533
    Keywords: Ultrastructure ; Schwann Cell ; Acoustic Neuroma ; Tumor
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Eine ultrastrukturelle Untersuchung von 50 Acusticusneurinomen wurde durchgeführt. Die lichtoptisch charakteristischen dichten, lockeren und vacuolären Areale dieses Tumors waren aus Zellen aufgebaut, die zwei gemeinsame ultrastrukturelle Eigenschaften aufweisen: a) Das Cytoplasma bildet Bündel sehr dünner, langer Fortsätze in engem Kontakt zueinander und/oder mit ähnlichen Fortsätzen benachbarter Zellen. Das zarte EPR scheint direkt für die Bildung dieser Fortsätze verantwortlich; b) alle diese Zellen und ihre Fortsätze waren stets von einer Basalmembran umgeben. Der extracelluläre Raum in vielen Tumoren erscheint entweder “leer” oder enthält ein feingranuläres Material und wenige kleine Bündel feiner Filamente. In jedem untersuchten Tumor enthielt der Extracellularspalt in den dichten Arealen bandförmige fusiforme Fasern (Luse-Körper) von sich wiederholenden 1200Å Makroperioden. Nur in einigen Tumoren enthielt der extracelluläre Raum der lockeren Gebiete natives fibröses Kollagen. Voll und teilweise bemarkte Nervenfasern mit hyperplastischen Schwann-Zellcytoplasma fanden sich in wenigen Geschwülsten. In einigen wurde auch eine konzentrische Anordnung von Zellen und Fortsätzen beobachtet. Ein Vergleich zwischen den untersuchten Tumoren und fetalen menschlichen peripheren Nerven führte zu dem Schluß, daß Schwann-Zellen und nicht Fibroblasten die meisten, wenn nicht alle Zellen von Acusticusnervengeschwülsten bilden. Das Perineurothel kann allerdings nicht als zweiter Sitz der Geschwulstbildung ausgeschlossen werden.
    Notes: Summary An ultrastructural study of 50 acoustic neuromas was made. The dense, loose, and vacuolated areas of light microscopy, characteristic of these tumors, were composed of cells exhibiting two common ultrastructural features: a) The cytoplasm formed bundles of very thin, long processes in intimate contact with each other and/or with similar processes from neighboring cells. The smooth endoplasmic reticulum appears to be directly responsible for the formation of these processes; and b) All of these cells and their processes were consistently surrounded by a basement membrane. The extracellular space in many tumors appeared either “empty” or contained a fine granular material and a few small bundles of fine filaments. In every tumor studied the extracellular space, in the dense areas, contained banded fusiform fibers (Luse bodies) of 1,200 Å repeating macroperiods. In only some tumors, the extracellular space of the loose areas contained native fibrous collagen. Fully myelinated and partially myelinated nerve fibers with hyperplastic Schwann cell cytoplasm were found in a few tumors. A tactoidal arrangement of cells and cell processes was also found in some tumors. A comparison between fetal human peripheral nerves and the tumors studied, led to the conclusion that the cells of Schwann and not fibroblasts form most, if not all the cells of acoustic nerve neoplasms. The perineurothelium, however, could not be excluded as a second site for the development of these tumors.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 4 (1969), S. 305-313 
    ISSN: 1432-0827
    Keywords: Decalcification ; Chromium Sulphate ; Ultrastructure ; Dentine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Une méthode nouvelle de décalcification histologique utilisant des solutions aqueuses de sulfate de chrome basique (III) est appliquée à des coupes fines de dentine humaine adulte. L'observation en microscopie électronique montre une bonne conservation structurale dans les régions extra-cellulaires. L'aspect de la matrice péricanaliculaire est particulièrement étudié. On y reconnait plusieurs couches bien individualisées. Une bonne concordance est notée entre les résultats obtenus par microscopie optique et électronique, permettant d'établir une hypothèse nouvelle sur la formation de la dentine péricanaliculaire.
    Abstract: Zusammenfassung Eine kürzlich entwickelte Methode zur histologischen Entkalkung mittels wäßriger Lösungen von basischem Chrom III-Sulfat wird an dünnen Schliffen von menschlichem Dentin Erwachsener angewandt. Darauffolgende Untersuchungen am Elektronenmikroskop zeigten eine sehr gute Wiedergabe der morphologischen Einzelheiten in den Extrazellulär-Regionen. Besonders beachtet wurde das Aussehen der peritubulären Matrix, innerhalb welcher gut differenzierte Schichten erkannt werden konnten. Eine wesentliche Übereinstimmung bestand zwischen Elektronenmikroskopie und kürzlich durchgeführten Untersuchungen an derselben Matric unter dem Mikroskop. Diese Methode ermöglicht es, eine neue Hypothese über die Bildung des peritubulären Dentins aufzustellen.
    Notes: Abstract A recently-developed method for histological decalcification using aqueous solutions of basic chromium (III) sulphate has been applied to thin sections of adult human dentine. Subsequent studies in the electron microscope show a very good retention of morphological detail in the extracellular regions. Special attention was given to the appearance of the peritubular matrix within which well-differentiated layers were recognised. There was substantial agreement between electron microscopy and recent studies of the same matric under the light microscope, allowing a novel hypothesis for the formation of the peritubular dentine.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 4 (1969), S. 193-201 
    ISSN: 1432-0827
    Keywords: Calcium ; Carbonate ; Gland ; Ultrastructure ; Spherolith
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Les cellules activement sécrétantes des glandes riches en calcium deLumbricus terrestris ont une forme en dôme. La partie basale de la cellule présente de nombreux prolongements ramifiés. Ces prolongements contiennent de nombreuses mitochondries, ainsi que des invaginations de la membrane formant des vésicules qui migrent dans diverses parties de la cellule. Le noyau irrégulier est en position centrale. La région supranucléaire contient surtout de l'ergastoplasme, plusieurs appareils de Golgi et de nombreuses granules provenant de l'appareil de Golgi. Ces granules augmentent de taille et sont rejetées dans le sinus de la glande, où elles se modifient et se calcifient pour donner des sphérolithes. Des radioautographics glandulaires, obtenues 1/2 heure après injection de Ca45, montrent une localisation isotopique, située presque exclusivement dans les cellules; 4–24 heures après, l'isotope se localise dans les sphérolithes de la cavité glandulaire. Ces cellules semblent assurer deux fonctions liées à la production de sphérolithes: 1. absorption et transport de calcium de la région basale vers la surface cellulaire et 2. formation d'une matrice protéique qui se calcifiera.
    Abstract: Zusammenfassung Die aktivsezernierenden Zellen der calcifizierenden Drüsen vonLumbricus terrestris sind annähernd kuppelförmig gestaltet. Der untere Teil dieser Zellen besteht aus unzähligen ineinandergreifenden Zellfortsätzen. Diese Fortsätze enthalten zahlreiche Mitochondrien und membranöse Einstülpungen, welche Bläschen bilden, die zu den verschiedenen Regionen der Zelle wandern. Der Zellkern ist unregelmäßig und zentral angeordnet. Die supranukleäre Region ist zu einem großen Teil mit grobem endoplasmatischem Reticulum und mehreren Golgi-Komplexen sowie zahlreichen Granula, die von den Golgi-Komplexen stammen, ausgefüllt. Diese Granula vergrößern sich und werden in den Drüseninus ausgestoßen, wo sie schließlich reorganisiert und mineralisiert werden, um Sphärolithen zu bilden. 1/2 Std nach Injektion von Ca45 wurde die Drüse entfernt; eine Radioautographie zeigte, daß das Isotop beinahe ausschließlich in den Zellen lokalisiert war; 4–24 Std später befand sich das Isotopin den Sphärolithen der Drüsenhöhlung. Diese Zellen sind anscheinend an zwei für die Bildung von mineralisierten Sphärolithen notwendigen Funktionen beteiligt: 1. an der Calcium-Absorption und deren Transport von der Basalregion bis zur Zelloberfläche; 2. an der Bildung einer Proteinmatrix, in welcher die Mineralisation stattfindet.
    Notes: Abstract The actively-secreting cells of the calciferous glands ofLumbricus terrestris are roughly dome shaped. The basal part of the cell consists of numerous interdigitating cell processes. These processes contain numerous mitochondria and membranous infoldings, forming vesicles which migrate to various regions of the cell. The nucleus is irregular and centrally located. The supranuclear region is occupied to a great extent by the rough endoplasmic reticulum, several Golgi complexes and numerous granules derived from the Golgi complexes. These granules enlarge and are extruded into the gland sinus, where they eventually become reorganized and mineralized to give rise to spheroliths. Radioautographs of glands removed 30 min following injection of45Ca showed uptake of the isotope located almost exclusively in the cells; 4–24 h later the isotope was located in the spheroliths in the gland cavity. These cells apparently perform two functions necessary for the production of mineralized spheroliths, 1, absorption and transport of calcium from the basal region to the cell surface and 2, the elaboration of a protein matrix in which mineralization occurs.
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  • 6
    ISSN: 1432-1106
    Keywords: Septal nuclei ; Afferent connexions ; Ultrastructure ; Synaptic degeneration
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Previous studies with the Nauta technique have established that fibres which originate in two important areas — the hippocampus and the hypothalamus — converge upon the cells of the septal nuclear complex. The purpose of this study was to investigate the anatomical basis of how the septal cells could differentiate between fibres from the two sources. Differences in the mode of termination of these two systems have been studied quantitatively at the electron microscope level by using the orthograde degeneration of terminals after lesions of the fimbria and the medial forebrain bundle. In the medial septal nucleus, the hippocampal fibres account for 35% of the terminals, and in the lateral septal nucleus, 43% of the terminals on the same side and a further 13% on the opposite side. These terminals are at least 98% axodendritic and 91% of them contain predominantly clear synaptic vesicles of 500 Å diameter. The hypothalamic fibres are the source of up to 19% of the axodendritic terminals in the medial septal nucleus, but considerably fewer in the lateral septal nucleus. In contrast to the hippocampal afferents, the hypothalamo-septal system has two characteristic features: firstly, the fibres give rise to up to 24% of the axosomatic terminals in the medial septal nucleus, and secondly, 63% of the terminals contain a population of vesicles with significantly higher proportions of dense centred vesicles of 800–1000 Å diameter.
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  • 7
    Electronic Resource
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    Springer
    Psychopharmacology 14 (1969), S. 18-22 
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Animal Behaviour ; Mice
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Mice were stained with pulverized charcoal and the resulting grooming behaviour observed. From 119 controls, the typical patterns indicated a late cleaning of the tail, the sacrum and the region between the ears. The following substances were tested: Imipramine, Desipramine, Trimeprimine, Amitriptyline, Nortriptyline, Chlordiazepoxide, Iproniazide, d-Amphetamine, Chlorpromazine, Haloperidol, Acetylsalicylic acid, Metronidazole. Of these Amitriptyline, Chlorpromazine, Haloperidol and Metronidazole were effective in doses less than 1/10 of LD 5.
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  • 8
    Electronic Resource
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    Springer
    Psychopharmacology 14 (1969), S. 62-73 
    ISSN: 1432-2072
    Keywords: Amphetamine ; Hallucinogens ; Drug Addiction ; Psychopharmacology ; Phenylethylamines
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The amphetamine analog, 2,5-dimethoxy-4-methylamphetamine (DOM), was studied in 18 volunteer subjects given single doses ranging from 2 to 14 mg. The former was a threshold dose, with definite psychotomimetic effects being evident from doses over 5 mg. The clinical syndrome greatly resembled that of the LSD-mescaline-psilocybin series of drugs, including its time-course. Somewhat more sedation was produced by DOM than would have been expected from the others, despite concomitant evidence of peripheral sympathetic stimulation. Just as with the other drugs, DOM increased plasma free fatty acids, decreased phosphorus and creatinine clearance, decreased circulating eosinophils and had little effect on catecholamine excretion. Performance of psychometric tests was impaired. Chlorpromazine treatment concurrently was found to attenuate the reaction. Tolerance rapidly developed when the drug was used chronically by patients.
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Psychopharmacology 14 (1969), S. 200-210 
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Hashish ; Cannabinoids ; Monkeys Amphetamine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary 1. The psychopharmacological activity of Δ 1-tetrahydrocannabinol, (I); Δ 1(6)-tetrahydrocannabinol (4′ hexyl), (II); Δ 1(6)-tetrahydrocannabinol, (III); 1-ethoxyhexahydrocannabinol, (IV); 8-ethoxy-iso-hexahydrocannabinol, (V); Δ 1(6)-tetrahydrocannabinolic acid Me ester, Isomer I, (VI); Δ 1(6)-tetrahydrocannabinolic acid Me ester, Isomer II, (VII); cannabigerol, (VIII); Δ 1(6)-tetrahydrocannabinol (3′ hexyl), (IX); cannabichromene, (X); has been examined in a variety of animal species. 2. Compounds (I) and (III) caused severe motor disturbances and a stuporous state in dogs and ptosis, “tameness” and peculiar postural changes in monkeys. In the latter animal, compound (II) elicited similar effects. 3. Compounds (I) and (III) after intraperitoneal but not subcutaneous administration, suppressed the gerbil digging activity; reduced the rat conditioned avoidance response and induced a cataleptoid reaction in mice, rats and gerbils. In addition, compound (I) reduced the performance of mice on the rotating-rod. Both compounds, administered subcutaneously, induced a measurable ataxic gait in rats. 4. Amphetamine reversed the behavioural changes elicited by compounds (I) and (III) in monkeys, as well as the cataleptoid reaction in rats. 5. None of the other compounds provoked observable changes in any of the species studied. 6. It is suggested that Rhesus monkeys might serve as a suitable model for assessing the psychopharmacological activity of active cannabinoids.
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  • 10
    Electronic Resource
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    Springer
    Psychopharmacology 14 (1969), S. 394-403 
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Morphine ; Skin Conductance
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Skin conductance changes during periods of stress induced by hypercapnia were studied during a cycle of addiction to morphine. Conductance changes were found to be dose dependent in both tolerant and non-tolerant states. The effects of morphine on skin conductance changes induced by hypercapnia were similar to those effects previously observed on changes induced by electric shock.
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    Psychopharmacology 15 (1969), S. 196-206 
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Animal Behavior ; Alcohol ; Atropine ; Discrimination
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Two operant procedures were used for training albino rats to make differential responses on the basis of their drug or nondrug condition. In the Conflict procedure, every fifth lever press was rewarded by a food pellet in one condition (drug for half the animals, saline for the other half) and was punished by electric shock in the other condition. For 6 animals the drug condition was ethyl alcohol (1200 mg/kg of a 10% v/v solution in isotonic saline, injected i.p. 5 min before the start of the session); for 4 animals the drug condition was atropine sulfate (10 mg/kg in 1 ml/kg saline injected i.p. 30 min before the start of the session). In the Choice procedure, food reward was obtained by the first press on one of two levers at a variable time interval, averaging one minute, after the prior food reward. The rewarded lever depended on the animal's drug or saline condition (alcohol for 7 animals, atropine for 5 animals, administered as in the Conflict procedure); the same right-hand or left left-hand lever was rewarded in the drug condition for half the animals and in the saline condition for the other half. The response associated with 1200 mg/kg alcohol was generally elicited in tests with sufficiently high doses of pentobarbital sodium (10–20 mg/kg), chlordiazepoxide hydrochloride (10–15 mg/kg) and chloral hydrate (90–120 mg/kg, administered orally). Lower doses of these compounds, and of alcohol, were perceived as less similar to the alcohol and therefore more similar to the saline condition. Substantial doses of chlorpromazine hydrochloride (2 mg/kg) and d-amphetamine sulfate (1 mg/kg) also were perceived as similar to the saline condition. The response associated with a centrally acting anticholinergic (10 mg/kg atropine) was generally elicited in tests with several doses of scopolamine hydrobromide (0.06 to 1.0 mg/kg) and of atropine (2.5–5.0 mg/kg). The saline response was elicited by a lower dose of scopolamine (0.03 mg/kg) and by a peripherally-acting anticholinergic, atropine methyl bromide, at a dose (5 mg/kg) equimolar with 10 mg/kg atropine sulfate. The same results, including closely similar ED50 doses, were generally found with the Conflict and Choice procedures, despite the differences between them in the motivational basis for the differential drug and nondrug responses. The similarities and dissimilarities among these compounds in perceived stimulus characteristics also correspond closely with those reported by Overton (1966) with a locomotor shock-escape procedure in tests which were generally limited to a single high dose of each drug.
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  • 12
    Electronic Resource
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    Psychopharmacology 15 (1969), S. 245-254 
    ISSN: 1432-2072
    Keywords: Aggression ; Lithium ; Psychopharmacology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The influence of lithium on aggressive behavior was studied in Siamese fighting fish, mice and golden hamsters. The fish stopped fighting when exposed to concentrations of 10 to 30 meq/l LiCl in the surrounding water. Also in mice and hamsters which ingested LiCl with the drinking fluid lithium abolished intraspecific aggression. Measurements of plasma and brain lithium levels revealed astonishing individual differences in the concentrations which were necessary for the antiaggressive effect. In all species normal aggressive behavior reappeared after lithium treatment was discontinued.
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  • 13
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Antidepressants ; Reserpine Emesis ; Apomorphine Pecking
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Seven psychic energizers have been quantitatively evaluated for their antidepressant and tranquillizing activity using antagonism of reserpine induced emesis and apomorphine induced pecking in pigeons as test procedures for the two activities respectively. Pheniprazine and deanol possess anti-reserpine activity only whereas imipramine, desmethylimipramine, amitriptyline, opipramol and orphenadrine possess both anti-reserpine as well as anti-apomorphine activity. It is suggested that the two tests form a simple and reliable combination for evaluating potential antidepressants.
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  • 14
    Electronic Resource
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    Psychopharmacology 15 (1969), S. 425-429 
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Methysergide ; Mania ; Lithium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Six manic patients were studied in an open sequential drug trial of placebo and the serotonin antagonist methysergide; lithium was then substituted double-blind. No dramatic change occurred in individual manic item scores or in mean daily mania ratings after 48 hours or seven days of methysergide, although several of the patients showed slight trends toward improvement. However, after a mean duration of 10.3 days of lithium treatment, all manic item scores improved dramatically and significantly, so that complete clinical remission was evident in all patients. In view of the discrepancy between these essentially negative findings and several recent positive reports on the efficacy of methysergide in the treatment of mania, the authors feel that the indolealkylamine hypothesis of affective disorders should be further investigated.
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  • 15
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    Psychopharmacology 15 (1969), S. 109-115 
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Hallucinogens ; Drug Effects ; Behavior Exploratory ; Monkeys
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The effect of Psilocybin on the behavior of the baboon Papiopapio has been studied. Animal watchfulness, as estimated from the E.E.G., is enhanced within the first five minutes after injection and then is not further modified. Psilocybin induces a decrease of spontaneous motility. Conversely, the frequency of eye movements is considerably increased. This pattern might be explained by alterations of visual perception.
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  • 16
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    Psychopharmacology 15 (1969), S. 134-143 
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Anti-Anxiety ; Controlled Trial ; Doxepin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Six patients with persistent anxiety symptoms were used in a preliminary assessment of a new anti-anxiety compound-Doxepin (Sinequan) with placebo. The factorial design is discussed as a potentially useful way of conducting a first-stage test of anti-anxiety compounds. Analysis of the results showed that Doxepin at 25 mg t.d.s. and 50 mg t.d.s. was associated with improvement in the patient's self ratings of anxiety symptoms.
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  • 17
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    Psychopharmacology 14 (1969), S. 142-149 
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Amphetamine ; Cholinergics ; Drug Interactions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Amphetamine was administered to a group of rats trained on a nondiscriminated avoidance procedure. An intraperitoneal dose of 2.0 mg/kg caused about a 75% increase in response rate for the three-hour session. Doses of atropine, Tremorine, eserine, and 4-(1-naphthylvinyl)-pyridine (NVP), an inhibitor of the enzyme choline acetylase, which were ineffective in themselves, markedly affected the increase in rate observed after amphetamine. The quarternary amine of NVP was without effect on the amphetamine response. Those agents that decreased cholinergic function, either by blocking the effect of acetylcholine or by preventing its synthesis, augmented the stimulating effect of amphetamine. Cholinergic stimulants, on the other hand, significantly antagonized the behavioral effects of amphetamine.
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  • 18
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    Psychopharmacology 14 (1969), S. 417-425 
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Psychoses ; Reflex, Abnormal ; Chlorpromazine ; Trifluopromazine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary According to our results in 117 subjects, recently taken medications, age and sex must be considered when duration of the Achilles-tendon reflex is used as a clinical test to assess thyroid status. Males have a shorter ATR than females. In older subjects the ATR lasts longer than in those below age 27. Fifty-two psychiatric patients before medication did not differ in ATR duration from 65 controls. However, after 28 patients took chlorpromazine and 24 received trifluoperazine, ATR was prolonged in the chlorpromazine group and shortened in the trifluoperazine group. Neither chlorpromazine concentrate, 1,800 mg, nor trifluoperazine concentrate, 180 mg, given during the first six days, affected ATR, but an additional 6,000 mg of chlorpromazine, or an additional 420 mg of trifluoperazine over the next six days, did significantly alter ATR-duration.
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  • 19
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Doxepin ; Diazepam ; Anti-Anxiety ; Antidepressant
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Doxepin and diazepam were evaluated for therapeutic effectiveness in a double blind study carried out with 69 primarily anxious neurotic outpatients attending either a municipal hospital clinic or a general practitioner's office. Doxepin produced more clinical improvement than diazepam in several questionnaire clusters measuring depressive symptomatology, but not in clusters measuring anxious symptomatology. According to several outcome criteria, doxepin tended to produce more clinical improvement in general practice than in clinic patients, while diazepam produced either equal improvement in both populations or slightly more improvement in the clinic. Possibly contributing to the present results are low daily dosage of diazepam, differential pharmacological drug effects, population differences in levels of anxiety and depression, and differences in population characteristics, primarily as related to social class.
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  • 20
    ISSN: 1432-2072
    Keywords: Nicotine ; Antimuscarinic Drugs ; Ganglion-Blocking Drugs ; Operant Conditioning ; Psychopharmacology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The effects of nicotine on bar-pressing behaviour in the rat are blocked by mecamylamine. The depressant phase of the effect is blocked by atropine, supporting the conclusion that this depression is mediated by released acetylcholine. The quaternary compounds chlorisondamine and atropine methylnitrate also antagonise the behavioural effects of nicotine but the doses required for this are far in excess of those which are effective peripherally, suggesting that the sites of interaction are central.
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  • 21
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    Psychopharmacology 15 (1969), S. 351-360 
    ISSN: 1432-2072
    Keywords: Nicotine ; Conditioned Stimulus ; Discrimination Learning ; Psychopharmacology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Rats were trained to respond for water rewards on different bars in a Skinner box depending on whether they had previously been injected with nicotine or with saline. No other drug tested could consistently elicit responses on the “nicotine correct” bar. Pre-treatment with mecamylamine abolished the rats' ability to distinguish between nicotine and saline but pretreatment with chlorisondamine did not.
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  • 22
    ISSN: 1432-2072
    Keywords: Lysergic Acid Diethylamide or LSD ; Methylphenidate or Ritalin ; Chlordiazepoxide or Librium ; Psychopharmacology ; Alcoholism and Drug Therapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Through the retrospective use of the 156 item DWM Card Sort, the experiences from a single intravenous dose of 200 mcg of LSD, 75 mg of methylphenidate (Ritalin) and 75 mg of chlordiazepoxide (Librium) were compared in a population of 99 chronic male alcoholics treated in an “LSD setting” in a double-blind study. Surprisingly, 96 of the 156 items proved significantly different among the 3 groups. LSD was unique in producing Sensory and Perceptual Distortions (including Hallucinations or Illusions), and Mystical, Religious or Paranormal Sensations. However, contrary to expectation, LSD did not uniquely produce the traditional “therapeutic” experience, but appeared to be surpassed in that area by methylphenidate. Both drugs also produced some anxiety, while chlordiazepoxide produced relaxation, and enhanced music appreciation.
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  • 23
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    Psychopharmacology 14 (1969), S. 248-254 
    ISSN: 1432-2072
    Keywords: Amphetamine ; Appetite Depressants ; Psychopharmacology ; Sympathomimetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary A method is described with which it is possible to measure locomotor activity and food intake simultaneously in the same rat or other small animal. From a study of a number of psychomotorstimulant drugs and anorectic agents it may be concluded that locomotorstimulation and appetite-suppression are two different effects that may or may not characterize the same drug. Methamphetamine and phenmetrazine are stimulants in doses that do not inhibit food intake. Amphepramon reduced food intake in low doses but acts as a stimulant in higher doses. Chlorphemternine and phenfluramine are anorectic agents that are not stimulants, even in high doses.
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  • 24
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    Psychopharmacology 15 (1969), S. 1-8 
    ISSN: 1432-2072
    Keywords: Cannabis (Marihuana) ; Lysergic Acid Diethylamide ; Hallucinogens (Psychopharmacology) ; Visual Perception ; Psychopharmacology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Four pigeons were trained on a visual discrimination task which required conditional responding along the independent dimensions of form and color. High doses of Cannabis sativa (marihuana) extract and lysergic acid diethylamide (LSD), which were equated on the basis of their effectiveness in suppressing responding, increased responding on a color dimension but not on a form dimension. High doses of LSD produced a decrement in discrimination performance while comparable doses of Cannabis did not effect accuracy. Treatment with Bromolysergic acid diethylamide, saline, and pentobarbital did not produce significant changes in performance. Results are discussed in terms of a break-down in stimulus control and central hallucinogenic activity.
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  • 25
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    Psychopharmacology 15 (1969), S. 19-27 
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Animal Behavior ; Nicotine-Physical Performance ; Motivation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary In sessions of ten runs each, swimming time of rats through a 4 m long water alley was measured. Four doses of nicotine (0.05; 0.1; 0.2; 0.4 mg/kg given intraperitoneally 30 minutes before testing) were tested in sessions with a braking load on the tails of the animals either in all 10 runs of a session, or in every second run, or in none of the 10 runs. Regardless of the swimming condition, nicotine produced a considerable, and at doses of 0.1 mg/kg and over, significant decrease of performance in the first two runs. From the third to the 10th run, the changes caused by nicotine were smaller and differed depending on the swimming conditions. A dose of 0.1 mg nicotine/kg improved performance in the “without-load-sessions” and the “without-load-runs” of the alternating sessions, while both 0.1 and 0.2 mg/kg improved performance of the “with-load-runs” of the alternating sessions. Performance in the “without-load-sessions” and the “without-load-runs” was depressed by 0.4 mg/kg and that in the “with-load-sessions” by 0.2 and 0.4 mg/kg.
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  • 26
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    Psychopharmacology 15 (1969), S. 28-38 
    ISSN: 1432-2072
    Keywords: Drugs ; Sleep ; Electroencephalography ; Psychophysiology ; Psychopharmacology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Sleep physiological patterns were examined following a single oral dose (500 mg) of the hypnotic drug alpha chloralose. The drug increased SW sleep and decreased REM sleep without affecting total sleep time or the amount of stage 2. These changes were accompanied by a shift to slower frequencies and greater EEG synchrony, as well as a decrease in the number of spontaneous arousals in all stages of sleep, and throughout the night of medication. Except for a slight decrease in eye movement density, the drug had no systematic effects on phasic phenomena such as electrodermal or cardio-respiratory fluctuations, nor was there a systematic change in basal heart and breathing rates. On the night following medication a “rebound” increase in percent stage REM was associated with a sharp decrease in SW sleep, and increases in spontaneous arousals and waking time. Such findings suggest that sleep stages are controlled by homeostatic mechanisms whose function is to maintain equilibrium. A comparison of the effects of alpha chloralose with those of the barbiturate secobarbital revealed some striking differences. Although both alpha chloralose and the barbiturate reduced the amount of stage REM and the frequency of brief arousals, the latter compound enhanced EEG fast activity and desynchrony, and suppressed such phasic phenomena as rapid eye movements during stage REM, sigma spindles in stage 2, nonspecific electrodermal responses during SW sleep and cardio-respiratory variability in all sleep stages. For secobarbital, the decrease in percent stage REM was compensated by an increase in stage 2 rather than SW sleep. Several studies in the cat suggest that in subanesthetic doses, alpha chloralose acts primarily on cortical inhibitory processes, causing release of the reticular activating system from inhibitory influences. The results of this study show that moderate doses in man probably act on both cortical and subcortical systems involved in the mediation of SW sleep, REM sleep and arousal.
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  • 27
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    Psychopharmacology 15 (1969), S. 64-72 
    ISSN: 1432-2072
    Keywords: Amphetamine ; Dextro Amphetamine ; Psychopharmacology ; Conditioning, Operant ; Pharmacodynamics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Bar pressing was maintained by food reinforcement of each fiftieth response (FR50 schedule). Rats were tested at 3 levels of food deprivation (60, 80 and 100% of ad libitum body weight) under three drug conditions (0, 0.2 and 0.4 mg of D-amphetamine per rat). Overall response rate was reduced by increasing doses of drug, but not significantly by deprivation, within the range studied. The components of response rate were analysed separately into the starting speed (latency of the first response of each ratio run of 50 responses) and running rate. Drug level affected running rate and first latency of the session, whereas body weight affected only first latency of the session. Only the first latency of the session showed an interaction of drug level and body weight. The lack of interaction raises the question, whether amphetamine is more properly administered as total dose per rat, rather than proportional to body weight.
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  • 28
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    Psychopharmacology 15 (1969), S. 144-152 
    ISSN: 1432-2072
    Keywords: Niacin ; Nicotinamide Adenine Dinucleotide ; Schizophrenia ; Phenothiazines ; Psychopharmacology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Two grams of NAD were administered orally to ten chronic schizophrenic patients for twenty-one days. Five of the patients were also receiving thioridazine. There was no gross clinical improvement noted in any of the patients despite the fact that related experiments suggested that the NAD was absorbed. In those patients who were not also receiving phenothiazines there was a distinct tendency towards increased hostility, aggressiveness and irritability beginning one week after the initiation of NAD treatment and lasting for nearly two weeks after the NAD was discontinued.
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  • 29
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    Psychopharmacology 14 (1969), S. 221-232 
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Animal Behaviour ; Nicotine ; Punishment
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The effects of nicotine, amphetamine, chlordiazepoxide and caffeine were studied in rats trained on a VI 2 crf schedule of water reward with all rewards accompanied by electric shock. Responding, partially suppressed by the shock, was restored by chlordiazepoxide and further suppressed by amphetamine. Nicotine resembled amphetamine in its effects on most rats but occasionally increased responding. Caffeine also increased responding in some rats indicating that this property is not always confined to tranquillising drugs.
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  • 30
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    Cell & tissue research 101 (1969), S. 98-118 
    ISSN: 1432-0878
    Keywords: Insect: Nerve ; Ultrastructure ; Regeneration ; Degeneration
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary After cutting a neck connective of Schistocerca gregaria, only 2% of the axons on each side of the lesion degenerate. The remainder show reactive changes, which last for approximately one week at 28° C. There is no morphological change in either of the pro/mesothoracic connectives after injury to the neck connective. Phagocytes invade the stumps, but attack only degenerating cells, and are absent by Day 7. Regeneration from the connective stumps begins a week after injury; a functional link may be formed by Day 10, but by Day 23 the new connective cannot function adequately for the locust's survival, if the undamaged connective is then cut. The chief morphological changes in the reactive axoplasm are increases in the number of mitochondria, neurotubules, vesicles and vacuoles. These changes appear to be a local response, and not to be influenced by the neuron cell bodies. Some glial cytoplasm (presumably enucleated), degenerates rapidly after injury, and replacement begins by Day 5. Tracheoles, never seen in normal connectives appear in the reactive connective from Days 3–8, this is interpreted as a migration from the ganglion in response to oxygen deficiency in the connective. The results are discussed in relationship to previous work.
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  • 31
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    Cell & tissue research 101 (1969), S. 167-174 
    ISSN: 1432-0878
    Keywords: Flounder ; Chloride Cell ; Ultrastructure ; Cell Type ; Pseudobranch Gland
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The free or “non-glandular” pseudobranch of the flounder Paralichthys lethostigma was studied with the electron microscope. Cells typical of glandular type pseudobranchs are found. This indicates that, at least in the flounder, the free pseudobranch should be called “glandular”. In addition, the chloride-type cells, commonly found in the gill, buccal epithelium, and surface epithelium of other fish, have been found in the pseudobranch, where they have not been described previously. The fine structure of both the chloride-type and the pseudobranch-type cell has been characterized and contrasted. We have not been able to confirm previous reports that the specific cells in both pseudobranch and gill are identical in the flounder.
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  • 32
    ISSN: 1432-0878
    Keywords: Lymphatic vessels ; Mesentery ; Ultrastructure ; Histochemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung Die ableitenden Lymphgefäße im Mesenterium des Dünndarms männlicher weißer Ratten wurden elektronenmikroskopisch und histochemisch untersucht. Elektronenmikroskopisch findet sich ein lückenloses Endothel mit reichlich pinocytotischen Vesikeln. Eine Basalmembran ist im Klappenbereich durchgehend, sonst nur bruchstückweise vorhanden. Die darunter gelegene Bindegewebsschicht (Lamina propria interna) ist sehr unterschiedlich ausgeprägt. Die lichtoptische Einteilung in muskelstarke und muskelschwache (klappennahe) Abschnitte des Lymphangions läßt sich elektronenmikroskopisch bestätigen. Die zahlreichen membrannahen Vesikel der Muskelfasern sind bei Kontraktion in zahnartigen Fortsätzen angereichert. Auch beim Normaltier treten sog. „aktivierte“ Muskelzellen auf. Osmiophiles Material ist nach Fettfütterung zwischen den Muskelzellen und in der Lamina propria interna der Gefäßwand vorhanden, nicht dagegen in den Klappen. Der Kontakt zwischen den Muskelzellen erfolgt mittels fingerartiger Fortsätze. Endothel und Klappen sind frei von nervösen Elementen. Nervenendigungen und Axone sind zwischen den Muskelfasern nicht zu beobachten, hingegen ganz selten Ganglienzellen. Histochemisch sind im Endothel starke Aktivitäten der sauren Phosphatase und der Monoaminooxydase nachzuweisen, auch unspezifische Esterasen, ATP-ase sowie verschiedene Dehydrogenasen sind vorhanden. Cholinesterase, Cholindehydrogenase und alkalische Phosphatase fehlen. In der Media sind unspezifische Cholinesterase, unspezifische Esterasen, ATPase, Monoaminooxydase, Succinodehydrogenase und NAD-Diaphorase nachweisbar. Im einzelnen kann die Stärke der Aktivität einem bestimmten Abschnitt (muskelstark/muskelschwach) des Lymphangions zugeordnet werden. Damit ist eine Einteilung der Lymphangione in klappentragende und muskelmanschettenhaltige Anteile auch histochemisch möglich. Im Gegensatz zur Adventitia der Blutgefäße gibt die der Lymphgefäße keine Reaktion auf alkalische Phosphatase. Die dort reichlich vorhandenen Mastzellen sind Naphthol-AS-D-chloracetat-esterase positiv.
    Notes: Summary The large lymphatic vessels in the mesentery of male white rats were investigated with ultrastructural and histochemical methods. Electron micrographs show an uninterrupted simple endothelial layer, the individual cells of which are rich in pinocytotic vesicles. A distinct continous basement membrane is to be found only in the region of the valves, otherwise it is lacking over wide parts of the vessel wall. The so-called lamina propria interna differs greatly in its extent. Electron microscopy confirms the subdivision of the lymphangion into segments rich in muscle cells and others (in the area of the valves) which are less rich in them. Muscle cells contain numerous vesicles in close connection with the cell membrane which in contracted cells are to be found predominantly in toothlike projections. Also in the normal rat, so-called “activated” muscle cells are to be found. After a meal rich in fat, osmiophilic material can be seen between the muscle cells and in the lamina propria interna, however, not in the valves. Muscle cells are in contact with each other by finger-like processes. The endothelial layer and the valves are lacking nervous elements. There are no nerve endings and no axons between the muscle cells, but very rarely ganglion cells can be found. Histochemically, strong activities of acid phosphatase and MAO have been demonstrated in the endothelial layer. Unspecific esterases, ATP-ase and various dehydrogenases are also present, while cholinesterase, cholindehydrogenase and alkaline phosphatase are lacking. In the media, unspecific esterases, unspecific cholinesterase, MAO, succinodehydrogenase and Naddiaphorase can be found. The intensity of enzymatic activities can be correlated to specific segments of the lymphangion. It is, therefore, possible to distinguish by histochemical methods the valve areas, which are poor in muscle cells, from the muscle-cuffs. In contrast to the blood vessels, the adventitia of the large lymphatics is alkaline-phosphatase negative. The mast cells, abundant in the adventitial layer, show α-Naphthol-AS-D-chloroacetate-esterase activity.
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  • 33
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    Cell & tissue research 101 (1969), S. 401-407 
    ISSN: 1432-0878
    Keywords: Myriapoda ; Kidney ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung Die Feinstruktur der Maxillarnephridien von Scutigerella immaculata Newport mit ihren drei Abschnitten Sacculus, Tubulus und Ausführgang wurde untersucht. Die Zellen des Sacculus sind typische Podocyten, an denen eine Ultrafiltration ablaufen kann. Möglicherweise wird die Filtration durch einen den Sacculus umgebenden Muskel unterstützt. Die Zellen des Tubulus zeigen basale Einfaltungen und im proximalen Teil auch Mikrovilli. Sowohl im Tubulus als auch im Ausführgang, dessen Zellen ebenfalls basale Einfaltungen aufweisen, werden Reabsorptionsprozesse vermutet.
    Notes: Summary The fine structure of the maxillary kidney of Scutigerella immaculata Newport (Symphyla) has been investigated. It may be compared with segmental organs of other Arthropoda having an end-sac which forms a primary urine by ultrafiltration. The filtration may be supported by a muscle surrounding the end-sac. The tubular part of the nephridium and the efferent duct show structures which may be involved in reabsorption.
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  • 34
    ISSN: 1432-0878
    Keywords: Oogenesis ; Nuclear-Cytoplasmic relationships ; Microtubules ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary For a limited period during the oogenesis of Protopterus, blebs of the perinuclear cistern contain, in addition to other inclusions, a special kind of microtubular elements. Most of these blebs face parts of multiple nucleolar bodies that extend toward and make contact with the inner nuclear membrane. The microtubular lumen contains a finely dispersed material of moderate electron density which seems to be in contact with this nucleolar material. Aside from these intracisternal structures there are, within both the perinuclear cytoplasm and the nucleoplasm, similar microtubular arrays without apparent connection with the nuclear envelope. These are either enclosed by membranes derived from those of the envelope or unconfined, having escaped through breaks in their respective bounding membranes. Extracisternal tubules are presumed to have passed their period of putative functional activity and to be undergoing a process of regression and subsequent disintegration. Among possible roles attributable to the intracisternal microtubular apparatus are the following: (1) It may serve for the transport of special nucleolar components to the cytoplasm, possibly to be incorporated in the matrix of developing perinuclear mitochondria; (2) it may provide openings in the nuclear membranes for the direct passage of particulate elements between nucleus and cytoplasm; (3) it may be instrumental in the breakdown of parts of the nuclear envelope prior to its restitution during the subsequent phase of oogenesis.
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  • 35
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    Cell & tissue research 102 (1969), S. 570-593 
    ISSN: 1432-0878
    Keywords: Neuroendocrine structures ; Gastropods ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Studies of possible neuroendocrine structures in the pulmonate gastropod Helisoma tenue show that cerebral fuchsinophilic neurons with electron-dense granules (mean diameter 1,500 Å) apparently release their secretory content in an “intercerebral commissure neurohemal area” near the mediodorsal bodies (MDB) or in the “median labial nerve neurohemal area”. The MDB cells have axon-like processes which branch and end at the cerebral surface, separated by a thin capsule from the cerebral fuchsinophilic cells. The presence of granules (mean diameter 800 Å) in the terminals of the MDB cells suggests cell body origin, distal transport and release of the granular secretory material. The secretory product may have an influence on cerebral fuchsinophilic neurons. Electron microscopy reveals the presence of granules of different sizes and densities in expanded neurites at the periphery of the intestinal nerve of the visceral ganglion which may indicate the presence of a neurohemal area. However, the granules in the intestinal nerve neurites and in the visceral ganglion fuchsinophilic cells are similar to granules found in the heart which also suggests that the granules may carry a neurotransmitter.
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  • 36
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    Cell & tissue research 101 (1969), S. 477-509 
    ISSN: 1432-0878
    Keywords: Insects ; Proctodeum ; Cuticle ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Résumé L'ultrastructure de la cuticule du rectum a été étudiée chez onze espèces d'Insectes, appartenant à neuf ordres. On s'est surtout intéressé aux espèces présentant des papilles rectales; dans ce cas on distingue toujours trois types de cuticule: cuticule de l'épithélium rectal, cuticule des papilles, cuticule du ≪cadre≫ entourant les papilles. La cuticule du cadre est formée d'une masse compacte et amorphe, sclérifiée, surmontée d'une cuticuline de structure normale. Les deux autres types de cuticules possèdent une structure plus classique: épicuticule comprenant cuticuline et zone dense, et endocuticule. La cuticule de l'épithélium rectal a toujours une structure comparable à celle d'une cuticule périphérique non sclérifiée. La cuticule des papilles est plus variable, et toujours différente de celle de l'épithélium rectal. Ces différences portent sur la cuticuline, la zone dense, les filaments épicuticulaires; l'endocuticule sur les papilles montre une organisation fibrillaire moins nette, qui paraît corrélative d'une réaction positive à l'APS. Des canaux poraires n'ont jamais été observés dans la cuticule des papilles; il en existe quelquefois dans la cuticule de l'épithélium rectal. Une sous-cuticule, contenant des mucopolysaccharides acides, est présente dans certains cas dans les deux types de cuticule. Dans les espèces ne possédant pas de papilles rectales, il n'existe qu'un seul type de cuticule rectale, variable suivant l'espèce. La cuticule des papilles montre, dans certaines espèces, des dépressions superficielles, d'un diamètre voisin de 0,2 μ, réparties uniformément mais sans ordre défini (≪dépressions épicuticulaires≫). De telles dépressions s'observent aussi dans quelques espèces dépourvues de papilles (Tenebrio). Au niveau de ces dépressions, la cuticuline a une structure particulière et la zone dense est réduite. Les rapports entre structure et perméabilité de la cuticule sont discutés. On envisage en particulier les rôles respectifs de la cuticuline, de la zone dense, des filaments épicuticulaires et des dépressions épicuticulaires.
    Notes: Summary The ultrastructure of the rectal cuticle was studied in eleven species of Insects from nine orders. Special attention was given to those having rectal papillae. In such species, three types of cuticule were observed: 1) the cuticle of the rectal epithelium, 2) the cuticle of the papillae, 3) the cuticle of the border of the papillae. The cuticle of the border is made of a compact amorphous substance, which is sclerotized and covered by a typical cuticulin layer. The two other types of cuticle exhibit a more conventional organization, namely the epicuticle comprising both the cuticulin and the dense layer, and the endocuticle. The cuticle of the rectal epithelium is similar to unsclerotized external cuticle. The cuticle of the papillae is more variable and always differs from the cuticle of the rectal epithelium. Variations occur with regards to the cuticulin, the dense layer and the epicuticular filaments. The endocuticle of the papillae has a less conspicuous fibrillar structure which we believe is correlated with the PAS-positive reaction found in this endocuticle. Pore canal sometimes are observed in the cuticle of the rectal epithelium but never above the papillae. In some cases, a sub-cuticular layer containing acid mucopolysaccharids is present in the two types of cuticle. In species lacking rectal papillae, the rectal wall is covered by only one type of cuticle, the features of which vary according to species. In some Insects, the cuticle of papillae shows numerous superficial depressions, each of about 0.2 μ in diameter. These “epicuticular depressions” are uniformly distributed throughout the papillae but are not arranged in any particular pattern. We have also found such depressions in other Insects lacking rectal papillae (e.g. Tenebrio). In the epicuticular depressions, the cuticulin exhibits a modified organization and the dense layer is reduced. The relations between ultrastructure and cuticular permeability are discussed. The possible roles of the cuticulin, the dense layer, the epicuticular filaments and the epicuticular depressions are examined.
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  • 37
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    Cell & tissue research 102 (1969), S. 1-30 
    ISSN: 1432-0878
    Keywords: Pineal organ ; Columba livia ; Electrical activity ; Ultrastructure ; Sensory (?) and secretory pinealocytes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung Direkte Belichtung oder Lichtreizung der Lateralaugen lösen im zentralen Teil der Taubenepiphyse keine elektrische Aktivität aus. Im Stielabschnitt sind dagegen kleine, durch Licht nicht beeinlußbare Dauerentladungen zu beobachten. Die Lage der Ableitungspunkte wurde durch den histologischen Nachweis der elektrolytisch gesetzten Eisenmarken bestimmt. Diese Ableitungsstellen befinden sich im Epiphysenparenchym. Ein stärkeres versilberbares Nervenbündel verläuft im Stiel der Epiphyse. Adrenerge Nervenfasern, die grün fluoreszieren, begleiten die Kapselgefäße und dringen mit diesen in das follikuläre Epiphysengewebe ein. Das Epiphysenparenchym zeigt nach Falck-Hillarp eine Gelbfluoreszenz mit umschriebenen apikalen oder basalen Anreicherungen der fluoreszierenden Substanz. Mit Reserpin kann nur ein Teil dieses Materials entspeichert werden. Elektronenmikroskopisch lassen sich in der Taubenepiphyse keine typischen pinealen Rezeptorzellen nachweisen. Regelmäßig lamellierte Außenglieder fehlen vollständig. Es finden sich lediglich cytoplasmareiche bulböse Zilien und zirkuläre Lamellenkomplexe, die in Tubuli übergehen. Die letzteren können sich mit einem dichten körnigen Material füllen. An einigen Stellen haben solche Lamellenverbände einen Zusammenhang mit keulenförmig verdickten Zilien. Diese Zone ist aber anders strukturiert als das für retinale und pineale Lichtsinneszellen charakteristische Verbindungsstück. Die Zeichen der sekretorischen Aktivität der Taubenepiphyse sind überzeugender als die für einen lichtempfindlichen Sinnesapparat sprechenden Strukturmerkmale. Ein bestimmter Typ der Pinealocyten ist reich an 800–1200 Å großen granulierten Vesikeln, die sowohl am apikalen als auch am basalen, auf die Blutgefäße ausgerichteten Zellpol angehäuft sein können. An den manchmal gelappten basalen Endfüßen sind Zeichen der Ausschleusung des Vesikelinhalts bzw. eines Materialschwundes aus dem granulierten Vesikelkern zu erkennen. Die sekretorische Aktivität der Taubenepiphyse wird mit Hinweis auf die in ihr reichlich vorkommenden 5-Hydroxyindole (Quay) und das Problem der Melatonin-Bildung diskutiert. Erörtert wird auch die Möglichkeit einer Stimulierung dieser Sekretion über den Sympathikus.
    Notes: Summary Direct illumination or stimulation with light of the lateral eyes induced no electrical activity in the central part of the pineal organ in the pigeon. In the pineal stalk, however, a train of impulses was observed that failed to respond to changes of illumination. The position of the tip of the recording electrode (iron deposit), was histologically clearly determined to be in the pineal parenchyma. A distinct nerve bundle could be traced down the pineal stalk. Adrenergic nerve fibers showing a green fluorescence accompanied pineal capsular vessels into pineal follicular tissue. Using the method of Falck-Hillarp, the pineal parenchyma showed high concentrations of yellow fluorescent material in the apical or basal parts of the pinealocytes. Only a part of the fluorescent material could be dispersed with reserpine. In the electron microscope, no typical photoreceptor cells were identified in the pineal organ. Only large bulbous cilia, and circular lamellar or tubular complexes, were observed; they sometimes contained a dense granular material. Occasionally, the lamellar complexes had a direct relation to cilia of club-shaped appearance. Signs of secretory activity were more definitive in the pigeon pineal organ than sensory structures. One type of pinealocytes contained many 800–1,200 Å diameter granular vesicles concentrated in the apical or basal (apposed to blood vessels) cell parts. At the occasionally lobulated basal end-feet, a disappearance of the content of the granular vesicles indicated a release mechanism. This secretory activity was discussed in relation to the 5-hydroxyindole content of the pigeon pineal organ (Quay) and the general problem of melatonin synthesis; also, the possibility was considered that the secretory activity may be stimulated by sympathetic nerve fibers.
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  • 38
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    Cell & tissue research 101 (1969), S. 323-337 
    ISSN: 1432-0878
    Keywords: Vitreous body ; Hyalocytes ; Three-dimensional network ; Fibers ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The vitreous body of the rat eye was studied by scanning electron microscopy. The freeze-dried specimens were either unfixed, freshly frozen or fixed and rinsed before being frozen. The vitreous body is surrounded by a coat of intercellular material covering a thin sheath of chiefly parallel fibers. The latter forms the base for a regularly organized three-dimensional network of fibers. The interfibrillar spaces are filled with ground substance and also contain a few cells. The shape of the cells varies from bipolar to polyhedronal. Their interconnected processes are usually undivided. The functional importance of this complex regular organization of the fibers and cells in the vitreous body is stressed.
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  • 39
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    Cell & tissue research 102 (1969), S. 31-39 
    ISSN: 1432-0878
    Keywords: Muscle ; Sarcoplasmic reticulum ; Ultrastructure ; Cytochemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The sarcolemma and T system and the sarcoplasmic reticulum were studied in a fast acting muscle, the extraocular muscle of Fundulus grandis. The predominant morphological fiber type contained abundant glycogen, a highly developed T system with triads at the A-I junction and a well developed sarcoplasmic reticulum. The numerous tubular profiles of T system and sarcoplasmic reticulum with their characteristic contents made this fiber especially suitable for cytochemical investigation. Revel's thorium dioxide technique for the ultrastructural localization of tissue polyanions was applied to thin sections of extraocular muscle. The results confirmed an earlier report by Goldstein and Philpott on fish branchial muscle. The polyanionic material was associated with the sarcolemma, the T system and the sarcoplasmic reticulum of these fibers. Both the distribution and the amount of polyanionic substance associated with these physiologically important membrane systems support the idea that the reactive material serves as an anionic substrate for binding cationic calcium.
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  • 40
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 1 (1969), S. 585-587 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 41
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 1 (1969) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 42
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    International Journal of Chemical Kinetics 1 (1969), S. 1-1 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 43
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    International Journal of Chemical Kinetics 1 (1969), S. 3-9 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: C—Cl and C—C bond energies in the chloroethanes and C—H, C—Cl, and C—C bond energies in the chloroethyl radicals are calculated from known heats of formation of chloroethanes and chloroethylenes and known C—H bond energies in chloroethanes.The results obtained show a dependence of bond energy on the isomeric structure of the molecules and radicals and on the type of bond broken (primary, secondary, or tertiary). Heats of formation and bond energies estimated from group property additivity rules are in close agreement with experimental values.
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  • 44
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    International Journal of Chemical Kinetics 1 (1969), S. 11-27 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study of the pressure dependence of the C5 products from the reaction of cis-butene-2 and methylene is reported. Methylene was produced by the photolysis of diazomethane with 4358 Å light at 23° or 56°, and by photolysis of ketene with 3200 Å radiation at 23° or 100°. The change with increasing pressure of the relative amounts of the characteristically “triplet products” (trans-1,2-dimethylcyclopropane, trans-pentene-2 (TP2), and 3-methylbutene-1 (3MB1)) and “singlet products” (cis-1,2-dimethylcyclopropane (CDMC) and cis-pentene-2 (CP2)) are discussed. The behavior is reminiscent of that found in 3CH2-cis-butene-2 systems and can be interpreted in terms of the rapid rate of rearrangement of an initial triplet diradical product component, due to 3CH2, relative to the slower rate and readier collisional stabilization of an initial vibrationally-excited dimethyl cyclopropane product component, due to 1CH2. Relative rates of reactions of 1CH2 with allylic CH:vinyl CH:C=C in the neat liquid were, for diazomethane, 1:1.1:7.2 and, for ketene, 1:1.2:6.7.
    Additional Material: 13 Ill.
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  • 45
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The use of iodine monochloride (ICl) as a thermal source of chlorine atoms in known concentration is discussed with particular reference to the suppression, by large excesses of iodine, of the chain processes normally associated with chlorine atom reactions. The kinetics and mechanism of the reaction of ICl with hydrogen are presented in a study covering the temperature range 205-337°C, and the pressure ranges: ICl, 6-20 torr; I2, 3-13 torr; and H2, 9-520 torr. The reaction, followed spectrophotometrically in a static system, is shown to be homogeneous, first order in ICl and in H2, and inverse half-order in I2, over several half-lifetimes of the ICl, yielding HCl as the sole product. The rate data obtained in this work for the reaction are combined with the critically evaluated results of other workers in an Arrhenius plot covering the temperature range 286-730°C, and three orders-of-magnitude in the rate constant, yielding the results, log k1/(1/mole sec) = 10.68-5.26/θ, where θ = 2.303RT in kcal/mole. This value of k1 is lower by a factor of about two than that proposed in a recent review by Fettis and Knox, and is clearly at variance by a factor of two or more with the most recent data of Clyne and Stedman.
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  • 46
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The temperature-jump method has been used to determine the nickel(II)- and cobalt(II)-arginine complexation kinetics. In the pH range studied, the neutral form of the ligand, HL, is the attacking, as well as the complexed, ligand species. The reactions reported on are of the type where n = 1, 2, 3 and M is Ni or Co. At 25° and ionic strength 0.1M the association rate constants are: for nickel(II) k1 = 2.3 × 103(±20%), k2 = 2.4 × 104(±20%), k3 = 3.5 × 104(±40%) M-1 sec-1; for cobalt(II) k1 = 1.5 × 105(±20%), k2 = 8.7 × 105(±20%), k3 = 2.0 × 105(±40%) M-1 sec-1. Arginine binds to metal ions less well than homologous chelating agents due to the electrostatic repulsion arising from the positively charged terminus of the zwitterion. Kinetically, the effect appears in the association rate constants with nickel reactions more strongly influenced than cobalt.
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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 spectrophotometric determination of the rate of iodine atom catalyzed geometrical isomerization of diiodoethylene in the gas phase from 502.8 to 609.1°K leads to a rate constant for the bimolecular reaction between I and trans-diiodoethylene of log kt-c(M-1 sec-1) = 8.85 ± 0.12 - (11.01 ± 0.30)/θ. Estimates of the entropy and enthalpy change for the addition of I atoms to trans-diiodoethylene (process a.b) lead to log Ka.b(M-1) = -2.99 - 4.0/θ, and thus to log kc (sec-1) = log kt-c - log Kab = 11.8 -7.0/θ for the rate constant for rotation about the single bond in the adduct radical. The theory for calculation of the rotation rate constant is presented and it is shown that while the exact value depends on the barrier height, a value of 6.8 kcal/mole for this quantity leads to log k (sec-1) = 11.8 -6.7/θ. The activation energy points to a better value of the group contribution to heat of formation of the group C-(I)2(H)(C) than one based on bond additivity.
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  • 48
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    International Journal of Chemical Kinetics 1 (1969), S. 69-87 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title reactions have been investigated in a fast flow system at pressures of about 2 torr and temperatures between 12 and 132°C. The following Arrhenius equations are derived for reaction (2) where the units of k2 are l/mole sec and of E2, cal/mole, and the limits are the 95% confidence limits assuming random errors.These equations are in good agreement with those which can be derived from previous investigations.
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  • 49
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    International Journal of Chemical Kinetics 1 (1969), S. 105-111 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction between carbon monoxide and atomic oxygen was studied in a gas flow over a temperature range of 136 to 230°C at atmospheric pressure. The rate constant of this reaction, considered to be one for a second-order reaction, was found to decrease with increasing temperature and to depend on the ratio of O2 to CO that was varied from 0.11 to 2.69. A conclusion was made that under the experimental conditions the reaction was third order The rate constant of this reaction was determined for a mixture of O2 and CO and it was found that the efficiency of O2 as particle M is four times that of CO.
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  • 50
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    International Journal of Chemical Kinetics 1 (1969), S. 113-126 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rates of solvolysis of benzyl chloride and of substituted benzyl chlorides have been measured in an acetone-water mixture (acetone mole fraction 0.147) at pressures ranging from atmospheric to 1 kbar. Pressure studies have also been made for p-methyl benzyl chloride in various acetone-water mixtures. Measurements have also been made of the partial molar volumes of the reactants. The plots of log k against pressure are fitted to a second-degree polynomial in P, and values of ΔV
    Additional Material: 5 Ill.
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  • 51
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The method of molecular-modulation spectrometry for studying photochemical reactions has been applied to methyl nitrite photolysis. The infrared absorption of the nitroxyl radical HNO has been observed in the gas phase at 3300 cm-1. Under the present experimental conditions the steady-state concentration of HNO under steady illumination was 1.1 × 1012 particles/cc, and the observed modulation amplitude was 4.5 × 1010 particles/cc. At 25°C and 1 atm of nitrogen, the cross section for infrared absorption by HNO at 3300 cm-1 is 1.7 × 10-19 cm2. The rate constant ratio b/c was found to be 8.0. From the literature value of the rate constant d , the observed rate constant for the reaction is e = (5 ± 1) × 10-11 cc/particle sec.
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  • 52
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 1 (1969) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 53
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The spectrophotometric determination of the rate of pyrolysis of 1,2-diiodoethylene from 305.8 to 435.0° (with additional data on the addition of iodine to acetylene from 198.1 to 331.6°) has resulted in the observation of both a (in part heterogeneous) unimolecular process (A), and an iodine atom catalyzed process (B). For the homogeneous unimolecular process, log (kA/sec-1) ≈ 12.5-46/θ would appear to be reasonable, while log (kB/M-1 sec-1) = 11.8-23.9/θ, where θ = 2.303RT in kcal/mole.It is suggested that a donor-acceptor complex intermediate may explain the observed rate constant of process B and analogous reactions in other systems.
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  • 54
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    International Journal of Chemical Kinetics 1 (1969), S. 133-146 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal isomerization of the title compounds was studied in the vapor phase. Over the temperature range from 445.1 to 477.5°K, 1,4-dimethylbicyclo[2.2.0]hexane underwent a homogeneous unimolecular reaction to 2,5-dimethyl-1,5-hexadiene, the rate constants being represented by the equation: k = 1.86 × 1011 exp (-31000 ± 1800/RT) sec-1. Over the temperature range from 630.0 to 662.2°K, 1,4-dimethylbicyclo[2.1.1]-hexane also underwent a unimolecular isomerization to the same product, the rate constants being given by the equation: k = 8.91 × 1014 exp (-56000 ± 900/RT) sec-1. The pyrolysis of 1,4-dimethylbicyclo[2.1.0]pentane gave 1,3-dimethylcyclopentene-1 and 2,4-dimethyl-1,4-pentadiene in the ratio of 9:1. The former reaction was influenced by surface effects but the latter was not. The rate constants for the formation of 2,4-dimethyl-1,4-pentadiene fitted the equation: k = 1.66 × 1017 exp (-57400 ± 3100/RT) sec-1. The effect of the two methyl groups at the bridgehead positions in these molecules in influencing the rate of decomposition is discussed in terms of the non-bonded repulsive forces between the substituents.
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  • 55
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    International Journal of Chemical Kinetics 1 (1969), S. 157-170 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Isotope effects, general acid catalysis, and relative reactivities show that proton transfer to one of the unsaturated carbon atoms is rate determining for the acidolysis of unsaturated alkylmercuric halides. For compounds, R1R2C=CHHgX, substitution of CH3 for H at R1 or R2 leads to an acceleration of a factor of ∼ 30. This relatively small acceleration, the relative facility of the reactions, and the magnitude of the Br- catalytic terms, suggests an olefin-mercuric halide complex as the product of the rate-determining step, rather than a simple carbonium ion.The Brøonsted catalysis law is obeyed with a variety of carboxylic acids, giving an ∝ of 0.69 ± 0.04, but acids of other structures give substantially deviant catalytic coefficients, in a pattern similar to that generated by other A-SE2 reactions. The acetic acid catalytic coefficient is larger by a factor of 102 than that predicted if it were due to specific hydronium ion-general base catalysis instead of true general acid catalysis.The overall solvent isotope effect, kH/kD, is 2.55 ± 0.10. The competitive isotope effect, κH/κD, is 6.84 ± 0.06. Taken with a model in which the proton is transferred directly from the H3O+ unit of the aquated proton to the substrate, these are sufficient to successfully predict the rate at all intermediate isotopic compositions.
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  • 56
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    International Journal of Chemical Kinetics 1 (1969), S. 171-191 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of azomethane-d6 has been studied. There is a short chain reaction, and measurements have been made of the rate of production of N2, CD4, and C2D6. A mechanism is suggested which accounts for these results fairly well. A comparison is made with some similar results of Forst for azomethane. Measurements have also been made of the reaction inhibited by NO. It is believed that the N2 production, extrapolated to zero NO pressure, measures the rate of the initial step CD3N2CD3 → 2 CD3 + N2. This has an activation energy at high pressures of 50.7 kcal per mole and an Arrhenius A·factor of 1015.49 sec-1. This is to be compared to values of 55.5 and 1017.3 found by Forst and Rice for CH3N2CH3 → 2 CH3 + N2. The pressure fall-off behavior for CD3N2CD3 → 2 CD3 + N2 has also been investigated and compared to the theoretical curves, which seem to fit satisfactorily except at the lowest pressure, where experimental errors may be large. Unexpectedly, the fall-off curve crosses that for CH3N2CH3 → 2 CH3 + N2. It is suggested that the extrapolation to zero NO pressure may not be entirely correct in the CH3N2CH3 case where the chain is longer than with CD3N2CD3. It is believed that the decomposition of azomethane-d6 is a better example for unimolecular-rate theory than is that of azomethane.
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  • 57
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    International Journal of Chemical Kinetics 1 (1969), S. 193-207 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: t-Butylperoxy α-phenylisobutyrate (I) decomposes thermally by concerted formation of carbon dioxide, t-butoxy, and cumyl radicals. Radical pair return in the solvent cage therefore does not affect the observed rate of decomposition, but is readily determined by means of galvinoxyl and other scavengers. In a series of 15 solvents the rate constant varies over a 2.8 fold range, being fastest in aromatic solvents. In the same solvent series the relative rates of diffusion and combination of radicals, measured by the cage effect, change by tenfold and are largely determined by the viscosity of the solvent. In all solvents of η 〉 8 mP, the reciprocal of the cage effect is a linear function of (T1/2/η), as recently observed for trifluoromethyl and methyl radicals [16]. This property of the cage effect provides a test by which it can be distinguished from other processes that reduce the efficiency of free-radical production from an initiator.
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  • 58
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    International Journal of Chemical Kinetics 1 (1969), S. 279-282 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 59
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of ozonation of C2H4 and C2H2 have been studied in the gas phase from -40 to -95°C (C2H4) and +10 to -30°C (C2H2). The O3 concentrations were near 10-4 M, and the hydrocarbons were present in 2- to 25-fold excess. A few experiments with propylene were also carried out. The reactions were followed by observing the rate of decay of O3 absorption at 2537 Å. Reaction stoichiometries and effects of added O2 were investigated. The second-order rate constant for C2H4 was log k(M-1 sec-1) = (6.3 ± 0.2) - (4.7 ± 0.2)/θ (θ = 2.3RT). The rate was independent of the presence of excess O2. Rate measurements for C3H6 were less accurate because of aerosol interference. Combined with room temperature measurements of other workers, the C3H6 rate constant was log k(M-1 sec-1) = (6.0 ± 0.4) - (3.2 ± 0.6)/θ. The C2H2 rate constant was log k(M-1 sec-1) = (9.5 ± 0.4) - (10.8 ± 0.4)/θ. In the case of C3H6 the major product was propylene ozonide. Ethylene did not yield the ozonide, and the products of the O3-C2H4 and O3-C2H2 reactions were not identified. Pre-exponential factors for the olefin reactions are consistent with a five-membered ring transition state formed by 1,3 dipolar cycloaddition of O3. For C2H2, however, the much higher observed A factor suggests a different mechanism. Possible transition states for the O3-C2H2 reaction are discussed.
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  • 60
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    International Journal of Chemical Kinetics 1 (1969) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 61
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methods are presented for rapidly estimating the entropies and heat capacities of free radicals from the known S0 and Cp0 of structurally similar compounds. The methods consist of estimating the differences due to changes in mass, vibration frequencies, spin, symmetry, and changes in rotational barriers. Tables of contributions to S0 and Cp0 by different frequencies over the temperature range 300-1500°K are presented to facilitate the tabulation of the above differences. Conjugated radicals, such as benzyl and allyl, are included. It is shown that the greatest uncertainties in the estimates arise from uncertainties in the barriers to rotation in the radicals.The results are applied to kinetic data on the pyrolysis of branched hydrocarbons and the reverse reactions of radical recombination. Major discrepancies exist in these data which can be nearly reconciled by postulating improbably high rotational barriers of 8 kcal for CH3 rotation in isopropyl and t-butyl radicals.It is shown that radical thermochemistry can be fitted into group schemes and tables of groups values are given for the rapid estimation of ΔHf0, S0, and Cp0 for different organic radicals, including those containing sulfur, oxygen, and nitrogen.
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  • 62
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of the reaction CH2I2 + HI ⇆ CH3I + I2 has been followed spectrophotometrically from 201.0 to 311.2°. The rate constant for the reaction fits the equation, log (k1/M-1 sec-1) = 11.45 ± 0.18 - (15.11 ± 0.44)/θ. This value, combined with the assumption that E2 = 0 ± 1 kcal/mole, leads to ΔHf298° (CH2I, g) = 55.0 ± 1.6 kcal/mole and DH298° (H—CH2I) = 103.8 ± 1.6 kcal/mole.The kinetics of the disproportionation, 2 CH3I ⇆ CH4 + CH2I2 were studied at 331° and are compatible with the above values.
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  • 63
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several hydrocarbons have been pyrolyzed in a single pulse shock tube. Rate parameters for the main bond breaking step have been found to be \documentclass{article}\pagestyle{empty}\begin{document}$$ k\left\{{{\rm iC}_3 {\rm H}_7 {-\!-} {\rm CH}\left({{\rm CH}_3} \right){\rm CH} {\raise1pt\hbox{$\Relbar \kern-4pt{\Relbar}$}} {\rm CH}_2 \longrightarrow {\rm iC}_3 {\rm H}_7 \cdot + \cdot {\rm CH}\left({{\rm CH}_3} \right){\rm CH} {\raise1pt\hbox{$\Relbar \kern-4pt{\Relbar}$}} {\rm CH}_2} \right\} = 10^{15.70} \exp \left({{{- 32,500} \mathord{\left/ {\vphantom {{- 32,500} T}} \right. \kern-\nulldelimiterspace} T}} \right)\sec ^{- 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k\left\{{{\rm iC}_3 {\rm H}_7 {-\!-} {\rm C}\left({{\rm CH}_3} \right)_2 {\rm C}_2 {\rm H}_5 \longrightarrow {\rm iC}_3 {\rm H}_7 \cdot + \cdot {\rm C}\left({{\rm CH}_3} \right)_2 {\rm C}_2 {\rm H}_5} \right\} = 10^{16.15} \exp \left({{{- 35,900} \mathord{\left/ {\vphantom {{- 35,900} T}} \right. \kern-\nulldelimiterspace} T}} \right)\sec ^{- 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k\left\{{{\rm C}_2 {\rm H}_5 {-\!-} {\rm C}\left({{\rm CH}_3} \right)_2 {\rm C}_2 {\rm H}_5 \longrightarrow {\rm C}_2 {\rm H}_5 \cdot + \cdot {\rm C}\left({{\rm CH}_3} \right)_2 {\rm C}_2 {\rm H}_5} \right\} = 10^{16.57} \exp \left({{{- 38,800} \mathord{\left/ {\vphantom {{- 38,800} T}} \right. \kern-\nulldelimiterspace} T}} \right)\sec ^{- 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k\left\{{{\rm iC}_3 {\rm H}_7 {-\!-} {\rm CH}_2 {\rm C}_6 {\rm H}_5 \longrightarrow {\rm iC}_3 {\rm H}_7 \cdot + \cdot {\rm CH}_2 {\rm C}_6 {\rm H}_5} \right\} = 10^{15.23} \exp \left({{{- 34,800} \mathord{\left/ {\vphantom {{- 34,800} T}} \right. \kern-\nulldelimiterspace} T}} \right)\sec ^{- 1} $$\end{document} In combination with similar studies carried out earlier and through application of the well-established experimental rule (kr2(AB)/kr(AA)kr(BB))1/2 ∼ 2 where A and B are radicals and the rate constants are for the combination of these radicals, rate parameters for the thermal decomposition of all the hydrocarbons formed from any pair of the following radicals: methyl, ethyl, isopropyl, t-butyl, t-amyl, allyl, methylallyl, and benzyl have been calculated. The available calculated and experimental values of the decomposition rate constants are in excellent agreement. It appears that, with the possible exception of reactions involving the ejection of methyl radicals, the frequency factors per bond are nearly constant, depending only upon the type of carbon-carbon bond that is being broken. These values are all lower than those expected from the radical recombination rates.Heats of formation of ethyl, t-amyl, benzyl, methylallyl, n-propyl, s-butyl, isobutyl, neopentyl, and 3-pentyl radicals have been derived.Rate parameters for the decomposition of some simple ketones and ethers have also been estimated.
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  • 64
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the photoinitiated reductions of methyl iodide and carbon tetrachloride by tri-n-butylgermanium hydride in cyclohexane at 25°C have been studied and absolute rate constants have been measured. Rate constants for the combination of CH3ċ and CCl3ċ radicals are equal within experimental error and are also equal to the values found for the self-reactions of most non-polymeric radicals in low viscosity solvents, i.e. ∼1-3 × 109 M-1 sec-1.Rate constants for hydrogen atom abstraction by CH3ċ and CCl3ċ radicals are both ∼1-2 × 105 M-1 sec-1. Tri-n-butyltin hydride is about 10-20 times as good a hydrogen donor to alkyl radicals as is tri-n-butylgermanium hydride.The strength of the germanium-hydrogen bond, D(n-Bu3Ge-H) is estimated to be approximately 84 kcal/mole.
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  • 65
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    International Journal of Chemical Kinetics 1 (1969), S. 353-356 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 66
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    International Journal of Chemical Kinetics 1 (1969), S. 325-337 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the thermally and radiation initiated chain reaction between trichloroethylene and cyclopentane to produce 1,1-dichlorovinylcyclopentane and hydrogen chloride have been investigated in the temperature range 250-360°C at high pressure in the gas phase. The rate governing step in the chain is (k3 = 3.3 × 109 exp -(4800/RT) cc mole-1 sec -1). The rate of the unimolecular decomposition of trichloroethylene is 1.4 × 1014 exp -(61,200/RT) sec-1.
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  • 67
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    International Journal of Chemical Kinetics 1 (1969), S. 297-314 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase, nitric oxide catalyzed positional isomerization of 3-methylene-1,5,5-trimethylcyclohexene (MTC) into 1,3,5,5-tetramethyl-1,3-cyclohexadiene (TECD) has been studied for temperatures ranging between 296° and 425°C. The major reaction was first order with respect to nitric oxide and to MTC.The major side product, mesitylene, usually amounted to less than 10% of the TECD isomer formed. Only at high temperatures and large conversions has up to 20% been observed.Conditioned pyrex or quartz vessels coated with KCl have been used. The nitric oxide catalyzed isomerization is apparently a homogeneous process, as demonstrated by the insensitivity of the observed rate constants towards a 15-fold increase in the surface to volume ratio of the reaction vessels. However, a residual, presumably heterogeneous, thermal isomerization of the starting material could not be eliminated. Good mass balances were obtained for both NO and hydrocarbons.After correcting for the thermally induced conversion the observed rate constants for the nitric oxide catalyzed isomerization yield log k1 (1 mole-1 sec-1) = (10.7 ± 0.2) - (37.3 ± 0.9)/θ where θ is 2.303 × 10-3 RT (kcal mole-1). Plotting log k1 versus the ratio of the starting materials (MTC/NO)0 it was found that for temperatures ≥ 365°C the rate constants were systematically too high.Using extrapolated values for the higher temperature range yields the more reliable corrected Arrhenius equation log k1corr = 8.6 - 31.7/θ. The reaction mechanism is outlined and the implications with respect to the stabilization energy generated in the MTCċ radical intermediate and the activation energy of the backreaction MTCċ + HNO are discussed.Using for the activation energy E-1 of the backreaction (Rċ + HNO) a literature value of 9.2 ± 0.9 kcal mole-1 reported for the cyclohexadiene—1,3—system, this yields 23.4 ± 2 kcal mole-1 for the stabilization energy in the methylenecyclohexenyl radical, which is to be compared with the corresponding values for the allyl (10.2 ± 1.4), methallyl (12.6 ± 1) pentadienyl (15.4 ± 1) and cyclohexadienyl (24.6 ± 0.7) radicals.The pre-exponential factor agrees well with the value of (8.4 ± 0.2) reported by Shaw and co-workers for the similar reaction of NO with 1,3-cyclohexadiene. It is noteworthy that HNO, acting as sole hydrogen donor in the system, is surprisingly stable under the reaction conditions used. Nitrous oxide, HCN, H2O and N2 are observed in the product mixture of experiments carried out to high conversions at higher temperatures.
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  • 68
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    International Journal of Chemical Kinetics 1 (1969), S. 339-351 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The following Arrhenius parameters have been determined for the hydrogen-abstraction reactions: R + (CH3)4Si → RH + (CH3)3SiCH3 TextRTemp. (°K)E (kcal/mole)Log A (mole-1 cc sec-1)Log k(400°K) (mole-1 cc sec-1)CF3330-4337.23 ± 0.0911.90 ± 0.057.95CH3396-47610.23 ± 0.3611.55 ± 0.185.68CD3396-49610.36 ± 0.1211.84 ± 0.066.20C2H5423-52211.40 ± 0.4811.88 ± 0.225.68The activation energies are in keeping with the strengths of the bonds formed during the reaction. By comparison with the activation energies for the analogous reactions of neopentane it is estimated that D((CH3)3SiCH2—H) ≃ 97 kcal/mole.The A factors for the above series of reactions fall within the range predicted by transition-state theory for this type of process and the validity of previous results of Kerr, Slater, and Young is seriously in doubt.
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  • 69
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    International Journal of Chemical Kinetics 1 (1969), S. 357-359 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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  • 70
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    International Journal of Chemical Kinetics 1 (1969) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 71
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    International Journal of Chemical Kinetics 1 (1969), S. 391-399 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the presence of elementary iodine, isobutyl iodide (2-methyl-1-iodopropane) undergoes isotopic exchange and also decomposes with production of additional iodine. Both reactions are approximately first order in isobutyl iodide and half order in iodine molecules. In degassed hexachlorobutadiene at 160°, the rate constants for exchange and decomposition are 7.5 × 10-6 and 11.4 × 10-6 (liter/mole)1/2sec-1, respectively. The decomposition is probably initiated by iodine atom abstraction of a β hydrogen atom, but comparison with rates for related compounds indicates that this hydrogen abstraction does not contribute significantly to the mechanism of exchange.
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  • 72
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics and mechanism of the reaction between iodine and dimethyl ether (DME) have been studied spectrophotometrically from 515-630°K over the pressure ranges, I2 3.8-18.9 torr and DME 39.6-592 torr in a static system. The rate-determining step is, where k1 is given by log (k1/M-1 sec-1) = 11.5 ± 0.3 - 23.2 ± 0.7/θ, with θ = 2.303RT in kcal/mole. The ratio k2/k-1, is given by log (k2/k-1) = -0.05 ± 0.19 + (0.9 ± 0.45)/θ, whence the carbon-hydrogen bond dissociation energy, DH° (H—CH2OCH3) = 93.3 ± 1 kcal/mole. From this, ΔH°f(CH2OCH3) = -2.8 kcal and DH°(CH3—OCH2) = 9.1 kcal/mole.Some nmr and uv spectral features of iodomethyl ether are reported.
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  • 73
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    International Journal of Chemical Kinetics 1 (1969), S. 371-380 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Arrhenius parameters have been determined for the hydrogen-abstraction reactions: R + SiHCl3 + RH + SiCl3 TextRTemp (°K)E(kcal/mole)Log A(mole-1 cc sec-1)Log k(400°K) (mole-1 cc sec-1)CF3323-4615.98 ± 0.0611.77 ± 0.038.50CH3333-4434.30 ± 0.0810.83 ± 0.044.48C2H5314-4135.32 ± 0.0711.54 ± 0.048.63The trend in activation energies ECH3 〈 EC2H5 〈 ECF3 is interpreted as indicating a polar effect in the reaction of CF3 with SiHCl3 and the similar reactivities of all three radicals appear to be due to the high exothermicity of the reactions.The A Factors for the reactions are normal for hydrogen abstraction reactions of free radicals. The previous results of Kerr, Slater, and Young for CH3 abstracting an H atom from SiHCl3 have been amended.
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  • 74
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    International Journal of Chemical Kinetics 1 (1969), S. 361-370 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Stable nitroxide radicals and ESR techniques have been used to investigate rotational and translational motions of molecules in the liquid state. It is found that for hydrocarbons and molecules with low polarity the rotational frequencies are about an order of magnitude faster than translational encounters. Arrhenius parameters are reported for the rates of both types of processes. A scheme is given for the relation of these motions to radical recombination in solution and also to reactions requiring activation energy. The consequences of this scheme are examined.Such important properties as hydrodynamic fluidity, thermal conductivity, processes of extraction and solution, occurring in the liquid phase as well as at the interface are determined by mobility of particles in the liquid. The problem of molecular mobility is of essential significance for the kinetics of chemical and chemico-physical processes in the liquid phase.Application of both ESR techniques and stable nitroxide radicals for kinetic studies of molecular motions in liquids and the correlation between molecular mobility and the kinetic parameters of liquid-phase radical reactions have been studied in the present paper.
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  • 75
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    International Journal of Chemical Kinetics 1 (1969) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 76
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    International Journal of Chemical Kinetics 1 (1969), S. 413-425 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis of pentafluoroacetone has been investigated in the 3130 Å region, from room temperature to 360°C. The ΦCO varies from 0.7 to 0.9 over this range, and the decomposition is represented by CF2HCOCF3 → CF2H + CO + CF3. The disproportionation/combination ratio for CF3 and CF2H (→ CF3H + CF2) radicals is found to be 0.09. Arrhenius parameters for hydrogen atom abstraction from the ketone are log10A = 12.7 (units are mole-1 cc sec-1) and E = 14.3 kcal mole-1 for CF2H, and log10A = 12.1 and E = 11.8, for CF3 radicals. At low pressures HF elimination reactions are observed from the vibrationally excited fluoroethanes, C2F5H* and C2F4H2*, formed in the system. A rough estimate of the activation energy for the process C2F5H → C2F4 + HF of 60-65 kcal mole-1 is made.
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  • 77
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The activating effects of a number of unsaturated groups and a cyclopropyl group have been evaluated in a solvent free system by determining the absolute rate constants, and energies and entropies of activation in the vapor phase pyrolysis of secondary and tertiary esters of the type RC(R′CH3) OAc where R′ = H or CH3 and R = c-Pr, i-Pr, CH3, CH2=CH, CH2=CHCH2, C6H5; the cyclopropyl showed only a moderate activating effect. The results are in contrast to the very significant activating effect of a cyclopropyl group in solvolysis of cyclopropylcarbinyl derivatives. Apparently marked activation by this group occurs only when a highly developed positive center forms adjacent to it. The lack of marked activation by the cyclopropyl group supports a mechanism for ester pyrolysis which involves a modest, but detectable, charge separation in the transition state [2] but questions a mechanism in which an intimate ion-pair was proposed [3].
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  • 78
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase reaction I2 + HCOOCH3 → HI + CH3I + CO2 has been studied spectrophotometrically in a static system over the pressure ranges I2 (6-39 torr) and HCOOMe (28-360 torr). In the temperature range 293-356°, the initial rate of disappearance of I2 is first order in [HCOOMe] and half-order in [I2]. The rate determining step is where k1 is given by \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} \left({k_1 /{\rm M}^{- 1} \sec ^{- 1}} \right) = \left({9.6 \pm 0.3} \right) - \left({22.4 \pm 0.8} \right)/\theta $$\end{document} where θ = 2.303 RT in kcal/mole. This activation energy gives a carbonyl C—H bond strength of 92.7 kcal/mole. At 356° there was no evidence of abstraction of a methoxy hydrogen, so a lower limit of 100 kcal/mole may be placed on this C—H bond strength. These ester C—H bond strengths are discussed in relation to comparable values in aldehydes and ethers.
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  • 79
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    International Journal of Chemical Kinetics 1 (1969), S. 439-450 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The relative rates of addition of difluorocarbene to a series of methyl-substituted olefins have been determined and correlated with similar data for dichlorocarbene, chlorofluorocarbene and ground-state oxygen atoms. The electrophilic nature and stabilization of difluorocarbene by the fluorine substituents is discussed. Relative activation energies for the difluorocyclopropane-forming reaction have been estimated and correlated with properties of the olefins as derived from molecular orbital theory.
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  • 80
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    International Journal of Chemical Kinetics 1 (1969), S. 451-458 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Data on the kinetics of S2F10 pyrolysis, which gives SF4 + SF6, have been reinterpreted to give a value for the equilibrium constant of S2F10 ⇆ SF4 + SF6. This, together with statistical estimates of the entropy and heat capacity of S2F10, can be used to give for this reaction values of ΔH298° = 19.7 ± 1.0 kcal/mole and ΔS300° = 47.6 ± 2 gibbs/mole. ΔHf°(S2F10) = -494 kcal/mole. A compatible mechanism is shown to be S2F10 ⇆ 2SF5 (fast); 2SF5 ⇆ SF6 + SF4 (slow) with step 2 rate-determining. The overall, best first order rate constant is proposed as kmeas = 1017.42-43.0/θ sec-1 = K1k2, where θ = 2.303RT in kcal/mole.Independent measurements of δHf° and S° for the SF5 radical, permits the evaluation of the equilibrium constant K1 = 108.92-(27.1 ± 6)/θ l./mole-sec and yields k2 = 108.50-15.9/θ l./mole-sec. The observed homogeneous catalysis by NO and CHCl = CHCl can be explained in terms of a direct abstraction of F from S2F10 : C + S2F10 → CF + S2F9, followed by S2F9 → SF5 + SF4 and SF5 + CF ⇆ SF6 + C (C ≡ NO or C2H2Cl2).
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  • 81
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    International Journal of Chemical Kinetics 1 (1969), S. 479-481 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 82
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    International Journal of Chemical Kinetics 1 (1969), S. 473-477 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase isomerization of 1,1-dimethyl-2-vinylcyclopropane to cis-2-methylhexa-1,4-diene has been studied in a static system. The isomerization is homogeneous and kinetically first order. The rate constants were independent of initial reactant pressure in the range 0.6 to 2 torr and of added nitrogen up to 180 torr. Rate constants determined at 10 temperatures in the range 200 to 254°C fitted the Arrhenius equation k = 1011.41±0.02 exp (-33,540 ± 47 cal/RT) sec-1The low A factor and activation energy are consistent with a concerted 1,5-hydrogen migration via a “tight” cyclic transition complex.
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  • 83
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    International Journal of Chemical Kinetics 1 (1969), S. 459-472 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The intramolecular elimination of isobutene from 2-d1-triisobutylaluminum has been studied in the gas phase for temperatures ranging between 102.4 and 184.6°C. The reaction is apparently homogeneous and obeys the first order rate law, yielding the following Arrhenius relationship: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log \,k_{{\rm el}im} \left( {\sec ^{ - 1} } \right) = 11.1 - {{27.2} \mathord{\left/ {\vphantom {{27.2} {\theta \,{\rm where}\,\theta \,{\rm equals}\,4.58 \times 10^{ - 3} }}} \right. \kern-\nulldelimiterspace} {\theta \,{\rm where}\,\theta \,{\rm equals}\,4.58 \times 10^{ - 3} }}T\left( {{}^ \circ {\rm K}} \right)\,{\rm in}\,{\rm units}\,{\rm of}\,{{{\rm kcal}} \mathord{\left/ {\vphantom {{{\rm kcal}} {{\rm mole}{\rm .}}}} \right. \kern-\nulldelimiterspace} {{\rm mole}{\rm .}}} $$\end{document} Excess ethylene was added to the starting material in order to avoid complications from the backreaction. The cyclic 4-center nature of the transition state proposed earlier has been unequivocally demonstrated by deuterium labelling. Mass-spectral analyses show that the isobutene formed contains no deuterium. The hydrolyses products of the mixed trialkylaluminum formed during the reaction consist of monodeuteroethane and 2-d1-isobutane. The observed negative entropy of activation of ∼12 cal/°-mole agrees with prediction and implies a reasonably tight transition state structure. Combined with the corresponding data for the non deuterized Al(i-bu)3 reported earlier, these data result in a primary kinetic deuterium isotope effect of kH/kD = 1.3 × 100.6/θ corresponding to a ratio of the isotopic rate constants of 3.7 at 25°C. This result is in excellent agreement with a predicted value of 1.4 × 100.7/θ and it is in line with literature data on similar reactions involving cyclic transition state complexes.
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  • 84
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    International Journal of Chemical Kinetics 1 (1969), S. 483-486 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 85
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    International Journal of Chemical Kinetics 1 (1969), S. 487-492 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 86
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    International Journal of Chemical Kinetics 1 (1969) 
    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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  • 87
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 1 (1969), S. 493-494 
    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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  • 88
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 89
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 1 (1969), S. 499-508 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gas phase bond isomerization of allyl fluoride, allyl chloride and allyl bromide, catalyzed by HBr and ultraviolet light, has been studied in the temperature range of 150-250° and at pressures of 3.5 to 50 mm. The reactions are very clean, first order in allyl halide and HBr, and have a light intensity exponent of unity. A quantum yield for allyl chloride of 3200 indicates a chain reaction. Dilution with inert gases is almost without effect, indicating that excited state intermediates are not involved. A small wall effect is observed. The evidence indicates a free radical reaction, involving hydrogen abstractions by bromine atoms, with replacement at the other end of the allylic radical.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 90
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By photolyzing (CF2H)2CO and (CFH2)2CO the hydrogen atom abstraction reactions of CF2H radicals with (CF2H)2CO, H2, D2, CH4, C2H6, n—C4H10 and iso—C4H10, and the reactions of CFH2 radicals with (CFH2)2CO and n—C4H10, have been studied. Arrhenius parameters for these reactions are compared with related systems. From a knowledge of the activation energies for the forward and reverse reactions a value of the bond dissociation energy, D(CF2H—H) = 97.4 ± 1.3 kcal mole-1 at a mean temperature of 543°K is obtained. This value is subject to much uncertainty due to possible compensation effects in the Arrhenius parameters. These effects are discussed for this and the other reactions, and the data suggest that D(CF2H—H) is approximately 100 kcal mole-1, and that D(CFH2—H) is very similar. Other literature data tend to confirm these approximate values.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 91
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 1 (1969), S. 527-539 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This review presents in tabular and graphical form rate data on the reactions of atomic oxygen (O3P) with methane and ethane. The reliability of these data is discussed and suggested values of the rate constants are given over specified temperature intervals. Specific values are given for 298 and 1000°K.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 92
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 1 (1969), S. 581-583 
    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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  • 93
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 1 (1969), S. 551-569 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A detailed kinetic model of the HCl chemical laser produced by the flash photolytically initiated H2—Cl2 explosion is described, and the results of computer calculations on such a system are discussed. It is shown that currently accepted values of the various rate constants, supplemented in a few cases by reasonable estimates of previously unmeasured rate constants, are adequate to approximate the observed laser behavior of this system. It is also shown that the chemistry of such a system is extremely complex, and exhibits a high degree of coupling between one reaction and another; therefore, great care is required to extract kinetic data from the optical behavior of such laser systems. It is further argued that different hydrogen halide lasers may behave quite differently from each other, depending on the relative magnitudes of the various rate constants involved.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 94
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 1 (1969), S. 541-549 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal dissociation of COS was investigated in shock waves with argon as carrier gas. The concentration was varied between 0.05 and 0.5% COS in argon, the total density from 2.5 × 10-5 mole/cm3 to 2.5 × 10-3 mole/cm3. Temperatures between 1500°K and 3100°K were applied.For the reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm COS}\left({^1 \Sigma} \right)\mathop {\longrightarrow}\limits^{K_{\rm 1}} {\rm CO}\left({^1 \Sigma ^ +} \right) + {\rm S}\left({^3 P} \right) $$\end{document} the rate constant was found to be \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{10} \approx 10^{14.2} \exp - \left({\frac{{61000}}{{RT}}} \right) \quad\quad ({\rm cm}^3 {\rm mole}^{- 1} \sec ^{- 1}) $$\end{document} in the low pressure range of the unimolecular reaction and \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{1\infty} \approx 10^{11.6} \exp - \left({\frac{{61000}}{{RT}}} \right) \quad\quad (\sec ^{- 1}) $$\end{document} in the high pressure range.
    Additional Material: 3 Ill.
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  • 95
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 1 (1969), S. 571-580 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The addition of methyl radicals to tetrafluoroethylene in the gas phase has been studied over the temperature range 80-180°C, using a material balance method. \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 3} + {\rm C}_2 {\rm F}_{\rm 4} \to {\rm CH}_3 {\rm C}_2 {\rm F}_4 $$\end{document}Arrhenius parameters of 1011.95±0.23 (mole-1 cm3 sec-1) and 5.7 ± 0.4 (kcal/mole) have been measured for the addition reaction.Electrophilic reagents such as O or CF3 appear to react almost equally readily with ethylene and tetrafluoroethylene but methyl radicals add much more rapidly to tetrafluoroethylene than to ethylene, the difference in reactivity being principally due to an activation energy difference of ∼2 kcal/mole.
    Additional Material: 3 Ill.
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  • 96
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 11 (1968), S. 140-156 
    ISSN: 1432-0533
    Keywords: Parenchyma Necrosis ; Freezing ; Epiphysis ; Ultrastructure ; Gliocytes ; Pineocytes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Nach Vereisung der Zirbeldrüse resultiert eine subtotale Kolliquationsnekrose, die zunächst von Leukocyten durchsetzt und dann vom 3. Tag an durch Makrophagen abgeräumt wird. Der enzymhistochemische Status und die Feinstruktur der Makrophagen weisen auf eine Identität mit den pinealen Gliocyten hin. Später treten Fibroblasten hinzu, die sich feinstrukturell und durch ihre intensive Bildung von kollagenen Fasern eindeutig von den Makrophagen abgrenzen lassen. Nach Beseitigung der Nekrose besteht das Reparationsgewebe aus wenigen Fibroblasten bzw. Fibrocyten, die inmitten kollagener Faserzüge gelegen sind sowie aus zahlreichen einförmigen Zellelementen, die sich durch intracytoplasmatische Gliofibrillogenese auszeichnen und am ehesten den pinealen Gliazellen entsprechen. Eine Regeneration von Pineocyten erfolgt nicht. — Die Gliocyten der Zirbeldrüse sind damit als interstitielle Zellen ausgewiesen und dürften in keinem direkten Zusammenhang mit der spezifischen Funktion dieser innersekretorischen Drüse stehen. Hinsichtlich der Genese dieser Zellen spricht aus ihrem funktionellen Verhalten manches für eine mesenchymale Abkunft, doch läßt ihre Feinstruktur einschließlich ihrer Befähigung zur intracellulären Bildung von Gliafilamenten eher an die gliöse Natur dieser Zellen denken, ohne daß ihre exakte Klassifizierung bisher möglich ist.
    Notes: Summary Freezing of the epiphysis results in subtotal colliquation necrosis which at first is penetrated by leucocytes. From the third day on, decomposition by macrophages is seen. Enzyme histochemical and electron microscopic findings of the macrophages indicate their identity with pineal gliocytes. Later on, fibroblasts occur, which by their ultrastructure and the intensive formation of collagen fibers are to be distinguished from macrophages. After decomposition of the necrosis, reparative tissue is formed by some fibroblasts or fibrocytes situated within collagen fiber bundels, and by numerous uniform cell elements characterized by intracytoplasmatic gliofibrillogenesis which, therefore, are regarded pineal glial cells. Regeneration of pineocytes is not to be demonstrated. Gliocytes of the epiphysis, therefore are identified as interstitial cells probably without direct connection with the specific function of this inner secretory gland. Their functional behaviour in some respect seem to indicate a mesenchymal genesis of the gliocytes. Their ultrastructure, including their possibility of intracellular formation of glial filaments, however, most probably indicate the glial nature of these cells. So far, an exact classification of the nature of these cells is not possible.
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  • 97
    ISSN: 1432-2072
    Keywords: Benzodiazepines ; Psychopharmacology ; Antianxiety ; Drug Tolerance
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Oxazepam has two opposing actions on behavior: a responsedecreasing or depressant action and a response-increasing or disinhibitory action. The course of the two actions in chronic dosing was determined in rats in a test in which punished and unpunished schedules of reinforcement were alternated. The depressant action (measured by a decrease in the rate of unpunished behavior) was observed to undergo tolerance after 3–4 doses, while the disinhibitory action (measured by an increase in the rate of punished behavior) failed to show tolerance and even increased throughout the chronic series. The selective tolerance of the depressant action is probably due to neuronal adaptation, but changes in metabolism also may be involved. The increase in the rate of punished behavior is attributed, at least in part, to a progressive unmasking of the disinhibitory action as tolerance to the depressive action develops.
    Type of Medium: Electronic Resource
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  • 98
    Electronic Resource
    Electronic Resource
    Springer
    Psychopharmacology 13 (1968), S. 118-128 
    ISSN: 1432-2072
    Keywords: Psychopharmacology ; Diagnosis ; Sampling Studies ; Statistics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Theoretical models for sample selection by diagnosis using one, one-out-of-two, two, two-out-of-three, and three concurring opinions are illustrated. These models are then applied to two categories, schizophrenia and depressive disorders, for an actual sample of patients diagnosed by multiple observers. The conclusion is reached that sample selection by a single opinion is not sufficiently reliable for research studies. The choice of alternative methods of selection depends on the needs of a particular study. Samples chosen on the basis of two-out-of-three concurring opinions provide the least total error. When erroneous inclusions are particularly undesirable, higher degrees of consensus—e.g. agreeing pairs or triplets—are necessary.
    Type of Medium: Electronic Resource
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  • 99
    Electronic Resource
    Electronic Resource
    Springer
    Psychopharmacology 13 (1968), S. 129-139 
    ISSN: 1432-2072
    Keywords: Electroencephalography ; Psychopharmacology ; Imipramine ; Amphetamine ; Physostigmine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The results of the interaction of imipramine, physostigmine and d/l amphetamine in various intravenously administered dosages were studied on the cortical and subcortical electrical activity of cats. Imipramine was shown to cause a cortical synchronization, hippocampal desynchronization, rise in the threshold of electrocortical arousal and limbic convulsive activity which was potentiated by amphetamine. Imipramine increased the amount of physostigmine, but decreased the amount of amphetamine needed for cortical desynchronization. The possible significance of these findings for the neuropsychopharmacological action of imipramine is briefly discussed.
    Type of Medium: Electronic Resource
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  • 100
    ISSN: 1432-2072
    Keywords: Indoleamine Metabolism ; Psychopharmacology ; Antidepressive Drugs ; Amphetamine Derivatives (Chlorinated) ; Depression
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary CMA (p-chloro-N-methylamphetamine) lowers the cerebral 5-HT concentration in test animals but has virtually no effect on the catecholamine concentrations. Moreover, this compound was found to behave in depressive patients like an antidepressive drug, not like a central stimulant of the amphetmine type. The study described was conducted in order to establish whether CMA influences the overall metabolism of indoleamines in man. Such an influence was clearly demonstrable. Our findings are consistent with the hypothesis that CMA releases 5-HT from its depots. It has not been explained why a considerable proportion of the released 5-HT is excreted unchanged and why the increase in 5-HIAA excretion is so small: the overall activity of MAO was found not to be inhibited. No indications of abnormal 5-HT degradation were found at this time. Patients with vital depressions who improved on CMA medication showed a lower 5-HIAA excretion before treatment than did patients who were refractory to CMA treatment. This is consistent with earlier observations. The possible cause of this phenomenon is discussed. Among the various possibilities considered, an abnormal 5-HT metabolism is regarded as the most plausible. Pertinent investigations are being continued.
    Type of Medium: Electronic Resource
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