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  • 1965-1969  (88)
  • 1920-1924
  • Physical Chemistry  (56)
  • Electron Microscopy  (32)
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 12 (1969), S. 329-338 
    ISSN: 1432-0533
    Keywords: Hypokalemic Periodic Paralysis ; Electron Microscopy ; Myopathy ; Sarcoplasmic Reticulum ; Glycogen, Muscular
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Licht- und elektronenoptische Untersuchungen wurden an Muskelbiopsien von 4 Fällen hypokaliämischer periodischer Paralyse durchgeführt. Die frühesten Veränderungen betreffen nach Meinung der Verfasser das sarkoplasmatische Reticulum: Vacuolisierung des Längssystems und vermutlich Multiplikation des Quersystems. Es wird vermutet, daß die Vacuolenbildung die Folge einer Fusion der Vesikeln des Quersystems darstellt. Destruktion von Myofibrillen und Vergrößerung der, interfibrillären Räume treten erst in späteren Phasen des Krankheitsprozesses auf. Ausdehnung und Intensität dieser Veränderungen bedingen das typische histologische Bild myogener Läsionen bei Fällen m klinisch fixierten Symptomen der Myopathie.
    Notes: Summary Light and electron-microscopic studies were performed on the muscles taken from 4 cases with hypokalemic periodic paralysis. The authors conclude that the earliest changes concern the sarcoplasmic reticulum: vacuolisation of the longitudinal system and probably, multiplication of the transverse system. It is suggested, that vacuoles are formed as a result of fusion of the vesicles of the transverse system. Destruction of myofibrilles and enlargement of the interfibrillar spaces appear at a later period of the disease process. Extensive and intensive changes of that kind present a typical appearance of myogenic changes in histological study observed in the cases with clinically fixed symptomes of myopathy.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 13 (1969), S. 1-11 
    ISSN: 1432-0533
    Keywords: Whipple's Disease ; Granulomatous Encephalitis ; Electron Microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Von 21 Fällen von Whipplescher Krankheit in der Sammlung des Armed Forces Institute of Pathology zeigten 4 Fälle neurologische Symptome mit besonders ausgeprägten Hirnläsionen. Lichtmikroskopisch bestanden die Herde aus knötchenförmigen Anhäufungen von Makrophagen, deren Cytoplasma mit Hämatoxylin-Eosin eine charakteristische schwachblaue und nach Durchführung der Perjodsäure-Schiff-Reaktion eine stark rote Färbung zeigte. Elektronenmikroskopisch fanden sich in den Hirnläsionen Bacillen, die morphologisch den im Darm beschriebenen glichen und die auch dieselben Degenerationserscheinungen aufwiesen. Die Perjodsäure-Schiff-Reaktion färbt Kapselmaterial und Zellwände,die auch nach Untergang der Bacillen noch nachweisbar sind. Diese Beobachtungen werden als weiterer Beweis für die infektiöse Ätiologie der Whippleschen Krankheit angeführt.
    Notes: Summary Among the 21 autopsied cases of Whipple's disease on file at the Armed Forces Institute of Pathology, 4 had neurological symptoms and prominent involvement of the central nervous system, By light microscopy the lesions were composed of nodular aggregates of macrophages having cytoplasm that stained a distinctive pale blue with hematoxylin-eosin and bright red with the periodic acid-Schiff technique. By electron microscopy the cerebral lesions revealed bacilli morphologically identical to and undergoing the same sequence of degenerative changes as those observed in the intestine. The periodic acid-Schiff reaction stains the walls and the capsular material that persists even after intact organisms disappear. These observations further support the infectious nature of Whipple's disease.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 13 (1969), S. 43-55 
    ISSN: 1432-0533
    Keywords: Subacute Dementia ; Jakob-Creutzfeldt Disease ; Brain Biopsy ; Histochemistry ; Electron Microscopy ; Basement Membrane ; Astroglia Dilatation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Die elektronenoptische und histochemische Untersuchung von Biopsiematerial bei zwei Fällen subakuter Demenz ergab Neurone mit reichlich Lipofuscin-Depots sowie erhöhter saurer Phosphatase-Aktivität. Obwohl diese Veränderungen eine Nervenzellerkrankung anzeigen dürften, werden sie wegen ihrer Ähnlichkeit sowie wegen des Vorliegens anderer, spezifischerer Zellveränderungen als Sekundärphänomene gedeutet. Im ersten Fall wird als primäre Läsion eine Verdickung der Basalmembran der Gefäße, im zweiten Fall eine Astrogliaschwellung angenommen. Da diese Strukturen wichtige Transportfunktionen haben dürften, könnten diese Anomalien leicht die neuronale Versorgung stören und dadurch die neuronalen Läsionen verursachen. Die Bedeutung des Glykogens in diesen Strukturen wird diskutiert.
    Notes: Summary The electron microscopic and histochemical findings in biopsies of two cases of subacute dementia have revealed neurons containing numerous lipofuscin bodies and increased acid phosphatase. Although these changes are considered to indicate neuron disease, they are believed to represent a secondary process because of their similarity and because other more distinctive cell alterations are present. In the first case, the primary abnormality is believed to be thickening of the vascular basement membrane, while in the second case, astroglial dilatation is considered a primary change. Since these structures appear to have important transport functions, these abnormalities could easily impair the nutrient supply to neurons and, in this way, produce the neuronal alteration. The significance of glycogen in these tissues is discussed.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 13 (1969), S. 131-142 
    ISSN: 1432-0533
    Keywords: Neuropathy, Chronical ; Hypertrophic Neuritis ; Schwann-Cell ; Onion Bulb ; Electron Microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Die wesentlichen Veränderungen bei dem mitgeteilten Fall von chronischer frühinfantiler Neuropathie bestehen in einer Modifikation der Schwann-Zellen, die zur Bildung eines konzentrischen Netzwerkes von Lamellen führt. Dieses wird durch eine doppelkonturierte Hülle der Basalmembran um zahlreiche große bemarkte und unbemarkte Fasern gebildet. Die Anomalien der Markscheiden sowie die Häufigkeit von Desmosomen sind bemerkenswert. Diese Besonderheiten unterscheiden diesen Fall von anderen, bisher beschriebenen chronischen Neuropathien. Trotzdem erscheint es derzeit nicht möglich, eine Aussage über die Spezifität der ultrastrukturellen Befunde am untersuchten Nerven zu treffen.
    Notes: Summary The principal lesion in this case of chronic early infantile neuropathy is a modification of the Schwann cell resulting in the formation of a concentric network of lamellae formed by a double-layered sheet of basement membrane around numerous, large myelinated and unmyelinated fibers. The abnormalities in the myelin sheaths and the frequency of desmosomes are noteworthy. These peculiarities distinguish this case from other chronic neuropathies described up to now. Nevertheless, it is impossible to say at present whether the ultrastructural aspect of the nerve studied here is in any way specific.
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  • 5
    ISSN: 1432-0533
    Keywords: Subacute Sclerosing Leucoencephalitis ; Electron Microscopy ; Tubular Inclusions ; Inclusion Bodies (Cristalline Rods, Fibrillar Bundles, Nuclear Bodies, Osmiophilic Particles)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Les auteurs rapportent 4 observations caractéristiques de LESS: L'analyse ultra-structurale montre: 10 — des inclusions tubulaires intra-nucléaires neuronales ou gliales et intra-axonales de morphologie superposable à celle des nucléocapsides des myxo-virus, de la rougeole en particulier. 20 — des formations non spécifiques: corps nucléaires, faisceaux cristallins et fibrillaires traduisant un trouble métabolique nucléaire, particules osmiophiles liées à une hyperactivité cellulaire. Les inclusions tubulaires virales sont présentes quelque soit la durée de la maladie (3 mois à 5 ans) indiquant l'absence d'autostérilisation virale dans le S.N.C. La LESS apparaît liée au virus rougeoleux mais le mécanisme indirect immunitaire ou métabolique de cette action est inconnu.
    Notes: Summary Four cases of S.S.L.E are reported. The electron microscopy findings show: 1. Tubulary inclusion bodies: They appear in three cases out of four, either in neuronal and glial nucleus or in axis cylinders. Their morphological features are similar to the nucleocapsides of myxoviruses and particularly measles-virus. 2. Other different types of nonspecific inclusions: nuclear bodies, cristalline-like rods and fibrillar bundles which may be considered as the result of a nuclear metabolic disorder, osmiophilic particles which may be seen as the result of a cellular intracytoplasmic hyperactivity. The tubules are found whatever the duration of the disease (3 months up to 5 years) may be. This might indicate that there is no autosterilization of the virus in the C.N.S. during the course of S.S.L.E. According to the most recent papers, such a disease might be interpreted as an infection indirectly induced by measles-virus with an unknown immunologic or metabolic mechanism.
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  • 6
    ISSN: 1432-0533
    Keywords: Marginal Siderosis ; Electron Microscopy ; Myelin-Sheath-Like Structures ; Plaques Fibromyéliniques ; Gliosis, Perivascular, Subpial
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Bei Kaninchen mit einer experimentell erzeugten Randzonensiderose des Zentralnervensystems konnten elektronenmikroskopisch in der Großhirnrinde eigentümliche Spiralstrukturen beobachtet werden. Diese Spiralen fanden sich vornehmlich im Bereich von subpialen und perivasculären Gliosen vor. Sie bestanden aus äußerst dünnen lamellären Astrocytenausläufern, welche um andere astrocytäre Zellfortsätze oder um Dendriten aufgewickelt waren. Die spiralisierten Astrocytenausläufer wiesen in ihrem Inneren feine Filamente mit einer ziemlich regelmäßigen Anordnung auf. In radiärer Richtung ließen die astrocytären Lamellenspiralen eine periodische Schichtung erkennen, welche etwas an die von echten Markscheiden erinnerte. Es wird in Betracht gezogen, daß sie das submikroskopische Äquivalent der sog. Plaques fibromyéliniques darstellen.
    Notes: Summary Peculiar spiral structures could be observed by electron microscopy in the cerebral cortex of rabbits with an experimentally produced marginal siderosis of the central nervous system. These spirals were found predominantly within areas of subpial and perivascular gliosis. They consisted of extremely thin lamellar astrocyte extensions winding around other astroglial processes or dendrites. The spirally coiled astrocyte extensions exhibited within their interior fine filaments having a rather regular arrangement. In the radial direction, the astrocytic lamellae spirals showed a periodic stratification somewhat resembling that of true myelin-sheaths. They were considered to represent the submicroscopic equivalent of the socalled plaques fibromyéliniques.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 12 (1969), S. 173-182 
    ISSN: 1432-0533
    Keywords: Sodium Deposits ; Electron Microscopy ; Perfusion with Hydroxyadipaldehyde-Antimonate ; Extracellular Space
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Eine Modifikation der Methode zur ultrastrukturellen Darstellung von Natrium wird beschrieben, die eine Perfusion mit leicht alkalischer Mischung von Hydroxydipaldehyd, Phosphatpuffer und Kalium-Pyro-Antimonat verwendet. Im normalen Gehirn werden keine Natrium-Deposite angetroffen. Das spricht dafür, daß im Gehirn keine intraoder extracelluläre Konzentration über 150 mM vorliegt. Bei Vorliegen hoher NaCl-Konzentration sieht man ein großes, dichtes Präcipitat, das nach direkter Injektion in den extracellulären Räumen, Neuronen und Astrocyten lokalisiert werden kann. Im Mark der vergifteten Ratten findet sich ähnlich wie nach direkter Natrium-Injektion ein diskretes, gleichfalls als Natrium aufgefaßtes Präcipitat an der Oberfläche von Oligodendrogliazellen, aber nicht innerhalb dieser Zellen. Ein elektronendichtes Deposit unklarer Herkunft findet sich in den Myelinspalten, die nach akuter TET-Vergiftung auftreten. Der Wechsel in Charakter und Lokalisation dieser elektronendichten Partikel mahnt zur Vorsicht in ihrer Interpretation bei histochemischen Untersuchungsmethoden.
    Notes: Summary A modification of the technique for the ultrastructural demonstration of sodium is described which involves a perfusion with a slightly alkaline mixture of hydroxyadipaldehyde, phosphate buffer and potassium pyroantimonate. No sodium deposits are found in normal brain indicating that no intra or extracellular concentration exceeding 150 mM is present in the brain. In the presence of high concentration of NaCl, a large dense precipitate can be seen which after a direct injection can be localized to extracellular spaces, neurons and astrocytes. In the white matter of tin poisoned rats, as well as after the direct injection of sodium, a discrete precipitate, also believed to represent sodium, is noted at the surface of oligodendrocytes but not within these cells. An electron dense deposit of dubious origin is present in the myelin clefts which occur as a result of acute triethyltin intoxication. The variations in the character and localization of these electron dense particles emphasize the caution which is required in their interpretation following histochemical procedures.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 12 (1969), S. 307-313 
    ISSN: 1432-0533
    Keywords: Swayback of Lambs ; Electron Microscopy ; Corpus Callosum ; Myelogenesis ; Axonal Changes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Elektronenmikroskopische Untersuchung des Corpus callosum normaler Lämmer und von solchen mit „Swayback” (enzootische Ataxia) ergab den morphologischen Nachweis normaler Myelinentwicklung in beiden Tiergruppen. Von zwei Zellfortsätzen umgebene Axone wurden häufig beobachtet. Reaktive Veränderungen wurden in Axonen der „Swayback”-Lämmer gefunden. Die Bedeutung dieser Befunde wird besprochen.
    Notes: Summary An electron microscopic study of the corpus callosum of normal and swayback lambs has revealed morphological evidence of normal myelinogenesis in both groups of animals. Axons wrapped by two cell processes were frequently encountered. Reactive changes were found in axons in the swayback lambs. The significance of these findings is discussed.
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 12 (1969), S. 103-115 
    ISSN: 1432-0533
    Keywords: Spongy Degeneration of the CNS ; Van Bogaert-Bertrand-Disease ; Electron Microscopy ; Astrocytic Mitochondria ; Abnormal Cerebral Edema
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Es wird über licht- und elektronenoptische Untersuchungen an Muskel-und Hirnbiopsien eines Falles von spongiöser Degeneration des ZNS berichtet. Die in der grauen und weißen Hirnsubstanz enthaltenen Vacuolen entsprechen a) Spalten in den Markscheiden infolge Aufsplitterung an der intraperiodischen Linie und b) geschwollenen Astrocytenperikaryen und-fortsätzen. Ungewöhnliche Mitochondrien mit Gehalt an kristallinem Material fanden sich nur in Astrocyten. Die ultrastrukturellen Befunde entsprechen denen des Hirnödems. Es wird angenommen, daß die Astroglia eine primäre Rolle in der Flüssigkeitsansammlung spielt, während die Markscheidenschwellung als eine Sekundärläsion aufgefaßt wird. Die mögliche Bedeutung abnormer Astrocyten-Mitochondrien wird diskutiert.
    Notes: Summary Light and electron microscopy study of skeletal muscle and cerebral biopsies from a case of spongy degeneration of central nervous system is reported. The multiple vacuoles present in cerebral gray and white matter correspond to (a) clefts within myelin sheaths resulting from splitting at the intraperiod line and (b) swollen astrocytic perikarya and processes. Unusual mitochondria containing crystalline-like material were observed only in astrocytes. The ultrastructural findings are consistent with cerebral edema. It is suggested that the astrocytes play a primary role in the fluid accumulation while the myelin swelling is a secondary lesion. The possible role of the abnormal astrocytic mitochondria is discussed.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 12 (1969), S. 183-188 
    ISSN: 1432-0533
    Keywords: Dystrophia myotonica ; Electron Microscopy ; Sarcolemmal Nuclei ; Myofibrillar Material
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung In fünf Fällen von Dystrophia myotonica zeigte die elektronenoptische Untersuchung von bioptisch entnommenem Material zentrale und subsarkolemmale Kerne, die komplexe vacuoläre Areale um myofibrilläres Material enthalten. Diese bisher nicht beobachtete Veränderung könnte durch Verlagerung von myofibrillärem Material in den Kern während seiner Wanderung in das Faserzentrum durch Invagination, aber nicht Durchbrechung der Kernmembran bedingt sein.
    Notes: Summary In five cases of dystrophia myotonica electron microscope preparations of muscle taken at biopsy showed both centrally placed and subsarcolemmal nuclei containing complex vacuolar areas enclosing myofibrillar material. It is suggested that this appearence, which has not been seen in any other condition, may be due to the forcing of myofibrillar material into the nucleus during its migration to the centre of the fibre invaginating but not breaching its membrane.
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 12 (1969), S. 276-299 
    ISSN: 1432-0533
    Keywords: Herpes simplex Virus ; CNS Tissue Culture ; Multiplication in vitro ; Cytopathic Alterations ; Electron Microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Die häufig diskutierte, (Mit)beteiligung von Herpes simplex-Virus (HSV) bei bestimmten Alterationen im ZNS sowie der hohe Neutropismus des HSV führte zur Frage, inwieweit sich HSV auch in in vitro gezüchteten, spezifischen Zellen vom Nerven-system vermehren und züchten läßt, und ob sich hierbei licht-und elektronenmikroskopisch charakteristische Alterationen nachweisen lassen. Es zeigte sich, daß sich das HSV in allen verschiedenen angezüchteten spezifischen Zellen (von Plexus chorioideus des Rhesusaffen, Kaninchenspinalganglien, menschlichen Oligodendrogliomen, Meningeomen sowie fibrillären und protoplasmatischen Astrocytomen) kultivieren und vermehren läßt. Hierbei kommt es in den spezifischen Zellen nicht nur lichtmikroskopisch zu charakteristischen cytopathischen Veränderungen, sondern auch biologisch zu einer signifikanten Vermehrung des Virus in diesen Zellen. Auch elektronenmikroskopisch lassen sich viele der charakteristischen Bildungs-, Reifungs- und Ausschleusungsstadien des Virus in den Kernen und im Cytoplasma der Zellen beobachten. Die Besonderheiten der elektronenmikroskopisch erhobenen ultrastrukturellen Befunde werden ausführlich beschrieben, und die sich daraus abzuleitenden Möglichkeiten werden im Hinblick auf die biologischen Eigenheiten des HSV bei in vivo-Infektionen, aber auch im Hinblick auf die Deutung lichtmikroskopisch histochemischer und immunhistologischer Befunde nach in vivo-Infektionen mit diesem Virus ausführlich diskutiert.
    Notes: Summary The participation of herpes simplex virus (HSV) in certain alterations of the CNS has been partially questioned and frequently discussed. Therefore, the question arose whether HSV can also be cultivated and multiplied in vitro in CNS specific cells, and if so, whether characteristic alterations and structures can be observed by means of light and electron-microscopic examinations. Our data demonstrate that HSV multiplies in all different specific cells originating from plexus chorioideus of rhesus monkeys, from spinal ganglia of rabbit, from human oligodendroglioma, meningeoma as well as from fibrillar and protoplasmatic astrocytoma. Characteristic cytopathic alterations of these specific cells and significant multiplication of the virus in these cells are to be found. Many of the characteristic forms of formation, maturation and release of HSV can be seen by electronmicroscopic examinations. The particular ultrastructural data observed by electron microscopy are described in detail and the resulting possibilities are broadly discussed not only with regard to the biologic particularity of HSV in in vivo infection but also in view of the interpretations, deriving from histochemical and immunohistological data obtained by light microscopy after in vivo infection.
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 13 (1969), S. 157-168 
    ISSN: 1432-0533
    Keywords: Gangliosides ; Tay-Sachs Disease ; Brain Subcellular Localization ; Hale Stain ; Electron Microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Die Reaktion von kolloidalem Eisen mit Sialomucinen (Hale stain) wurde zur elektronenmikroskopischen Darstellung der neuraminsäurehaltigen Ganglioside in den subcellulären Fraktionen des Gehirns angewandt. Zunächst wurde mit Hilfe tritiummarkierter Ganglioside überprüft, ob bei der Gewinnung subzellulärer Fraktionen Ganglioside nicht unspezifisch subcellulär adsorbiert werden. Eine nennenswerte Adsorption konnte ausgeschlossen werden. Das Verfahren wurde zuerst auf die aus Meerschweinchengehirnen isolierten Fraktionen angewandt. Da Nervenendigungen, Mitochondrien und Synapsenbläschen Hale-positiv reagierten, dienten Enzyminkubationen mit Neuraminidase und Hyaluronidase zur Differenzierung von anderen Hale-positiven sauren Substanzen. Schließlich wurde die Methode auf die cytoplasmatischen multilamellären Körperchen (MCB) übertragen, die aus Gehirnen an Tay-Sachs'scher Krankheit Verstorbener isoliert wurden. Aus den Versuchen konnte abgeleitet werden, a) daß die Hale-Färbung auch Ganglioside anfärbt, b) daß Ganglioside auf der Oberfläche der Membran von den multilamellären Körperchen und mit hoher Wahrscheinlichkeit auch auf der Membran der Nervenendigungen lokalisiert sind, c) daß die Synapsenbläschen eine positive Reaktion ergeben, die jedoch nicht mit Sicherheit auf vorhandene Ganglioside zurückgeführt werden kann, d) daß die äußere Mitochondrienmembran Hale-positive Substanzen enthält, deren Natur unbekannt ist.
    Notes: Summary The reaction of colloidal ferric oxide with sialomucins (Hale stain) was applied to sialic acid-containing gangliosides in subcellular fractions of the brain, in order to investigate their localization by electron microscopy. Prior to all experiments, a check was made, by means of tritium-labeled ganglioside, to confirm that the ganglioside content in the subcellular particles was not the result of an unspecific adsorption during the isolating procedure. No considerable unspecific adsorption could be registered. Hale stain was first applied to subcellular fractions obtained from guinea-pig brains. Since nerve-endings, mitochondria and synaptic vesicles gave a positive staining reaction, incubations with neuraminidase and hyaluronidase were carried out in order to achieve a differentiation. Finally, the method was applied to the membranous cytoplasmic bodies (MCB) which were isolated from the brain of a patient with Tay-Sachs disease. It was concluded that: a) Hale stain stains gangliosides also, b) gangliosides are localized in the membrane of membranous cytoplasmic bodies and also very probably in the membrane of nerve-endings, c) synaptic vesicles give a Hale-positive reaction which cannot with certainty be attributed to gangliosides, d) the outer membrane of mitochondria contains Hale-positive substances, the nature of which is not known.
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 13 (1969), S. 197-216 
    ISSN: 1432-0533
    Keywords: Peripheral Nerves ; Axons ; Myelin Sheaths ; Schwann Cells ; Electron Microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Eine kombinierte licht- und elektronenmikroskopische Untersuchung am normalen N. suralis von 7 Menschen im Alter von 15–59 Jahren wurde vorgenommen. Qualitative und quantitative Beobachtungen an Schwann-Zellen und Fibroblasten, markhaltigen und marklosen Fasern wurden an isolierten Faszikeln durchgeführt. Schwannzellen überwiegen gegenüber Fibroblasten im Verhältnis von etwa 9:1. Die meisten Schwannzellen (etwa 80%) liegen an marklosen Fasern. Die Faktoren, welche die Dichte dieser Zellen pro Querschnittsareal beeinflußen, werden diskutiert. Einige ultrastrukturelle Befunde an bemarkten Fasern werden beschrieben und ihre Zahl pro mm2 sowie die Häufigkeitsverteilung ihrer Dicke wird angegeben. Eine indirekte Methode zur Bestimmung der mittleren Internodienlänge für jede der Markfasergrößenpopulationen an Querschnitten von Faszikeln normaler Nerven durch Bestimmung des Verhältnisses der markhaltigen Fasersegmente zu ihrer Kernzahl wird vorgeschlagen. Die Ultrastruktur der marklosen Nervenfaern wird beschrieben und die Identifizierung dieser Axone mit extremen Durchmessern diskutiert. Ihre Dichte und Größenfrequenzhistogramme sind die ersten, die am Menschen durch systematische elektronenoptische Untersuchungen veröffentlicht werden. Das mittlere Verhältnis von marklosen zu bemarkten Fasern ist etwa 3,7:1 und schwankt in den Faszikeln der Einzelindividuen.
    Notes: Summary A combined light and electron microscope study of the normal sural nerve in 7 people aged 15–59 years is reported. Qualitative and quantitative studies of the Schwann cells and fibroblasts, myelinated and unmyelinated fibres are made in isolated fascicles. Schwann cells predominate over fibroblasts in the ratio of about 9-1. Most Schwann cells, almost 80%, are attached to unmyelinated fibres. Factors influencing the densities of these cells per cross sectional area are discussed. Some ultrastructural features of the myelinated fibres are described and their numbers per sq.mm and frequency distribution of their sizes are produced. An indirect method is proposed for assessing the mean internodal length for earch of the myelinated fibre size populations in cross sections of fascicles of normal nerves by estimating the proportion of myelinated segments cut through their nucleus. The ultrastructure of unmyelinated fibres is described and the identification of axons of extreme diameter is discussed. Their densities and size frequency histograms are the first to be reported in man by systematic electron microscope studies. The average ratio of unmyelinated to myelinated fibre density is about 3.7:1 though it varies in the fascicles of the different individuals. The implications of axonal diameter in the presence of myelin are commented on.
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  • 14
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    Springer
    Acta neuropathologica 13 (1969), S. 289-293 
    ISSN: 1432-0533
    Keywords: Oligodendroglioma ; Nuclear Inclusions ; Electron Microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Es wird die Ultrastruktur von intranucleären stabförmigen Gebilden bei einem Oligodendrogliom beschrieben.
    Notes: Summary Ultrastructure of intranuclear rodlets in an oligodendroglioma is described.
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  • 15
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    Acta neuropathologica 14 (1969), S. 118-125 
    ISSN: 1432-0533
    Keywords: Carbon Monoxide Poisoning ; Electron Microscopy ; Myelin Disintegration ; Cerebral Anoxia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Nach experimenteller CO-Vergiftung fanden sich schwerere und ausgedehntere Läsionen in der weißen als in der grauen Hirnsubstanz. Zwischen akuter und chronischer CO-Vergiftung ergaben sich keine wesentlichen qualitativen Unterschiede der Hirnveränderungen. Die Läsionen nach chronischer Intoxikation waren jedoch schwerer als nach akuter Vergiftung. Die Nervenzellen zeigten leicht dilatiertes oder fragmentiertes EPR und Golgi-Komplexe, doch boten die Mitochondrien meist keine pathologischen Veränderungen. Bei chronischen Fällen fand sich gelegentlich eine deutliche Schwellung des EPR von Oligodendrogliazellen. Die Capillaren blieben intakt und die perivasalen Astrogliaendfüßchen waren nicht geschwollen. Im Mark kam es zu teilweisem Ausfall der normalen Markscheidenbestandteile. Die Marklamellen zeigten mäßige Exfoliation sowie eine Umwandlung in homogene oder strukturlose Substanz. Bemarkte Axone waren teilweise kontrahiert und zeigten auf Querschnitten unregelmäßige Form. Gelegentlich fand sich eine Vergrößerung der axonalen Mitochondrien und Zerstörung ihrer inneren Parallelstrukturen. Als Hauptfaktoren in der Pathogenese der Hirnveränderungen nach experimenteller CO_Vergiftung werden zerebrale Anoxie infolge CO-Hämoglobinbildung, cytotoxische Wirkung von CO auf das Hirngewebe und eine Störung der Blutzirkulation angenommen.
    Notes: Summary In experimental carbon monoxide poisoning, more marked and widespread pathological changes in the brain were seen in the white matter as compared with the gray matter. No essential difference, in the appearance of cerebral alterations, was detected between acute and chronic carbon monoxide poisoning. It was confirmed that the changes resulting from chronic poisoning showed a higher degree of severity as compared with those resulting from acute poisoning. Nerve cells with slightly dilated or fragmented endoplasmic reticulum and Golgi complex in the gray matter were found infrequently. However, most mitochondria did not show any kind of abnormality in such cells. A remarkable dilatation of the endoplasmic reticulum of oligodendrocytes was sometimes seen in chronic cases. Capillaries remained intact and astrocytic perivascular foot-plates were not swollen. In the white matter, the normal constituents of the myelin sheath were partially lost and the myelin lamellae showed moderate exfoliation, or a change into homogenous or structureless substance. Myelinated axons were partially contracted and showed an irregularity in shape in transverse sections. Enlargement of occasional axonal mitochondria and the destruction of their internal parallel structures were observed. Cerebral anoxia caused by carboxyhaemoglobin, together with the cytotoxic action of carbon monoxide on the brain tissue and the disturbance of blood circulation in the brain are suggested as the chief factors in the pathogenesis of the cerebral alterations induced by experimental carbon monoxide poisoning.
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  • 16
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    Acta neuropathologica 14 (1969), S. 185-193 
    ISSN: 1432-0533
    Keywords: Hypoxia ; Sodium Azide ; Electron Microscopy ; Ferritin ; Capillary Permeability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Experimentelle histotoxische Hypoxämie wurde in Ratten durch Natriumacid-Vergiftung erzeugt. Die mikroskopische Untersuchung der Hirne ergab keine Veränderung, aber bei der elektronenmikroskopischen Untersuchung fanden sich als Frühveränderungen in der Hirnrinde und im Subcortex eine Erweiterung der intercellulären Räume und eine Anschwellung der pericapillären Astrocytenfortsätze. Ferritinalbumin-Mischung, die als Indicator des Eiweißtransportes benutzt wurde, zeigte keine Vermehrung der Capillarpermeabilität. Es wird vermutet, daß Natriumacid den Wasserstoffwechsel beeinträchtigt, wobei es eine osmotische Ausgleichstörung im Gehirn erzeugt.
    Notes: Summary Histotoxic hypoxia was experimentally produced in the rat brain by sodium azide intoxication. In spite of the absence of light microscopic alterations, electron micrographs showed the early changes in the cerebral cortex and subcortex which consisted of widening of the intercellular space and swelling of the pericapillary astrocytic end-feet. However, ferritin-albumin mixture, used for the tracer of protein transport, did not show any increase in the capillary permeability. Sodium azide was considered to disturb the water metabolism, producing osmotic unbalance in the brain.
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  • 17
    ISSN: 1432-0533
    Keywords: Methamphetamine Poisoning (Artificial Psychosis) ; Synapses ; Nerve Conduction and Transmission ; Electron Microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Amphetaminchlorid in Mengen von 1 mg pro kg pro Tag wurde 8 männlichen Meerschweinchen ungefähr 1 Jahr lang täglich injiziert, um eine chronische Amphetaminvergiftung zu erzeugen. Bei jedem vergifteten Tier wurde die Feinstruktur des Gehirns elektronenmikroskopisch untersucht. Die Befunde waren folgende: 1. Verschmelzung der Membranen zwischen Axonen in den Nervenendigungen sowie zwischen Axonen und Dendriten wurden in der Großhirnrinde, im limbischen System, im Thalamus und Hypothalmus beobachtet; ferner wurde eine sich vom Cytoplasma bis zur Nervenendigung erstreckende Membranstruktur in diesen Hirnbereichen festgestellt. 2. Im Frontal-, Parietal-, Temporal- und Occipitalhirn sowie im limbischen System fanden sich vermehrt membranbegrenzte Vesikel im Cytoplasma der Nervenzellen und verdicktes und vermehrtes ER in den Nervenfasern. In Anbetracht klinischer Symptome der Patienten mit Amphetaminvergiftung wurde angenommen, daß die Verschmelzung von Membranen zwischen Nervenfortsätzen und das Auftreten der Membranstrukturen in allen Teilen des Nervenzellcytoplasmas vom Perikaryon bis zur Nervenendigung die wichtigsten Befunde sind, die darauf hindeuten, daß die Vergiftungsvorgänge einen wesentlichen Einfluß auf das Leitungssystem der Nerven ausüben können.
    Notes: Summary In 8 male albino strain guinea pigs, 1 mg/kg of methamphetamine HCl was injected daily for 7 months to 1 year to produce chronic methamphetamine intoxication and to study the fine structure of the brain electron microscopically. The following results were obtained: 1. Coalescence of membranes, between axons at the nerve endings and between axons and dendrites, was found in the cortex of the cerebrum and limbic system, in the thalamus and hypothalamus. Membranous structures were found in all portions of the cytoplasm of the nerve cells. 2. Within the cytoplasm of the nerve cell, coated vesicles were increased in number with hypertrophy and increase of endoplasmic reticulum within nerve fibres in the frontal, parietal, temporal and occipital regions, and in the limbic system. In view of these findings, as well as the clinical neurological symptoms in patients with methamphetamine poisoning, the coalescence of membranes between nerve processes and the appearance of membranous structures in all portions of nerve cell cytoplasm from body to nerve endings appear to represent the most important findings, they probably produce a profound disturbance in the system of nerve conduction and transmission.
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  • 18
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    Acta neuropathologica 14 (1969), S. 237-249 
    ISSN: 1432-0533
    Keywords: Electron Microscopy ; Wallerian Degeneration ; Nodal Changes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Es wird über ultrastrukturelle Veränderungen in den Ranvierschen Knoten des N.suralis der Ratte im Laufe der Wallerschen Degeneration berichtet. Die Untersuchungen erfolgten 12 und 120 Std nach einer örtlichen Quetschungsverletzung. Die ersten bemerkbaren Veränderungen finden sich im Axon. Nodale und paranodale Anhäufungen von Mitochondrien, multivesikulären und lamellären Körpern, wie auch kleinen blasen- und röhrenartigen Bildungen sind teilweise in den Knoten sichtbar und am deutlichsten nach 24–36 Std erkennbar. Gleichzeitig erfolgt eine Aufsplitterung der Neurofilamente und Neurotubuli, die ihre Liniengestaltung verlieren und sich zusammenballen. Die Zone der erhöhten Dichte gerade unterhalb des nodalen Axolemmas bleibt erhalten. Veränderungen im Myelin beginnen etwas später und bestehen in einem vesikulären Verfall der Endomyelinlamellen und einer Trennung der Endomyelinschlaufen vom Axolemma durch Schwannzellenfortsätze. Dieser Vorgang schien mit einem Zurückziehen des Myelins vom Knoten im Zusammenhang zu stehen. Schwannzellenfortsätze erstrecken sich auch so weit, daß sie das nodale Axon bedecken, wobei sie die nodalen Schwannzellenfortsätze vom Axolemma trennen. Das Endstadium ist die Unterbrechung des nodalen Axons und die Verschmelzung der Myelinenden als Teil der Ovoidbildung.
    Notes: Summary Observations are reported on the ultrastructural alterations at the nodes of Ranvier in the rat sural nerve during the course of Wallerian degeneration. These were examined between 12 and 120 hours after a localized crush injury. The earliest detectable changes are in the axon. Nodal and paranodal accumulations of mitochondria, multivesicular bodies, lamellar bodies and small vesicular and tubular profiles are seen at a proportion of the nodes and are most evident at 24–36 hours. Concomitantly with this, the neurofilaments and neurotubulus fragment, lose their alignment and clump together. The zone of increased density just beneath the nodal axolemma is preserved. Changes in the myelin begin slightly later and consist of vesicular breakdown of the terminal myelin lamellae, and separation of the terminal myelin loops from the axolemma by Schwann cell processes. The latter event appeared to be associated with retraction of the myelin from the node. Schwann cell processes also extend to cover the nodal axon, separating the Schwann cell nodal processes from the axolemma. The final stage is the interruption of the nodal axon and the fusion of the ends of the myelin as part of ovoid formation.
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  • 19
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    Acta neuropathologica 13 (1969), S. 149-156 
    ISSN: 1432-0533
    Keywords: Electron Microscopy ; Leucodystrophy, Metachromatic ; Enzyme Histochemistry, Electronmicroscopical ; Lysosomes ; Neurochemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Dans la leucodystrophie métachromatique, les lipides anormaux s'accumulent dans les lysosomes des cellules gliales et des phagocytes. Les inclusions lipidiques les moins organisées sont les plus riches en phosphatases acides. Celles dont l'ultrastructure est prismatique ont une activité enzymatique très faible et semblent plus proches de corps résiduels que de lysosomes actifs. Il semble que l'absence d'arylsulfatase lysosomiale induise la persistance des sulfatides accumulés dans les lysosomes alors que les autres lipides provenant de la dégénérescence myélinique, seraient normalement catabolisés. Un remaniement progressif de l'ultrastructure du contenu des lysosomes en est la conséquence.
    Notes: Summary In metachromatic leucodystrophy abnormal lipids are stored within the lysosomes of the glial cells and phagocytes. The lipid inclusions which are the less structured are the richest in acid phosphatases. Those of which the ultrastructure is prismatic show a very low enzymatic activity and are more similar to residual bodies than to active lysosomes. It appears that the lack in lysosomal arylsulfatase leads to an accumulation of the sulfatide moiety of the stored lipids while the other lipids originating from the myelin breakdown, would be normally catabolized. This leads to a progressive transformation of the ultrastructure of the lysosome contents.
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  • 20
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    Acta neuropathologica 13 (1969), S. 169-181 
    ISSN: 1432-0533
    Keywords: Japanese Encephalitis ; Experimental ; Electron Microscopy ; Virus Particles in Neurons
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Groß- und Kleinhirnrinde, Plexus chorioideus und Rückenmark von Mäusen wurden nach intracerebraler Inoculation einer Hirnemulsion mit Virus der Encephalitis japonica (JEV) elektronenoptisch untersucht, um den Ort der JEV-Replikation zu bostimmen. 72 Std nach der Inoculation bei Beginn der encephalitischen Symptome enthielten 70 bis 80% aller Rindenneurone und Vorderhornzellen viele sphärische Partikel, die meist im zarten endoplasmatischen Reticulum (EPR) und vereinzelt im granulären EPR lokalisiert waren. Die Einzelpartikel zeigten eine gleichförmige Substruktur aus einem elektronendichten zentralen Hof von 25–30 mμ Durchmesser, einer äußeren, weniger elektronendichten Zone und einer äußersten Grenzmembran von 40 mμ Durchmesser. 96 Std nach der Inoculation zeigte das Cytoplasma der Rinden- und Vorderhornneurone sehr viele Vacuolen und Vesiceln. Partikel wurden weit verstreut in den Vacuolen und Vesiceln sowie erstmals im ERP der Sternzellen und Purkinjezellen angetroffen, allerdings in geringerer Zahl. Keine derartigen Partikel wurden in Kontrolltieren und normalen Mäusegruppen angetroffen. Sogenannte eosinophile intranucleäre Einschlüsse in Epithelzellen des Plexus chorioideus zeigten keine derartigen Partikel im Kern oder in den cytoplasmatischen Bläschen. Nachdem keine als JEV identifizierbaren Partikel in Glia- und Endothelzellen nachzuweisen waren, wird angenommen, daß das JEV echt neurotrop ist und sich im EPR der Nervenzellen repliziert.
    Notes: Summary Cerebral and cerebellar cortices, choroid plexus and spinal cord of mice, inoculated intracerebrally with a brain emulsion containing Japanese encephalitis virus (JEV), were studied electronmicroscopically to determine the cell type and the site of JEV replication. 72 hours after inoculation, when the mice began to show encephalitic symptoms, 70 to 80% of all cortical neurons and anterior horn cells contained many spherical particles mostly located in the smooth endoplasmic reticulum and a few in the granular endoplasmic reticulum. The individual particles demonstrated an uniform substructure consisting of an electron dense central core of 25–30 mμ diameter, an outer less electron dense zone and an outermost limiting membrane of 40 mμ diameter. 96 hours after inoculation, the cytoplasm of cortical neurons and anterior horn cells was observed to contain very many vacuoles and vesicles. Particles were found widely scattered throughout the vacuoles and vesicles, and were observed for the first time in the endoplasmic reticulum of the stellate neurons and in Purkinje cells, though fewer. No such particles were observed in control and normal mouse groups. So-called eosinophic intranuclear inclusions of epithelial cells of choroid plexus failed to show any particles in their nuclei or cytoplasmic vesicles. Considering that no particulate matter, identifiable as JEV, was identified within any of the glial cells or endothelium in this examination, it was concluded that JEV was really neurotropic and replicates in the endoplasmic reticulum of the neurons.
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  • 21
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    Acta neuropathologica 13 (1969), S. 250-266 
    ISSN: 1432-0533
    Keywords: Electron Microscopy ; Congenital Myopathy ; Nemaline Myopathy ; Z-band Structure ; Sarcoplasmic Masses
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé L'étude ultrastructurale d'une observation de «Nemaline-Myopathy» a été centrée sur les rapports structurels entre bâtonnets et stries Z normales dans différentes conditions de fixation. L'aspect des stries Z, en section transversale, varie en effet avec la fixation: réseau de ponts «obliques» (par rapport à l'alignement quadratique régulier des terminaisons des filaments fins) après fixation osmiée, réseau de ponts «transversaux», isolé ou superposé au premier réseau, après fixation aldéhydique initiale. L'aspect des bâtonnets en section transversale varie également avec la fixation; la disposition quadratique des filaments constitutifs des bâtonnets est visible après l'une et l'autre fixation, mais un réseau quadratique régulier, de 75 Å de côté, n'est clairement apparent qu'après fixation aldéhydique. Le point important est que ce dernier aspect diffère complètement du réseau «oblique» des stries Z normales, et peut être rapproché au contraire du réseau «transversal» de la strie Z obtenu après fixation aldéhydique; l'hypothèse est ainsi soulevée de la constitution des ponts dans les bâtonnets aux dépens d'un seul des deux constituants morphologiques de la strie Z. La topographie des bâtonnets a été également étudiée: tantôt périphérique, au sein de masses sarcoplasmiques latérales, tantôt centrale, au sein de petits foyers de désintégration myofibrillaire. La structure des plaques motrices visibles dans les préparations était normale. La spécificité de la lésion élémentaire et l'autonomie de ce type de myopathie sont ensuite discutées.
    Notes: Summary Ultrastructural study of an observation of “Nemaline Myopathy” has been focused on structural relationships between rods and normal Z-bands in different conditions of fixation. The Z-band structure studied in transversal section, varies with the fixation: network of “oblique” (relative to the regular quadratic pattern of the thin filament endings) bridges after osmic fixation; network of “transversal” bridges, alone or associated to the first network, after aldehydic fixation. The rod structure, in transversal section, is also varying with the fixation: a quadratic disposal of the filamentary content is visible after both fixations, but a regular quadratic network, 75–85 Å side, is clearly appearent only after aldehydic fixation. This last network differs from the “oblique” network of the normal Z-band; it can be compared to the “transversal” one obtained in the Z-band after aldehydic fixation. The hypothesis that bridges in the rods are formed only by one of the two normal morphological components of the Z-band, is raised. Topography of the rods in muscle fibers has been studied: either in peripheral sarcoplasmic masses, or in small central-located foci of myofibrillar disintegration. The end-plates structure was normal. Specificity of the elementary lesion, and autonomy of that type of myopathy is discussed.
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  • 22
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    Acta neuropathologica 13 (1969), S. 301-323 
    ISSN: 1432-0533
    Keywords: Meningiomas ; Electron Microscopy ; Endotheliomatous, Fibromatous Type ; Light Cells ; Dark Cells ; Histogenesis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung 17 chirurgisch entfernte Meningiome vom endotheliomatösen und 5 vom fibromatösen Typ wurden elektronenmikroskopisch untersucht. Unterschiede im Entwicklungsgrad der cytoplasmatischen Fortsätze und der Beziehungen zwischen den Plasmamembranen der Tumorzellen wurden in den endotheliomatösen Meningeomen beobachtet. In 4 fibromatösen Tumoren sind die zelligen Areale von bindegewebigen Räumen umgeben. Auch wenn die meisten Tumorzellen helle Zellen sind und sich nicht wesentlich von den Tumorzellen der endotheliomatösen Meningiome unterscheiden, ist die histologische Anordnung der fibromatösen klar von derjenigen der endotheliomatösen Meningeome zu trennen. Ausschlaggebend dafür ist die starke Entwicklung des Bindegewebes. Die Dunkelzellen lassen sich in zwei Typen gliedern: Typ I wird in vier Tumoren mit stark ausgebildetem Bindegewebe angetroffen. Die Analyse der inneren Zellstruktur sowie das Vorliegen von Übergängen zwischen hellen und dunklen Zellen machen es wahrscheinlich, daß diese nur verschiedene Typen einer einzigen Ursprungszelle darstellen. Die Bedeutung dieser verschiedenen Erscheinungsformen der Meningiomzellen wird diskutiert. Die Ultrastruktur der Tumorzellen ähnelt derjenigen der normalen arachnoidalen Zellen. Rückschlüsse auf die blastodermale Herkunft der normalen und tumoralen meninigalen Zellen auf Grund ihrer ultrastrukturellen Merkmale erscheinen verfrüht.
    Notes: Summary Seventeen surgically removed meningiomas of the endotheliomatous and five of the fibromatous type were investigated with an electron microscope. Differences of the development of cytoplasmic processes and the relations between plasma membranes of blastomatous cells were observed in endotheliomatous meningiomas. In four of the fibromatous tumors the cell groups were surrounded by spaces of connective tissue. Although most of the tumor cells were light cells and are not essentially different from the tumor cells of the endotheliomatous meningiomas, the histological structure of fibromatous meningiomas is clearly distinguished from the endotheliomatous type, because of the greater amount of connective tissue. The dark cells may be divided into two types: the first was found in those four tumors, where the connective tissue is well developed, while the second one only occurred in one of the tumors. The analysis of the inner cell structure as well as the presence of interstages between dark and light cells makes it probable that dark and light cells are different types of one original cell. The cause of this different appearance of the menigioma cells is discussed. The fine structure of the tumor cells showed a great similarity with that of normal arachnoidal cells. Conclusions on the blastodermic origin of normal and blastomatous meningial cells on the basis of ultrastructural characteristics, however, seem to be premature.
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  • 23
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    Acta neuropathologica 14 (1969), S. 201-214 
    ISSN: 1432-0533
    Keywords: Electron Microscopy ; Epilepsy, Experimental ; Focus ; Cobalt Gelatine ; Plasmatic Infiltration ; Brain Edema
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Bei 25 erwachsenen Ratten wurde ein epileptogener Kobaltgelatineherd in einer Standardregion der Hirnrinde erzeugt. Die Tiere wurden am 1., 3., 5., 8., 14. 21. und 28. Tag nach der Operation getötet. Das Gebiet des epileptogenen Herdes wurde elektronenmikroskopisch untersucht. Die frühesten Veränderungen bestanden in ödem. Später traten Veränderungen der Astrocytenfortsätze auf, die sich an die Basalmembranen der Capillaren anlegten; die Intercellularräume erweiterten sich, füllten sich mit elektronenoptisch dichten Massen und entwickelten ein “plasmatisches Infiltrat”. Allmählich breitete sich dieses Exsudat weiter um die Capillaren aus; es trat an Orten auf, wo die Astrocytenfortsätze und die Dendriten schwer geschädigt waren und erfüllte die weiteren Intercellularräume des Neuropils. Die Nervenzellen zeigten eine auffallende Widerstandsfähigkeit gegenüber diesem pathologischen Prozeß. Manchmal waren sie umschlossen von Exsudatmassen und zum Teil oder ganz der zarten neuralen und Astrocytenfortsätze beraubt, von denen sie normalerweise umgeben sind. Unsere Befunde werden als das ultrastrukturelle Korrelat der Schols'schen “plasmatischen Infiltration” interpretiert.
    Notes: Summary In 25 adult rats an epileptogenic cobalt-gelatine focus was produced in a standard region of the cerebral cortex. The animals were killed successively on the 1st, 3rd, 5th, 8th, 14th, 21st and 28th day after operation and the region of the epileptogenic focus was examined electron microscopically. The earliest changes were those of oedema. Later there occurred disturbances of the astrocytic processes which cling to the basement membranes of the capillaries; the intercellular spaces widened and filled with rather E. M. dense masses and a “plasmatic infiltrate” developed. Gradually this exudative substance spread even further from the capillaries. It appeared in places where the astrocytic processes were severely demaged and the dendrites were partly dissipated and it filled out the wide intercellular spaces of the neuropil. The nerve cells showed a striking resistance toward this pathological process. Sometimes they floated in the exudative masses but were partly or totally deprived of the fine neural and astrocytic processes which normally surround them. Our findings are interpreted as the ultrastructural correlate of Scholz's “plasmatic infiltration”.
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  • 24
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    Calcified tissue international 3 (1969), S. 151-162 
    ISSN: 1432-0827
    Keywords: Calcification ; Physiologic ; Phosphonic Acids ; Phosphates ; Crystallization ; Electron Microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé On a étudié la formation de l'hydroxyapatite de calcium cristallin à partir de solutions d'ions de calcium et de phosphate et l'inhibition de la croissance de cristaux de l'hydroxyapatite de calcium au moyen de polyphosphonates et de polyphosphates. Les polyphosphonates, éthane hydroxy-1-diphosphonate-1,1 de disodium et dichlorométhanediphosphonate de disodium, sont inhibiteurs efficaces contre la croissance de cristaux de l'hydroxyapatite de calcium. Les polyphosphates sont aussi inhibiteurs efficaces contre la croissance de cristaux de l'hydroxyapatite de calcium tant que le niveau exigé de polyphosphate intact est présent dans le système. Cependant, à cause de leur instabilité hydrolytique, qui est soulignée par une température élevée, valeur de pH basse, et certaines enzymes, la concentration du polyphosphate diminue avec le tempsin vitro, et son activité comme inhibiteur est perdue. Au contraire aux polyphosphates, les polyphosphonates sont hydrolytiquement stables. Les polyphosphonates sont chimiosorbés sur la surface des microcristallites de l'hydroxyapatite de calcium, ainsi empêchant l'occurrence d'autre croissance de cristaux semblable à l'action d'autres poisons connus de croissance de cristaux. On propose l'extension de cette action sur la formation de l'apatite et cette stabilité des polyphosphonates aux applications médicales et dentaires concernant le metabolisme pathologique de calcium et de phosphate.
    Abstract: Zusammenfassung Die Bildung des kristallinen Calciumhydroxyapatit aus Lösungen, welche Calcium- und Phosphationen enthalten, und die Hemmung der Bildung von kristallinen Calciumhydroxyapatit durch Polyphosphonate und Polyphosphate wurden untersucht. Polyphosphonate, Dinatriumäthan-1-hydroxyl-1,1-diphosphonat und Dinatriumdichloromethandiphosphonate verhindern das Kristallwachstum des Calciumhydroxyapatits. Die Polyphosphate verhindern ebenfalls das Kristallwachstum des Calciumhydroxyapatits, solange die notwendige Konzentration des nicht hydrolysierten Polyphosphats vorhanden ist. Wegen ihrer hydrolytischen Unbeständigkeit, die durch hohe Temperatur, niedrige pH und bestimmte Enzyme erhöht wird, vermindert sich jedoch die Konzentration des Polyphosphats allmählichin vitro, und ihre Hemmungsaktivität geht verloren. Im Gegensatz zu den Polyphosphaten sind die Polyphosphonate hydrolytisch beständig. Die Polyphosphonate werden an der Oberfläche der Mikrokristallite des Calciumhydroxyapatits chemisorbiert und verhindern, wie andere bekannte Kristallwachstumsgifte, auf diese Weise weiteres Kristallwachstum. Die Beständigkeit der Polyphosphonate und ihre Chemisorption an dem Apatit empfehlen ihren Gebrauch in der ärztlichen und zahnärztlichen Praxis, soweit sie den pathologischen Calcium- und Phosphatstoffwechsel betreffen.
    Notes: Abstract The formation of crystalline calcium hydroxyapatite from solutions of calcium and phosphate ions and the inhibition of calcium hydroxyapatite crystal growth by polyphosphonates and polyphosphates have been studied. The polyphosphonates, disodium ethane-1-hydroxy-1,1-diphosphonate and disodium dichloromethane diphosphonate, are effective inhibitors of calcium hydroxyapatite crystal growth. The polyphosphates are also effective inhibitors of calcium hydroxyapatite crystal growth as long as the required level of intact polyphosphate is present in the system. However, because of their hydrolytic instability, which is enhanced by high temperature, low pH, and certain enzymes, the concentration of the polyphosphate decreases with timein vitro, and its activity as an inhibitor is lost. In contrast to the polyphosphates, the polyphosphonates are hydrolytically stable. The polyphosphonates are chemisorbed on the surface of the microcrystallites of calcium hydroxyapatite and, in the manner of other known crystal growth poisons, thus prevent further crystal growth. The stability of the polyphosphonates and their chemisorption on apatite suggest their use in medical and dental applications involving pathological calcium and phosphate metabolism.
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  • 25
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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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  • 26
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    New York, NY : Wiley-Blackwell
    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.
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  • 27
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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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  • 28
    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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  • 29
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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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  • 30
    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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  • 31
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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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  • 32
    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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  • 33
    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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  • 34
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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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  • 35
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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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  • 36
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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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  • 37
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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
    Additional Material: 2 Ill.
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  • 38
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    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
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  • 39
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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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  • 40
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    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.
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  • 41
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    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
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  • 42
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    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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  • 43
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    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.
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  • 44
    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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  • 45
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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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  • 46
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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
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  • 47
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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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  • 48
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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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  • 49
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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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  • 50
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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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  • 51
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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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  • 52
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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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  • 53
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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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  • 54
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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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  • 55
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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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  • 56
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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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  • 57
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    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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  • 58
    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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  • 59
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    New York, NY : Wiley-Blackwell
    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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  • 60
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    New York, NY : Wiley-Blackwell
    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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  • 61
    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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  • 62
    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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  • 63
    Electronic Resource
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    New York, NY : Wiley-Blackwell
    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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  • 64
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    New York, NY : Wiley-Blackwell
    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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  • 65
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    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.
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  • 66
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    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.
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  • 67
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    New York, NY : Wiley-Blackwell
    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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  • 68
    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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  • 69
    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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  • 70
    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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  • 71
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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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  • 72
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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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  • 73
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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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  • 74
    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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  • 75
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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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  • 76
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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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  • 77
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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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  • 78
    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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  • 79
    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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  • 80
    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.
    Type of Medium: Electronic Resource
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  • 81
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 11 (1968), S. 122-139 
    ISSN: 1432-0533
    Keywords: Juvenile Lipidosis ; Electron Microscopy ; Histochemistry ; Biochemistry ; Granular Lipid Inclusions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Elektronenmikroskopische, histochemische und biochemische Untersuchungen eines Falles von juveniler Lipidose werden mitgeteilt. Die neuronalen Einschlüsse sind zumeist von einer unit membrane umgeben und zeigen fingerabdruckähnliche Muster. Membranovesiculäre Körperchen finden sich ebenfalls in den Nervenzellperikaryen; typische granuläre Lipofuscinkörperchen werden aber nicht gesehen. Die Astrocyten der Rinde enthalten eine ähnliche Art von Einschlüssen, von denen aber die Einschlüsse in den Astrocyten der Marksubstanz völlig verschieden sind. Die Lokalisation der Aktivität von saurer Phosphatase in allen Einschlußtypen läßt an ihre mögliche lysosomale Natur denken. Die biochemische Analyse deckt keine spezifischen Abweichungen auf.
    Notes: Summary Electron microscopic, histochemical and biochemical studies of a case of juvenile lipidosis have been presented. The neuronal inclusions were mostly unit membranebound with fingerprint-like patterns. Membrano-vesicular bodies were also found in the neuronal perikarya, but “typical” granular lipofuscin bodies were not seen. Cortical astrocytes contained a similar type of inclusion but the inclusions in the astrocytes in the white matter were quite different. The localization of acid phosphatase activity in all types of inclusions suggests their possible lysosomal nature. Biochemical analysis failed to pin-point any specific abnormalities.
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  • 82
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    Electronic Resource
    Springer
    Acta neuropathologica 11 (1968), S. 330-337 
    ISSN: 1432-0533
    Keywords: Pick's Disease ; Pick Bodies ; Hirano Bodies ; Electron Microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Hirngewebe eines Falles von Pickscher Krankheit wurde licht-und elektronenmikroskopisch untersucht. Intraneuronale argentophile Picksche Körper wurden am zahlreichsten in den Pyramidenzellen des Hippocampus gefunden. Elektronenoptisch bestanden die Einschlußkörper aus einer Zusammenballung von körnigen Gebilden, die in einem unregelmäßigen Netz von vermehrten Neurofilamenten verstreut lagen. Viele eosinophile Hiranosche Körper fanden sich in nächster Nachbarschaft von Nervenzellen. Diese Körper bestanden aus verflochtenen Schichten von geperlten oder glatten Filamenten. Die mögliche Lokalisation der Hiranoschen Körper innerhalb von degenerierenden Axonendigungen wird diskutiert.
    Notes: Summary Brain tissue from an autopsied case of Pick's disease was studied by light and electron microscopy. Intraneuronal argentophilic Pick bodies were most numerous in the pyramidal cells of the hippocampus. By electron microscopy, these inclusions consisted of a conglomeration of granules enmeshed in an irregular network of proliferated neurofilaments. There were also multiple eosinophilic juxtaneuronal structures (Hirano bodies). By electron microscopy these consisted of interwoven sheaves of beaded and continuous filaments. The possible location of the Hirano bodies within degenerating axonal terminals is discussed.
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  • 83
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    Electronic Resource
    Springer
    Acta neuropathologica 11 (1968), S. 82-86 
    ISSN: 1432-0533
    Keywords: Electron Microscopy ; Lenticular Nucleus ; Coma Hepaticum ; Astrocytes ; Lipopigment, Astroglial
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Elektronenmikroskopische Autopsieuntersuchung des Linsenkernes von 2 menschlichen Fällen, die im Leberkoma starben. Als Veränderungen fanden sich Schwellung und Vakuolisierung der Astrocyten. Außerdem waren Lipofuscin- und Lipid-ähnliche Substanzen in den gleichen Zellen vermehrt vorhanden. An den Markfasern, Neuronen und kleinen Blutgefäßen fanden sich keine Veränderungen.
    Notes: Summary Electron microscopic post mortem examination of the lenticular nuclei of two human cases who died in hepatogenic coma is reported. Lesions were found to be swelling and vacuolation of astrocytes. In addition an excess of lipofuscin and lipid like substances were present in the same cells. No changes were found in myelinated fibres, neurons and small blood vessels.
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  • 84
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    Electronic Resource
    Springer
    Acta neuropathologica 11 (1968), S. 93-102 
    ISSN: 1432-0533
    Keywords: Diabetic Neuropathy ; Hypertrophic Changes ; Nerve Biopsy ; Electron Microscopy ; Segmental Demyelination
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Beobachtungen an Nervenbiopsien bei 10 aufeinanderfolgenden Patienten mit diabetischer Neuropathie wurden unternommen. 1 Patient wies die für eine hypertrophische Neuropathie typischen licht-und elektronenmikroskopischen Veränderungen auf. 5 zeigten typische hypertrophische Veränderungen, die aber nur bei elektronenmikroskopischer Untersuchung sichtbar waren; bei weiteren wurden ähnliche geringe Veränderungen entdeckt. Es wird angenommen, daß diese Veränderungen durch segmentale Demyelinisation verursacht wurden.
    Notes: Summary Observations have been made on 10 consecutive nerve biopsies from patients with diabetic neuropathy. 1 patient showed the typical appearances of hypertrophic neuropathy on light and electron microscopy. 5 displayed typical hypertrophic changes visible only on electron microscopy and minor abnormalities of a similar nature were seen in 2 others. It was considered that they were likely to have resulted from recurrent segmental demyelination.
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  • 85
    ISSN: 1432-0533
    Keywords: Hypertrophic Neuritis ; Onion Bulb Structures ; Electron Microscopy ; Segmental Demyelination ; Schwann Cell Lesion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Histochemische und elektronenoptische Befunde eines Patienten mit hypertrophischer Neuritis von 25 Jahren Dauer mit Beginn der Erkrankung in der Kindheit werden mitgeteilt. Die erhobenen Befunde sowie andere jüngste Beobachtungen bilden die Grundlage einer Diskussion der verschiedenen pathogenetischen Hypothesen der “Zwiebelschalen”-Strukturen in den Nerven von Patienten mit hypertrophischer Neuritis. Die Zwiebelschalenbildung wird als unspezifische Manifestation einer chronischen segmentalen Entmarkung infolge primärer oder erworbener Anomalie der Schwann-Zellen interpretiert.
    Notes: Summary Histochemical and electron microscopic data are presented from a patient with hypertrophic neuritis of 25 years duration with onset in childhood. The present observations and those of recent investigators form the basis of a discussion of various pathogenetic hypotheses for “onion bulb” structures in the nerves from patients with hypertrophic neuritis. It is concluded that the onion bulb lesion is a nonspecific manifestation of chronic segmental demyelinization resulting from a primary or acquired abnormality of Schwann cells.
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  • 86
    ISSN: 1432-0533
    Keywords: Beta Irradiation ; Initial Brain Lesions ; Histochemistry ; Electron Microscopy ; Mucoproteid Globuli
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Die Köpfe von insgesamt 17 Meerschweinchen beiderlei Geschlechts wurden mit 17 MeV-Betastrahlen homogen bestrahlt. Die Einzeitbestrahlungen erfolgten mit Dosiswerten von 500–5000 R und einer Dosisleistung von 100 R pro Minute. Sämtliche Tiere wurden 24 Std nach der Bestrahlung getötet. Durch PAS- und Astrablau-Reaktionen konnten Globuli, die Mucoproteide und saure Mucopolysaccharide enthalten und vorzugsweise in der weißen Substanz vorkommen, nachgewiesen werden. Die regionäre Verteilung ist von der Dosierung abhängig. Von 2000 R an finden sich in der marknahen Großhirnrinde und Medulla oblongata geschrumpfte und nekrotische Ganglienzellen. Ebenso verhalten sich die Purkinje-Zellen. Diese Veränderungen werden im ultrastrukturellen Bereich bestätigt. Das Ödem findet sich in den Astrocyten; der extracelluläre Raum der grauen Substanz des Cortex ist nicht erweitert.
    Notes: Summary The heads of 17 guinea pigs of both sexes were irradiated homogenously by 7 MeV-beta irradiation. The dosage of the one-time irradiation was 500–5000 R with a dosage of 100 R/minute. All the animals were killed 24 hrs after the irradiation. By means of PAS- and Astrablue reactions globuli containing mucoproteids and acid mucopolysaccharides could be detected mainly in the white matter. Their regional pattern depends on the dosage. Beginning from 2000 R, shrinked and necrotic nerve cells are seen in the deep cerebral cortex and medulla oblongata. Similar lesions are seen in the Purkinje cells. These lesions are confirmed by ultrastructural findings. Edema is found in astrocytes. The extracellular spaces of the cortical gray matter are not enlarged.
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  • 87
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    Springer
    Naunyn-Schmiedeberg's archives of pharmacology 261 (1968), S. 118-132 
    ISSN: 1432-1912
    Keywords: Lysosomes ; Leucocytes ; Enzymes ; Melittin ; Membrane Permeability ; Electron Microscopy ; Lysosomen ; Leukocyten ; Enzyme ; Melittin ; Membranpermeabilität ; Elektronenmikroskopie
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Das basische Polypeptid Melittin bewirkt die Freisetzung von β-Glucuronidase, Kathepsin, saurer Phosphatase und alkalischer Phosphatase aus isolierten lysosomalen Granula polymorphkerniger neutrophiler Leukocyten und aus intakten Leukocyten vom Rind. An polymorphkernigen Leukocyten setzt Melittin außerdem Lactat-Dehydrogenase und Glutamat-Pyruvat-Transaminase frei. Das mitochondriale Enzym (GPT) wird zeitlich später solubilisiert als Kathepsin. Elektronenoptisch zeigen isolierte Granula nach Einwirkung von Melittin Verringerung des Durchmessers, Verdichtung der Matrix und Membranbrüche. Intakte Zellen werden degranuliert. Es kommt zur Auflösung lysosomaler Granula in cytoplasmatischen Vacuolen. Ein Mastzellen-lysierendes Polypeptid aus Bienengift war in Konzentrationen bis zu 2 · 10−5 M/l an isolierten Granula unwirksam. Mit Hilfe der Änderung der Lichtdurchlässigkeit von Granulasuspensionen wurden andere basische Polymere auf ihre membranschädigende Wirkung untersucht. Ihre Wirkungsstärke war von der Basizität und der Kettenlänge abhängig.
    Notes: Summary The cationic polypeptide Melittin effects the liberation of acid and alkaline phosphatase, β-glucuronidase and cathepsin from isolated lysosomal granules of polymorphonuclear neutrophilic bovine leucocytes as well as from intact leucocytes. In addition Melittin releases LDH and Glutamate-Pyruvate-Transaminase. The mitochondrial enzyme (GPT) is solubilized later than cathepsin. Electron microscopy of isolated granules, after treatment with Melittin shows a reduction of their diameter, an increase in density of the matrix and membrane fractures. Intact cells are degranulated and there occurs a lysis of lysosomal granules in cytoplasmic vacuoles. Another mast cell-degranulating polypeptide from bee venom in concentrations up to 2×10−5 M/l was ineffective on isolated granules. Other cationic polymers were studied with regard to their membrane-damaging effect by means of changes in optical density of suspended granules. The intensity of their effect was dependent on the number of cationic charges and on chain length.
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  • 88
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    Springer
    Naunyn-Schmiedeberg's archives of pharmacology 261 (1968), S. 239-251 
    ISSN: 1432-1912
    Keywords: Leucocytes ; Lysosomes ; Enzymes ; Membrane Permeability ; Electron Microscopy ; Sulfhydryl Groups ; Leukocyten ; Lysosomen ; Enzyme ; Membranpermeabilität ; Elektronenmikroskopie ; Sulfhydrylgruppen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Hg-haltige Sulfhydrylreagentien bewirken an isolierten lysosomalen Granula von polymorphkernigen Leukocyten des Rindes in Konzentrationen von 10−3–10−7 M/l Abnahme der optischen Dichte sowie Freisetzung von Kathepsin, saurer Phosphatase und basischen Polypeptiden. Elektronenoptisch kommt es nach Einwirkung von Mersalyl zur Vacuolisierung und Abnahme der elektronenoptischen Dichte der Matrix. Höhere Konzentrationen führen zur Ruptur der Granulamembran. Blockiert man in der Membran von intakten Granula 1 Mol SH pro 22000 g Granulaprotein mit p-Chlormercuribenzoat, so kommt es zur Erhöhung der Permeabilität der Partikel für Enzymproteine.
    Notes: Summary A number of mercury sulfhydryl-reagents act on isolated lysosomal granules of bovine polymorphonuclear leucocytes in concentrations of 10−3 to 10−7 M/l to cause a decrease of optical density and the liberation of acid phosphatase, cathepsin and cationic polypeptides. Electron microscopy of isolated granules after treatment with mersalyl showed a decrease in electron density of the matrix and vacuolisation. Concentrations up to 10−3 M/l destroyed the particles and ruptured their membranes. The number of sulfhydryl groups was estimated at 1 Mol SH per 22000 g of granule protein. Blocking these groups with p-chlormercuribenzoate causes an increase in membrane permeability for enzymes of the lysosomal particles.
    Type of Medium: Electronic Resource
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