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  • 1975-1979
  • 1970-1974  (3,225)
  • 1970  (3,225)
  • Polymer and Materials Science  (1,970)
  • Inorganic Chemistry  (809)
  • Analytical Chemistry and Spectroscopy  (346)
  • Biochemistry and Biotechnology  (73)
  • Electron microscopy
Material
Years
  • 1975-1979
  • 1970-1974  (3,225)
Year
Keywords
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 132 (1970), S. 107-157 
    ISSN: 1432-0568
    Keywords: Differentiation ; Down feathers ; Electron microscopy ; Keratinization ; Keratohyalin granules ; Periderm granules
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The morphology of the developing chick feather germ (down feather) was studied at the ultrastructural level from 8 to 18 days of incubation. The process of keratinization in the developing feather germ was described, discussed and compared to keratinization in mammalian skin and hair. This study has shown that: 1. Apico-basal gradients of differentiation and different cell types are recognizable at the ultrastructural level in the developing feather germ. 2. The hypothesis that keratin is synthesized de novo by ribosomes is probably correct, because the largest number of these organelles is present at the time when keratin formation is most prominent. 3. Intercellular gaps in the developing feather germs facilitate the reorientation and rearrangement of different cell types into definitive feather structures. 4. The sources of nutrition and energy for the completion of keratinization during later developmental stages of feather germs are the supportive and the barb medullary cells and large stores of glycogen. 5. Keratohyalin granules are not precursors of feather keratin, since no such structures were observed in feather germs. 6. Two distinct modes of keratinization occur in feather germs. Keratinization in sheath cells is similar to that which occurs in mammalian epidermal cells. Barb and barbule cell keratinization resembles that of hair. 7. The basal lamina is probably involved in transport of synthetic material from the pulp cavity to the epidermal cells. The lamina may also provide mechanically strong connections between the feather germ and the dermis. It is suggested that desmosomal tonofilaments provide a framework which orients the synthesis of keratin. It is also suggested that the periderm granules provide mechanically weak areas in the sheath and facilitate the fragmentation of this structure.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 130 (1970), S. 216-233 
    ISSN: 1432-0568
    Keywords: Guinea-pig ; Placenta ; Syncytiotrophoblast ; Fetal capillaries ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Es wurde elektronenmikroskopisch die reife Hauptplacenta von 31 Meerschweinchen untersucht. Die Ergebnisse zeigen, daß das Organ aus, drei morphologisch unterscheidbaren Gebieten aufgebaut ist: Interlobär- und, Randsyncytium, Läppchenperipherie und Läppchenzentrum. Zwischen diesen Zonen befinden sich noch zwei Übergangszonen, die die Eigenschaften der angrenzenden Hauptgebiete haben. Das Interlobär- und Randsyncytium enthält keine fetalen Capillaren, besitzt, aber teilweise ein sehr gut entwickeltes endoplasmatisches Reticulum mit zum Teil parallel angeordneten Zisternen sowie vielen Einschlüssen und verschiedenartigen vacuolären Gebilden. Nach dem Vorkommen dieser Bestandteile unterscheiden wir vier unregelmäßig verteilte Syncytioplasmazonen: a) mit vielen Vacuolen, b) mit vielen Filamenten, c) mit Vacuolen und Filamenten und d)— am häufigsten — Gebiete, die fast frei von derartigen Strukturen sind. Der Trophoblast besitzt an der den mütterlichen Lacunen zugewandten Oberfläche viele Mikrovilli und unterschiedliche polypartige Gebilde. Die Läppchenperipherie ist reich an fetalen Capillaren. Die Trophoblastbalken sind dünn und zeigen unterschiedlichen Organellengehalt. Oft kommen viele Vesikel vor. Das endoplasmatische Reticulum ist um die mitochondrien angeordnet. Das Läppchenzentrum zeigt häufig eine vacuolisierte, netzartige Struktur. Im Syncytiotrophoblast sowie in den Endothelzellen werden ausgedehnte endoplasmatische Zisternen gesehen. Die Oberfläche der fetalen Capillaren besitzt viele polypartige Gebilde. In funktioneller Hinsicht wird das Rand- und Interlobärsyncytium mit der Proteinsynthese in Zusammenhang gebracht. Trotz des Fehlens embryonaler Gefäße können sich hier Resorptionsvorgänge abspielen (positive ATP'ase-Reaktion). In der Läppchenperipherie überwiegt möglicherweise der Austausch der Atemgase und niedermolekularer Substanzen. Das Läppchenzentrum scheint wieder in Beziehung zum Proteinaustausch und zum Lipidumsatz zu stehen. Es gibt Hinweise, daß über alle Placentazonen hinweg eine lebhafte Cytoplasmaströmung erfolgt.
    Notes: Summary The mature main placenta of 31 guinea-pigs was investigated by means of electron microscopy. It is shown that the organ consists of 3 morphologically different regions, i.e. interlobar and marginal syncytium, lobular periphery and lobular centre. Between these regions there are 2 transitional zones having the morphological characteristics of both adjacent main regions. The interlobar and marginal syncytium is devoid of fetal capillaries However, in some parts it has an extremely developed endoplasmic reticulum, in parts of which the cisternae are arranged in parallel. In addition it has many inclusions and various vacuolated structures. According to the presence or absence of these structures four irregularly distributed syncytioplasma zones can be distinguished: a) containing large numbers of vacuoles, b) containing large numbers of filaments, c) containing vacuoles and filaments and d)— the main group —regions which are almost entirely free from these structures. On the surface facing the maternal lacunae the trophoblast has an abundance of microvilli as well as various polypoid structures. The lobular periphery is rich in fetal capilaries. The trabeculae of the trophoblast are thin and show a varying of organelles. Frequently large numbers of vesicles are observed. The endoplasmic reticulum is arranged around the mitochondria. The lobular centre frequently shows a vacuolized net-like structure. Extensive endoplasmic cisternae are observed in the syncytiotrophoblast as well as in the endothelial cells. The surface of the fetal capillaries shows an abundance of polypoid structures. From a functional point of view it seems likely that the interlobar and marginal syncytium is involved in protein synthesis. Despite the lack of fetal capillaries, absorptive processes can take place in this region. It is suggested that the main function of the lobular periphery is exchange of the respiratory gases and of substances of low molecular weight. The lobular centre seems to be associated with protein synthesis and lipid turnover.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 10 (1970), S. 276-282 
    ISSN: 1432-1106
    Keywords: Chlorpromazine ; Rabbit hypothalamus ; Glycogen ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The tuber cinereum of hypothalamus, cerebral cortex, cerebellar cortex and caudate nucleus of rabbits were examined under the electron microscope following intramuscular administration of chlorpromazine with special consideration of ultrastructural changes in amount and distribution of glycogen granules in their hypothalamus. In these regions, normal astrocytes and their processes contain glycogen granules diffusely scattered in the cytoplasm. In the neurons of the normal hypothalamus and cerebellar cortex, glycogen granules are seen in some presynaptic endings and distal parts of dendrites but not in the perikaryal cytoplasm. In the tuber cinereum of the hypothalamus, after chlorpromazine administration, abundant glycogen granules accumulate at the postsynaptic sites, especially in peripheric parts of dendrites, and clusters of glycogen granules appear in the perikaryal cytoplasm of the nerve cells. These findings are interpreted as an increase of glycogen in these cellular regions and the suggestion is made that chlorpromazine inhibits the glycolytic metabolism in the distal parts of dendrites, particularly at postsynaptic sites and in the perikarya of nerve cells of the hypothalamus.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 11 (1970), S. 387-391 
    ISSN: 1432-1106
    Keywords: Trifluoperazine ; Rabbit pallidum ; Glycogen ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Following administration of trifluoperazine (a psychotropic drug of the phenothiazine group), the brains of rabbits were examined by electron microscopy, with special reference to the glycogen changes in the globus pallidus, and were compared with the normal materials. After seven days' intramuscular injections of trifluoperazine (10 mg/kg/day), abundant glycogen granules were accumulated in dendrites of pallidum. Those animals showed extrapyramidal symptoms throughout the period. The administration of the drug might inhibit either neural activity or the glycolytic metabolism in dendrites of the pallidum.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 10 (1970), S. 1-16 
    ISSN: 1432-1106
    Keywords: Cerebral cortex ; Laminar lesions ; Degeneration ; Dendrites ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The morphological characteristics of dendrites in layers of the cerebral cortex above laminar lesions induced by ionizing particle irradiation have been studied in the striate field of rat at various survival times. Within two weeks following irradiation an increasing number of dendrites display unusual alterations inferred to be signs of degeneration. Degenerating dendrites can be characterized by a dense cytoplasmic matrix, disruption of mitochondria, presence of dense bodies, irregular outline and a marked alteration of the plasmalemma in its dimensions and staining properties. Some degenerating dendrites possess a large accumulation of dense subsynaptic material and are contacted by synapses with enlarged and altered synaptic clefts. A few dendrites contain extensive membranous whorls. Engulfment by reactive astrocyte processes is a common feature and often includes the presynaptic axonal knob, but only the degenerating dendrite has been observed within glial cytoplasm. The inference that the majority of degenerating dendrites in this material are apical dendrites of pyramidal cells suggests that either shaft synapses are common for these cells, protuberances may retract during degeneration, or spines are lost due to loss of afferent terminals.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Experimental brain research 11 (1970), S. 528-538 
    ISSN: 1432-1106
    Keywords: Visual pathway ; Hypothalamus ; Arcuate nucleus ; Rat ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Degenerating nerve fibres and boutons were searched with the aid of the electron microscope in the arcuate nucleus of rats 2–7 days after bilateral destruction of the retina. In the arcuate nucleus of the control animals as well as in the operated animals, 4 types of boutons were distinguished on the basis of vesicular contents and glial ensheathment. In the operated animals changes interpreted as degenerating were found in small myelinated axons and boutons of type II (boutons containing both synaptic and granular vesicles). The changes were similar to those described in the literature as the “dark” type of degeneration in experimentally interrupted axons and boutons. Similar changes were not found in the unoperated animals. The conclusion is reached, that a small number of fibres of the optic tract reach the arcuate nucleus to terminate here.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Cell & tissue research 111 (1970), S. 316-345 
    ISSN: 1432-0878
    Keywords: Electron microscopy ; Histophysiology of median eminence ; Avian neurohypophysis ; Neurosecretion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Résumé Les effets de l'adénohypophysectomie et de diverses sollicitations de l'axe hypothalamo-hypophysio-corticosurrénalien sur l'ultrastructure de l'Eminence Médiane (E.M.) ont été étudiés chez le Pigeon. 1. Chez le Pigeon entier, l'Eminence Médiane Caudale (E.M.C.) se distingue de l'Eminence Médiane Rostrale (E.M.R.) essentiellement par l'absence dans les deux couches les plus externes (couches palissadique et superficielle) de l'E.M.C. de granules de gros calibres (1600 à 1900 Å), la rareté de granules de diamètre moyen (1200–1400 Å) et la prédominance de petites vésicules à cœur dense de 600–800 Å. 2. La préhypophysectomie entraine: a) dans l'E.M.R. la quasi disparition de granulations dans les deux couches externes; b) dans l'E.M.C. la ≪vidange≫ de nombreux axones, mais un enrichissement relatif, parmi les granulations restantes, des granulations de gros calibre (1600–1900 Å) aux dépens des granules de plus petit calibre. 3. Un shock insulinique entraine des modifications du même ordre: a) déplétion des granules denses, limitée dans ce cas à la portion la plus antérieure des deux couches externes de l'E.M.R.; b) enrichissement relatif des granulations de moyen (1200–1400 Å) et de gros (1600–1900 Å) calibre dans l'E.M.C. avec, en plus dans l'E.M.C., un enrichissement en vésicules de type synaptique. 4. Un traitement à la métopirone produit un accroissement du nombre des granulations de moyen (1200–1400 Å) calibre dans les couches externes de l'E.M.R. et de l'E.M.C., et un enrichissement important de l'E.M.C. en vésicules de type synaptique. 5. Le traitement à la prednisolone conduit à un enrichissement très marqué des couches externes de l'E.M.R. en grains de 1200–1400 Å, et à un enrichissement des couches externes de l'E.M.C. en granulations de 1000 Å. Ces résultats sont discutés dans la perspective des régulations hypothalamo-corticotropes, particulièrement en ce qui concerne les granules de 1200–1400 Å.
    Notes: Summary The effects of adenohypophysectomy, and of several experimental interventions on the hypothalamo-pituitary-adrenal cortical axis have been studied in relation to the fine structure of the median eminence in the pigeon. 1. In control animals, the following morphological features of the caudal median eminence (C.M.E.) distinguish it from the rostral median eminence (R.M.E.): a) the absence in both external layers of the C.M.E. of large (1,600–1,900 Å) electron-dense granules, b) the presence in the C.M.E. of a small number of medium-size (1,200–1,400 Å) granules, and c) the predominance in the C.M.E. of small (600–800 Å) dense-core vesicles. 2. Adenohypophysectomy leads to: a) almost complete disappearance of electron-dense granules in both external layers of the R.M.E., and b) “emptying” of numerous axons and a relative increase in the number of large (1,600–1,900 Å) granules in the C.M.E. 3. Insulin shock produces modifications similar to those of adenohypophysectomy. The depletion of electron-dense granules from the axons is, however, restricted to the most anterior part of the R.M.E., and, in the C.M.E., the relative increase in the number of larger granules affects the 1,200–1,400 Å and the 1,600–1,900 Å size granules. 4. Metopirone enhances the number of medium-size (1,200–1,400 Å) granules in the external layers of both the R.M.E. and the C.M.E. and causes a significant increase in the number of synaptic-like vesicles in the C.M.E. 5. Prednisolone treatment leads to a marked enrichment of the external layers of the R.M.E. with 1,200–1,400 Å granules, and of the external layers of the C.M.E. with 1,000 Å granules. These results have been discussed with special reference to the hypothalamic control of the adrenocorticotropic function, especially reviewing the role of the 1,200–1,400 Å granules.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Cell & tissue research 106 (1970), S. 451-472 
    ISSN: 1432-0878
    Keywords: Hemocytopoiesis ; Insects ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung Mikroskopische Beobachtungen an normalen „phagozytären Geweben“ (im Sinne der älteren Autoren) entlang des dorsalen Diaphragmas der beiden Orthopteren-Arten Gryllus bimaculatus und Locusta migratoria zeigen übereinstimmend, daß diese Bildungen eine hematopoietische Struktur haben. Bei beiden Arten entwickeln sich die blutbildenden Stammzellen aus einer großen Anzahl sog. Retikularzellen mesodermalen Ursprungs, die den Retikularzellen der blutbildenden Gewebe der Vertebrata sehr stark ähneln. Wie bei den Vertebrata differenzieren sich bei den Insekten die Blutzellen in sog. isogenen Zellgruppen von gleichem Typus und gleichem Entwicklungsstadium. Die starke phagozytäre Neigung der Retikularzellen erklärt, warum die blutbildenden Gewebe der Orthoptera von den älteren Autoren als phagozytäre Organe angesprochen wurden. Die hämatopoietische Differenzierung der Retikularzellen in reife Blutzellen (Haemozyten) findet entweder in einem lockeren Gewebe entlang des dorsalen Blutgefäßes, wie bei Locusta, statt, oder im inneren mehrerer, an das Herz gebundener, hoch organisierter blutbildender Organe, wie bei Gryllus, die noch stärker an die klassischen Strukturen der Vertebrata erinnern. Wir beschreiben im einzelnen beide Strukturtypen, insbesondere bei Gryllus die Einteilung der Organe in einen Cortex, in dem sich die Blutzellen bilden, und eine Medulla, in welcher sich die reifen Haemozyten ansammeln können. Nach starken Blutverlusten zeigen besonders die blutbildenden Gewebe von Gryllus eine dramatische Stimulierung der Hämatopoiese an; die Punktion der hämatopoietischen Organe kann also ebenfalls experimentell nachgewiesen werden.
    Notes: Summary Microscopic observations of the normal “phagocytic tissues” (in the sense of the classic authors) of the dorsal diaphragm in the two Orthopterans Gryllus bimaculatus and Locusta migratoria unequivocally demonstrate the hematopoietic nature of these cellular accumulations. In the two species, the hematopoietic elements develop from a large number of so-called reticular cells of mesodermic origin, which resemble closely the reticular cells of the hematopoietic organs of Vertebrates. As it is the case in Vertebrates, the differentiation of the hematopoietic elements into mature blood cells occurs in the two Orthopterans also in isogenic cell islets. The phagocytic activity of the reticular cells explains the fact that these organs were classically considered in the Orthopterans as simple phagocytic organs. The hematopoietic differentiation of the reticular cells can occur either in a poorly organized, loose tissue located along the dorsal vessel, as is the case in Locusta, or in a group of highly organized hematopoietic organs, as in Gryllus, which resemble far more the classical hematopoietic structures of Vertebrates. We give a detailed description of both types of organization, especially of the subdivision in Gryllus, of the hematopoietic organs into a cortex, where the haemocytes differentiate, and a medulla, where they can accumulate. After severe hemorrhages, the hematopoietic organs of Gryllus show all the features of a dramatic stimulation of hematopoiesis; their function can thus be experimentally demonstrated.
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Cell & tissue research 106 (1970), S. 523-538 
    ISSN: 1432-0878
    Keywords: Ependyma ; Intracytoplasmic lipid bodies ; Histochemistry ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung Bei erwachsenen Feuersalamandern und bei Salamanderlarven konnten in Ependymzellen sowie in subependymären Zellelementen des Gehirns und Rückenmarks zahlreiche rundliche intrazytoplasmatische Körper von starker Osmiophilie beobachtet werden, deren Durchmesser bis zu 12 μ betrug. Vereinzelt fanden sich diese voluminösen Gebilde auch im Cytoplasma von Satellitenzellen der Hirnnerven- und Spinalganglien. Das histochemische Verhalten und das Ultrastrukturbild der intrazytoplasmatischen Körper sprechen dafür, daß sie hauptsächlich aus Lipiden bestehen. Ihre funktionelle Bedeutung konnte bisher nicht eindeutig geklärt werden.
    Notes: Summary The ependymal and subependymal cells of the ventricular system and the central canal in adult und larval salamanders contain numerous unusually large intracytoplasmic osmiophilic spherical bodies with a diameter of up to 12 μ. Sporadically the bodies are found within satellite cells of peripheral ganglia. Histochemical and ultrastructural examination suggests that the bodies consist mainly of lipids. Their functional significance is unknown.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Cell & tissue research 109 (1970), S. 384-397 
    ISSN: 1432-0878
    Keywords: Heart muscle cells ; Electron microscopy ; Quantitative ; Asphyxia ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung Normale und hypoxische Herzmuskelzellen aus der Wand des linken Ventrikels der Ratte wurden quantitativ-morphologisch anhand von elektronenmikroskopischen Längsschnitten nach Perfusionsfixierung untersucht. In normalen Zellen waren alle Myofibrillen relaxiert, die mittlere Sarcomerlänge betrug 2,2 μm. Die Schnittfläche wurde zu 55% von Myofibrillen, zu 27% von Mitochondrien und zu 18% von Grundplasma und Reticulum eingenommen. Die zwischen den Myofibrillen liegenden Mitochondrien waren längsoval und im Mittel 2,3mal so lang wie breit. Es bestand kein Unterschied zwischen subendokardial und subepikardial gelegenen Zellen. 10 min nach Erstickung der Tiere waren in den sonst unauffälligen Muskelzellen die Glycogengranula vermindert. Nach 20 min führte die Hypoxie zu einer Zunahme der relativen Schnittfläche der Mitochondrien um etwa 16% und zu einer beginnenden Kontraktur der Myofibrillen (Sarcomerlänge 2,0 μm). 20 min Hypoxie in Hypothermie (25–30°C intrathorakal) veränderte die normale Zellstruktur dagegen kaum. Wenn die Herzen während der 20 min dauernden Hypoxie in Normothermie mit einer procainhaltigen sauerstoff- und glucosefreien Blutersatzlösung durchspült wurden, waren die Myofibrillen relaxiert, die Schwellung der Mitochondrien dagegen wurde nicht reduziert. 30 min nach Erstickung wurde die Kontraktur stärker (Sarcomerlänge 1,7 μm). Nach 60 min bildeten sich Superkontraktionsknoten, einzelne Myofibrillen waren in Höhe der I-Bänder unterbrochen. Die Cristae der Mitochondrien wichen auseinander, die Schnittfläche der Mitochondrien hatte um 27% zugenommen. Während in Normotherapie eine Asphyxie des Tieres bereits nach 10 min die Herzmuskelzellen funktionell schwer schädigt, ist die Schädigung morphologisch erst nach 20 min eindeutig. Das bedeutet, daß für die elektronenmikroskopische Präparation eine Hypoxie von unter 10 min bedeutungslos ist. Hinsichtlich der morphologischen Manifestationszeit für die Unterbrechung der Sauerstoffversorgung stimmen unsere Befunde an Herzmuskelzellen gut mit vergleichbaren Angaben an Leberzellen überein.
    Notes: Summary In heart muscle cells of the left ventricle of rats the distribution of cell organelles and their reaction to hypoxia were investigated by electron microscopy. In normal hearts fixed by perfusion with aldehydes, the mean sarcomere length was 2.2 μm. 27% of the longitudinal sectional area was occupied by mitochondria, 55% by myofibrils and 18% by sarcoplasmic reticulum and ground plasm. The mitochondria situated in rows between the fibrils were oval and measured 2.3 times more in length than in width. There was no difference between cells from subendocardial and subepicardial regions. 10 min hypoxia (complete occlusion of the trachea) did not affect the appearance of muscle cells but diminished the number of glycogen granules. After 20 minutes the area occupied by mitochondria was increased by 16%, the mitochondria between the myofibrils were more spherical and only 1.5 times longer than wide. The sarcomeres shortened to 2.0 μm. With hypothermia (25–30°C) hypoxia of 20 minutes duration did not affect the cell structure. Perfusion of the heart by a saline solution, which contained procaine but neither oxygen nor glucose, for 20 minutes prevented shortening of the sarcomeres but not swelling of the mitochondria. 30 minutes after occlusion of the trachea the myofibrils shortened to a sarcomere length of 1.7 μm. After 60 minutes irregularly and excessively contracted myofibrils appeared and some sarcomeres were interrupted at the level of the I-bands. In some of the swollen mitochondria the cristae were widely separated. The increase of the area occupied by mitochondria was 27%. Asphyxia affects heart muscle cells severely with respect to function within 10 min, but morphologically it takes 20 min before a definite effect can be noticed. As to the time after which lack of oxygen is manifested morphologically, our results are consistent with findings in liver cells.
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    Cell & tissue research 109 (1970), S. 431-449 
    ISSN: 1432-0878
    Keywords: Contractile ring ; Cytokinesis ; Cell division ; Cytochalasin B ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Techniques of individual cell selection and precise ultramicrotomy have been employed to demonstrate that the contractile ring of cleaving HeLa cells is a transitory cytoplasmic organelle of distinctive fine structure and location. The contractile ring is an uninterrupted annulus encircling the equator of dividing cells exactly where the cleavage furrow forms. It is about 10 microns wide, up to 0.2 microns in thickness, and is composed exclusively of circumferentially aligned thin filaments 40–70 Å in diameter. Contractile ring filaments appear to be associated with the overlying plasma membrane. Controlled experiments with a mold metabolite (cytochalasin B) reveals that within a few minutes the drug abolishes the ability of HeLa cells to undergo cytokinesis. Cytochalasin B seems to decompose the contractile ring. It has no other clearly identifiable effects on other cell structures, notably the mitotic apparatus. Cytochalasin B is the only drug known which selectively inhibits cytokinesis in animal cells. In conclusion, the contractile ring is the most likely organelle responsible for cytokinesis in HeLa cells. Similar organelles probably occur in all cleaving animal cells. Successful cleavage depends upon the structural and functional integrity of the contractile ring.
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    Cell & tissue research 110 (1970), S. 153-165 
    ISSN: 1432-0878
    Keywords: Reptiles ; Skin ; Keratin ; Electron microscopy ; Evolution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The different patterns of keratin formation that have evolved in the class Reptilia are all variations of a common process. In Squamata (snakes and lizards), a sequence of layers composed of α or β keratin is formed periodically, after which the old epidermal generation is shed. In Chelonia (turtles and tortoises), the epidermis of the shell is composed of only β keratin, whereas the skin of the neck and leg is composed exclusively of α keratin. Molting in toto does not occur and shedding is a continuous process comparable to that in avian and mammalian epidermis. In Crocodilia (crocodiles, caimans, alligators) there is only a single layer of cornified cells, but the composition of the layer varies in different parts of the scale. The hinge regions have many of the morphological characteristics of α and β keratin whereas the center resembles β keratin. The living cells beneath contain accumulations of keratohyalin. There are four ultrastructural characteristics of a keratinized α layer: 1) cellular outlines remain distinct, 2) a thickened plasma membrane forms during keratinization, 3) 80 Å filaments embedded in an amorphous matrix can be seen, and 4) PAS-positive material accumulates in extracellular spaces between the desmosomes. The β layer exhibits none of these features. Instead the cells more or less (depending on species) coalesce into a compact layer which becomes attenuated in the hinge regions. A 30 Å filament pattern can be seen. The mesos layer of squamates resembles the hinge region of crocodilians, exhibiting a combination of the characteristics of both α and β keratin.
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Cell & tissue research 106 (1970), S. 309-321 
    ISSN: 1432-0878
    Keywords: Red nucleus ; Substantia nigra ; Neuroglia ; Pericytes ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The morphology of perivascular and perineuronal cells in the substantia nigra and red nucleus was studied in Nissl, silver carbonate, and electron microscopic preparations. In light microscopic preparations of the red nucleus and substantia nigra oligodendrocytes and astrocytes are located adjacent to blood vessels and nerve cells. Pericytes are also found adjacent to blood vessels. Scattered perineuronal oligodendrocytes and astrocytes are present in the magnocellular portion of the red nucleus and in the substantia nigra, whereas a distinguishing morphological feature of the parvocellular portion of the red nucleus is the clustering of perineuronal oligodendrocytes around a single neuron. In the present electron micrographs of the red nucleus and substantia nigra oligodendrocytes are separated from the vascular basement membrane (basal lamina) by astrocyte processes and therefore are not truly perivascular. Pericytes are easily identified by the basement membrane which encompasses their cell bodies and processes. Characteristic of the neuropil in the red nucleus are astrocytic processes that approximate dendrites. In contrast, astrocytic processes in the substantia nigra rarely contact dendrites which are covered by a mosaic of synaptic endings. A “third type of neuroglial element” is also present in the neuropil of the substantia nigra and the red nucleus.
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  • 14
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    Cell & tissue research 108 (1970), S. 324-338 
    ISSN: 1432-0878
    Keywords: Human myocardium ; Innervation ; Nerve endings ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Electron microscope studies of axons, distributing singly or in small bundles in the human ventricular and atrial myocardium, indicate a few per-cent of the axon profiles to be significantly large in diameter (1.5–3.0 μ). They are characteristically packed with a profuse number of mitochondria along with large granular vesicles, glycogen rosettes, lysosomic bodies; and some of them terminate on a “specific terminal cell” (Knoche and Schmitt). These mitochondria-rich, large axons are assumed to be terminal portions of the cardiac afferents. About half of the axons encountered in the ventricle and 2/3 in the atrium are non-vesiculated, usually less than 0.5 μ. in diameter. The varicosities containing numerous vesicles are mostly 0.5–1.5 μ in diameter and are assumed to be terminal portions of the cardiac efferents. The ratio between the number of axon profiles containing small granular vesicles and that of axon profiles containing agranular vesicles without small granular vesicles is 2∶1 in the ventricular myocardium and 1∶1.7 in the atrial myocardium.
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  • 15
    Electronic Resource
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    Cell & tissue research 109 (1970), S. 33-45 
    ISSN: 1432-0878
    Keywords: Testis ; Interstitial cells ; Reptiles ; Hormone Production ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Résumé L'ultrastructure des cellules interstitielles du testicule de Lacerta vivipara a été étudiée entre le printemps et l'automne pendant deux années. Le retioulum endoplasmique lisse, et les mitochondries à crêtes tabulaires sont les organites les plus remarquables comme dans les autres cellules productrices de stéroïdes, mais les liposomes et l'appareil de Golgi sont bien représentés aussi. Les variations ultrastructurales les plus significatives apparaissent entre le printemps et le début de l'été. Au printemps, alors que les caractères sexuels secondaires sont hypertrophiés, un système remarquable de vésicules et de vacuoles se développe à partir du reticulum et probablement aussi du Golgi. Au début de l'été, lorsque les caractères sexuels secondaires sont atrophiés, les vacuoles sont moins nombreuses et le reticulum forme un réseau dense de tubules typiques, souvent étroitement associés aux liposomes; les crêtes mitochondriales sont gonflées. Ces images sont discutées en fonction de l'activité saisonnière d'élaboration d'hormones. L'hypertrophie des systèmes membranaires au printemps correspond probablement à la production ou (et) à l'excrétion des hormones androgènes. Au début de l'été, la cellule n'élabore pas d'androgènes, mais n'est peut-être pas complètement inactive: elle pourrait stocker des précurseurs hormonaux.
    Notes: Summary Interstitial cells of the testis of Lacerta vivipara have been studied electronmicroscopically in animals obtained between spring and autumn. Smooth endoplasmic reticulum and mitochondria with tubular cristae are the most prominent organels, lipid droplets and Golgi apparatus being also well developed. The most significant ultrastructural changes occur between spring and the beginning of summer. In spring, during the hypertrophy of secondary sexual characters, a conspicuous system of vesicles and vacuoles originates from the smooth endoplasmic reticulum and probably also from the Golgi apparatus. At the beginning of summer, when secondary sexual characters are atrophied, vacuoles are less prominent and the smooth endoplasmic reticulum consists of a dense network of typical tubules, often closely associated with the lipid droplets; the cristae of the mitochondria are swollen. These ultrastructural findings are discussed in relation to the production of hormones. The hypertrophy of membrane systems in spring corresponds presumably to production or (and) release of androgen hormones. In the beginning of summer the cell does not produce androgens, but probably is not completely inactive: it may store precursors of hormones.
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  • 16
    ISSN: 1432-0878
    Keywords: Neurosecretion ; Gastropoda ; Fluorescence ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung Durch Vergleich fluoreszenz- und elektronenmikroskopischer Untersuchungen am zentralen Nervensystem von Planorbarius corneus L. wird nachgewiesen, daß in den Schlundringganglien Neurosekretzellen vorkommen (Nachweis mit Pseudoisocyaninchlorid), die mit Nervenzellen nicht identisch sind, die durch ihren hohen Gehalt an biogenen Aminen auffallen (Nachweis durch die Methode von Falck und Owman, 1965). Es können daher im Schlundring von Planorbarius corneus peptiderge und aminerge Neurosekretzellen unterschieden werden. Die PSC-positiven Neurosekretzellen enthalten elektronendichte Elementargrana und die aminergen Neurone „dense-core“ Vesikel. Der Nachweis biogener Amine in einigen Nervenzellen von Planorbarius corneus spicht für deren chemische Identität mit Transmittersubstanzen, ihre hohe Konzentration aber für eine Abgabe in die Körperflüssigkeit.
    Notes: Summary The neurosecretory system of the snail Planorbarius corneus has been investigated by fluorescence and electron microscopy. With the fluorochrome Pseudoisocyanin the established neurosecretory system in the cerebral ganglia and single neurosecretory cells in the other ganglia show an intensive yellow fluorescence. Electron micrographs reveal the presence of electron dense granules (elementary granules) in the pericarya and the axons of neurones which have the same localisation in the ganglia as the pseudoisocyanin-positive cells. The fluorescence technique for biogenic amines produces yellow and green fluorescence within neurons and in the neuropil and nerves. The fluorescence obtained in determinable areas and neurones correlates well with the electron microscopic location of “dense-core” vesicles within the pericarya and axons of cells in even the same areas. It is discussed, that in this animal both types of cells are so-called “neurosecretory cells”, because the high content of elementary granules in the “peptidergic neurosecretory cells” and of “dense-core” vesicles in the “aminergic neurosecretory cells” is an indication for secretion of these products in neurohaemal areas (circulatory channels).
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  • 17
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    Cell & tissue research 110 (1970), S. 321-335 
    ISSN: 1432-0878
    Keywords: Thymus ; Lymphocyte ; Analysis ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Thymic small lymphocytes of dd-mice were qualitatively and quantitatively studied by electron microscopy. Differences in fine structure were revealed between cortical and medullary small lymphocytes. Cortical small lymphocytes are rounded in cell outline with a round nucleus. The cytoplasm surrounding the nucleus as a narrow rim is scanty and appears relatively dense due to an abundance of free ribosomes. The cell organelles are not well developed. On the other hand, medullary small lymphocytes are more irregular in shape with uneven cell membranes. Their nuclei are also more irregular in outline with frequent infoldings of the nuclear membrane. The cytoplasm is more abundant and paler with less numerous ribosomes. The cell organelles are better developed. Quantitative analysis was made of both cortical and medullary small lymphocytes by means of the point counting method. The nuclei of both cortical and medullary small lymphocytes are almost the same in size (a diameter of 4.9 μ). The cell sizes are different between cortical and medullary lymphocytes: cortical small lymphocytes with a diameter of 5.5 μ were smaller than medullary ones with a diameter of 6.4 μ. Cortical small lymphocytes are very sensitive to the destructive effects of hydrocortisone, whereas the medullary ones are resistant. Periarteriolar lymphoid sheath in the splenic white pulp, which is known to be a thymus-dependent area, contains small lymphocytes that were similar in cytological details to medullary small lymphocytes of the thymus. In the light of the recent knowledge about a recirculating long-lived small lymphocyte pool, it appears probable that medullary small lymphocytes represent a contribution to the pool and that small lymphocytes with a long life span can be cytologically identified by electron microscopy.
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  • 18
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    Cell & tissue research 110 (1970), S. 386-400 
    ISSN: 1432-0878
    Keywords: Autonomic nerves ; Perineurial sheath ; Termination ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung Das Perineurium kleiner Mesenterial- und Trachealnerven besteht aus einer Lage platter, beiderseits von einer Basalmembran umschlossener Zellen. Im Bereich von Abzweigungen kleiner Nerven bildet das Perineurium ein gekammertes, stark kollagenfibrillenhaltiges Hüllensystem. Die Endigung der einschichtigen Perineuralhülle hat die Form einer in das Interstitium geöffneten Röhre. Im ansatznahen Drittel des Mesenteriums und in der Schleimhaut der Trachea wurden ausschließlich perineuriumfreie Nerven gefunden. Es liegt nahe, diese perineuriumfreien Bezirke zu funktionellen Endräumen zusammenzufassen. In perineuriumfreien Bezirken wird das gehäufte Auftreten von Nervenauftreibungen mit Vesikeln, die Transmittersubstanz enthalten, und Mitochondrion beobachtet. Die erhobenen Befunde werden mit den an dickem Perineurium gewonnenen Ergebnissen verglichen und diskutiert.
    Notes: Summary The perineurial sheath of small tracheal and mesenteric nerves consists of a layer of flat, basement membrane coated cells. Its ramifications form a complicated layered system, interspersed with collagen fibrils. The tube formed by the thin perineurial sheath ends openly, which affords communication between the respective interstitial spaces. The mesenteric nerves close to the duodenum as well as the nerves in the vicinity of the tracheal epithelium show no perineurial sheath. Peripheral nerves lacking a perineurial layer seem to be close to their terminations. Their fibers show varicosities containing transmitter vesicles and mitochondria with longitudinally orientated cristae. Our results are compared with those found in thick, multilayered perineurial sheaths and functional differences are discussed.
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  • 19
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    Cell & tissue research 111 (1970), S. 51-63 
    ISSN: 1432-0878
    Keywords: Purkinje cell ; Golgi apparatus ; Dendrites ; Differentiation ; Histochemistry ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The morphology of postnatal differentiation of the Golgi apparatus, the nucleus, the perikaryon, and the dendrites was studied in Purkinje cells of the rat cerebellum for 30 days after birth using histochemical, histological, and electron microscopic methods. The Golgi apparatus during differentiation undergoes morphological and positional changes. From the 1st to 7th postnatal day, the Golgi apparatus is found in a supranuclear position, and is connected with the axes of differentiating primary dendrites by beam-like processes. From days 8 to 11 this connection disappears, and most of the Golgi apparatus assumes a lateronuclear and infranuclear position. After the 11th or 12th day, the Golgi apparatus is found in perinuclear and peripheral cytoplasmic positions. The formation of granular endoplasmic reticulum occurs in the vicinity of the perinuclear Golgi apparatus. The differentiation of cell and nuclear forms requires approximately 20 days. The morphological changes of differentiation are discussed in relation to the participation of the Golgi apparatus in the differentiation of dendrites and in the formation of the granular endoplasmic reticulum.
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  • 20
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    Cell & tissue research 111 (1970), S. 149-159 
    ISSN: 1432-0878
    Keywords: Rabbit ovum ; Fertilization ; Pronucleus ; Cleavage ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Fertilized ova were flushed from the Fallopian tubes of New Zealand White rabbits at 15 to 30 hours after mating and examined with the electron microscope. Between 21 and 22 hours intact pronuclei with extensive interdigitation of apposing surfaces were found in most ova. In some, an appearance suggesting internuclear communication was observed. In other ova disrupted pronuclear membranes surrounded centrally placed chromosome aggregates. In still others an advanced cleavage furrow was already present. By 23 hours all ova were in the two-cell stage.
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  • 21
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    Cell & tissue research 103 (1970), S. 382-397 
    ISSN: 1432-0878
    Keywords: Adrenal cortex ; Newborn rat ; Stereology ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The structure of the zona glomerulosa and the zona fasciculata of the newborn rat adrenal cortex has been studied by the light and the electron microscope. The ultrastructural features of the cells of both zones are described. By morphometric methods the relative volumes occupied by mitochondria and by lipid droplets have been evaluated. The “membrane profile concentration” (i.e. the average number of microns of smooth reticulum profiles per square micron of cytoplasm) has been also measured. The most significant ultrastructural differences between the cells of the two zones concern the mitochondria, the lipid droplets, and the smooth endoplasmic reticulum. The mitochondria show typical lamellar cristae in the elements of the zona glomerulosa, and vesicular cristae in the cells of the zona fasciculata. They occupy the same relative volume in both elements. The lipid droplets and the smooth reticulum show no qualitative differences in the two cell types, but they are found in a larger amount in the cells of the zona fasciculata. These ultrastructural findings are discussed in relation to the numerous biochemical data, suggesting that the cells of the zona glomerulosa are resting elements at birth, while the cells of the zona fasciculata are active steroid-secreting elements already in late gestation.
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  • 22
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    Cell & tissue research 103 (1970), S. 398-409 
    ISSN: 1432-0878
    Keywords: Adrenal cortex ; Newborn rat ; Electron microscopy ; Lysosomes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The structural changes of the zona juxtamedullaris of the rat adrenal cortex at birth, have been examined by the light and the electron microscope. In this zone clusters of medullary cells lying among the strands of cortical tissue were observed. In the inner portion of the zona juxtamedullaris two types of adrenocortical cells were found: light and very-dark cells. The latter are smaller than the light cells and are always in close connection with the medullary tissue. The ultrastructural features of the very-dark cells suggest that these elements are in degeneration. This finding supports the hypothesis that at birth there is a partial degeneration of the rat zona juxtamedullaris, i.e. the zone corresponding to the “fetal zone” of some mammalian species. It is proposed that in all mammalian species at birth there is a partial regression of the zona juxtamedullaris and that the regression of the “fetal zone” is only the quantitative increase of this phenomenon. This hypothesis is discussed in relation to numerous data demonstrating that there are enzymatic conditions in the rat during fetal life, which permit a discrete hypertrophy of the adrenal cortex.
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  • 23
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    Cell & tissue research 103 (1970), S. 341-350 
    ISSN: 1432-0878
    Keywords: Catecholamines ; Brain ; Insects ; Electron microscopy ; Cytochemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary In the brain of the cockroach Periplaneta americana, the beta lobes of the corpora pedunculata respond with an intense positive reaction to a specific fluorescence histochemical method for catecholamines. The fluorescence reaction disappears completely after prolonged treatment of the cockroaches with reserpine. An ultrastructural examination of the beta lobes in formaldehyde-glutaraldehyde-osmium fixed preparations reveals the presence of two types of fibres: 1) Fibres and nerve endings containing small clear vesicles and sligthly larger vesicles with a semi-dense content. The appearance and size distribution of these vesicles ist not affected by treatment with reserpine. 2) Fibres containing larger and denser vesicles, but practically no clear vesicles. The size distribution of these dense vesicles is only slightly affected by treatment of the cockroaches with reserpine. If brain slices are incubated in a medium containing noradrenaline or α-methyl-noradrenaline and fixed in permanganate, small vesicles with electron-dense central cores show up, similar to those which have been described in vertebrate adrenergic nerve fibres (“small granular vesicles”). They are confined to one of the two types of fibres (a and b) visible in these preparations, namely to type b, whose correspondence with type 2 fibres of formaldehyde-glutaraldehyde-osmium fixed preparations is discussed.
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  • 24
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    Cell & tissue research 104 (1970), S. 345-357 
    ISSN: 1432-0878
    Keywords: Photoreceptor ; Lumbricus ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung Die Feinstruktur der Photorezeptorzellen in der Epidermis, in kleineren Nervenästen und im Zerebralganglion von Lumbricus terrestris wurde untersucht. Das Vorhandensein eines zentralen, intrazellulären Lumens (Phaosom), das mit Mikrozotten gefüllt ist, erinnert in der Struktur der Photorezeptorzelle des Regenwurms an Lichtsinneszellen von Hirudo. Außer Mikrozotten findet man im Phaosom einige Zilien vom Typ 9×2+0; solche Zilien sind von den Mikrozotten strukturell unabhängig. Durch eine Aufzweigung des Phaosoms in kleinere Buchten, die tief in das umgebende Zytoplasma eindringen, erhält es ein labyrinthartiges Aussehen. Glatte Zisternen in Gruppen von 2 bis 5 wurden oft um das Phaosom im Zytoplasma beobachtet. Charakteristische Bestandteile der Zelle sind noch Vesikel und Vakuolen, die mit einer Substanz von wechselnder Elektronendichte gefüllt sind. Die Photorezeptorzellen werden von Gliazellen und Gliafortsätzen umgeben, die an vielen Stellen die Zelloberfläche tief einstülpen (Trophospongium).
    Notes: Summary Photoreceptor cells in the epidermis and nerve branches of the prostomium and in the cerebral ganglion of Lumbricus terrestris were investigated with the electron microscope. The photoreceptor cell is similar to the visual cell of Hirudo by having a central intracellular cavity (phaosome) filled with microvilli. Besides microvilli, several sensory cilia can also be found in the phaosome but they are structurally independent of the microvilli. A gradual branching of the phaosome cavity into smaller cavities makes its sectional profile extremely labyrinthic. Flattened smooth-surfaced cisternae in stacks of 2 to 5 are frequently observed around the phaosome. Characteristic constituents of the cytoplasm are vesicles and vacuoles filled with a substance of varying density. The photoreceptor cell is covered by glial cells or by their processes which at many places deeply invaginate the cell surface (trophospongium).
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  • 25
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    Cell & tissue research 105 (1970), S. 176-187 
    ISSN: 1432-0878
    Keywords: Ependyma ; Salamandra maculosa ; Neuronal elements ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Description / Table of Contents: Zusammenfassung Zwischen den eigentlichen Ependymzellen des Zentralkanals adulter Feuersalamander kommen amphorenartig gestaltete Elemente vor, die sich aufgrund ihrer synaptischen Kontakte mit Axonendigungen als Neurone identifizieren lassen. Diese intraependymalen Nervenzellen weisen einen apikalen Fortsatz auf, der sich mit einer warzen- oder knotenförmigen Protrusion in das Lumen des Zentralkanals erstreckt. Die Protrusion ist gewöhnlich mit stereozilienartigen Ausläufern besetzt. Die funktionelle Bedeutung der beschriebenen neuronalen Elemente konnte bisher nicht geklärt werden.
    Notes: Summary The ependyma of the canalis centralis of adult salamanders was examined by electron microscopy. Between the ependymal cells occur amphora-like elements identifiable as neurons by their synaptic contacts with axon terminals. These intraependymal nerve cells exhibit an apical outgrowth extending into the lumen of the canalis centralis with a wart-like or knob-like protrusion. The latter usually bears extensions resembling stereocilia. The functional significance of the neuronal elements is still unknown.
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  • 26
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    Cell & tissue research 105 (1970), S. 515-525 
    ISSN: 1432-0878
    Keywords: Cuticle ; Rotifer ; Development ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Ultrastructural studies of developing Asplanchna brightwelli embryos support the following hypothetical scheme of cuticle formation. First the external hypodermal membrane invaginates, and deposition of a dense intracellular layer commences next to this membrane. Then the rough endoplasmic reticulum synthesizes fibrous protein which is transferred to the Golgi complex. Here polysaccharide is synthesized and added to the protein, and the resulting filamentous complex is enclosed in large irregularly shaped vesicles which bud off from the Golgi elements. Maturation of the filamentous material to condensed cuticle material occurs as the vesicles move to the invaginations. Each vesicle fuses with an invagination, thus forming a hypodermal bulb; then the cuticle material is discharged through the neck of the bulb to its extracellular location. After the bulbs are formed, new, smaller, spherical vesicles begin to bud off from the Golgi elements. They too contain the filamentous complex which is refined to condensed cuticle material as the vesicles near the bulb. These vesicles fuse with the hypodermal bulbs contributing the cuticle and membrane necessary for the growth of the hypodermis of the embryo and newborn animal. Ruthenium red staining has confirmed that the cuticle consists of glycoprotein.
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  • 27
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    Documenta ophthalmologica 28 (1970), S. 191-200 
    ISSN: 1573-2622
    Keywords: Acomys Cahirinus ; Retinal capillary basement membrane width ; Age modifications ; Electron microscopy ; Morphometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé L étude morphométrique des capillaires rétiniens de souris à piquants de différents âges (3, 6, 12 et 36 mois) a démontré un épaississement des membranes basales et un élargissement des diamètres capillaires en fonction de l'âge et, en outre, l'existence d'une corrélation positive entre ces deux paramètres.
    Abstract: zusammenfassung Die morphometrische Untersuchung von Retinakapillaren verschieden Alter (3, 6, 12 und 36 Monate) Stachelmäuse (Acomys cahirinus) ergab eine altersabhängige Zunahme sowohl der Basalmembrandicke als auch des Kapillardurchmessers. Zudem wurde eine positive Korrelation zwischen diesen beiden Parametern gefunden.
    Notes: Abstract Specimens of four age groups of non-diabetic, non-obese spiny mice (Acomys Cahirinus), 3, 6, 12, 36 months old respectively, were examined for changes in retinal capillaries. Morphometrical evaluation of electron-micrographs allowed to conclude that capillary basement membrane width, as well as capillary diameter, increase during ageing: the values in the four different age groups were found to be 656, 925, 1098, 1772 Ångström units for the average basement membrane width, and 3,72, 4,08, 4,58, 5,60 microns for average capillary diameter. The differences between the age groups proved to be significant at a p 〈 0,01. Furthermore, a positive correlation between capillary diameter and capillary basement membrane width seems to be highly probable.
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  • 28
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    New York : Wiley-Blackwell
    Biopolymers 9 (1970), S. 811-824 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The root-mean-square end-to-end distance has been calculated for a model allowing free rotation about glycoside bonds for the general case of polysaccharides having a disaccharide repeating unit. Numerical estimates are given for several naturally occurring structures based on an idealized pyranose unit in the C1 chair conformation. Extrapolation procedures which make use of the intrinsic viscosity [η] in good solvents to obtain unperturbed dimensions do not represent, data for hyaluronic acid very well, especially at low molecular weights. However, order-of-magnitude estimates suggest that this polymer behaves similarly to other polysaccharides, and probably has stiffer local structure than typical non-ionic synthetic polymers. A double logarithmic plot of the product of [η] and M̄w, the weight-average molecular weight, against the degree of polymerization in the range for M̄w of 104 to 2 × 104 permits a straight-line fit of available data for all the glycosaminoglycans, including heparin and the chondroitin sulfates, as well as sodium carboxymethyl cellulose. This result suggests similarity of short-chain hydrodynamic behavior of these polymers.
    Additional Material: 4 Ill.
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  • 29
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    New York : Wiley-Blackwell
    Biopolymers 9 (1970), S. 875-875 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 30
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    New York : Wiley-Blackwell
    Biopolymers 9 (1970) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 31
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    New York : Wiley-Blackwell
    Biopolymers 9 (1970), S. 865-874 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A common approximation for deriving solutions to the Lamm equation is to neglect diffusion. This paper presents a singular perturbation technique that allows one to estimate the band spreading due to nonzero diffusion coefficient. We illustrate the general mathematical technique by its application to sedimentation when pressure effects are important. Comparison of the approximate solution with accurate numerical solutions shows that the relative errors are of the order of 1% both for concentration and concentration gradient for parameters of chemical interest.
    Additional Material: 3 Ill.
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  • 32
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    New York : Wiley-Blackwell
    Biopolymers 9 (1970), S. 891-896 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Glycogen acquires a negative charge in both alkaline and acidic solutions and can move in an electrical field, its mobility being related to the degree of alkalinity or acidity. There is a slight increase in relative viscosity at both ends of the pH spectrum. These effects and the changes in nuclear magnetic resonance as a function of pH are interpreted.
    Additional Material: 3 Tab.
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  • 33
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The viscosity of bovine liver glutamate dehydrogenase solutions was studied at 10 and 20° C in 0.2.M sodium phosphate buffer at pH 7, in the concentration range 0.1-8 mg/ml. A method for the study of the viscosity of very dilute solutions of associating enzymes is described. It was found that the reduced specific viscosity ηsp/c of glutamate dehydrogenase continuously increases with increasing enzyme concentration, from about 4 ml/g at the lowest concentrations to about 16 ml/g at 8 mg/ml. In the presence of 10-3M GTP and 10-3M NADH the viscosity increase is much smaller and the results can be extrapolated to zero enzyme concentration to yield an intrinsic viscosity [η] = 3.2. The values of ηsp/c in phosphate buffer alone apparently extrapolate to the same value of [η], or to a value close to it. We also observe that, in the presence of toluene ηsp/c increases very much more with enzyme concentration: ηsp/c already equals 16 ml/g at a concentration of 0.75 mg/ml. These observations are in good agreement with the hypothesis that the active oligomer of glutamate dehydrogenase (MW = 312,000) associates with increasing enzyme concentration to form linear rodlike polymers of indefinite length. This association is strongly diminished by the addition of 10-3M GTP, 10-3M NADH. Toluene, on the other hand, promotes reversible association to linear polymers of very high molecular weight. The transverse and axial rotary frictional coefficients of macroscopic bodies, similar to a physical model for the structure of glutamate dehydrogenase recently advanced, were determined. Assuming that the viscosity of the model is equal to that of an ellipsoid of rotation with identical frictional coefficients, we calculate [η] = 3.26 ml/g according to Kuhn and 3.20 ml/g according to Simha, for the glutamate dehydrogenase oligomer, in good agreement with the result derived from the study of enzyme solutions.
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  • 34
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    Biopolymers 9 (1970), S. 911-922 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular monolaycrs of poly(β-benzyl L-aspartate) spread at. an air-water interface have been studied. The results obtained both by direct observations on the monlayer and from examination of collapsed films with polarized infrared spectroscopy and electron diffraction are consistent with the presence of right handed α-helices in the mono-layer when the molecular weight is high. When 1% (v/v) isopropanol is present in the subphase the right-handed helix prevails, provided that the monolayer is first spread on water. Monolayers of low molecular weight polymer appear to form the crossed-β structure. Orientated collapsed films of high molecular weight polymer can be converted to the left-handed α-helical and to the ω-conformation, and the mechanisms are discussed. The surface chemistry of this polymer is compared with that of related polymers and a consistent pattern of behavior emerges.
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  • 35
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    Biopolymers 9 (1970), S. 1017-1028 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Low-angle light scattering results reported previously demonstrated that measurements on high molecular weight native DNA must be made at angles below 30° in order to obtain correct molecular weights. Earlier light-scattering data obtained on denaturated DNA at angles above 30° showed no change in molecular weight upon denaturation, even though other techniques clearly showed that strand separation occurred. This paper reports low-angle measurements on solutions of calf thymus and T7 DNA denatured under acidic conditions. The results demonstrate that a halving of molecular weight consistent with strand separation is detected by light scattering only when low-angle data are used to obtain correct molecular weights for native material. As expected from theoretical considerations, the scattering from denatured DNA is a linear function of sin2(θ/2), where θ is the angle of observation. This result shows that anticipated experimental artifacts have no significant effect on the low-angle measurements and demonstrates that the curvature in the scattering envelope observed for native DNA below 30° is an inherent property of the native molecule.
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  • 36
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics for the cis-trans isomerization of long-chain poly-L-proline has been studied as a function of pressure, temperature, and solvent composition in the acetic acid + n-propanol solvent system. Our complete kinetic curves were fitted by Monte Carlo techniques, and rate constants for nucleation, growth, and termination were estimated. It was found that for the formation of a cis-helix, high pressure, low temperature, and increased acetic acid content of the solvent, lowered the rate of nucleation relative to growth. The inverse seems to be t rue for the formation of a trans-helix. Molecular models suggest that this behavior of the kinetic constants can be due to the exposure of peptide units to solvent in the transition state for trans nucleation, and the burying of peptide units in the transition state for cis nucleation. It is further suggested from our analysis of complete kinetic curves that at least one of the assumptions usually made in the analysis of relaxation kinetics is invalid for poly-L-proline.
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  • 37
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    Biopolymers 9 (1970), S. 1039-1047 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Solutions of amylose in ethylenediamine yield a crystalline film complex upon evaporation of solvent. The x-ray analysis indicates the presence of a tetragonal-shaped cell with a symmetry approximating that of space group P212121. The amylose sixfold helix has a diameter of 13.3 Å and a translation period of 8.0Å. Chemical and physical analyses support a complexing ratio of one ethylenediamine molecule to every two glucose units. The structure is nearly identical to any amylose-dimethyl sulfoxide complex previously examined. The square mode of packing arrangement appears to result from complexation between amylose chains. Such complexing indicates a much greater degree of amylose interaction than is observed in amylose complex structures having a hexagonal close-packing arrangement.
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  • 38
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    Biopolymers 9 (1970), S. 1049-1058 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: pH titration measurements of poly- S-carboxymethyl-L-cysteine were undertaken in the aqueous Nacl solution in relation to the β form-random coil transition. The titration curves show a marked molecular weight dependence because of the shortened chain length of materials. Comparison of the optical rotatory dispersion parameter a0 with the titration curve reveals that the titration curve apparently reflects a β structure-random coil transition. The β form of this polymer is assumed to be an intramolecular β form, rather than a β structure stabilized by an intermolecular hydrogen bond, at least in the polymer concentration range considered here. The standard free energy change per amino acid residue for the transition from un-ionized random coil to un-ionized β form is estimated to be about -750 cal/mole residue in the range of 0.005-0.2M NaCl concentration.
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  • 39
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    Biopolymers 9 (1970), S. 1059-1077 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The circular dichroism (CD) spectra of the four usual deoxymononucleosides, all sixteen deoxydinucleotides, and a number of trinucleotides have been measured. The dimer spectra are quite different from the sum of the spectra of their constituent monomers. This indicates the presence of base-stacked conformations analogous to those found for ribonucleoside diphosphates. The CD spectra of several deoxytrinucleotide diphosphates and single-strand f 1 DNA can be calculated fairly well by using a semi-empirical nearest-neighbor approach. There is little or no effect of terminal phosphate or of salt concentration on the optical properties of most deoxy oligomers. The possibility of simultaneous analysis of mixtures of deoxypurine or deoxypyrimidine sequence isomers has been examined. This seems to be a viable approach for the analysis of purine runs but cannot promise much success for pyrimidine runs.
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  • 40
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    Biopolymers 9 (1970), S. 1079-1103 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The circular dichroism spectra of all 16 ribodinudeoside phosphates containing the bases adenine, uracil, cytosine, and guanine have been measured at room temperature and neutral pH. These results are compared with the circular dichroism spectra of the corresponding deoxy compounds. From the optical properties it is clear that the geometry of the base-stacked conformation of ribo compounds must differ substantially from that of deoxy compounds. Because of this, it is not possible to draw firm conclusions about the relative extent of stacking in most ribo and deoxy compounds. The optical rotatory dispersion of about a dozen deoxy and ribodinucleoside phosphates has been studied as a function of temperature. These results confirmed the conclusions drawn earlier from measurements at a single temperature. Several dinucleoside phosphates containing a 2′ → 5′ phosphodiester bond have also been examined. These compounds have a substantial degree of base stacking at room temperature. The geometry of the stacked conformation is different from that of either the normal ribo dimer or the deoxy dimer. The role of the 2′-hydroxyl group in stabilizing base stacked geometries has been examined by studies on C-2′-O-methyl-pC. This compound has optical properties almost identical to those of CpC. This suggests that the effect of the 2′ hydroxyl is felt indirectly through its perturbation of the geometry of the sugar ring rather than directly by hydrogen bonding. It is not possible at present to identify precise conformational differences among deoxy-, ribo-and 2′ → 5′ ribodinucleoside phosphates.
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  • 41
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    Biopolymers 9 (1970), S. 1119-1124 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 42
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    Biopolymers 9 (1970), S. 1349-1360 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The influence of single-strand breaks on the kinetics of the relaxation of DNA in a solution of low ionic strength has been investigated by a temperature jump method. The relaxation of DNA after a jump of 0.7 °C in the melting region has been monitored by measuring the extinction at 260 nm. For essentially monodisperse T4 DNA (M = 130 × 106) two distinct relaxation times have been observed, that depend markedly on the initial extent of denaturation 1 - θ. The larger relaxation time decreases from 450 sec to about 300 sec, the smaller one from 55 see to 30 when 1 - θ increases from 0.03 to about 0.8. The dependence of these relaxation times on the average number of single-strand breaks per molecule (p) appears to be very small up to p = 100. However, the relative contribution of the slow process decreases sharply when p increases from 0.6 to 30 and remains nearly constant for larger p. The observations are discussed in the light recent theories of the kinetics of denaturation.
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  • 43
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    Biopolymers 9 (1970), S. 1361-1372 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Measurements have been made of the intensity of light scattered from aqueous solutions of calf thymus DNA with and without the application of electric fields. For fields approaching 150 V/cm and frequencies below 2.5 KHz, changes (ΔI) of up to 10% in the residual scattered intensity were observed. In agreement with previous dielectric and electric birefringence measurements, a low frequency dispersion of ΔI was observed, from which a rotary diffusion constant (D) of 1200 s-1 was determined. Interpreting the electric field data in terms of the classical dipolar orientation theory led to values of 2.4 × 10-25 cm (7.4 × 10-14 esu) and 4.3 × 10-25 cm (13 × 10-14 esu) for the permanent dipole moment and the anisotropy of the electric polarisabilities respectively. Furthermore the permanent dipole moment was along the major molecular axis and the particles orientated in the field as rigid entities. The zero field data indicated a molecular shape which was not rodlike but corresponded to the Kratky-Porod “stiffness” parameter of x = 24 for the wormlike coil model. Although curved, the molecules appeared to orientate in low-intensity electric fields as rigid, but not rodlike molecules. The implications of this on recent discrepancies in D determined by two or more dynamic relaxation methods is briefly discussed.
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  • 44
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    Biopolymers 9 (1970), S. 1391-1402 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The buoyant density of T-4 DNA was determined by equilibrium sedimentation in a density gradient, of mixed solutions of cesium and magnesium chlorides and bromides. The preferential hydration was calculated from these data, allowing appropriately for the exchange equilibrium of DNA with Cs+ and Mg++ ions. The charge and intrinsic solvation of the counterions were found to have no appreciable effect on the hydration of the DNA, the extent of solvation depending only on the thermodynamic, activity of the water. Various reasonable hypotheses are discussed to account for these results.
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  • 45
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    Biopolymers 9 (1970), S. 1373-1389 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of 27 SMS2 RNA with formaldehyde normally results in an unfolded, 13.4 S form. At acidic pH, however, and under the proper ionic conditions, a compact component sedimenting at 36-40 S was obtained. The molecular weight of this species corresponds to a dinner. The formaldehyde concentration was not critical, and approximately the same number of base pairs had been opened in the compact and in the unfolded form. Presumably dimers, which had been specifically formed under defined conditions, were stabilized by formaldehyde-induced crosslinks. Similar dimers were formed by 16 S and by 23 S ribosomal RNA, but not by tRNA.
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  • 46
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    Biopolymers 9 (1970), S. 445-457 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The change in apparent molal volume φ of DNA on thermal denaturation in carbonate buffer at pH 11.0 has been determined by the dilatometric method. It was found that φ increases sigmoidally during the helix-coil transition. Several methods, including a colorimetric technique that closely simulates the conditions used in the dilatometric experiments, were employed to estimate the protons lost by the DNA during the transition. These measurements indicated that the extent of the proton loss depends on the counterion present, increasing in the order Li+ 〈 Na+ 〈 K+ 〈 Cs+. The major part of the volume changes observed during the denaturation is due to the volume changes expected to accompany the transfer of protons from the bases guanine and thym ne to carbonate ions. As has been previously reported for the denaturation of DNA at neutral pH, the volume change directly due to the change in shape of the polymer molecules is so small as to be experimentally undetectable.
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  • 47
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    Biopolymers 9 (1970), S. 569-588 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The coupling of theoretical optical calculations with experimental data provides a check of the validity of the theory or provides conformational information. The theory was validated by studies in which the approximate conformation was located independently. These studies have shown that a theory restricted to the two lowest energy transitions for each chromophore gives qualitative agreement with experiment. On the other hand, for some of the proline derivatives, the theoretical treatment allows detailed conformational assignments. Both successes and failures in correlating theory with experiment are discussed. The results presented provide a basis for assessing the prospects for relating protein and polypeptide optical activity to their conformations.
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  • 48
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ethidium bromide inhibits the formation of ultraviolet-induced pyrimidine dimers in DNA. The efficiency of dimer inhibition increases with increasing energy of the exciting photons. The efficiency of energy transfer from the DNA singlet to the dye singlet, as monitored by sensitized fluorescence, is independent of wavelength. The efficiency of singlet-singlet transfer agrees with that for dimer inhibition at photon energies corresponding to excitation of the lowest singlet state of DNA. Our results support a model in which dimers are formed both directly from the singlet state and also from the triplet state, with triplets arising from higher vibrational levels of the singlet.
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  • 49
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    Biopolymers 9 (1970), S. 689-696 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The intercalation model of DNA-hydrocarbon binding appears reasonable, but rests on indirect evidence only. To test the model, a size criterion for binding has been proposed. The size criterion is based on the assumption that hydrophobic forces play a major role in the binding of hydrocarbons to DNA. It states that hydrocarbons which are small enough to intercalate into DNA and be well protected from contact with the medium, will be found to bind to DNA; those that are too large will not. We report results on the binding of fourteen polycyclic aromatic hydrocarbons to DNA. Predictions based on the size criterion were found to be valid in all cases tested.
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  • 50
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    Biopolymers 9 (1970), S. 697-715 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dialysis data of Huang and Ts'o for the cooperative binding of adensine to polyuridylic acid are analyzed here using a grand-partition function Ising model method similar to that originally employed for polyelectrolytes by Rice and Nagasawa. An appropriate modification permitting the treatment of the sliding degeneracy of the two polyuridylic acid strands is also included. In addition to the previously estimated stacking energy of about -6 kcal/mole one also obtains the free energy change F̄ for the transfer of a single adenosine molecule from a fixed site in solution to a fixed site on the polyuridylic acid. This binding energy falls in the range F̄ = -140 to +620 cal/mole, indicating that binding in the 1:2 (purine: pyrimidine) complex is either very weak or repulsive. The absence of any comparable cooperative stacking of adenosines in solution at the same concentration together with the likely repulsive character of the binding implies that the stacking energy must contain a significant contribution from other processes than simple stacking of adenosines. A generalization of the theory to treat multicomponent binding and longer-range interactions is effected, and the form applicable to simultaneous binding of both adenosine and guanosine by polyuridylic acid is presented.
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  • 51
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    Biopolymers 9 (1970), S. 739-744 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The present communication describes a new way of studying helix-random coil transformations of polypeptide, poly-(γ-benzyl L-glutamate), in benzene-trifluoracetic acid (TFA) and chloroform-TFA systems. The difference between the PMR chemical shift of TFA with and without the polypeptide, measured as Δ, may be used to follow the conformational transition. This technique is particularly useful for concentrated solutions, where the PMR peaks of the polymer are so broad that no valuable information may be derived. As the TFA content increases in the system (at constant polymer concentration), Δ decreases normally whether the polymer is helical or random. However, Δ changes in a different way in the helix-random coil transition region, and actually increases with increasing TFA content. This peculiar behavior is explained in terms of the solvation of the helix and random coil structures.
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  • 52
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    Biopolymers 9 (1970), S. 745-748 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 53
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    Biopolymers 9 (1970), S. 717-738 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new procedure for evaluating u and σ characterizing σ-helix-forming polypeptides in solution was derived from Nagai's theory for the helix-coil transition of such polymers. Here u is the activity for helix formation from random coil, and σ is the helix initiation parameter. The necessary data are the helical content fN at fixed solvent and temperature as a function of N, where N is the degree of polymerization of the polypeptide sample. Such data were obtained from ORD measurements on a number of fractionated samples of poly-N5-(3-hydroxypropyl)-L-glutamine (PHPG) in mixtures of water and methanol covering the complete range of composition and at various termperatures (5-40°C). When analyzed in terms of the proposed procedure, they yielded values of σ which were in the range (3.2 ± 0.6) × 10-4, substantially independent of solvent composition and temperature. These values were much larger than those obtained recently for σ of poly(β-benzyl-L-aspartate) in m-cresol and in a mixture of chloroform and DCA. The data for [η] and s0 (limiting sedimentation coefficient) as functions of molecular weight indicated that the molecular shape of PHPG in pure methanol is essentially rodlike, whereas that in pure water is not entirely randomly coiled but rather may be regarded as an interrupted helix. These indications were consistent with the results from ORD measurements. When plotted against the corresponding values of fN, the values of [η] and [s0] for PHPG in mixtures of water and methanol of various compositions and temperatures formed smooth composite curves, and we attributed these phenomena to the fact that σ of PHPG was nearly constant under these solvent conditions. Here [s0] stands for a reduced limiting sedimentation coefficient which is equal to the inverse friction factor of the solute molecule.
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  • 54
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    Biopolymers 9 (1970) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 55
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    Biopolymers 9 (1970), S. 765-782 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction of purine with DNA, tRNA, poly A, poly C, and poly A. poly U complex was investigated. In the presence of purine, the nucleic acids in coil form (such as denatured DNA, poly A and poly C in neutral solutions, or tRNA) have lower optical rotations. In addition, hydrodynamic studies indicate that in purine solutions the denatured DNA has a higher viscosity and a decreased sedimentation coefficient. These findings indicate that through interaction with purine, the bases along the poly-nucleotide chain are unstacked and are separated farther from each other, resulting in increased assymmetry (and possibly volume) of the whole polymer. Thus, the de-naturation effect of purine reported previously can be explained by this preferential interaction of purine with the bases of nucleic acids in coil form through a hydrophobic-costacking mechanism. Results from studies on optical rotation and helix-coil transition show that the interaction of purine is greater with poly A than with poly C. The influence of temperature, Mg++ concentration, ionic strength, and purine concentration on the effect of purine on nucleic acid conformation has also been investigated. In all these situations the unraveling of nucleic acid conformation occurs at much lower temperatures (20-40°C lower) in the presence of purine (0.2-0.6M).
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  • 56
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The characteristic ratio of unperturbed cellulose chain was computed as a function of the angle τ at, the bridge oxygen atom and the degree of polymerization. Very high values of the order of 40 or more, depending on the angle at the bridge oxygen atom, have been obtained for this ratio, indicating that cellulose chains are highly extended. The average dimensions of cellulose chains are found to be sensitive even for small changes in the angle at the bridge oxygen, and these chains attain the character of a random coil in very high molecular weight range (degree of polymerization greater than 2000). The large differences in the unperturbed dimensions of cellulosic chains observed in different solvents have been attributed to the possible small changes in the angle τ caused by specific solvent, interactions.
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  • 57
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformational properties of block copolymers of poly-L-leucine in water have been examined. The degree of polymerization of the poly-L-leucine block was 11 and 21, respectively, for samples prepared by the Merrifield procedure, and 56 for a sample prepared by the polymerization of leucine N-carboxyanhydride. The optical rotatory dispersion parameter b0 was used to obtain the helix content θh at various temperatures. Application of the Lifson-Roig theory gave the following parameters for the transition of a residue from a coil to a helical state: v = 0.05-0.011, ΔH = +100 cal/mole, ΔS = +0.70-1.00 e. u. These parameters, as well as those for other polyamino acids, are accounted for by hydrophobic bonds involving the nonpolar side chains in the helical and randomly coiled forms. From the data for poly-L-alanine and theoretical values of the thermodynamic parameters for hydrophobic bond formation, the parameters for formation of a polyglycine helix are computed. By separating the contributions of the backbone, it is possible to obtain a set of thermodynamic parameters for the side-chain contributions of a number of polyamino acids. Increased size of the nonpolar side chain (with a larger contribution from hydrophobic bonding) makes a larger contribution to the stability of the α-helix which is reflected, among other ways, in a higher helix content at given temperature.
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  • 58
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of DL-β-phenylalanine N-carboxyanhydride (NCA) initiated by poly(N-benzylglycine)diethylamide (DEA) and poly(N-methyl-DL-alanine)DEA has been investigated. As previously reported, polysarcosine DEA, poly-N-ethylglycine DEA, and poly-N-n-propylglycine DEA showed marked accelerations in the polymerization of DL-β-phenylalanine NCA as compared with the polymerization initiated by low molecular weight, amines having similar base strength. However, this phenomenon (the chain effect) was not observed with the two polymer catalysts studied in the present investigation With poly-N-methyl-DL-alanine DEA, adsorption of DL-β-phenylalanine NCA onto the polymer chain takes place, though not so effectively as with other polypeptides, so the absence of chain effect was ascribed to a reduced flexibility of the polymer chain. With poly(N-benzylglycine)DEA, the reactivity of terminal base group was found to be much lower than that of other polymer catalysts. However, the absence of the chain effect would be attributed to the rigidity of polymer chain of poly-N-benzylglycine DEA due to the bulkiness of the N-benzyl group.
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  • 59
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    Biopolymers 9 (1970), S. 799-810 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular weights by osmometry (M̄n), light scattering (M̄w), and sedimentation-diffusion (MsD) were determined for selected fractions and unfractionated samples of hyaluronic acid in the molecular weight range 3 × 104-1.7 × 106. For the determination of MsD from the sedimentation coefficient s, a calibration procedure based on the data of Laurent, Ryan, and Pietruszkiewicz gave the following relations in 0.2M NaCl: log (s-1)0 = 14.681 - 0.413 log MsD and log D0 = -3.828 - 0.568 log MsD, where subscript, zero refers to zero concentration and D is the diffusion coefficient. The average Mandelkern-Flory parameter β in 0.2M NaCl is 3.0 × 106. Data for the intrinsic viscosity [η] may be fitted for M 〉 105 by [η] = K′Ma, where K′, a are in 0.2M NaCl, 0.0228, 0.816; in 0.5M NaCl, 0.0318, 0.777; in 0.1 M HCl, 0.0279, 0.763, respectively. Below M = 105, [η] appears to fall below the values calculated, possibly due to non-Gaussian behavior of short chains. The second virial coefficient A2 in 0.5M NaCl approaches the ideal Donnan value, decreasing slightly with increasing molecular weight. The friction parameter P is about 20% smaller than that of uncharged polymers of similar dimensions. The flexible coiling nature of this polymer is confirmed.
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  • 60
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    Biopolymers 9 (1970), S. 843-864 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The formation of a slowly sedimenting form of 23-S ribosomal RNA from E. coli has been investigated by analytical ultracentrifugation and thermal denaturation in aqueous solution and in formamide. Evidence is presented that the slow form of 23-S arises as a result of nucleate damage to the RNA in the 50-S ribosome. The 30-S ribosome (and 16-S RNA), is unaffected. The slow form of 23-S RNA cannot be demonstrated under conditions of complete denaturation in formamide, but only by partial denaturation in aqueous solution of low ionic strength (〈 0.01M Na). Apparent maintenance of the integrity of 23-S RNA in formamide after nuclease treatment suggests that this may not be a simple linear molecule. An alternative model is suggested containing a circular element in the structure.
    Additional Material: 9 Ill.
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  • 61
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    Biopolymers 9 (1970), S. 825-842 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Uniform LiDNA fiber specimens of nearly 20 m length have been prepared with a wet-spinning method developed by the author. Samples immersed in the spinning bath (80% ethyl alcohol containing 0.4M LiCl) have been subjected to mechanochemical study involving stretching, relaxation, and contraction measurements. A special technique was developed to transfer the sample from the Teflon-coated cylinder used in spinning to the sample column of the mechanochemical apparatus without stretching or removing the sample from the spinning bath. Force-strain curves of samples consisting of two fiber bundles showed an initial region of low slope followed by a region of high slope and a second region of low slope up to rupture. Some thicker specimens showed an aging effect which abolished the initial low-slope region and was interpreted as indicative of crystallization. Force-strain curves of two-bundle samples showed a strong influence of temperature with a complete loss of tensile strength of the LiDNA fibers in the spinning bath at about 55°C. Furthermore, samples at zero strain exhibited a contractile force when subjected to temperatures above about 40°C; the contractile process was pronounced with samples kept above 48°C. On contraction these samples obtained a zero-force length 20-30% of the original. These data are taken as evidence for a helix-to-coil transition occurring in the DNA, the low melting temperature being caused by the chemical influence of the ambient aqueous alcohol-LiCl bath.
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  • 62
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    Biopolymers 9 (1970), S. 1029-1038 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The molecular weight of native DNA is shown to decrease by at least a factor of two on denaturation by heat or alkali. This result is obtained only if low-angle (〈30°) light-scattering measurements are used. High-angle measurements (〉30°) do not reveal a decrease in molecular weight on denaturation due to the incorrect value for native DNA. The dn/dc value for both native and denatured DNA is 0.166 ml/g ± 0.003 ml/g. Methods are described for the clarification of native and denatured DNA solutions for light scattering by the use of membrane filters.
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  • 63
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    Biopolymers 9 (1970), S. 991-1000 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Electric dichroism studies on poly(γ-benxyl L-glutamate) show that the addition of small amounts (up to 5%) of trifluoroacetic acid causes complete disappearance of dichroism in contrast to the electric birefringence, which drops to an observable plateau at 20% of its initial value. This loss of dichroism cannot be explained simply by a decrease in the effective dipole moment of the benzyl ester side chains, and the nature of this interaction is explored by nuclear magnetic resonance and infrared spectral studies. Theories of the helix-coil transition which require an initial protonation of the helix backbone to form a more flexible rod consisting of helical segments interrupted by regions of random coil are shown to be inadequate to describe the changes in poly(γ-benzyl L-glutamate) effected by small amounts of trifluoroacetic acid. Rather, trifluoroacetic acid in small amounts interacts with the ester carbonyl oxygen in the side chain, either by hydrogen bonding or protonation, before there is evidence of any effect on the backbone or of loss of helix content.
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  • 64
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    Biopolymers 9 (1970), S. 1229-1237 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Raman spectra of poly-L-lysine hydrochloride and poly-∊-carbobenzoxy-L-lysine in the solid state have been obtained and are consistent with the presence of an α-helical structure. The Raman spectrum of poly-L-lysine in aqueous solution suggests the presence of random coil structures.
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  • 65
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 66
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    Biopolymers 9 (1970) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 67
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The nonbonded interaction energy of disaccharides, mannobiose and galactobiose and polysaccharides mannan and galactan have been computed as a function of dihedral angles (φ,ψ). The conformation (40°, -20°) has been preferred for the mannan chain from nonbonded interaction energy considerations. The O5…O3′ type of intramolecular hydrogen bond has been found to be possible in the above conformation. Comparison of the allowed region of mannan with those of cellulose and xylan indicates that the monomer unit, in mannan chain has slightly higher freedom of rotation than that of cellulose and less than that of xylan. As in cellulose and mannan, the freedom of rotation of the monomer units in β-1,4′ galactan is highly restricted. Unlike mannan (which prefers an extended conformation) the β-1,4′ galactan prefers a helical conformation similar to amylose. Just as in amylose the O2…O3′ type hydrogen bond between contiguous residues is also possible in β-1,4′ galactan.
    Additional Material: 7 Ill.
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  • 68
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 23 Ill.
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  • 69
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    Biopolymers 9 (1970), S. 1475-1502 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The predictions of the presently accepted molecular exciton model for the optical activity of helical polypeptides are in reasonable agreement with experimental spectra in the accessible wavelength range. However, crucial verification requires the detect of a significant negative rotatory hand just below the accessible range. A computer-oriented method is utilized to obtain information concerning the inaccessible range. Optical rotatory dispersion computed by evaluation of the Kronig-Kramers integral transform from the experimentally determined circular dichroism of several helical homopolypeptides in solution are compared with the experimentally determined optical rotatory dispersion. Computed and experimental curves are congruent within an uncertainty approaching that of the experimental technique, whatever the polypeptide sample lot, side chains, and solvent. It is shown that t his agreement is not a computational or experimental artifact. These results can be interpreted in two ways: (1) that the predicted band does not exist, and (2) that the perturbation of the predicted band is being negated by other inaccessible bands in the vacuum ultraviolet. Arguments are presented to show that the first of these two possibilities is more probable.
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  • 70
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    Biopolymers 9 (1970), S. 1511-1530 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The potential problem is formulated for rodlike macroions and reduced to a single dimensionless equation with appropriate boundary conditions. A method of solution based on piecewise linearization of the potential equation is detailed and compared with two other approaches. It is suggested that the present method yields improved estimates of macroion charges. Some numerical results are included, and the relation between electrophoretic charge and macroion charge is considered.
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  • 71
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 104-111 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Properties of FluoromethyldialkylaminesFluoromethyldialkylamines (3a-f) are prepared from N,N-acetals (aminals) by cleavage with carboxylic acid fluorides or l-fluoro-2,4-dinitrobenzene. They are low-boiling liquids and are characterized by a covalent carbon-halogen bond. Their reactivity is similar to that of the analogous carbimonium chlorides, bromides and iodides.
    Notes: Fluormethyl-dialkyl-amine (3a-f) werden durch Spaltung von Aminalen mit Carbonsäurefluoriden oder l-Fluor-2.4-dinitro-benzol gewonnen. Sie sind niedrigsiedende, durch eine kovalente Kohlenstoff-Halogen-Bindung charakterisierte Flüssigkeiten und zeigen ähnliche Reaktionsfähigkeit wie die analogen Carbimoniumchloride, -bromide oder -jodide.
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  • 72
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 133-146 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterosubstituted Fulvenes, IV In the 5-Membered Ring Unsubstituted 6,6-DiaminofulvenesAlkylation of tetrasubstituted thioureas with methyl iodide leads to S-methyl isothiuronium iodides 3, which have been transformed to 6,6-diaminofulvenes 1 by condensation with cyclopentadienyl sodium. Some compounds of type 1 are also obtainable from the reaction between cyclopentadiene and chloroformamidinium chlorides 4 in the presence of triethylamine. I.r., u.v., and n.m.r. spectra of 1 and 3 are discussed.
    Notes: Tetrasubstituierte Thioharnstoffe lassen sich mit Methyljodid in die S-Methyl-isothiuroniumjodide 3 überführen, die ihrerseits mit Cyclopentadienylnatrium die 6.6-Diamino-fulvene 1 bilden. Einzelne Vertreter von 1 sind auch aus Cyclopentadien und Chlorformamidinium-chloriden 4 in Gegenwart von Triäthylamin zugänglich. Die IR-, UV- und NMR-Spektren von 1 und 3 werden diskutiert.
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  • 73
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 183-192 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: VinylsulfonylmethylidsThe preparation of dimethylsulfonio-(vinylsulfonylphenylsulfonylmethanide) (5), triphenyl-phosphonio-(vinylsulfonylphenylsulfonylmethanide) (6) and triphenylphosphonio-(vinyl-sulfonylbenzoylmethanide) (8) is described. The u. v. spectra of 5 and 6 are similar to the u.v. spectrum of the bis(phenylsulfonyl)methane anion (9). Because of the interaction of the SO2-groups with the ylide carbanions, the SO2-stretching frequencies compared to those of vinylsulfonylphenylsulfonylmethane (4) are shifted 20 -30/cm to lower wave numbers. This interaction causes a higher electron density in the vinyl groups of the ylids compared to 4, as shown by n. m. r. measurements. The mass spectra of 5, 6 and 8 are discussed.
    Notes: Die Synthese von Dimethylsulfonio-[vinylsulfonyl-phenylsulfonyl-methanid] (5), Triphenyl-phosphonio-[vinylsulfonyl-phenylsulfonyl-methanid] (6)undTriphenylphosphonio-[vinyl-sulfonyl-benzoyl-methanid] (8) wird beschrieben. Die Elektronenspektren von 5 und 6 sind mit dem UV-Spektrum des Bis-phenylsulfonyl-methan-Anions (9) vergleichbar. Durch Wechselwirkung der SO2Gruppen mit den Ylidcarbanionen werden die SO2-Valenzschwingungsfrequenzen im Vergleich zu Vinylsulfonyl-phenylsulfonyl-methan (4) um 20 - 30/cm zu kleineren Wellenzahlen verschoben. Diese Wechselwirkung bedingt eine höhere Elektronendichte in den Vinylgruppen der Ylide als bei 4, was NMR-spektroskopisch nachweisbar ist. Die Massenspektren von 5, 6 und 8 werden diskutiert.
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  • 74
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 173-182 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Cyclopentadienones with Aliphatic Diazo Compounds, 6 Experiments with „Indanocyclone“„Indanocyclone“ 3, prepared from ninhydrin (1) and dibenzylketone (2), reacts with an ethereal diazomethane solution to form an 1 :1-adduct 4a and two isomeric 1 : 2-adducts, presumably 12 and 13. Elimination of N2 from 4a leads to the formation of the cyclopropane 7, the fluorenone 6 and, by way of phenyl migration, the new cyclone 8a; elimination of N2 from 12 and 13 leads to undefined products. 5 is converted via its hydrazone into the diazo compound 10. Ring enlargement of 6 with diazomethane produces the phenanthrene 9.Reaction of diazoethane with 3 gives the instable 1 :1-adduct 4b, which yields the new cyclone 8b by N2-elimination and phenyl migration. 8b also forms an 1 :1-adduct (11?). Phenyl diazomethane adds to 3 giving a rather stable 1 :1-adduct 14, the isomeric 16 and the epoxide 15. Elimination of N2 from 14 yields the fluorenone derivative 17, which upon treatment with excess diazomethane undergoes ring enlargement to form the phenanthrene derivative 18.
    Notes: Das aus Ninhydrin(l)und Dibenzylketon(2) erhältliche, Indanocyclon‘ 3 gibt mit ätherischer Diazomethanlösung ein 1 :1-Addukt 4a und zwei isomere 1 : 2-Addukte, vermutlich 12 und 13. 4a zerfällt unter N2-Abspaltung zum Cyclopropanderivat 7, zum Fluorenonderivat 6 und unter Phenylwanderung zum neuen Cyclon 8a; 12 und 13 geben bei der N2-Abspaltung keine definierten Produkte. Aus 5 wird über sein Hydrazon die Diazoverbindung 10 und mit Diazomethan unter Ringerweiterung das Phenanthrenderivat 9 erhalten.Mit Diazoäthan entsteht aus 3 das instabile I :1-Addukt 4b, das bei der N2-Abspaltung unter Phenylwanderung das Cyclon 8b bildet; dieses gibt erneut ein Diazoathan-Addukt (11?).Mit Phenyldiazomethan liefert 3 ein ziemlich stabiles 1 :1-Addukt 14 und sein Isomeres 16 sowie das Epoxid 15. Bei der N2-Abspaltung entsteht aus 14 das Fluorenonderivat 17, das mit Diazomethan zum Phenanthrenderivat 18 ringerweitert wird.
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 222-235 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Orthoamides, X: Reaction of Vinylogous Amide Acetals, Aminalesters and Amide AminalsDerivates of vinylogous orthoformic acid amides react with Grignard compounds to give l,3-bis(dimethylamino)-l-alkenes (4-7), with methylene active compounds to give derivates of N.N-disubstituted 4-amino-l,3-butadienes (17  - 29) and with primary aromatic amines to form vinylogous, N,N,N′-trisubstituted amidines (31-36, 38-40).
    Notes: Vinyloge Orthoameisensäureamid-Derivate geben mit Grignard-Verbindungen 1.3-Bis - dimethylamino-alkene-(l) (4-7), mit methylenaktiven Verbindungen N.N-disubstituierte 4 - Amino-butadien-(l.3)-Derivate (17-29) und mit primären aromatischen Aminen vinyloge N.N.N′-trisubstituierte Amidine (31-36, 38-40).
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    Berichte der deutschen chemischen Gesellschaft 103 (1970) 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 17-22 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Pyrimidines, VIII Synthesis and Properties of Uracil-4-carbaldehyde Hydrazone. The First Inner Orbital Complex of a Pyrimidine with CopperUracil-4-carbaldehyde (1) reacts with stoechiometric amounts of hydrazine to yield the azine 2. Under mild conditions (30 per cent hydrazine, room temperature) the azine is cleaved to uracil-4-carbaldehyde hydrazone (3). This cleavage by hydrazine is typical for the azomethine group in position 4 of the uracil ring. In aqueous or aqueous-alcoholic solution 3 reacts readily with aliphatic, aromatic and heterocyclic aldehydes to form mixed azines in good yield. With copper(II)-acetate 3 yields in aqueous solution a new type of symmetrical inner orbital complex in which the ratio of pyrimidine to copper is 2 :1. The crystalline and insoluble paramagnetic complex 13 presumably has a planar structure. Substitution of the amino group, even with a methyl group, prevents complex formation. 13 is decomposed by mineral acids to the respective copper salt and azine 2. In analogy to 1 2-thiouracil-4-carb-aldehyde forms the corresponding hydrazone 12.
    Notes: Uracil-carbaldehyd-(4) (1) liefert mit stöchiometrischer Menge Hydrazin das symmetrische Azin 2, welches unter milden Bedingungen (30proz. Hydrazin, Raumtemperatur) zum Uracil-carbaldehyd-(4)-hydrazon (3) gespalten wird. Die schonende Hydrazinolyse ist spezifisch für die Azomethingruppe in 4-Stellung des Uracilrings. 3 liefert in wäßriger bzw. Wäßrig-alkoholischer Lösung mit aliphatischen, aromatischen und heterocyclischen Aldehyden in guter Ausbeute gemischte Azine. Mit Kupfer(II)-acetat bildet 3 einen neuartigen symmetrischen Innerkomplex der Art Pyrimidin : Kupfer = 2:1. Analog zu Uracil-carb-aldehyd-(4) (1) erhält man aus 2-Thio-uracil-carbaldehyd-(4) mit Hydrazin das entsprechende Hydrazon 12.
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 46-49 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Crystal Structure of l,2,3,4,4a,9a-hexahydro-4a,9-propanocarbazolium HydrobromideThe crystal structure of the title compound has been determined by X-ray structure analysis. From these results a twist angle of 64.5° of the orbital of the nitrogen is derived.
    Notes: Auf röntgenographischem Weg wurde die Kristallstruktur der Titel-Verbindung bestimmt. Aus den so erhaltenen Ergebnissen resultiert ein Verdrillungswinkel des Orbitals am Stickstoff von ϕpH = 64.5°.
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 76-81 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Enthalpy of Formation of Tungsten Hexafluoride and Tungsten PentafluorideThe heat evolved on combustion of tungsten and tungsten pentafluorid in fluorine was measured in a bomb calorimeter. The enthalpies of formation calculated from these values were found to be ΔH°298(WF6, g) = -411.7 ± 0.5 kcal mol-1 and ΔH°298 (WF5, c) -346.1 ± 2.6 kcal mol-1.
    Notes: Die Verbrennungswärmen von Wolfram und Wolframpentafluorid in Fluor wurden in einem Bombenkalorimeter gemessen. Die aus den Meßdaten errechneten Bildungsenthalpien betragen ΔH°298(WF6, gas) -411.7 ± 0.5 kcal Mol-1 und ΔH°298(WF5, fest) -346.1 ± +2.6-1.0 kcal Mol1.
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 97-103 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Inorganic Small Ring Compounds, III Cyclic Silyl-alkylidene PhosphoranesA simple method has been deviced for the synthesis of silyl-substituted alkylidene phosphoranes of the type F. Two members of this series, [(CH3)3PCSi(CH3)2]2 (1) and [( PCSi(CH3)2]2 (2), were prepared from methylene trimethyl and methylene tri-n-butyl phosphorane, resp., and dimethyl dichlorsilane and characterized by means of chemical analysis and n. m. r. spectroscopy. The pathway of the reactions is discussed and a possible mechanism confirmed by an independent preparation of the most likely intermediates. Among these the difunctional open-chain ylid 4, (CH3)3P= CH=Si(CH3)2=CH = P(CH3)3, is of special interest.
    Notes: Ein einfaches Darstellungsverfahren ermöglicht die Synthese von Silyl-alkylidenphosphoranen mit viergliedrigem Ringsystem des Typs F. Zwei Vertreter dieser Reihe, [(CH3)3PCSi(CH3)2]2 (1) und [(n-C4H9)3PCSi(CH3)2]2 (2), wurden aus Trimethyl-methylen- bzw. Tri-n-butyl-methylen-phosphoran und Dimethyldichlorsilan in guten Ausbeuten erstmals hergestellt und analytisch und NMR-spektroskopisch charakterisiert. Der Reaktionsablauf der Synthese wird diskutiert und durch die getrennte Darstellung möglicher Zwischenprodukte belegt. Unter letzteren ist das offenkettige difunktionelle Ylid 4, (CH3)3P=CH  -  Si(CH3)2  -  CH - P-(CH3)3, von Bedeutung.
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  • 81
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 147-155 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterosubstituted Fulvenes, V 6,6-Diaminofulvenes with Electronegative Substituents in the 5-Membered RingCondensation of tetramethyl chloroformamidinium chloride (5) with methoxycarbonyl-, bis(methoxycarbonyl)-, and cyanocyclopentadienyl salts leads to the correspondingly substituted 6,6-bis(dimethylamino)fulvenes 6, 7 and 8. Vilsmeier formylation of 6,6-bis(dimethyl-amino)fulvene yields the diformyl derivatives 9 and 11. Structure elucidation of the fulvenes obtained is based on spektroscopic data; the temperature dependence of the n.m.r. spectra is discussed.
    Notes: Tetramethyl-chlorformamidinium-chlorid (5) bildet mit Methoxycarbonyl-, Bis-methoxy-carbonyl- und Cyan-cyclopentadienylsalzen die im 5-Ring entsprechend substituierten 6.6-Bis-dimethylamino-fulvene 6, 7 und 8; Vilsmeier-Formylierung des 6.6-Bis-dimethylamino-fulvens liefert zwei Diformyl-Derivate 9 und 11. Die Strukturzuordnung der erhaltenen Fulvene erfolgt spektroskopisch; die Temperaturabhängigkeit der NMR-Spektren wird diskutiert.
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  • 82
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 205-209 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Compounds with Urotropin Structure, XLVI Synthesis of the 6-Thia-l,3-diazaadamantane Ring System.A synthesis of the hitherto unknown 6-thia-l,3-diazaadamantane ring system starting from N-benzenesulfonyl-diallylamine (1), is described. The first stage of the synthesis is the sulfurdichloride addition to 1, resulting in Nbenzenesulfonyl-2,6-bis(chloromethyl)thiomorpho-line (2).2 was converted with alkali into N-benzenesulfonyl-2,6-dimethylenethiomorpholine (6) and subsequently oxidized to the sulfone 7. Addition of benzylamine followed by removal of the benzyl and the benzenesulfonyl groups yielded 9-thia-3,7-diazabicyclo[3.3.l]nonane 9,9-dioxide (11), which reacted with formaldehyde to produce 6-thia-l,3-diazaadamantane 6,6-di-oxide (12).
    Notes: Ausgehend von Benzolsulfonsäure-diallylamid (1) wird das bisher noch unbekannte 6-Thia-1.3-diaza-adamantan-Ringsystem synthetisiert, wobei im ersten Schritt die Schwefeldichlorid-Addition an 1 zu 4-Benzolsulfonyl-2.6-bis-chlormethyl-thiomorpholin (2) erfolgt. 2 wurde mit Alkali in 4-Benzolsulfonyl-2.6-dimethylen-thiomorpholin (6) und durch anschließende Oxydation in das Sulfon 7 übergeführt. Benzylamin-Addition an 7 und anschließende Abspaltung des Benzyl- und Benzolsulfonyl-Restes führte zum 9-Thia-3.7-diaza-bicyclo[3.3.1]-nonan-9.9-dioxid (11), das mit Formaldehyd das 6-Thia-s-l.3-diaza-adamantan-6.6-dioxid (12) lieferte.
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  • 83
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Orthoamides, XII: Synthesis of Acyl Isocyanate O,N- or -N,N-Acetals from Amide Acetals or from an Aminal tert-Butylester and N-Halogencarbonamides, Halogen Ureas and N-ChlorourethanesDimethylformamide dialkylacetals (2) and aminal-tert-butylester 5 [bis(dimethylamino)-tert-butoxymethane] react with N-halogen carboxylic acid amides, halogen ureas and N-chlorourethanes to give acyl isocyanate-O,N -or -N,N-acetals (isoureas 3 or guanidines 6, respectively).
    Notes: Dimethylformamid-dialkylacetale (2) und Aminal-tert.-butylester 5 (Bis-dimethylamino-tert.-butyloxy-methan) bilden mit N-Halogen-carbonsäureamiden, Halogenharnstoffen und N-Chlor-urethan Acylisocyanat-O.N- bzw. -N.N-acetale (Isoharnstoffe 3 bzw. Guanidine 6).
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  • 84
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 256-264 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Orthoamides, XIII Studies on the Mechanism of Electrophilic Substitution of the Formyl-H Atom in Ortho Formic Acid AmidesOrtho formic acid amides and N-halogen carboxylic acid amides, halogen ureas or N-chloro urethanes primarily react to give adducts; these form ylides in the presence of bases. The ylides react by an intramolecular SE1- or SNi-mechanism to give O,N-acetals of the corresponding acyl isocyanates (isoureas).
    Notes: Bei der Umsetzung von Orthoamiden mit N-Halogen-carbonsäureamiden, -harnstoffen und N-Chlor-urethan wurden Primär-Addukte nachgewiesen. Diese bilden in Gegenwart von Basen Ylide, welche über einen intramolekularen SE1- oder SNi-Mechanismus C-N-Knüpfung eingehen unter Bildung von O.N-Acetalen der entsprechenden Acylisocyanate (Isoharnstoffe).
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  • 85
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 281-288 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Boron Azides, X Aminoazidoboranes and AlkoxyazidoboranesThe bis(dialkylamino)azidoboranes l a and 1b, the dialkylaminodiazidoboranes 2a and 2 b, diethylaminoazidophenylborane (3), and the dialkoxyazidoboranes 4 a and 4 b are formed from chloroboranes, chlorine being substituted by the N3-group with LiN3 or Bu3SiN3, respectively, as substitution agents. The monoazidoboranes 1, 3, and 4 are decomposed in a kinetically controlled manner at a noticeable rate only beyond 250° C; hydrolysis of the polymeric material gives the amines Et2NNH2 (from 1b), PhNH2 (from 3) and CH3ONH2 (from 4 a), respectively, indicating a rearrangement process during the thermolysis. The saltlike compounds (NH4N4 and (Et2NH2)N3, respectively, are the main products from the decomposition of the diazidoboranes 2a and 2b at 210°. The thermal decomposition of la in cyclohexene yields under participation of the solvent the diazadiborete derivative 6. From the photolytic decomposition of 1a and 1b, respectively, trisaminoboranes (as dismutation products) and the tetraaminodiazadiboretes 10 a and 10 b (as rearrangement products) are isolated.
    Notes: Die Bis(dialkylamino)azidoborane l a und l b, die Dialkylaminodiazidoborane 2 a und 2 b, Diäthylaminoazidophenylboran (3) und die Dialkoxyazidoborane 4 a und 4 b erhält man aus den entsprechenden Chlorboranen durch Azidierung mit LiN3 bzw. (im Falle von 4a) mit Bu3SiN3. Die Monoazidoborane 1, 3 und 4 zerfallen in kinetisch kontrollierbarer Weise mit nennenswerter Geschwindigkeit erst oberhalb 250°; neben N2 erhält man harzige Produkte, aus denen sich durch Verseifung die aus einer Umlagerungsreaktion hervorgegangenen Amine Ät2NNH2 (aus l b), PhNH2 (aus 3) bzw. CH3ONH2 (aus 4a) freimachen lassen. Der thermische Zerfall der Diazidoborane 2a und 2b bei 210° liefert neben N2 die salzartigen Azide (NH4)N3 bzw. (Nät2H2)N3. Der thermische Zerfall von l a in Cyclohexen führt unter Beteiligung des Lösungsmittels zum Diazadiboret-Derivat 6. Tetraaminodiazadiborete 10 a und 10 b sind neben Trisaminoboranen die Hauptprodukte des photolytischen Zerfalls von l a und l b.
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  • 86
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Wir berichteten vor einiger Zeit über die Pyrolyse von Silbertetrafluorphthalat (1) und äußerten die Vermutung, daß als Hauptprodukt isolierte Octafluorbiphenylen seine Bildung dem intermediären Auftreten des Tetrafluorbenz-ins verdankte. Um diese Vermutung zu bestätigen, wurde die Pyrolyse von 1 in Gegenwart eines potentiellen Benz-in-Abfängers durchgeführt. In Anlehnung an McNelis setzten wir dafür Tetraphenylcyclopentadienon (Tetracyclon) (2) ein.
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  • 87
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 322-324 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 88
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 788-798 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: A New Method for Synthesis of Peptides: Activation of the Carboxyl Group with Dicyclohexylcarbodiimide using 1-hydroxybenzotriazoles as Additives1-Hydroxybenzotriazole and a number of substituted 1-Hydroxybenzotriazoles are suitable additives in the synthesis of peptides using the dicyclohexylcarbodiimide method1). The glc-racemisation test described by Weygand and coworkers2) was used to determine the influence of these additives on the racemisation during peptide synthesis. The newly employed additives decrease racemisation, prohibit the formation of N-acylurea and afford peptides in excellent yield and a high state of purity.
    Notes: 1-Hydroxy-benzotriazol sowie verschiedene kernsubstituierte 1-Hydroxy-benzotriazole eignen sich als Zusätze bei der Dicyclohexylcarbodiimid-Methode zur Synthese von Peptiden. Ihr Einfluß auf die Racemisierung bei Peptidsynthesen wurde unter Anwendung des gaschromatographischen Racemisierungstests von Weygand u. Mitarbb.2) untersucht. Die neuen Zusätze senken die Racemisierung, verhindern die N-Acyl-harnstoffbildung und führen in hoher Ausbeute zu sehr reinen Peptiden.
    Additional Material: 9 Tab.
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  • 89
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 426-439 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Stereochemistry of Sigmatropic 1,5-Hydrogen ShiftsAt 250° (S)-cis,trans-3-methyl-7-deutero-octa-4,6-diene (5) rearranges by a non-catalysed first order reaction to a mixture of (R)-trans,cis-3-methyl-7-deutero-octa-3,5-diene (3) and (S)-cis,cis-3-methyl-7-deutero-octa-3,5-diene (4). Therefore the sigmatropic 1,5-hydrogen shift proceeds in this system preferentially by way of a suprafacial transition state, which is at least 8 kcal/mol lower in energy than the antarafacial one.
    Notes: (S)-cis,trans-3-Methyl-7-deutero-octadien-(4.6) (5) lagert sich bei 250° in einer nichtkatalysierten Reaktion erster Ordnung in ein Gemisch aus (R)-trans,cis-3-Methyl-7-deutero-octadien-(3.5) (3) und (S)-cis,cis-3-Methyl-7-deutero-octadien-(3.5) (4) um. In diesem System durchläuft die sigmatrope 1.5-Wasserstoffverschiebung damit bevorzugt einen suprafacialen Übergangszustand, der um mindestens 8 kcal/Mol gegenüber dem antarafacialen Übergangszustand begünstigt ist.
    Additional Material: 7 Ill.
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  • 90
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 855-862 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Catalytic Hydroalumination of 1,5-HexadieneThe hydroalumination of 1,5-hexadiene normally yields (cyclopentylmethyl)dialkylaluminium instead of the expected dimetallated hexane derivative. Titanium tetrabutoxide catalyses the reaction and favours the formation of the dimetallated product. - When the reaction is carried out in the absence of a catalyst but in the presence of electron donors such as ethers or tertiary amines, the two-fold hydroaluminated product is also formed exclusively. In such cases the reaction velocity is, however, drastically reduced. Titanium tetrabutoxide has now been found to act as an extraordinarily effective catalyst for this reaction, even in the presence of complex-forming agents. Certain amines or tetrahydrothiophene even intensify the catalytic activity of the titanium (IV) compound.
    Notes: Die Hydroaluminierung von Hexadien-(1.5) führt normalerweise nicht zu dem erwarteten dimetallierten Hexanderivat, sondern zum Cyclopentylmethyl-dialkyl-aluminium. Titantetrabutylat katalysiert die Reaktion und lenkt sie in Richtung des dimetallierten Produktes. Bei Durchführung der Reaktion ohne Katalysator, jedoch in Gegenwart von Elektronendonatoren wie Äthern oder tertiären Aminen wird ebenfalls ausschließlich das zweifach hydroaluminierte Reaktionsprodukt gebildet. Die Reaktionsgeschwindigkeit wird dabei allerdings drastisch vermindert. Titantetrabutylat katalysiert nun die Reaktion auch bei Anwesenheit der Komplexbildner außerordentlich wirksam. Durch einige tertiäre Amine oder auch durch Tetrahydrothiophen wird die katalytische Aktivität der Titan (IV)-Verbindung sogar noch verstärkt.
    Additional Material: 5 Tab.
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  • 91
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 486-495 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Hydrazine Reactions, X Studies on Inversion-isomeric 1-Chloro-and 1-Aminoaziridines. Dependence of the 1H-C-14N-Coupling on the Konformation of the free Electron PairThe 1H-C-14N coupling depends on the conformation of the nitrogen lone-pair electrons. In 1-chloroaziridine for protons „cis“ to the nitrogen lone-pair electrons great values were found and for „trans“ protons smaller ones. The AA' BB'-system in the n.m.r. spectrum of 1-chloroaziridine is unsymmetrical. Irradiating of 14N frequency gives decoupling of 14N from other nuclei and the spectrum becomes symmetrical. In 1-amino-2-phenylaziridine the isomer with phenyl and amino group in „trans“ position is favoured. The variation of chemical shift in benzene solution of 1-amino- and 1-chloroaziridines are discussed.
    Notes: Die 1H-C-14N-Kopplung ist von der Konformation des freien Elektronenpaares abhängig und besitzt im 1-Chlor-aziridin für zum freien Elektronenpaar„cis“-ständige Protonen große, für „trans“-ständige kleine Werte. Das AA' BB'-System des NMR-Spektrums von 1-Chloraziridin ist daher unsymmetrisch und zeigt erst beim Einstrahlen der 14N-Frequenz infolge Spinentkopplung Symmetrie. 1-Amino-2-phenyl-aziridin liegt bevorzugt als das Inversionsisomere vor, in dem Phenyl- und Aminogruppe „trans“ zueinander stehen. Die Signalverschiebungen von 1-Amino-und 1-Chlor-aziridinen in Benzol werden diskutiert.
    Additional Material: 2 Tab.
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  • 92
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 534-538 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Structure of SphaerophysineSphaerophysine-formerly described as 1 or 2- is shown by n.m.r. and mass spectrometry to have structure 3 (N-(4-aminobutyl)-N-(3-methyl-2-butenyl)-guanidine). Dihydro-3 (7) has been synthesised.
    Notes: Sphaerophysin wurde bisher als 1-Isopentenylamino-4-guanidino-butan 1 oder 2 angesehen. Wir zeigen anhand von NMR- und Massenspektren sowie durch Synthese der Dihydro-verbindung, daß es die Struktur 3 eines N[4-Amino-butyl]-N-[3-methyl-buten-(2)-yl]-guanidins hat.
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  • 93
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 564-572 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterosubstituted Acetylenes, XXV Chain-Extension of Aldehydes and Ketones by two Carbon Atoms with Ynamines: Synthesis of Substituted AcrylamidesThe addition of ynamines to carbonyl groups, especially of aldehydes and ketones, leads to derivatives of acrylamides by reduction of which with lithiumaluminiumhydride and hydrogenation amines are available. The stereochemistry of the condensation has been investigated. cis- acrylamides are stereospecifically obtained by a kinetically controlled reaction from aldehydes.
    Notes: Die Addition von Inaminen an Carbonylverbindungen, insbesondere Aldehyde und Ketone. Führt zu Acrylamidderivaten, aus denen mit Lithiumaluminiumhydrid und durch Hydrierung Amine erhältlich sind. Die Stereochemie der Addition wurde untersucht: Aus Aldehyden entsteht kinetisch gesteuert und stereospezifisch das cis-Acrylamid.
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  • 94
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 648-651 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Tab.
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  • 95
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 659-662 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Polycyclic Hydrocarbons by Cycli-alkylation, IV. Cycli-alkylations of Benzene and Partially Hydrogenated Polycyclic Aromatic Hydrocarbons with 1.2-Bis(bromomethyl)cyclohexaneThe reactions of benzene and partially hydrogenated aromatic hydrocarbons such as tetrahydronaphthalene and symm. octahydrophenanthrene with a mixture of cis- and trans 1.2-Bis (bromomethyl)cyclohexane in the presence of aluminiumchloride lead to the partially hydrogenated polycyclic hydrocarbons 2-6; the dehydrogenation with Pd/C yields the corresponding aromatic compounds.
    Notes: Die Reaktionen von Benzol and teilhydrierten Aromaten, wie Tetrahydronaphthalin und symm. Octahydrophenanthren, mit einem Gemisch aus cis- und trans-1.2-Bis-brommethyl-cyclohexan in Gegenwart von Aluminiumchlorid führen zu den partiell hydrierten polycyclischen Kohlenwasserstoffen 2-6, deren Dehydrierung mit Pd/C die entsprechenden Aromaten ergibt.
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  • 96
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 685-693 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions with Alkylidenetriphenylphosphoranes, XXV. A New Synthesis of α.β-Unsaturated Carboxylic AcidsThe reaction between alkylidenetriphenylphosphoranes (1) and α-bromo-or α-iodocarboxylic esters (2) (ratio 2:1) gives rise to the formation of α,β-unsaturated carboxylic esters (4), triphenylphosphine and phosphonium salts. The mechanism and the sterochemistry of this reaction are discussed.
    Notes: Triphenylphosphinalkylene (1) reagieren mit α-Brom-oder α-Jod-carbonsäureestern (2) im Molverhältnis 2:1 zu α.β-ungesättigten Carbonsäureestern (4), Triphenylphosphin und Phosphoniumsalzen. Der Mechanismus und die Stereochemie dieser Reaktion werden diskutiert.
    Additional Material: 2 Tab.
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  • 97
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 1463-1476 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Rearrangement Reactions, V. A Kinetic Study on the Mechanism of the Wolff-RearrangementFor the thermal Wolff-rearrangement in the presence of nucleophiles such as alcohols or amines, the nitrogen evolution is measured as a function of the nucleophile concentration. With triphenylacetyldiazomethane and diacyldiazomethanes no influence of benzyl alcohol or aniline on the decomposition constants was found, whereas with phenylbenzoyldiazomethane, 2-oxo-1-diazocyclohexane and -dodecane a linear increase with the nucleophile concentration is observed. Benzyl alcohol, aniline and N-methylaniline are more active than pyridine, benzylamine or polar compounds such as nitrobenzene or bromobenzene. This acceleration is evidently a consequence of proton activity of the nucleophiles and not of an addition according to 2 → 3. The same effect is also observed with diazo compounds which cannot undergo the Wolff-rearrangement.
    Notes: Für die thermische Wolff-Umlagerung in Gegenwart von Nucleophilen (Alkohole, Amine) wird die Geschwindigkeit der Stickstoffentwicklung in Abhängigkeit von der Nucleophil-Konzentration gemessen. Bei Triphenylacetyl-diazomethan (7) sowie Diacyl-diazomethanen wird kein Einfluß von Benzylalkohol oder Anilin auf die Zersetzungskonstanten beobachtet, bei Phenyl-benzoyl-diazomethan, 2-Oxo-1-diazo-cyclohexan und -dodecan dagegen ein linearer Anstieg mit der Nucleophil-Konzentration. Benzylalkohol, Anilin und N-Methyl-anilin sind wirksamer als Pyridin, Benzylamin oder rein polare Zusätze wie Nitro- und Brombenzol. Diese Beschleunigung ist offenbar eine Folge der Protonaktivität der Nucleophile und nicht einer Einlagerung gemäß 2 → 3. Sie tritt auch bei Diazoverbindungen auf, die zur Wolff-Umlagerung nicht befähigt sind.
    Additional Material: 3 Ill.
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  • 98
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    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 1512-1521 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses of Aromatic Erythrina-Alkaloids, XIII. A Direct Course to cis-15,16-Dimethoxyerythrinane-1,8-dioneThe enollactam 5 is obtained from ethyl dihydroresorcinol-2-acetate via the diketalamide 16. Cyclisation by heating with phosphoric acid yields the ketolactam 6; the overall yield of the five steps synthesis is 20%.
    Notes: Aus Dihydroresorcin-2-essigester wird über das Diketalamid 16 die Cyclisierungsvorstufe 5 gewonnen. Sie liefert beim Erhitzen mit Phosphorsäure das Ketolactam 6 mit einer Ausbeute von 20% über 5 Stufen.
    Type of Medium: Electronic Resource
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  • 99
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 1168-1173 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Arylidene Isophorones Preparation and Properties of a Halochromic Polymethine SystemIsophorone (1) and araldehydes condense to give aryliden-isophorones 2-19. The yellow ary-dien-one systems of 2-19 form red polymethine cations like 21. Compounds of vinylogous carbonic acid structure yield red polymethine anions like 22. Differences between cation and anion are spectroscopically small with 6 relative to benzaurin (20).
    Notes: Aus Isophoron (1) und Araldehyden erhält man die Arylidenisophorone 2-19. Das gelbe Aryl-dien-on-System in 2-19 addiert leicht Protonen zu roten Polymethin-Kationen wie 21; vinyloge Carbonsäuren wie 6 bilden durch Dissoziation rote Polymethin-Anionen (22).Kation und Anion von z. B. 6 sind einander spektroskopisch ähnlicher als die analogen Salze des Benzaurins (20).
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 100
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 1216-1224 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterosubstituted Acetylenes, XXX1). A new Mechanism of Nucleophilic Halogen Substitution at Acetylene Triple BondsThe combination of nucleophilic and directiospecific addition in β-position to halogen 1) (except fluorine) with subsequent onium rearrangement is proposed as a new mechanism of nucleophilic halogen substitution at the acetylene triple bond. The reactions of chloro-tertbutyl-acetylene (1) with phenolate and thiophenolate are described as examples. The β-adducts 2,5 und 6 are formed directiospecifically. 5 and 6 give rise photochemically and thermally to the thermodynamically more stable isomer 8 in which the chlorine atom and the thioether residue have migrated and changed their C-atoms. All thioether isomers produce the tert-butylethinyl-thioether 10 upon elimination of HCl.
    Notes: Die Kombination von nucleophiler directiospezifischer Addition in β-Stellung zum Halogen1) (außer Fluor) mit anschließender Onium-Umlagerung 2) und Halogen-Anion-α-Eliminierung wird als neuer Mechanismus der nucleophilen Halogensubstitution an der Acetylendreifachbindung vorgeschlagen. Als Beispiel für diese Reaktionsschritte werden die Umsetzungen von Chlor-tert.-butyl-acetylen (1) mit Phenolat und mit Thiophenolat beschrieben. Directiospezifisch entstehen die β-Addukte 2,5 und 6. Thermisch und photochemisch bildet sich aus 5 und 6 das thermodynamisch stabilere Isomere 8, in welchem Chlor und der Thioätherrest unter Vertauschung der C-Atome gewandert sind. Alle Thioäther-Isomeren liefern bei der HCl-Abspaltung den tert.-Butyläthiny-thioäther 10.
    Type of Medium: Electronic Resource
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