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  • 1970-1974  (78)
  • 1930-1934
  • 1970  (78)
  • Physics Chemistry  (51)
  • Electron microscopy
  • 1
    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.
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  • 2
    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.
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  • 3
    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.
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  • 4
    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.
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  • 5
    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.
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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.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    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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  • 8
    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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  • 9
    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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  • 10
    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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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    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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  • 12
    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.
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  • 13
    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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  • 14
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    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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  • 15
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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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  • 16
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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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  • 17
    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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  • 18
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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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  • 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 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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  • 22
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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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  • 23
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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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  • 24
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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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  • 25
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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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  • 26
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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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  • 27
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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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  • 28
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 2 (1970) 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 29
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    International Journal of Chemical Kinetics 2 (1970), S. 71-74 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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  • 30
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase dehydrogenation of cyclopentene to cyclopentadiene catalyzed by iodine in the range 178-283°C has been found to obey a rate law consistent with the slow rate-determining step, \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm I} + {\rm c} - {\rm C}_5 {\rm H}_8 \stackrel{4}{\rightarrow}{\rm HI} + {\rm c} - {\rm C}_5 {\rm H}_7 $\end{document}, log [k4/(1 mole-1 sec-1)] = 10.25 ± 0.08 - (12.26 ± 0.18)/θ, where θ = 2.303RT in kcal/mole. Surface effects are not important. This value of E4 leads to a value of DHf2980 = 82.3 ± 1 kcal/mole and ΔHf298 = 38.4 ± 1 kcal/mole. From difference in bond strengths in the alkane and the alkene, the allylic resonance stabilization in the cyclopentenyl radical is 12.6 ± 1.0 kcal/mole, in excellent agreement with the value for the butenyl radical.Arrhenius parameters for the other steps in the mechanism are evaluated. The low value of A4 (compared with A4 for cyclopentane) suggests a “tighter” transition state for H-atom abstraction from alkenes than from alkanes.
    Additional Material: 2 Ill.
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  • 31
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    International Journal of Chemical Kinetics 2 (1970), S. 101-114 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The absolute rate constants have been measured for several gas-phase chlorine atom-molecule reactions at 25°C by resonance fluorescence. These reactions and their corresponding rate constants in units of cm3 mole-1 sec-1 are: The effects of varying the substrate pressure, total pressure, light intensity and chlorine-atom source on the value of the bimolecular rate constants have been investigated for all these reactions. Conditions under which no competing side reaction occurs were established and the reported rate constants were measured under these conditions. For reactions (2), (5), (6), (7), and 8, there is a discrepancy of a factor of two between the rate constants measured in this work and values in the literature; it is suggested that this is due to an error in the previously measured value of kCH4/kH2 upon which the relative measurements in the literature ultimately depend.
    Additional Material: 5 Ill.
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  • 32
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 2 (1970), S. 157-166 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics and absolute rate constants for the free-radical chain reaction of tri-n-butyltin hydride with di-t-butyl disulfide have been measured in cyclohexane at 30°. The rate controlling step for chain propagation involves the cleavage of the disulfide bond by an attacking tributyltin radical. The rate constant for this bimolecular homolytic substitution at sulfur is ∼8 × 104 Mole-1 sec-1. Chain termination involves the self-reaction of two tributyltin radicals.The rate constants for attack of tributyltin radicals on some other disulfides and on elemental sulfur have also been measured. The results are compared with literature data for homolytic substitutions on these compounds by a variety of radicals which have their unpaired electron centered on carbon.
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  • 33
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    International Journal of Chemical Kinetics 2 (1970), S. 185-189 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: O(1D), produced from the photolysis of N2O at 2139 Å, reacts with N2O in accord with: \documentclass{article}\pagestyle{empty}\begin{document} $$ \begin{array}{*{20}c} {(2)} & {{\rm O}(^1 D) + N_2 {\rm O} \to {\rm N}_2 + {\rm O}_2 } \\ \end{array} $$ \end{document}\documentclass{article}\pagestyle{empty}\begin{document} $$ \begin{array}{*{20}c} {(3)} & { \to 2{\rm NO}} \\ \end{array} $$ \end{document}We have used the method of chemical difference to obtain an accurate measure of k2/k3 = 0.59 ± 0.01. Furthermore, the quantum yield of production of O(3P), either on direct photolysis or on deactivation of O(1D) by N2O, is less than 0.02 and probably zero.
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  • 34
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    International Journal of Chemical Kinetics 2 (1970), S. 175-184 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method for constructing potential energy surfaces previously proposed by the author has been extended to hydrogen transfer reactions between halide, oxygen, and carbon atoms. A qualitative relation was found between the repulsive energy and the number of anti-bonding electrons. In general, the calculated kinetic isotope effect is in satisfactory agreement with observed values and the contributions by H-atom tunneling to the rate of reaction is smaller than that obtained from other surfaces.
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  • 35
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    International Journal of Chemical Kinetics 2 (1970), S. 265-280 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the nitric oxide catalyzed, homogeneous, gas-phase isomerization of 1,trans-3,trans-5-heptatriene have been studied for temperatures ranging between 130°C and 241°C. The very clean reaction involves exclusive geometrical isomerization about the 5,6-π-bond. The observed rate constants for \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm NO} + trans - {\rm 3,}trans{\rm - 5}\stackrel{1}{\rightarrow}trans - 3,cis - 5 + {\rm NO} $\end{document} can be represented (with standard errors) by log k1 = (7.18 ± 0.06) - (16.75 ± 0.12)/θ, where θ = 2.303 RT in kcal/mole. The consecutive-step reaction mechanism involves addition of NO to the double bond (Ka, b = ka/kb), followed by rotation of the 5,6-C—C bond in the adduct radical (kc.)Analysis of the observed activation parameters shows, that kc is rate-controlling and consequently k1 = kcKa, b. Estimates of kc and Ka, b lead to a value of k1 in good agreement with experiment.Comparing our data with those previously obtained for the similar 1,3-pentadiene system results in a value for the extra stabilization energy generated in the 1,3-heptadienyl radical of 18.5 ± 1.7 kcal/mole. This value is discussed in view of comparable data in the literature.
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  • 36
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 2 (1970), S. 299-309 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Arrhenius parameters have been measured for the abstraction of hydrogen from the C Si, Ge, and Sn tetramethyls: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {k({\rm ml m}^{ - {\rm 1}} {\rm s}^{ - {\rm 1}} )} \hfill & {{\rm for}} \hfill & {{\rm C}({\rm CH}_{\rm 3} )_4 = {{10^{12.0} {\rm e}^{ - 8370} } \mathord{\left/ {\vphantom {{10^{12.0} {\rm e}^{ - 8370} } {RT}}} \right. \kern-\nulldelimiterspace} {RT}}} \hfill \\ {k({\rm ml m}^{ - {\rm 1}} {\rm s}^{ - {\rm 1}} )} \hfill & {{\rm for}} \hfill & {{\rm Si(CH}_{\rm 3} {\rm )}_{\rm 4} = {{10^{11.9} {\rm e}^{ - 7300} } \mathord{\left/ {\vphantom {{10^{11.9} {\rm e}^{ - 7300} } {RT}}} \right. \kern-\nulldelimiterspace} {RT}}} \hfill \\ {k({\rm ml m}^{ - {\rm 1}} {\rm s}^{ - {\rm 1}} )} \hfill & {{\rm for}} \hfill & {{\rm Ge(CH}_{\rm 3} {\rm )}_{\rm 4} = {{10^{11.7} {\rm e}^{ - 7370} } \mathord{\left/ {\vphantom {{10^{11.7} {\rm e}^{ - 7370} } {RT}}} \right. \kern-\nulldelimiterspace} {RT}}} \hfill \\ {k({\rm ml m}^{ - {\rm 1}} {\rm s}^{ - {\rm 1}} )} \hfill & {{\rm for}} \hfill & {{\rm Sn(CH}_{\rm 3} {\rm )}_{\rm 4} = {{10^{11.7} {\rm e}^{ - 7250} } \mathord{\left/ {\vphantom {{10^{11.7} {\rm e}^{ - 7250} } {RT}}} \right. \kern-\nulldelimiterspace} {RT}}} \hfill \\ \end{array} $$\end{document} The rate constants correlate with the proton chemical shift, which is related to a polar effect. In all cases except carbon, a hot-molecule β-fluorine rearrangement-elimination reaction occurs following radical combination: \documentclass{article}\pagestyle{empty}\begin{document} $$ ({\rm CF}_3 {\rm CH}_2 {\rm M}({\rm CH}_3 )_3 )^* \to {\rm CF}_2 {\rm CH}_2 + {\rm FM}({\rm CH}_3 )_3 $$ \end{document} We suggest the occurrence of a radical exchange reaction for the Si, Sn, and Ge systems, \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CF}_3 + {\rm M}({\rm CH}_3 )_4 \rightleftharpoons{\rm CF}_3 {\rm M}({\rm CH}_3 )_4 \to {\rm CH}_3 + {\rm CF}_3 {\rm M}({\rm C}{\rm H}_3 )_3 $$\end{document} with kexchange (CF3 + Sn(Me)4) ∼ 107 ml m-1 s-1.
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  • 37
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 2 (1970), S. 123-136 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of 1,2-dichloropropane at atmospheric pressure has been studied in the temperature range 227-590°C, in a flow system. Above 450°C, the reaction is homogenous and unimolecular with a rate constant: \documentclass{article}\pagestyle{empty}\begin{document}$$k = 10^{12.95 \pm 0.15} \exp (- 53,070 \pm 500/RT)\sec ^{ - 1}$$\end{document}Below 450°C, a low activation energy, probably heterogenous process competes with the gas phase reactionThe primary reaction products are HCl and the monochloropropene isomers; the relative amounts of each isomer depend on the temperature in the low but not in the high temperature region. The direction of the HCl elimination is discussed in terms of substituent effects at the α- and β-carbon positions and compared with literature data on similar reactionsSecondary products are formed principally by further pyrolysis of allyl chloride. The first-order rate constant of this reaction is given by: \documentclass{article}\pagestyle{empty}\begin{document}$$ k = 10^{8.54 \pm 0.2} \exp (- 37,275 \pm 700/RT)\sec ^{ - 1} $$\end{document}.
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  • 38
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    International Journal of Chemical Kinetics 2 (1970), S. 137-155 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A record of the time dependence of the difference between two signals, one proportional to the concentration of a reactant or product in one reaction mixture and the other proportional to the concentration of the same or a corresponding substance in another mixture in which the reaction is initiated at the same time as the first, makes it possible to obtain not only the ratio, but also the individual values, of the rate constants for the two reactions. The effects of the experimental variables on a number of measurable parameters are examined, the errors associated with a number of different ways of evaluating the rate constants and their ratio are discussed, and it is shown how conditions can be selected that should provide values whose precisions compare favorably with those attainable by other techniques.
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  • 39
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    International Journal of Chemical Kinetics 2 (1970), S. 115-122 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: At 540°C, H2S (0.1 to 5 mm Hg) diminishes the initial rate of pyrolysis of C2H6 (50 mm Hg) into C2H4 + H2 and, even more strongly, the rate of appearance of the traces of nC4H10; on the contrary, the initial rate of formation of the traces of CH4 is practically not modified.A mechanism is proposed in order to interpret these experimental facts.
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  • 40
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    International Journal of Chemical Kinetics 2 (1970), S. 167-173 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 41
    Electronic Resource
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 2 (1970) 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 42
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    International Journal of Chemical Kinetics 2 (1970), S. 337-337 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 43
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    International Journal of Chemical Kinetics 2 (1970), S. 311-323 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A check of the data from comparative rate single-pulse shock tube experiments have been carried out through the use of a new standard reaction, the decyclization reaction of ethylcyclobutane. The rate expressions for cyclohexene and 2,2,3-trimethylbutane have been found to be \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} k({\rm C}_{\rm 6} {\rm H}_{{\rm 10}} \to 1,3 - {\rm C}_4 {\rm H}_6 + {\rm C}_2 {\rm H}_4 ) = 10^{15.3} \exp ( - 33,690/T)\sec ^{ - 1} ,950^ \circ - 1100^ \circ {\rm K,2} - {\rm 6atm} \\ k(t{\rm C}_4 {\rm H}_9 - {\rm iC}_3 {\rm H}_7 \to t{\rm C}_{\rm 4} {\rm H}_{\rm 9} \cdot + {\rm iC}_{\rm 3} {\rm H}_7 \cdot ) = 10^{16.5} {{\exp ( - 36,830} \mathord{\left/ {\vphantom {{\exp ( - 36,830} T}} \right. \kern-\nulldelimiterspace} T})\sec ^{ - 1} ,1000^ \circ - 1100^ \circ {\rm K,2} - {\rm 6atm} \\ \end{array} $$\end{document} in excellent agreement with previously published results. Most of the small discrepancy that does exist is apparently due to the differences between the present and earlier (decomposition of isopropyl bromide) "standard" reaction. For the latter process, the present study yields \documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm iC}_{\rm 3} {\rm H}_7 {\rm Br} \to {\rm C}_{\rm 3} {\rm H}_6 + {\rm HBr}) \to 10^{13.73} {\rm exp(}{{ - 23,970} \mathord{\left/ {\vphantom {{ - 23,970} {T\sec ^{ - 1} ,800^ \circ - 1000^ \circ {\rm K,2} - {\rm 6}}}} \right. \kern-\nulldelimiterspace} {T\sec ^{ - 1} ,800^ \circ - 1000^ \circ {\rm K,2} - {\rm 6}}}{\rm atm)} $$\end{document} These results confirm the correctness of previously published comparative rate single-pulse shock tube experiments. They demonstrate once again that for the decomposition of paraffin hydrocarbons, calculated preexponential factors are at least an order of magnitude higher than the directly measured number and that the accepted value of the heat of formation of t-butyl radicals ΔHf300(tC4H9·) = 29 kJ (6.8 kcals) is at least 10 kJ too low. Finally, attention is called to recent studies on neopentane decomposition in flow and static systems which are in complete agreement with the present conclusions.
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  • 44
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 2 (1970) 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 45
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 2 (1970), S. 65-68 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 46
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    International Journal of Chemical Kinetics 2 (1970), S. 23-36 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dilute mixtures of 4-methyl-l-pentyne have been pyrolyzed in a single-pulse shock tube. The decomposition process involves bond breaking: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm HC} \equiv {\rm C} - {\rm CH}_2 ({\rm i - C}_{\rm 3} {\rm H}_{\rm 7} )\stackrel{k_B}{\longrightarrow}{\rm HC} \equiv {\rm C} - {\rm CH}_2 \cdot ({\rm propynyl}) + {\rm i - C}_{\rm 3} {\rm H}_{\rm 7} \cdot $$\end{document} as well as a molecular reaction: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm HC}\equiv {\rm C} - {\rm CH}_{\rm 2} ({\rm \rm i - C}_{\rm 3} {\rm H}_{\rm 7} )\stackrel{k_M}{\rightarrow}{\rm C}_{\rm 3} {\rm H}_4 ({\rm allene}) + {\rm C}_3 {\rm H}_6 . $$\end{document} The rate parameters are: \documentclass{article}\pagestyle{empty}\begin{document}$$k_{\bf B} = 10^{15.56} \exp {\rm (} - 34,940/T){\rm (sec}^{ - {\rm 1}}) $$ $$\begin{array}{*{20}c} k_{\rm M} = 10^{13.1} \exp {\rm (} - {\rm 29,670/}T){\rm (sec}^{ - {\rm 1}})&{\rm 1100}^ \circ {\rm K, 1}{\rm .5} - 5{\rm atm}\end{array}$$\end{document} The heat of formation of propynyl radical is thus ΔHf300 = 338 kJ mol-1 (80.7 kcal mol-1)· This leads to a propynyl resonance energy of 40 kJ mol-1 (9.6 kcal mol-1).
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  • 47
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    International Journal of Chemical Kinetics 2 (1970), S. 37-61 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the ethane pyrolysis have been studied at temperatures from 550 to 596°C and with 0 to 62% of added nitric oxide. The rates of production of various products were studied by gas chromatography; ethylene, hydrogen, methane, nitrogen, water, nitrous oxide and acetonitrile were found as primary products, with hydrogen cyanide, carbon monoxide, acetaldehyde, n-butane, 1-butene, cis- and trans-2-butene and 1,3-butadiene as secondary products. For all the primary products the orders with respect to C2H6and NO were determined, as were the activation energies at two different percentages of NO (15.7 and 45.5%).Nitric oxide was found to be rapidly consumed with a finite initial rate, and the rate of production of H2O was close to that of C2H4 at higher nitric oxide pressures.A mechanism is proposed which gives good agreement with all of the observed results. Its main features are: (1) Initiation takes place mainly by the unimolecular dissociation of ethane; there is no evidence for or against the process NO + C2H6 → HNO + C2H5; (2) NO scavenges ethyl radicals to form acetaldoxime which decomposes, and in this way the breakdown of C2H5 is hastened; (3) termination takes place mainly by the unimolecular decomposition of acetaldoxime to give inactive products. Some of the relevant rate parameters are evaluated. Reactions are proposed to account for the formation of the secondary products observed.
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  • 48
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    International Journal of Chemical Kinetics 2 (1970), S. 191-197 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nitrogen quantum yields are reported for the photolysis of C2F5N=NC2F5 at 3660 Å over the pressure range 2-10 cm from 25° to 150°c. The Stern-Volmer plots obtained are discussed and compared with those obtained with azoethane and azoisopropane.
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  • 49
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    International Journal of Chemical Kinetics 2 (1970), S. 199-213 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the decomposition of benzotrifluoride was studied from 720°c to 859°c in a flow system with and without carrier gas. Consideration of the product distribution made possible the study of the decomposition into CF3 and C6H5 radicals, which appeared to be truly homogeneous in character. The first-order rate constant of the C—C bond fission, log k (sec-1) = (17.9 ± 0.5) (99.7 ± 2.5)/θ, did not change with change of initial concentration, pressure of the carrier gas, or contact time. The Arrhenius parameters have been related to the appropriate thermodynamic data. Assumption of 0 kcal/mole for the activation energy of the reverse combination reaction yielded DH298°(C6H5—CF3) = 103.6 ± 2.5 kcal/mole and ΔHf298°(C6H5) = 77.1 ± 3.0 kcal/mole.Applicability of the simple first-order formula to calculation of the rate constant has been also dealt with.
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  • 50
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    International Journal of Chemical Kinetics 2 (1970), S. 215-234 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Combination reactions of the methyl radical have been studied by following the decay of the absorbance of the methyl radical during the course of the reaction by means of kinetic spectroscopy. The limiting values of the second-order rate constants at high pressure were determined for two reactions at room temperature: \documentclass{article}\pagestyle{empty}\begin{document}$ \begin{array}{*{20}c} {{\rm CH}_{\rm 3} + {\rm CH}_{\rm 3} ( + {\rm M}) \to {\rm CH}_{\rm 3} {\rm CH}_{\rm 3} ( + {\rm M}):k_1 = (2.6 \pm 0.3) \times 10^{10} 1{\rm mole}^{ - {\rm 1}} \sec ^{ - 1} } \\ {{\rm CH}_{\rm 3} + {\rm NO }( + {\rm M}) \to {\rm CH}_{\rm 3} {\rm NO }( + {\rm M}):k_2 = (2.4 \pm 0.2) \times 10^9 1{\rm mole}^{ - {\rm 1}} \sec ^{ - 1} } \\ \end{array} $\end{document} The extinction coefficient of the methyl radical was found to have a maximum value of (1.02 ± 0.06) X 104 1 mole-1 cm-1 at 216.4 nm. Integration of the extinction coefficient over the absorption band of the methyl radical gave an oscillator strength of 1.0 X 10-2.
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  • 51
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A simple electrostatic model of point dipoles is used which permits direct calculation of the activation energies for the addition of the molecules H2O, H2S, H3N, and H3P to olefins. These calculated values agree with the known experimental data to within ±2 kcal/mole on the average. It was found that the best fit could be obtained with a polar transition state that corresponded to a reduction in bond order from 1 to ½ for the bond-breaking coordinates and an increase in bond order from 0 to 0.18 for the bond-forming coordinates. The replacement of a hydrogen atom of the species H2O, H2S, H3N, or H3P by a polarizable methyl group is expected to stabilize the charge on the central atoms. The following stabilization energies for the pairs H2O—CH3OH, H2S—CH3SH, H3N—CH3NH2, H3P—CH3PH2 were calculated: -4.8 kcal/mole, -0.7 kcal/mole, -1.9 kcal/mole, -0.8 kcal/mole, respectively.
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  • 52
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    International Journal of Chemical Kinetics 2 (1970), S. 263-264 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 53
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    International Journal of Chemical Kinetics 2 (1970), S. 257-262 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of trifluoromethyl radicals with ammonia in the gas phase has been studied in the temperature range 30-352°. Product formation is not explicable simply in terms of the reactions: \documentclass{article}\pagestyle{empty}\begin{document}$\begin{array}{*{20}c} {{\rm CF}_{\rm 3} + {\rm NH}_{\rm 3} \to {\rm CF}_3 {\rm H} + {\rm NH}_2 } \\ {2{\rm CF}_3 \to {\rm C}_2 {\rm F}_6 } \\\end{array}$\end{document} and curvature of the Arrhenius plot at high and low temperatures suggests that there are additional sources of fluoroform.
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  • 54
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    International Journal of Chemical Kinetics 2 (1970) 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 55
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The quantitative kinetics of pyrolysis of some cyclic and polycyclic compounds are examined from the point of view of biradical intermediates. Transition state methods for estimating the Arrhenius parameters of the lowest free energy biradical pathway to products in cyclic and polycyclic compound reactions are described and illustrated. A large number of the polycyclic reactions are found to have Arrhenius parameters consistent with the biradical mechanism estimates. Other reactions are found to have much faster experimental rates and must therefore be concerted. The value of activation energy and activation entropy estimates as discriminatory tests of mechanism, i.e., single step (concertedness) or consecutive step processes, is discussed.
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  • 56
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 57
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    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gas-phase reaction CH3COCH3 + I2 ⇄ CH3COCH2I + HI have been measured spectrophotometrically in a static system over the temperature range 340-430°. The pressure of CH3COCH3 was varied from 15 to 330 torr and of I2 from 4 to 48 torr, and the initial rate of the reaction was found to be consistent with \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm CH}_3 {\rm COCH}_3 + {\rm I}^{\rm .} \stackrel{1}{\rightarrow}{\rm CH}_{\rm 3} {\rm COCH} + {\rm HI} $\end{document} as the rate-determining step. An Arrhenius plot of the variation of k1 with temperature showed considerable scatter of the points, depending on the conditioning of the reaction vessel. After allowance for surface catalysis, the best line drawn by inspection yielded the Arrhenius equation, log [k1/(M-1 sec-1)] = (11.2 ± 0.8) - (27.7 θ 2.3)/θ, where θ = 2.303 RT in kcal/mole. This activation energy yields an acetone C—H bond strength of 98 kcal/mole and δHf0 (CH3COĊH2) radical = -5.7 ± 2.6 kcal/mole. As the acetone bond strength is the same as the primary C—H bond strength in isopropyl alcohol, there is no resonance stabilization of the acetonyl radical due to delocalization of the radical site. By contrast, the isoelectronic allyl resonance energy is 10 kcal/mole, and reasons for the difference are discussed in terms of the π-bond energies of acetone and propene.
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  • 58
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    International Journal of Chemical Kinetics 2 (1970), S. 63-64 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 59
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    International Journal of Chemical Kinetics 2 (1970), S. 1-10 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reinvestigation of the gas phase thermal reaction of 1,1,2,2-tetramethylcyclopropane (699-759°K) gave for the unimolecular disappearance of reactant, k(TMC) = 1015.27-63.93/θ sec-1, in good agreement with the original results of Frey and Marshall. However, evidence for a high activation energy (E = 79 ± 5 kcal/mole), competitive unimolecular decomposition to 2,3-dimethyl-1 and -2-butenes was also obtained. It is proposed that the serious discrepancy noted [1] between the experimentally observed Arrhenius parameters for the overall reaction kinetics, and those predicted by transition state calculations assuming a biradical mechanism for the isomerization reactions (previously believed to be the only primary reaction mode) can be explained in terms of the increasing importance of the decomposition reactions at higher reaction temperatures.
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  • 60
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    International Journal of Chemical Kinetics 2 (1970), S. 69-70 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 61
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    International Journal of Chemical Kinetics 2 (1970) 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 62
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    International Journal of Chemical Kinetics 2 (1970), S. 77-79 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 63
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    International Journal of Chemical Kinetics 2 (1970), S. 75-76 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 64
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gas-phase dehydrogenation of cyclopentane to cyclopentene is found to be consistent with a slow attack by an I atom (step 4, text) on cyclopentane in the range 282-382°C. The measured rate constants fit the Arrhenius equation, log k4 = 11.95 ± 0.08 - (24.9 ± 0.23)/θ 1 mole-1 sec-1, where θ = 2.303RT in kcal/mole. This leads to a value of ΔHf,2980 = 24.3 ± 1 kcal/mole and a bond dissociation energy DH = 94.9 ± 1 kcal/mole. The latter value is identical with DH0(i-Pr-H) = 95 ± 1 kcal/mole and signifies that cyclopentane and the cyclopentyl radical have the same strain energy. Arrhenius parameters are deduced for all six steps in the reaction mechanism. Surface reactions are shown to be unimportant.Cyclopentyl iodide is an unstable intermediate in the reaction and the rate constant for its bimolecular formation from HI + cyclopentene is found to be log k6 = 8.40 ± 0.29 - (26.9 ± 0.8)/θ 1 mole-1 sec-1. Together with the equilibrium constant, this yields for the unimolecular elimination of HI from cyclopentyl iodide, the rate constant, log k5 = 13.3 ± 0.3 - (42.8 ± 1.2)/θ sec-1.
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  • 65
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    International Journal of Chemical Kinetics 2 (1970), S. 325-334 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The competitive reactions of Br atoms with CH4 and CD4 were studied over the temperature range of 562° to 637°K. Over this temperature interval, the kinetic isotope effect, kH/kD, varied from 3.05 to 2.47 for the reactions \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{\rm Br} + {\rm CH}_{\rm 4} \stackrel{k_H}{\rightarrow}{\rm HBr} + {\rm CH}_3 } \\ {{\rm Br} + {\rm CD}_{\rm 4} \stackrel{k_D}{\rightarrow}{\rm DBr} + {\rm CD}_3 } \\ \end{array} $$\end{document} The rate constant ratio kH/kD, expressed in Arrhenius form, was found to equal (1.10 ± 0.05) exp (1030 ± 60/RT). A comparison is presented between the experimental result and the result obtained theoretically from absolute rate theory using the London-Eyring-Polanyi-Sato (LEPS) method of constructing the potential energy surface of the reaction. The agreement between theory and experiment is very poor, and this is believed to arise from the highly unsymmetrical nature of the potential energy surface involved in these reactions. A comparison is also presented between the kH/kD values obtained in the Br + CH4-CD4 experiments and the available data on the corresponding Cl + CH4-CD4 reactions.
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  • 66
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    International Journal of Chemical Kinetics 2 (1970), S. 339-339 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 67
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    International Journal of Chemical Kinetics 2 (1970), S. 343-347 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reversible isomerization of cis-hepta-1,3-diene to cis-2-trans-4-heptadiene via a 1,5 hydrogen shift has been investigated kinetically at nine temperatures in the range of 475° to 531°K. Equilibrium is reached near 94% reaction. Some cis-2-cis-4-heptadiene is also formed, but at a rate some 60 times slower than the cis,trans isomer. A least-squares analysis of the data yielded the Arrhenius equation for the isomerization of the cis-hepta-1,3-diene: \documentclass{article}\pagestyle{empty}\begin{document}$$ {{\log k_1 } \mathord{\left/ {\vphantom {{\log k_1 } {\sec ^{ - 1} = {{(11.110 \pm 0.087) - ([33,210 \pm 200]{\rm cal mole}^{ - {\rm 1}} )} \mathord{\left/ {\vphantom {{(11.110 \pm 0.087) - ([33,210 \pm 200]{\rm cal mole}^{ - {\rm 1}} )} \theta }} \right. \kern-\nulldelimiterspace} \theta }}}} \right. \kern-\nulldelimiterspace} {\sec ^{ - 1} = {{(11.110 \pm 0.087) - ([33,210 \pm 200]{\rm cal mole}^{ - {\rm 1}} )} \mathord{\left/ {\vphantom {{(11.110 \pm 0.087) - ([33,210 \pm 200]{\rm cal mole}^{ - {\rm 1}} )} \theta }} \right. \kern-\nulldelimiterspace} \theta }}} $$\end{document} Possible errors in the equilibrium constant measurements are discussed, and employing an equilibrium constant calculated by using group additivity estimates together with the values of k1, we obtained for the reverse reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {{\log k_2 } \mathord{\left/ {\vphantom {{\log k_2 } {\sec ^{ - 1} = (11.1 \pm 0.15) - ([35,800 \pm 300])}}} \right. \kern-\nulldelimiterspace} {\sec ^{ - 1} = (11.1 \pm 0.15) - ([35,800 \pm 300])}}{{{\rm cal mole}^{ - {\rm 1}} )} \mathord{\left/ {\vphantom {{{\rm cal mole}^{ - {\rm 1}} )} \theta }} \right. \kern-\nulldelimiterspace} \theta } $$\end{document} where \documentclass{article}\pagestyle{empty}\begin{document}$$ \theta = 2.303RT $$\end{document}.
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  • 68
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    International Journal of Chemical Kinetics 2 (1970), S. 349-379 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the acetaldehyde pyrolysis have been studied at temperatures from 450° to 525°C, at an acetaldehyde pressure of 176 torr and at 0 to 40 torr of added nitric oxide. The following products were identified and their rates of formation measured: CH4, H2, CO, CO2, C2H4, C2H6, H2O, C3H6, C2H5CHO, CH3COCH3, CH3COOCH=CH2, N2, N2O, HCN, CH3NCO, and C2H5NCO. Acetaldehyde vapor was found to react with nitric oxide slowly in the dark at room temperature, the products being H2O, CH3COOCH3, CO, CO2, N2, NO2, HCN, CH3NO2, and CH3ONO2. The rates of formation of N2 and C2H5NCO depend on how long the CH3CHO-NO mixture is kept at room temperature before pyrolysis; the rates of formation of the other products depend only slightly on the mixing period.The pyrolysis of “clean” CH3CHO-NO mixtures (i.e., the results extrapolated to zero mixing time, which are independent of products formed in the cold reaction) are interpreted as follows: (1) There are two chain carriers, CH3 and CH2CHO, their concentrations being interdependent and influenced by NO in different ways: the CH3 radical is both generated and removed by reactions directly involving NO, whereas CH2CHO is generated only indirectly from CH3 but is also removed by direct reaction with NO. (2) An important mode of initiation by NO is its addition to the carbonyl group with the formation of which is converted into ; this splits off OH with the formation of CH3NCO or CH3 + OCN. (3) Important modes of termination are \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{\rm CH}_3 + {\rm NO} \to {\rm CH}_3 {\rm NO} \to {\rm CH}_2 {\rm NOH} \to {\rm HCN} + {\rm H}_2 {\rm O}} \\ {{\rm CH}_{\rm 2} {\rm CHO} + {\rm NO} \to {\rm CH}_2 ({\rm NO}){\rm CHO} \to {\rm CH}({\rm NOH}){\rm CHO} \to {\rm HCN} + {\rm H}_2 {\rm O} + {\rm CO}} \\ \end{array} $$\end{document} The steady-state equations derived from the mechanism are shown to give a good fit to the experimental rate versus [NO] curves and, in particular, explain why there is enhancement of rate by NO at higher CH3CHO pressures and, at lower CH3CHO pressures, inhibition at low [NO] followed by enhancement at higher [NO].The cold reaction is explained in terms of chain-propagating and chain-branching steps resulting from the addition of several NO molecules to CH3CHO and the CH3CO radical. In the “unclean” reaction it is found that the rates of N2 and C2N5NCO formation are increased by CH3NO2, CH3ONO, and CH3ONO2 formed during the cold reaction. A mechanism is proposed, involving the participation of α-nitrosoethyl nitrite, CH3CH(NO)ONO.It is suggested that there are two modes of behavior in pyrolyses in the presence of NO: (1) In the paraffins, ethers, and ketones, the effects are attributed to the addition of NO to a radical with the formation of an oxime-like compound. (2) In the aldehydes and alkenes, where there is a hydrogen atom attached to a double-bonded carbon atom, the behavior is explained in terms of addition of NO to the double bond followed by the formation of an oxime-like species.
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  • 69
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Equilibrium constants for the reaction CH3COCH2CH3 + I2 ⇌ CH3COCHICH3 + HI have been computed to fit the kinetics of the reaction of iodine atoms with methyl ethyl ketone. From a calculated value of S2980(CH3COCHICH3) = 93.9 ± 1.0 gibbs/mole and the experimental equilibrium constants, ΔHf0(CH3COCHICH3) is found to be -38.2 ± 0.6 kcal/mole. The Δ(ΔHf2980) value on substitution of a hydrogen atom by an iodine atom in the title compound is compared with that for isopropyl iodide. The relative instability of 2-iodo-3-butanone (3.4 kcal/mole) is presented as further evidence for intramolecular coulombic interaction between partial charges in polar molecules. The unimolecular decomposition of 2-iodo-3-butanone to methyl vinyl ketone and hydrogen iodide was also measured in the same system. This reaction is relatively slow compared to the formation of the above equilibrium. Rate constants for the reaction over the temperature range 281°-355°C fit the Arrhenius equation: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log(}{{k_{\rm 3} } \mathord{\left/ {\vphantom {{k_{\rm 3} } {{\rm sec}^{ - 1} }}} \right. \kern-\nulldelimiterspace} {{\rm sec}^{ - 1} }}{\rm )} = {\rm 13}{\rm .4} - {{(41.9 \pm 0.5)} \mathord{\left/ {\vphantom {{(41.9 \pm 0.5)} \theta }} \right. \kern-\nulldelimiterspace} \theta } $$\end{document} where θ = 2.303RT kcal/mole. The stability of both the ground and transition states is discussed in comparing this activation energy with that reported for the unimolecular elimination of hydrogen iodide from other secondary iodides. The kinetics of the reaction of hydrogen iodide with methyl vinyl ketone were also measured. The addition of HI to the double bond is not rate controlling, but it may be shown that the rate of formation of 1-iodo-3-butanone is more rapid than that for 2-iodo-3-butanone. Both four- and six-center transition complexes and iodine atom-catalyzed addition are discussed in analyzing the relative rates.
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  • 70
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    International Journal of Chemical Kinetics 2 (1970), S. 419-422 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 71
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    International Journal of Chemical Kinetics 2 (1970), S. 475-477 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Numerical Methods were used to solve the differential equation for diffusion of a trace gas into a flowing carrier gas having a parabolic velocity profile in a cylindrical tube. Steady state solutions are given in the form of contour diagrams of constant trace gas concentration.
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  • 72
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    International Journal of Chemical Kinetics 2 (1970), S. 457-473 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of nitrogen atoms with methylacetylene has been studied using a fast-flow low-pressure reactor coupled to a mass spctrometer by a nozzle-beam sampling system. Hydrogen atom concentrations were measured by ESR analysis. Experimental second-order rate constants for the consumption of N atoms, of C3H4, and for the formation of N2 were determined in the temperature range of 283° to 485°K. Product profiles of all stable species and of hydrogen atoms and methyl radicals were obtained for different initial concentrations of the reactants. Two different reaction pathways can be distinguished: one provides for recombination of N atoms, and the second leads to the formation of cyano compounds and other hydrocarbons. Only the latter process is influenced by the addition of hydrogen atoms. Mechanisms for the two pathways are discussed.
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  • 73
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The vibrationally excited molecules CF3CH3* and CF3CD3* have been synthesized by radical combination (produced by ketone photolysis), and HF and DF elimination from them studied as a function of temperature and pressure. Using RRK theory many calculations have recently been made of critical energies for the decomposition of "hot" fluoroethane molecules. Taking CF3CH3* as an example, it is concluded that the empiricism involved in such calculations renders results of doubtful significance. The non-equilibrium kinetic isotope effect is kH/kD = 3.1 at 470°K. Arrhenius parameters are also presented for radical abstraction reactions from the ketone source molecules.
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  • 74
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    International Journal of Chemical Kinetics 2 (1970), S. 335-335 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 75
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    International Journal of Chemical Kinetics 2 (1970), S. 409-418 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the bimolecular reactions of ethylene and propylene to form radicals and to form cyclobutane or its derivatives have been calculated using thermodynamic and kinetic data. Comparison of these rates with the kinetics of the thermal reactions of ethylene and propylene show that cyclobutane and its derivatives are probably not important intermediates in the processes forming radicals.
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  • 76
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    International Journal of Chemical Kinetics 2 (1970) 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 77
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase reaction of iodine (2.8-43.3 torr) with methyl ethyl ketone (MEK) (7.4-303.4 torr) has been studied over the temperature range 280-355°C in a static system. The initial rate of disappearance of I2 is first order in MEK and half order in I2. The rate-determining step is the abstraction of a secondary hydrogen atom by an iodine atom: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_3 {\rm COCH}_2 {\rm CH}_2 {\rm } + {\rm I}^{\rm .} \stackrel{1}{\longrightarrow}{\rm CH}_{\rm 3} {\rm COCHCHL3 + HI} $$\end{document} where k1 is given by \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{{\rm 10}} ({{k_1 } \mathord{\left/ {\vphantom {{k_1 } {{\rm M}^{ - 1} \sec ^{ - 1} }}} \right. \kern-\nulldelimiterspace} {{\rm M}^{ - 1} \sec ^{ - 1} }}) = {{(10.76 \pm 0.15) - (22.0 \pm 0.4)} \mathord{\left/ {\vphantom {{(10.76 \pm 0.15) - (22.0 \pm 0.4)} \theta }} \right. \kern-\nulldelimiterspace} \theta } $$\end{document} and θ = 2.303RT in kcal/mole. This activation energy is equivalent to a secondary C—H bond strength of 92.3 ± 1.4 kcal/mole and ΔHf 2980 of the methylacetonyl radical = -16.8 ± 1.7 kcal/mole. By comparison with 95 kcal/mole for the secondary C—H bond strength, when delocalization of the unpaired electron with a pi bond is not possible, the resonance stabilization of the methylacetonyl radical is calculated to be 2.7 ± 1.7 kcal/mole. This value is 10 kcal/mole less than the stabilization energy of the isoelectronic methylallyl radical. The difference in pi bond energies in the canonical forms of the methylacetonyl radical is shown to account for the variation in stabilization energies.
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  • 78
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    International Journal of Chemical Kinetics 2 (1970), S. 479-492 
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of CF3 radicals with the C3 to C7 cyclanes and spiropentane were studied and the following Arrhenius parameters were obtained for the reaction CF3 + c-RH → CF3H + c-R: Textc-RHlog A (cm3mole-1sec-1)E (kcal/mole)D(c-R - H) (kcal/mole)Cyclopropane11.548.73100.7Cyclobutane11.666.4895.7Cyclopentane12.306.1894.3Cyclohexane12.126.2694.9Cycloheptane12.435.8994.0Spiropentane11.918.1298.8The CF3 radicals were generated by photolysis of hexafluoroacetone or CF3I and a comparison is made of the utility of the two compounds as radical sources. The Arrhenius parameters are compared with those for corresponding reactions of CH3 radicals with cyclanes, and the general reactivity of cyclic compounds toward free radicals is discussed. An Evans-Polanyi treatment is used to derive C—H bond dissociation energies in cyclanes; and these results, based on the reactions of CF3 with cyclanes, agree well with those previously obtained using CH3 plus cyclanes. The final mean values are shown above.
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