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  • 1970-1974  (445)
  • 1965-1969  (91)
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  • Physical Chemistry  (345)
  • Bone
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 14 (1974), S. 309-315 
    ISSN: 1432-0827
    Keywords: Osteoblast ; Matrix ; Bone ; Scanning electron microscope
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Les territoires sécrétoires des ostéoblastes d'os pariétal de rats sont déterminées en utilisant la microscopie électronique à balayage. Le territoire moyen de 4.620 cellules, dans 19 territoires, est de 154 μm2 par ostéoblaste. Les valeurs extrêmes par champ varient de 136 à 177 μm2 par ostéoblaste. Quatre cent cellules sont mesurées individuellement; la valeur moyenne par ostéoblaste est de 143 μm3 avec une déviation standard de 33. Le taux d'apposition journalier, mesuré par la tétracycline pendant 8 jours, est de 3.12 μm (déviation standard 0.22). Ce qui correspond à une production matricielle journalière d'environ 470 μm3 par ostéoblaste.
    Abstract: Zusammenfassung Die Ausscheidungsbereiche von Ratten-Osteoblasten des Scheitelbeines wurden mit dem Raster-Elektronenmikroskop direkt gemessen. Der durchschnittliche Bereich von 4620 Zellen in 19 Gesichtsfeldern war 154 μm2 per osteoblast. Der Streubereich lag in den verschiedenen Gesichtsfeldern zwischen 136 und 177 μm2 per Osteoblast. 400 Zellen wurden einzeln gemessen. Bei diesen war der Durchschnittswert per Osteoblast 143 μm2, mit einer Standard-Abweichung von 33. Die tägliche Anlagerungsrate während einer Periode von 8 Tagen war 3,12 μm (Standard-Abweichung 0,22); sie wurde mittels Tetracyclinmarkierung der Mineralisierungsfront gemessen. Dies ergab eine tägliche Produktionsrate der Matrix von etwa 470 μm3 per Osteoblast.
    Notes: Abstract The secretory territories of rat osteoblasts on the parietal bone were measured directly using scanning electron microscopy. The mean territory of 4620 cells in 19 fields was 154 μm2 per osteoblast. The range for the fields was 136 to 177 μm2 per osteoblast. Four hundred cells were measured individually—for these the mean value per osteoblast was 143 μm2 with a standard deviation of 33. The daily rate of apposition over an 8 day period was 3.12 μm (standard deviation 0.22) measured by tetracycline marking of the mineral front. This gave a daily matrix production rate of approximately 470 μm3 per osteoblast.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 14 (1974), S. 327-331 
    ISSN: 1432-0827
    Keywords: Bone ; Piezoelectricity ; Collagen ; Aging
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract The piezoelectric constant of mature and immature bone (defined herein) has been measured in an effort to determine whether it varies with age. It was found that the average value of the piezoelectric constantd 14 of femur from three week old calves was 58% of the value of femur from three year old bulls. The results were interpreted to indicate qualitative differences in the corresponding collagen matrices. Mature human tibia from males ranging in age from 21 to 53 years of age showed a small but significant increase ind 14 with age. Some data concerning diseased human bone, and well-preserved human bone excavated in Peru are also presented.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 14 (1974), S. 333-337 
    ISSN: 1432-0827
    Keywords: Bone ; Materials ; Histology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Des métaux poreux et des céramiques sont implantés dans l'osin vivo et sont prélevés, après différents intervalles, pour étudier histologiquement la colonisation tissulaire. Les implants prélevés sont fixés avec les tissus environnants et inclus dans des epoxy-résines, de faible viscosité. Les échantillons sont coupés à l'aide d'une scie diamantée et fixés sur des lames pétrographiques, pour être ensuite amincis à environ 75 μm. Ils sont légèrement colorés au bleu de méthylène et à l'alizarine rouge S, qui donne un bon contraste entre tissus durs et mous et démontrent la présence d'os calcifié dans les implants poreux métalliques et céramiques.
    Abstract: Zusammenfassung Poröse Metall- und Keramikstücke wurden in vivo in Knochen implantiert und nach verschiedenen Intervallen entnommen, um histologisch zu untersuchen, wie weit sie ins Gewebe eingewachsen waren. Die entnommenen Implantate mit dem sie umgebenden Gewebe wurden fixiert, dehydriert und in ein niedrigvisköses Epoxy-Harz eingebettet. Die Proben wurden mit einer Diamantsäge in dicke Schnitte zerteilt, auf Steinscheiben zementiert und von Hand auf etwa 75 μm geschliffen. Sie wurden mit Methylenblau und Alizarin-Rot S schwach gefärbt; dies ergibt einen großen Kontrast zwischen Knochen und Weichgewebe und zeigt die Bildung von verkalktem Knochen innerhalb poröser Metall- und Keramik-Implantate deutlich.
    Notes: Abstract Porous metals and ceramics were implanted in bonein vivo and retrieved at intervals for histological evaluation of tissue ingrowth. Recovered implants with surrounding tissues were fixed, dehydrated and embedded in a low-viscosity epoxy resin embedding medium. The embedded samples were cut into thick sections with a diamond saw, cemented to petrographic slides, and hand-ground to approximately 75 μm. They were lightly stained with methylene blue and Alizarin Red S, which provided great contrast between the bone and soft tissues, and clearly demonstrated the formation of calcified bone within porous metal and ceramic implants.
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  • 4
    ISSN: 1432-0827
    Keywords: Osteogenesis ; Osteoinduction ; Bone ; Matrix ; Cell
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract Bone matrix demineralized in 0.6 N HCl at 2° for 24 h and implanted in muscle in allogeneic rats possesses consistently reproducible bone morphogenetic activity. Experiments on implants of matrix, obtained from donors injected with3H-tyrosine or3H-tryptophan, or Na35SO4, suggest that bone morphogenetic property is a protein or apart of a protein that is (1) insoluble in buffer solutions, pH 3.6 and 5.0; (2) degraded in buffer solutions at pH 7.4 by an endogenous sulfhydryl-group neutral proteinase; (3) digested by trypsin at 15° within 8 h without solubilization of the helical regions, possibly even without degradation of the nonhelical ends of the bone collagen molecule, and without any loss of the periodic ultrastructure of the collagen fibrils; (4) degraded or removed by 0.1 N NaOH at 2° within 24 h without solubilization of collagen; (5) biologically active even after nitration of tyrosyl groups with tetranitromethane. The release of only one-third of the radioactivity with loss of nearly all yield of new bone by limited tryptic digestion of3H-borohydride-reduced matrix indicates that the bone morphogenetic response is the function of a non-collagenous component. Autoradiographs of implants of matrix with non-collagenous proteins labelled with3H-tryptophan,3H-tyrosine, or both3H-tyrosine and3H-phenyl-alanine demonstrate random dissemination of the radioactive constituents and no evidence of local transfer of labelled proteins or soluble protein derivatives. Hypothetically, the bone morphogenetic response is controlled by an insoluble acidic bone morphogenetic protein or polypeptide (BMP) and a soluble neutral proteinase (BMP-ase) resembling trypsin in activity except functionally more specific for BMP. Firmly bound but separable from bone collagen, BMP is one of many short-lived morphogenetic substances appearing and disappearing throughout embryonic development and persisting in postfetal life. Where the BMP receptor resides and how it activates cell mechanisms of differential repression and derepression of such genes as code for osteogenesis is unknown.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 15 (1974), S. 333-339 
    ISSN: 1432-0827
    Keywords: Vitamin D ; Bone ; Resorption ; Calcium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract A series of analogues of vitamin D have been tested for their ability to stimulate bone resorption in two test systems used previously to investigate the metabolites of vitamine D. These analogues were tested (a) by directly comparing their action on bone explants of mouse half-calvariain vitro, and (b) by injecting them into young mice and measuring the degree of resorptionin vitro when explants were prepared 18 hours after the injection. It is concluded that the key functional groups concerned with enhancing the activity of vitamin D3 are the 1α- and the 25-hydroxyl,both together; the cis ring structure for ring A appears necessary. 1α-Hydroxycholecalciferol (1α-OHD3) is about as active as 25-OHD3 in the direct test, but its potency is much nearer to that of 1,25-(OH)2D3 when tested by the second (indirect) method; it seems likely that 1α-OHD3 is converted into 1,25-(OH)2D3 in vivo. The results are discussed in relation to the designing of analogues for clinical and experimental use.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 16 (1974), S. 145-152 
    ISSN: 1432-0827
    Keywords: EHDP ; Bone ; Chemistry ; Serum ; Rabbits
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract The effects of disodium ethane-1-hydroxy-1,1-diphosphonate (EHDP) on bone and serum chemistry were investigated in adult rabbits. EHDP was administered by subcutaneous injection at doses of 0.25, 2.5 and 10 mg/kg body weight/day for of 28 days. Blood samples were obtained weekly from each rabbit and serum levels of total calcium, ionized calcium, inorganic phosphate and alkaline phosphatase were determined. At the end of the treatment period all rabbits were sacrificed and the tibiae removed for chemical analysis and histological evaluation. The effect of EHDP administration on serum chemistry was both dose- and time-related. The highest of the three doses, 10 mg/kg/day, resulted in a time-related decrease in total serum calcium. This dose also caused a rapid but transient reduction in serum ionized calcium. The effect of EHDP on serum inorganic phosphate was biphasic. Administration of 2.5 mg/kg/day resulted in a time-related elevation in this parameter, whereas the 10 mg/kg/day dose resulted in a time-related hypophosphatemic response. There were no significant drug-related changes in tibial fat-free dry weight, ash weight, total calcium or total phosphorus values. However, administration of 2.5 and 10 mg/kg/day EHDP resulted in increased osteoid tissue as measured histologically. These results are compared with data from other EHDP studies, and discussed in relation to the maturity and growth-state of the experimental animals.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 16 (1974), S. 261-275 
    ISSN: 1432-0827
    Keywords: Dentine ; Bone ; Mineralization ; Density gradient fractionation ; Proteoglycans
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract In order to obtain enough material to analyse the organic matrix of mineralizing tissue a technique for preparative separation according to the degree of mineralization was developed. The method employs ultracentrifugation of powdered material in density gradients made from acetone and bromoform. The density range of the fractions is checked by refractive index measurements of the gradient medium. The amount of the material in the fractions is checked by weighing and their degree of mineralization is estimated by determining the Ca/N and P/N ratios. The homogeneity of the fractions is determined by soft X-ray microscopy. Isolated dissected microscopic bone structure (osteones and lamellar bone fragments) with different degrees of mineralization were fractionated in this way. Chromatography on Sepharose 2B of proteoglycans from costal cartilage exposed to an acetone-bromoform gradient revealed no effect of the gradient medium on the molecular size of the proteoglycans.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 14 (1974), S. 153-160 
    ISSN: 1432-0827
    Keywords: Lysosomes ; Bone ; Resorption ; Osteoclast
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Des techniques histochimiques de microscope photonique et électronique montrent que les ostéoclastes métaphysaires chez des rats “sans incisive” présentent des quantités plus importantes de phosphatase acide, d'acryl sulfatase et de trimétaphosphatase acide lysosomiales. L'activité en phosphatase lysosomiale à pH neutre est aussi plus élevée dans les ostéoclastes métaphysaires, sauf dans les cellules situées sous la métaphyse, où l'enzyme est absente. L'absence de résorption de la matrice organique semble en rapport avec l'absence de bordures en brosse et une absence d'enzyme lysosomiale extracellulaire. Malgré cette absence, une dissolution de cristaux inorganiques a été mise en évidence au microscope électronique, suggérant que la dissolution minérale est un processus distinct de la désintégration enzymatique de la matrice organique.
    Abstract: Zusammenfassung Histochemische Techniken für Licht- und Elektronenmikroskopie zeigten, daß metaphysäre Osteoklasten “Schneidezahl-loser” (SL) Ratten erhöhte Mengen von lysosomaler saurer Phosphatase, von Arylsulfatase und von saurer Trimetaphosphatase enthielten. Die Aktivität der lysosomalen Phosphatase bei neutralem pH war in den metaphysären Osteoklasten ebenfalls erhöht, außer in den Zellen direkt unterhalb der Wachstumsplatte, wo dieses Enzym nicht vorkam. Es konnte überhaupt keine Resorption der organischen Matrix festgestellt werden, was übereinzustimmen schien mit der Abwesenheit eines gekräuselten Saumes und einer gleichzeitigen Abwesenheit des extrazellulären lysosomalen Enzyms. Trotzdem wurde im Elektronenmikroskop das Verschwinden anorganischer Kristalle festgestellt, was darauf schließen läßt, daß die Auflösung des Minerals nicht derselbe Vorgang ist wie die enzymatische Auflösung der organischen Matrix.
    Notes: Abstract Histochemical techniques for light and electron microscopy showed that metaphyseal osteoclasts in “incisors absent” rats contained greater than normal amounts of lysosomal acid phosphatase, aryl sulfatase and acid trimetaphosphatase. Lysosomal phosphatase activity at neutral pH was also elevated in the metaphyseal osteoclasts except in those cells immediately beneath the growth plate, where this enzyme was absent. The failure of any discernable resorption of organic matrix appeared to correlate with the absence of a ruffled border and a concomittant absence of extracellular lysosomal enzyme. Despite this failure, electron microscopic evidence of inorganic crystal removal was noted, suggesting that mineral dissolution represents a separate process from the enzymatic breakdown of organic matrix.
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 16 (1974), S. 13-36 
    ISSN: 1432-0827
    Keywords: Osteoclast ; Bone ; Resorption ; Crystals ; Organic-inorganic relationships
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract The organic-inorganic relationships in bone matrix undergoing osteoclastic resorption have been studied in rat tibial diaphyses using electron microscope techniques in an attempt to identify the steps of the resorption process. Results suggest that bone resorption occurs in two phases: the first, an extracellular phase, leads to bone matrix fragmentation and partial dissolution, and the second, an intracellular phase, to complete digestion of the breakdown products of the bone matrix. The first component of the bone matrix to be attacked by the osteoclast is the ground substance. This induces the release of the crystals lying between, and on, the collagen fibrils; any crystals lying within fibrils are released later, when the fibrils break up. As this stage proceeds, the collagen fibrils retain their normal intrinsic texture, but gradually loose their lateral aggregation, appearing as individual fibrils (some of them uncovered by crystals), mixed with fragments of fibrils and many free crystals. The loosened but otherwise structurally normal collagen fibrils, and their fragments, are strongly argyrophilic. Complete dissolution of the disaggregated fibrils occurs outside the cell, both in the resorption zone and in the initial portion of the channels of the ruffled border. The free crystals present in the resorption zone and those phagocytosed in cytoplasmic vacuoles are organic-inorganic structures, whose organic component (the crystal ghost) is, at least in part, of proteoglycan nature. Dissolution of inorganic material occurs within the cytoplasmic vacuoles of the osteoclasts. Results are viewed in relation to the process of bone resorption and, as far as crystal ghosts are concerned, to that of bone calcification. A tentative summary of the various steps involved in the mechanism of bone resorption is given.
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  • 10
    ISSN: 1432-0827
    Keywords: Bone ; Parathyroid ; 25-Hydroxycholecalciferol ; Adenosine 3′, 5′ cyclic monophosphate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract Phenytoin, at a concentration which is known to inhibit parathyroid extract-induced bone resorptionin vitro, has been shown to have no significant effect on either the cyclic AMP content of four-day-old mouse calvaria which had been in tissue culture for 48 h or on the increase in cyclic AMP content occurring after the addition of parathyroid extract to the medium. Phenytoin has also been shown to be an effective inhibitor of bone resorptionin vitro induced by 25-hydroxycholecalciferol. These observations suggest that the inhibitory effect of phenytoin on parathyroid extract and hormone-induced bone resorption takes place beyond the cyclic AMP stage.
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 16 (1974), S. 219-226 
    ISSN: 1432-0827
    Keywords: Bone ; Phosphate ; ATP ; Calcium ; Mitochondria
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract An active constituent of the leaves ofSolanum malacoxylon (SM) is shown to promote calcium resorption and citrate production in embryonic chick frontal bone culturedin vitro. When injected into rats, SM reduces the ATP content of liver and kidneys. This phenomenon may be related to the ability of SM to stimulate mitochondrial ATPase activity at pH 9.4. SM significantly reduces the concentration of phosphate necessary to alter the uptake of calcium and respiration of siolated mitochondria. The data suggest that SM influences calcium and phosphate metabolism by affecting ion movements into and out of mitochondria.
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    Anatomy and embryology 143 (1974), S. 159-183 
    ISSN: 1432-0568
    Keywords: Bone ; Femur ; Development ; Gravity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The significance of similitude principles for the postnatal development of the cross-sectional area at midlength of the human and rat femur has been subjected to an investigation based both on theory and on observation. Cross sections were taken from 69 femora of female Sprague-Dawley rats 34, 72, 102, and 840 days old and from the right human femora of 94 males and 58 females ranging from 1 day to 89 years of age. The regression of the square-root of the cross-sectional area divided by π on femur length is linear in the rats. The empirical regression line estimated by the method of least squares from the measurements and the theoretical curve calculated on the assumption of adaptive allometric growth and centrically applied loads are more or less alike in slope and elevation. The corresponding empirical relationship in the human femora turned out statistically nonlinear in the males and linear in the females. Comparing the empirical regression functions with five theoretical curves, it has been revealed that the observations are best approximated by two curves calculated on the assumption of centrically or eccentrically applied loads and adaptive allometric growth of the cross-sectional diameter. It was further uncovered that the cross-sectional diameters at midlength of the femur are not changed isometrically with femur length both in rats and in man. Considering a simple model of the human body in the stance phase of slow walking gait on the scale of a neonate and an adult male, the hypothesis was advanced that the stresses at midlength of the femur are not altered much while the femur grows from neonate to adult size, because the outer and inner radii of the femur actually change during growth in such a way that the effects due to scale are appropriately compensated.
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 14 (1974), S. 251-255 
    ISSN: 1432-0827
    Keywords: Cartilage ; Bone ; Vitamin A ; Phosphatases
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Au cours d'une étude du cartilage épiphysaire de poulets normaux et déficients en vitamine A, la composition organique et l'activité phosphatasique du cartilage au repos, du cartilage en voie d'ossification et de l'os nouvellement formé ont été mesurées. Le cartilage en voie d'ossification et l'os nouvellement formé ont un contenu plus élevé en matériel inorganique, phosphate et collagène que le cartilage au repos. Une déficience en vitamine A provoque une augmentation du contenu en phospholipide de tous les trois tissus. Le cartilage au repos, en cas de déficience en vitamine A, présente, après homogénéisation et centrifugation, un surnageant dont l'activité en phosphatase alcaline et en glycérophosphatase est plus élevée que celle des témoins. Il semble que les effets enzymatiques de l'avitaminose A soient liés à des altérations de la membrane lysosomiale avec décharge de phosphatases. La minéralisation normale semble aussi faire intervenir une activité phosphatasique.
    Abstract: Zusammenfassung Diese Arbeit beschreibt Untersuchungen des Epiphysenknorpels bei normalen Küken und solchen mit Vitamin-A-Mangel. Die organische Zusammensetzung und die Phosphatase-Aktivität in ruhendem Knorpel, ossifizierendem Knorpel und neugebildetem Knochen wurden gemessen. Der ossifizierende Knorpel und der neugebildete Knochen hatten einen höheren Gehalt an anorganischem Material, an Phosphat und Kollagen als der ruhende Knorpel. Vitamin-A-Mangel führte zu einem erhöhten Phospholipidgehalt in allen drei Geweben. Nach Homogenisierung und Zentrifugierung fand sich im Überstand des ruhenden Knorpels von Vitamin-A-Mangelgewebe eine höhere alkalische Phosphatase- und Glycero-phosphatase-Aktivität als bei den Kontrollen. Es wird angenommen, daß die Wirkung des Vitamin A-Mangels auf die Enzyme im Zusammenhang steht mit der Schädigung der lysosomalen Membran, wobei Phosphatasen freigesetzt werden, und daß die normale Mineralisierung die Phosphatasen-Aktivität ebenfalls anregt.
    Notes: Abstract This paper reports studies of the epiphyseal cartilage in normal and vitamin A deficient chicks. The organic composition and the phosphatase activity in the resting cartilage, ossifying cartilage and new bone were measured. The ossifying cartilage and new bone had a higher content of inorganic material, phosphate and collagen than the resting cartilage. Vitamin A deficiency caused increase in the phospholipid content of all three tissues. The resting cartilage from vitamin A deficient tissue had, after homogenisation and centrifugation, a supernatant with an activity of alkaline phosphatase and glycerophosphatase higher than that in control samples. It is considered that effects of vitamin A deficiency on enzymes are related to defects of the lysosomal membrane with release of phosphatases, and that normal mineralisation also involves phosphatases activity.
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  • 14
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 14 (1974), S. 283-289 
    ISSN: 1432-0827
    Keywords: Sodium fluoride ; Osteoporosis ; Bone ; Strength ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé L'utilisation thérapeutique de fluorure de sodium a été recommandée dans le traitement de diverses maladies osseuses ostéopéniques. Cet emploi est basé principalement sur les effects ostéosclérotiques bien connus du fluorure de sodium, mais on connait mal son effet sur la force de résistance osseuse. L'influence de diverses concentrations de fluorure de sodium sur la force de résistance osseuse de jeunes rats soumis à des régimes riches et pauvres en calcium a été étudiée. L'administration de fluorure de sodium augmente le diamètre osseux, indiquant une stimulation de la formation de l'os périosté, mais la force de résistance osseuse est réduite ou non modifiée par l'ingestion de fluor.
    Abstract: Zusammenfassung Die therapeutische Verwendung von Natriumfluorid ist für eine Anzahl von Knochenmangel-Krankheiten empfohlen worden. Die Empfehlungen basieren hauptsächlich auf den bekannten osteosklerotischen Wirkungen von Natriumfluorid; über dessen Effekt auf die Knochenstärke ist wenig bekannt. In dieser Arbeit wurde der Einfluß verschiedener Konzentrationen von Natriumfluorid auf die Knochenstärken von wachsenden Ratten mit hoher und niederer Calciumeinnahme untersucht. Die Verabreichung von Natriumfluorid erhöhte den Knochendurchmesser, was auf eine Stimulierung der Periostbildung hinwies, die Knochenstärke wurde jedoch durch Fluorideinnahme herabgesetzt oder nicht beeinflußt.
    Notes: Abstract The therapeutic use of sodium fluoride has been recommended in a variety of osteopenic bone diseases. The recommendations are based mainly on the known osteosclerotic effects of sodium fluoride and little information is available as to its effect on bone strength. The influence of various concentrations of sodium fluoride on bone strength in growing rats on high and low calcium diets was studied. The administration of sodium fluoride increased bone diameter, indicating stimulation of periosteal bone formation, but bone strength was reduced or not affected by fluoride ingestion.
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  • 15
    Electronic Resource
    Electronic Resource
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    Calcified tissue international 14 (1974), S. 291-299 
    ISSN: 1432-0827
    Keywords: Bone ; Collagenase ; Lysozyme
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Du lysozyme de blanc d'œuf, ainsi que des protéines basiques, telles que de l'histone et une base dépourvue de protamine, semblent inhiber la collagénase osseuse de souris. L'inhibition de collagénase osseuse de souris par le lysozyme est mise en évidence lorsque l'activité de la collagénase est étudiée en utilisant du collagène comme substrat à l'état solide, mais non lorsque le collagène est utilisé en solution. D'autre part, l'inhibition de l'activité en collagénase par l'histone et une base dépourvue de protamine est observée dans les deux systèmes. L'inhibition de collagénase ossuese de souris par des molécules polyanioniques est intéressante, étant donné que des travaux antérieurs ont montré que plusieurs molécules polyanioniques telles que l'héparine, le sulfate de dextrane et l'acide polyethylenesulfonique augmentent l'activité de collagénase osseuse de souris dans les mêmes conditions expérimentales. Comme le lysozyme est largement présent dans les tissus conjonctifs et que sa concentration carie avec l'ampleur du remaniement tissulaire, l'inhibition de la collagénase osseuse de souris suggère un role éventuel dans la régulation de la dégradation du collagène, pendant le remaniement des tissus collagéniquesin vivo au cours d'états normaux et pathologiques.
    Abstract: Zusammenfassung Lysozyme aus Hühnereiweiß sowie Basis-Proteine, wie z. B. Histon und Protamin-freie Basen, erwiesen sich als Hemmer der Mäuseknochen-Kollagenase. Diese Hemmung durch Lysozym wurde festgestellt, wenn für die Messung der Kollagenase-Aktivität Kollagen in Substanz als Substrat verwendet wurde, nicht aber, wenn das Substrat aus gelöstem Kollagen bestand. Andererseits wurde die Hemmung der Kollagenase-Aktivität durch Histon und Protamin-freie Basen in beiden Versuchssystemen festgestellt. Die Hemmung von Mäuseknochen-Kollagenase durch polykationische Moleküle ist interessant, vor allem im Hinblick auf frühere Feststellungen, daß mehrere polyanionische Moleküle, wie Heparin, Dextransulfat und Polyaethylensulfonsäure, die Aktivität der Mäuseknochen-Kollagenase unter denselben experimentellen Bedingungen erhöhen. Da Lysozym in Bindegeweben überall verteilt ist und da dessen Konzentration mit der Neubildungsrate des Gewebes variiert, läßt die Hemmung der Mäuseknochen-Kollagenase durch Lysozym dessen mögliche Rolle in der Regulierung des Kollagenabbaues vermuten, und zwar während der Neubildung von Kollagengeweben in vivo in normalen und pathologischen Zuständen.
    Notes: Abstract Egg white lysozyme, as well as basic proteins such as histone and protamine-free base, were found to inhibit mouse bone collagenase. The inhibition of mouse bone collagenase by lysozyme was detected when the activity of the collagenase was assayed using collagen as the substrate in the solid state, but not when the collagenase activity was assayed using collagen in solution as the substrate. On the other hand, the inhibition of collagenase activity by histone and protamine-free base was observed in both assay systems. The inhibition of mouse bone collagenase by polycationic molecules is interesting in light of previous findings that several polyanionic molecules, such as heparin, dextran sulfate and polyethylenesulphonic acid, enhance the activity of mouse bone collagenase under the same experimental conditions. Since lysozyme is widely distributed in connective tissues and its concentration varies with the rate of tissue remodeling, the inhibition of mouse bone collagenase by lysozyme suggests its possible role in the regulation of collagen degradation during the remodeling of collagenous tissuesin vivo during normal and pathological states.
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  • 16
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    Calcified tissue international 15 (1974), S. 11-20 
    ISSN: 1432-0827
    Keywords: Bone ; Growth ; Resorption ; Caudal ; Vertebra ; Fluorescence
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Une méthode de mesure de l'apposition et de la résorption osseuse est mise au point au niveau de la septième vertèbre caudale de jeunes rats, pesant 25–90 g, pendant la période de croissance. Cette pièce osseuse a des avantages certains par rapport à d'autres localisations, car elle est symétrique en coupe transversale et non affectée par des forces corticales. En utilisant trois marqueurs d'os différents, fluorescents en lumière ultra-violette, administrés à des intervalles de 3, 5 ou 7 jours, les modifications de croissance sont observées sur des coupes transversales centrales, non décalcifiées, de la septième vertèbre caudale. Une formation osseuse linéaire se développe à une vitesse moyenne de 10.0 μ/jour et une résorption linéaire de 6.1μ/jour est notée. Pendant la période de croissance observée, la formation osseuse s'observe exclusivement à la surface du périoste et la résorption se fait le long de la surface de l'endoste. A ce niveau l'os est totalement résorbé, chez des animaux de 25 g en 22–26 jours. Il semble que chez des animaux plus âgés, une formation osseuse endostée se développe rendant alors impossible toute étude prolongée dans cette région.
    Abstract: Zusammenfassung Es wird eine Methode zur Messung der Knochenbildungs- und Resorptionsgeschwindigkeiten im siebten Caudalwirbel junger Ratten während ihrer Wachstumsperiode von 25–90 g beschrieben. Dieser Knochen hat gegenüber jenen, die vorgängig untersucht wurden, den großen Vorteil, in transversalen Schnitten symmetrisch und unbeeinflußt von kortikalen Unregelmäßigkeiten zu sein. Die Art der Wachstumsveränderungen wurden an nichtentkalkten zentralen Transversalschnitten der siebten Caudalwirbeln bestimmt; dazu wurden drei verschiedene, farbige, im UVbereich fluoreszierende Knochenmarkierungssubstanzen verabreicht und zwar in 3-, 5- oder 7tägigen Intervallen. Die lineare Knochenbildung fand mit einer mittleren Geschwindigkeit von 10,0 μ pro Tag statt, die lineare Knochenresorption mit einer solchen von 6,1 μ pro Tag. Während der untersuchten Wachstumsperiode fand die Knochenbildung ausschließlich an der Periostoberfläche und die Knochenresportion an der endostalen Oberfläche statt. Der Knochen, der beim 25 g schweren Tier an diesem Ort vorlag, verschwand durch die endostale Resorption innerhalb von 22–26 Tagen
    Notes: Abstract A method for measuring bone formation and resorption rates in the seventh caudal vertebra of young rats during the growth period from 25–90 g is reported. This bone site has unique advantages over those previously studied, being symmetrical in transverse section and uncomplicated by cortical drift. Utilising three different coloured ultraviolet fluorescent bone labelling substances administered at either 3, 5 or 7 day intervals, the nature of growth changes was determined from undecalcified central transverse sections of the seventh caudal vertebrae. Linear bone formation occurred at a mean rate of 10.0 μ/day and linear bone resorption at 6.1 μ/day. During the growth period studied, bone formation occurred exclusively on the periosteal surface and bone resorption on the endosteal surface. Bone existing in this site in 25 g animals was completely removed by endosteal resorption within 22–26 days. Evidence exists that in older rats endosteal bone formation occurs and renders the site unsuitable for long term studies.
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  • 17
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    Calcified tissue international 15 (1974), S. 315-324 
    ISSN: 1432-0827
    Keywords: Bone ; Mineral ; Osteogenesis ; Interference microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract A method based on tetracycline labeling was developed for selecting, in frozen sections of fetal mouse femur, bone foci approximately 6, 24, 48 and 72 h of age. Microinterferometric measurements of these foci permitted a calculation of the effective thickness (t) and refractive index (n) of each focus. After demineralizing the sections by a method which left the organic portion of the bone intact, the foci were re-measured andt andn of the organic compartment of each focus were determined;t andn of the mineral compartment were calculated by difference. A sharp decrease and subsequent rise in then of whole bone occurred between 6 and 48 h. These changes derived from the mineral compartment, and were thought to have resulted from the formation of amorphous calcium phosphate and hydroxyapatite, respectively. The mineral present in 6 h foci, however, was believed to be some precursor of amorphous calcium phosphate.
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  • 18
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    Calcified tissue international 15 (1974), S. 329-332 
    ISSN: 1432-0827
    Keywords: Microradiography ; Bone ; X-ray
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract A low cost, self-contained, commercially available, X-ray apparatus which possesses the essential qualifications necessary to produce high resolution microradiographs of undecalcified bone is described. The widespread current use of this machine in pathology laboratories may make purchase of such a unit optional.
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  • 19
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    Calcified tissue international 16 (1974), S. 73-88 
    ISSN: 1432-0827
    Keywords: Dentine ; Bone ; Histocytochemistry ; Physiological Calcification
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract Histochemical methods were used to detect differences in amino acid reactive groups between bone and osteoid, dentine and predentine. Three major differences were found: Predentine and osteoid contained more reactive sulphydryls than their mineralized counterparts. The greatest reaction for this reactive group was obtained at the mineralizing front. Dentine and bone contained a complex between amino and carboxylic acid groups; predentine and osteoid did not have this complex and carboxylic acid residues were less in these tissues. Dentine and bone contained much greater amounts of histidine or a histidine-like component than did predentine and osteoid. It is proposed that these differences are involved in initiation of mineralization.
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  • 20
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    Calcified tissue international 16 (1974), S. 169-182 
    ISSN: 1432-0827
    Keywords: Histochemistry ; Alkaline phosphatases ; Calcification ; Bone ; Teeth
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract Activity of alkaline phosphatases in unfixed cold microtome setions from the lower first molar area of newborn mice was recorded by histochemical methods. A substrate specificity test included the following phosphate compounds: ATP, CTP, GTP, UTP, ADP, AMP, GP, PPi, MDP and naphthol AS-TR phosphate. Intense staining was obtained in osteoblasts, stratum intermedium of the enamel organ and odontoblasts with all the substrates, except PPi and MDP. Staining of skeletal muscle fibres was obtained only with triphosphates as substrates. Addition of-SH groups decreased the hydrolysis of triphosphate compounds in cells involved in mineralization while the hydrolysis of monophosphate was inhibited. In contrast triphosphatase activity in striated muscle was enhanced when-SH compounds were added. Demineralization with EDTA diminished the cytoplasmic staining but induced a nuclear staining in hard tissue forming cells when triphosphates were used as substrates. No cytoplasmic and only slight nuclear staining was seen with GP or AMP as substrates. The triphosphate hydrolyzing capacity of tongue muscle fibres was, however, increased after the decalcification treatment. Addition of Mg2+ ions to the incubation media distinctly lowered the hydrolysis of triphosphates in the investigated tissues whereas the hydrolysis of ADP, AMP, GP and naphthol AS-TR phosphate remained unchanged. In view of the findings the triphosphatase activities at alkaline pH of muscle fibres and of cells related to hard tissue formation are considered to be due to activity of separate enzymes. The orthophosphate liberating enzyme activities at alkaline pH in osteoblasts, stratum intermedium and odontoblasts may be expressions of the catalytic functions of one common enzyme. Furthermore, the results indicate that CaATP might be the substrate used by the alkaline ATPase in mineralizing areas.
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  • 21
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    Calcified tissue international 16 (1974), S. 239-250 
    ISSN: 1432-0827
    Keywords: EHDP ; Bone ; Collagen ; Histology ; Bone chemical analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract The purpose of this study was to determine the short-term effects of various systemic doses of disodium ethane-1-hydroxy-1,1-diphosphonate (EHDP) on bone organic matrix and to relate these effects to the corresponding dose-related changes in bone mineral. EHDP was administered daily by subcutaneous injection at doses of 0.25, 2.5 and 40 mg/kg body weight for periods of one and two weeks. At both time intervals, rat tibiae were quantitatively analyzed for mineral content (ash, calcium and phosphorus) and for organic matrix content (matrix weight, nitrogen and certain amino acids). The latter data were correlated with semiquantitative histological analyses of the tibiae. Results of this study demonstrate that the short term effects of EHDP on bone chemistry and histology are variable and depend on the systemic dose and the duration of treatment. Systemic doses of 0.25 and 2.5 mg/kg EHDP following daily administration for one week resulted in transitory decreases in bone mineral content compared to controls. Following two weeks of treatment, both of these dose levels resulted in increased bone mineral content and, in addition, the 2.5 mg/kg dose resulted in tibiae which contained more organic matrix compared to control bones. In contrast to the low dose effects, a high systemic dose of EHDP—e.g. 40 mg/kg administered daily for 1 or 2 weeks—appears to act solely by inhibiting mineralization of newly-formed matrix.
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  • 22
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    Calcified tissue international 14 (1974), S. 31-48 
    ISSN: 1432-0827
    Keywords: Bone ; Cartilage ; Calcification ; Collagen ; Phosphate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Une méthode pour l'étude de la croissance des os longs de foetus de rat, en culture d'organe, dans un milieu chimiquement défini, a été mise au point. Les extrémités cartilagineuses et les parties centrales de l'os sont analysées séparément pour leur croissance et minéralisation en étudiant leur contenu en collagène, calcium et phosphate, poids sec, et incorporation de proline marquée en hydroxyproline. La croissance et la minéralisation des parties centrales osseuses sont plus lentes dans un milieu chimiquement défini qu'in vivo. La croissance peut être accélérée en ajoutant au milieu des acides aminés non essentiels, de l'albumine ou du sérum. Les extrémités cartilagineuses présentent une augmentation plus importante en poids et contenu en collagène que les parties centrales et l'adjonction de diverses substances a moins d'effet sur la croissance. La croissance et la minéralisation des parties centrales sont augmentées en élevant la concentration du milieu en phosphate de 1.5 à 4.5 mM, avec ou sans adjonction de sérum ou d'albumine. A une concentration faible de calcium (0.5 mM), la croissance et la minéralisation des parties centrales sont arrêtées. A une concentration faible en magnésium (0.5 mM), la minéralisation est augmentée, mais la croissance est arrêtée.
    Abstract: Zusammenfassung Es wird eine Methode beschrieben, mit welcher das Wachstum der Röhrenknochen von Rattenembryos in einem chemisch bestimmten Medium in Organkultur untersucht werden kann. Die Knorpelenden und Knochenschäfte wurden gesondert auf Wachstum und Mineralisation geprüft, indem Collagen-, Calcium- und Phosphatgehalt, das Trockengewicht und der Einbau von markiertem Prolin in Hydroxyprolin gemessen wurden. Wachstum und Mineralisation des Knochenschaftes waren langsamer in einem chemisch bestimmten Medium als in vivo. Das Wachstum konnte beschleunigt werden, indem dem Medium nicht-essentielle Aminosäuren, Albumin oder Serum beigegeben wurden. Die Knorpelenden zeigten eine viel stärkere Zunahme an Gewicht und Collagengehalt als die Schäfte, und Anreicherung des Mediums hatte weniger Wirkung auf ihr Wachstum. Das Wachstum und die Mineralisation der Knochenschäfte nahmen zu, wenn die Phosphatkonzentration im Medium zwischen 1,5 und 4,5 mM erhöht wurde, und zwar unabhängig davon, ob dem Medium Serum oder Albumin beigegeben wurde oder nicht. Bei niederer Calciumkonzentration (0,5 mM) im Medium wurden Wachstum und Mineralisation der Knochenschäfte beeinträchtigt. Bei niedriger Magnesiumkonzentration (0,5 mM) wurden die Mineralisation erhöht, das Wachstum hingegen gehemmt.
    Notes: Abstract A method for studying the growth of fetal rat long bones in a chemically defined medium in organ culture is described. Cartilage ends and bone shafts were analyzed separately for growth and mineralization by measuring the collagen, calcium, and phosphate content, dry weight, and incorporation of labeled proline into hydroxyproline. Growth and mineralization of the bone shaft were slower in a chemically defined medium thanin vivo. Growth could be enhanced by supplementation of the medium with non-essential amino acids, albumin or serum. Cartilage ends showed a greater increase in weight and collagen content than the shafts, and medium supplements had less effect on their growth. Bone shaft growth and mineralization were enhanced by increasing medium phosphate concentration over a range of 1.5 to 4.5 mM whether or not the medium was supplemented with serum or albumin. At a low medium calcium concentration (0.5 mM) bone shaft growth and mineralization were impaired. At a low magnesium concentration (0.5 mM) mineralization was enhanced, but growth was impaired.
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  • 23
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    Calcified tissue international 14 (1974), S. 83-86 
    ISSN: 1432-0827
    Keywords: Bone ; Reproductive cycle ; Pigeons ; Amorphous ; Crystalline
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Une étude de diffraction aux rayons X, au cours du cycle de ponte d'oeufs de pigeon, a été entreprise pour évaluer les modifications de la proportion entre les phases de phosphate de calcium amorphe et apatitique. La partie médullaire du fémur de pigeon est totalement résorbée au cours du cycle de reproduction. Au cours de ce processus, l'os contenant plus de phosphate de calcium amorphe est résorbé avant celui qui est riche en cristaux. Ainsi l'os à contenu amorphe plus élevé est métaboliquement plus actif que l'os riche en cristaux. L'os médullaire qui peut être induit chez le pigeon mâle par traitement aux oestrogènes, ressemble, au point de vue diffraction aux rayons X, à l'os médullaire des femelles au début du cycle de reproduction.
    Abstract: Zusammenfassung Mittels Röntgen-Diffraktion wurden die Veränderungen in den prozentualen Mengen der amorphen und der kristallinen Calciumphosphat-Phasen im Femur der Taube während des Eierlegens untersucht. Der medulläre Teil des Taubenfemur wird während des Fortpflanzungscyclus vollständig resorbiert. Dabei wird der Teil des Knochens, der mehr amorphes Calciumphosphat enthält, vor dem kristallreichen Teil resorbiert. Daraus folgt, daß der Stoffwechsel des Knochens mit höherem amorphem Gehalt aktiver ist als derjenige des Knochens mit höherem kristallinem Gehalt. Weiter konnte mittels Röntgendiffraktion festgestellt werden, daß der medulläre Knochen, welcher in männlichen Tauben durch Oestrogenbehandlung erzeugt werden kann, dem weiblichen medullären Knochen am Anfang des Fortpflanzungscyclus gleicht.
    Notes: Abstract This is an X-ray diffraction study of the changes in the proportional amounts of the amorphous and apatitic calcium phosphate phases in pigeon femur during the egg-laying cycle. The medullary portion of pigeon femur is completely resorbed in the reproductive cycle. In this process the portion of bone which is higher in amorphous calcium phosphate is resorbed before the crystal-rich portion. Thus, bone with a higher amorphous content is more metabolically active than more crystalline bone. Finally, medullary bone which can be produced in male pigeons by estrogen treatment was found by X-ray diffraction to resemble female medullary bone at the beginning of the reproductive cycle.
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  • 24
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    Calcified tissue international 14 (1974), S. 49-58 
    ISSN: 1432-0827
    Keywords: Glycosaminoglycans ; Intracellular ; Chondrocytes ; Cartilage ; Embryonal ; Bone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Les glycosaminoglycanes acides de chondrocytes isolés, en suspension, sont étudiés. La matrice extracellulaire est isolée par traitement successif à la trypsine et à la collagénase d'os d'embryons de poulet, âges de 15 à 17 jours. Après digestion à la papaïne et élimination des acides nucléïques par traitement à la DNAse et à la RNAse, les glycosaminoglycanes sont précipités par le CPC et isolés sous la forme de leur sel sodique. Les analyses des propriétés de solubilité du CP glycosaminoglycane par le microfractionnement d'Antonopoulos et coll. (1964) révèlent la présence de glycosaminoglycanes intracellulaires de poids moléculaire et/ou de densité de charge nettement plus faibles que ceux de la matrice extracellulaire. Sur des électrophorèses de microzones, une petite partie des glycosaminoglycanes intracellulaires isolées présente une mobilité similaire à celle des solutions témoins de sulfate de chondroitine, alors que la portion la plus importante ne se déplace qu'à mi-distance de l'acide hyaluronique et montre une large trainée, indiquant une faible charge négative. Ce fait semble dû à une perte de l'influence de régulation des composants matriciels éliminées, sur la synthèse des glycosaminoglycanes et au rejet dans le milieu de glycosaminoglycanes initialement synthétisé. Pour la première fois, une faible quantité d'acide hyaluronique intracellulaire est mise en évidence par une mobilité électrophorétique typique.
    Abstract: Zusammenfassung Saure Glykosaminoglycane von isolierten Chondrocyten in Suspension wurden untersucht, und die extracelluläre Matrix von 15–17 Tage alten Knochen von Kükenembryos wurde durch die aneinanderfolgende Behandlung mit Trypsin und Collagenase erhalten. Nach der Papain-Verdauung und Beseitigung der Nucleinsäuren mittels DNS- und RNSase-Behandlung wurden die Glykosaminoglycane mit CPC gefällt und als Natriumsalz isoliert. Untersuchungen der Löslichkeit der CP-Glykosaminoglycane mittels des Mikrofraktionierungsverfahrens von Antonopouloset al. (1964) zeigten intracelluläre Glykosaminoglycane mit meist niedrigerem Molekulargewicht und/oder niedrigerer Ladungsdichte als diejenigen der extracellulären Matrix. In der Mikro-Zonen-Elektrophorese zeigte nur ein kleiner Teil der isolierten intracellulären Glykosaminoglycane eine Mobilität, die dem Standard des Chondroitinsulfats entsprach. Der größte Teil legte nur die halbe Distanz der Hyaluronsäure zurück und zeigte breites “Tailing”, was auf eine niedrigere negative Ladung hindeutet. Die Ursache dafür wurde interpretiert als Verlust eines regulierenden Einflusses der entfernten Matrixkomponenten auf die Glykosaminoglycan-Synthese und als Abgabe ursprünglich synthetisierter Glykosaminoglycane in das Medium. Es wurde erstmals, anhand der typischen elektrophoretischen Beweglichkeit, eine kleine Menge von intracellulärer Hyaluronsäure nachgewiesen.
    Notes: Abstract Acid glycosaminoglycans were studied from isolated chondrocytes in suspension and the extracellular matrix obtained by sequential trypsin and collagenase treatment of 15- to 17-day-old embryonic chick bone. After papain digestion and removal of the nucleic acids by treatment with DNAse and RNAse, the glycosaminoglycans were precipitated by CPC and isolated as their sodium salt. Analyses of the CP-glycosaminoglycan solubility properties with the microfractionation procedure of Antonopouloset al. (1964) showed intracellular glycosaminoglycans of predominantly lower molecular weight and/or charge density than those of extracellular matrix. On micro-zone electrophoresis, only a minor part of the isolated intracellular glycosaminoglycans showed a mobility similar to that of the chondroitin sulphate standards while the major part moved only half the distance of hyaluronic acid and showed broad tailing, indicating a low negative charge. This was considered to be due to loss of a regulatory influence of the removed matrix components upon glycosaminoglycan synthesis and to release of originally synthesized glycosaminoglycans into the medium. For the first time, a small amount of intracellular hyaluronic acid was shown by typical electrophoretic mobility.
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  • 25
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    Calcified tissue international 14 (1974), S. 161-168 
    ISSN: 1432-0827
    Keywords: Diphosphonates ; Osteoid Synthesis ; Hydroxyproline ; Bone ; Formation-Resorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Deux diphosphonates, à savoir l'éthane-1-hydroxy-1,1-diphosphonate (EHDP) et le dichlorométhane diphosphonate (Cl2MDP), inhibentin vitro la résorption osseuse qui est stimulée soit par la parathormone ou par voie intrinsèque dans un système de culture d'os en remaniement. Alors que le Cl2MDP est plus efficace que l'EHDP dans l'inhibition de la résorption, ce fait semble en rapport avec une diminution de le formation de tissu ostéoide. Il s'en suit une diminution biochimique et morphologique marquée du remaniement osseux avec le Cl2MDP à une concentration équivalent à 10 μg de phosphore/ml de milieu de culture. La différence d'activité entre l'EHDP et le Cl2MDP peu être liée à leur affinité relative pour les surfaces du minéral osseux et, par suite, à leur concentration effective dans la fluide extracellulaire osseux. Les diphosphonates pourraient aussi affecter l'os indirectement si l'on admet que le degré de minéralisation de la matrice est important pour l'induction et la régulation de l'activité ostéoblastique dans l'os en voie de remaniement.
    Abstract: Zusammenfassung Zwei Diphosphonate, Aethan-1-hydroxy-1,1-diphosphonat (EHDP) und Dichloromethylen-Diphosphonat (Cl2MDP) hemmen in vitro die Knochenresorption. Diese wird verfolgt entweder mittels Stimulierung durch PH oder in einem Kultursystem, in welchem normale Knochenneubildung stattfindet. Während Cl2MDP die Resorption wirksamer hemmt als EHDP, scheint es ebenfalls eine Verminderung der Osteoidbildung zu verursachen. Dies bewirkt eine deutliche biochemische und morphologische Herabsetzung der Knochenneubildung, bei einer Cl2MDP-Konzentration von 10 μg Phosphor/ml Kulturmedium. Die unterschiedliche Wirksamkeit von EHDP und Cl2MDP läßt sich wahrscheinlich auf ihre verschiedenen Affinitäten zu der Oberfläche des Knochenminerals und somit auf ihre tatsächliche freie Konzentration in der extracellulären Flüssigkeit des Knochens zurückführen. Ausgehend von der Annahme, daß die Anregung und Regulierung der Osteoblasten-Aktivität bei der Knochenneubildung vom Ausmaß der Matrix-Mineralisation bestimmt wird, läßt sich die Vermutung aufstellen, daß die Diphosphonate die Knochenbildung auch indirekt beeinflussen können.
    Notes: Abstract Two Diphosphonates, ethane-1-hydroxy-1,1-diphosphonate (EHDP) and dichloromethylene diphosphonate (Cl2MDP) inhibitin vitro bone resorption, which is either stimulated by parathyroid hormone or intrinsic in a bone remodeling culture system. While Cl2MDP is more effective than EHDP in inhibiting resorption, it also appears to result in a related diminution in osteoid formation. This effect causes a marked biochemical and morphological depression of bone remodelling with Cl2MDP at a concentration equivalent to 10-μg-phosphorus/ml of culture medium. The difference in activity between EHDP and Cl2MDP may be related to their relative affinities for the bone mineral surfaces and hence their effective free concentration in the bone extracellular fluid. It is hypothesized that diphosphonates may also affect bone formation indirectly if one assumes that the degree of mineralization of the matrix is important in the induction and regulation of osteoblastic activity in remodelling bone.
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  • 26
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    Calcified tissue international 14 (1974), S. 195-210 
    ISSN: 1432-0827
    Keywords: Bone ; Fossil bone ; Bone resorption ; Boring channels ; Fungi
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé L'action ostéoclasique exercée par un champignon appartenant au genreMucor sur des os inhumés a été étudiée au point de vue morphologique. L'érosion ossuse donne lieu à des cavités et à des canalicules de percement, dont les parois apparaissent régulièrement calcifiées jusqu'a l'interface avec le champignon, ce qui veut dire que la réabsorption intéresse en même temps la matrice organique et les cristallites. Au contraire des ostéoclastes, la membrane du champignon ne montre jamais un bord en brosse au niveau des points où elle se met en contact avec le tissu osseux. De même l'examen au microscope électronique ne décele apparemment aucun passage de matériel dans l'épaisseur de la membrane ainsi que dans le protoplasme du champignon, ce qui porte à admettre qu'un processus de solubilisation a lieu au préalable. Seulement dans le cas où le champignon présente des phénomènes de vieillissement, des données font prévoir la libération d'une substance capable de décalcifier la matrice organique. Tous les résultats ci-dessu sont discutés de façon analytique et comparés à ceux fournis par les canalicules de percement des os fossiles.
    Abstract: Zusammenfassung Die osteoklastische Aktivität eines der Mucor-Gattung angehörenden Pilzes auf begrabene Knochen wurde morphologisch untersucht. Die Wirkung dieses Pilzes in der Knochenerosion führt zu Resorptionshöhlen und Bohrkanälen, deren Wände scharf und bis zur Oberfläche gut verkalkt sind; das bedeutet, daß die Knochenresorption gleichzeitig die Kristalliten und die organische Matrix in Mitleidenschaft zieht. Im Gegensatz zu den normalen Osteoklasten zeigt die Membran des Pilzes an den Berührungsstellen mit dem Knochengewebe keinen Bürstensaum. Ebenfalls läßt eine elektronenmikroskopische Untersuchung keinen Durchgang von Substanzen durch die Membran und das Protoplasma des Pilzes erkennen, so daß man annehmen muß, daß vorher ein Auflösungsprozeß stattgefunden hat. Die Vermutung liegt nahe, daß eine Substanz, welche den anorganischen Knochenanteil aufzulösen vermag, sich
    Notes: Abstract A morphological investigation has been carried out on the osteoclastic activity revealed by a fungus of theMucor genus on buried bone. The hallmark of its activity in eroding bone is the finding of resorption pits and boring channels whose walls are sharp and well calcified up to the free edge, suggesting that bone resorption affects crystallites and the organic matrix simultaneously. Unlike normal osteoclastic cells, the fungal membrane in contact with the bone shows no brush border. As the electron microscope reveals no migration of material to the fungal membrane and its protoplasm, the view is expressed that the material which reaches the fungus has been previously solubilized. There is good reason for supposing that a substance capable of solubilizing the inorganic bone fraction spreads freely through bone tissue, decalcifying the matrix, where, but only where, hyphae show the effects of ageing. All the findings are thoroughly discussed and compared with those furnished by the boring channels in fossil bone.
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  • 27
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    Calcified tissue international 14 (1974), S. 245-249 
    ISSN: 1432-0827
    Keywords: Bone ; Repair ; Histology ; Implant
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Um modèle expérimental, destiné à l'étude de la cicatrisation osseuse, est mis au point. Il permet d'obtenir du tissu osseux pour des études qualitatives et quantitatives. Des tubes de nylon sont implantés dans l'alvéole d'incisives extraites de cobayes. Une étude histologique de coupes longitudinales montrent que les implants de nylon ne retardent pas la cicatrisation des lésions osseuses et contiennent suffisamment de tissus pour des études biochimiques.
    Abstract: Zusammenfassung Es wurde ein Modellsystem zum Studium der Knochenwiederherstellung entwickelt, mit Hilfe dessen man von dem sich wiederbildenden Knochengewebe Proben für die qualitative und quantitative Bestimmung entnehmen kann. Dazu wurden in die Alveolen extrahierter Schneidezähne von Meerschweinchen Nylonschläuchlein eingelegt. Die histologische Untersuchung von Längsschnitten zeigte, daß die Nylonimplantate den Wiederherstellungsprozeß des Knochendefektes nicht verzögerten, daß sie herauspräpariert werden konnten und genügend Gewebe enthielten, um für biochemische Untersuchungen verwendet zu werden.
    Notes: Abstract A model system for the study of bone repair has been developed which allows the recovery of repairing osseous tissue for qualitative and quantitative evaluation. Nylon tubes were implanted in the alveoli of extracted incisors in guinea pigs. A histological study of longitudinal sections showed that the nylon implants did not delay the reparative processes of the bony defect, could be dissected out and contained sufficient tissue to be used in biochemical studies.
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  • 28
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    Calcified tissue international 15 (1974), S. 45-54 
    ISSN: 1432-0827
    Keywords: Bone ; Fluoride ; Microhardness ; Mineralization ; Strength
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract Microhardness was measured in sampling sites in the tibial diaphysis of control rats that received less than 1 ppm fluoride in the drinking water, and experimental rats that received 30, 90 and 120 ppm fluoride in the drinking water for 17 days. The latter dose was toxic, as evidenced by a decreased final body weight in this group. By means of tetracycline labelling, it was possible to measure bone hardness in four zones of increasing bone age: I) 3 days, II) 8 days, III) 13 days and IV) 22 days. Zones I through III represented bone formed during fluoride treatment, and Zone IV bone formed before fluoride treatment. In the control group, microhardness increased from Zone I to II, probably because mineral concentration was relatively low in Zone I, and remained constant thereafter. In the 90 and 120 ppm fluoride-treated groups, maximum microhardness was not achieved until Zone III. This delay was probably due to the fact that fluoride in large doses inhibits the rate of mineralization. In the 30 ppm fluoride-treated group, there was no delay in achievement of maximum microhardness; microhardness values in Zones I and III were greater than those in control animals, and microhardness in Zone III was higher than that in Zone IV. These results show that: 1) bone microhardness is increased in bone formed during fluoride treatment in rats given 30 ppm fluoride in the drinking water, 2) toxic doses of fluoride delay, but do not prevent achievement of normal maximum microhardness, and 3) changes in microhardness are seen only in bone formed during fluoride treatment.
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  • 29
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    Calcified tissue international 15 (1974), S. 71-76 
    ISSN: 1432-0827
    Keywords: Bone ; Calcium ; Deficiency ; Osteoporosis ; Species
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract 21-day-old rats and mice were fed a low-calcium diet (0.02% Ca) or a normal diet (0.5% Ca) for two weeks. Administration of the low-calcium diet resulted in greater decreases in femur ash content and serum calcium in rats than in mice. Microscopic examination revealed that metatarsal bones from a majority of the rats fed a low-calcium diet displayed moderate or severe osteoporotic changes whereas bones from mice were either normal or displayed only slight osteoporotic changes under the same experimental conditions. These results indicate that mice are better able to adapt to a low-calcium diet than are rats of the same age.
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  • 30
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    Calcified tissue international 15 (1974), S. 111-123 
    ISSN: 1432-0827
    Keywords: Fluoride ; Calcium ; Phosphorus ; Bone ; Periosteum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Une méthode d'estimation de la surface périostée de l'os en voie de minéralisation est mise au point et appliquée à des porcs recevant 2 mg de fluorure par Kg de poids et par jour pendant 10 mois. L'adjonction de fluor intervient significativement dans le cas d'une déficience en calcium et phosphore. La surface en voie de minéralisation est nettement réduite. Lorsque le calcium et phosphore sont normaux, l'addition de fluorure augmente nettement la surface en voie de minéralisation. Le microscope électronique à balayage permet de mettre en évidence au niveau de l'os une perte de l'orientation longitudinale des fibers et des surfaces poreuses irrégulières chez les animaux soumis au floor.
    Abstract: Zusammenfassung Zur Bestimmung der verkalkenden Oberfläche des Periosts wurde eine Methode entwickelt und bei Schweinen angewandt, welche während etwa 10 Monaten 2 mg Fluorid per kg Körpergewicht und per Tag erhalten hatten. Dieses zusätzliche Fluorid hatte eine signifikante Wirkung bei Calcium- und Phosphormangel. Die verkalkende Oberfläuche ging stark zurück, während jedoch, wenn kein Calcium- und Phosphormangel bestand, das zusätzliche Fluorid die verkalkende Oberfläche vergrößerte. Beobachtungen mit dem Raster-Elektronenmikroskop am Knochen zeigten, daß die Längsorientierung der Fasern fehlte und daß Knochen von mit Fluorid gefütterten Tieren unregelmäßige, poröse Oberflächen aufwiesen.
    Notes: Abstract A method for estimating periosteal bone-mineralizing surface was developed and applied to swine fed 2 mg of fluoride/kg of body weight/day for about 10 months. Added fluoride interacted significantly with calcium and phosphorus deficiency. Mineralizing surface was greatly reduced, whereas when calcium and phosphorus were adequate, added fluoride greatly increased mineralizing surface. Scanning electron microscope observations of bone disclosed loss of longitudinal orientation of fibers and irregular porous surfaces in bone from fluoride-fed animals.
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  • 31
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    Calcified tissue international 15 (1974), S. 125-132 
    ISSN: 1432-0827
    Keywords: Bone ; Collagen ; Formic Acid ; Crosslinkages ; Cyanogen Bromide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract Bovine and chicken bone collagens have been solubilized and presumably denatured (gelatin) by treatment of demineralized, powdered tissue with 70% formic acid. Short periods of extraction such as four hours at 30°, conditions commonly used during cyanogen bromide cleavage of collagen, solubilized 50% and 15% of the chicken and bovine bone collagens respectively. Treatment of the tissues with sodium borohydride partially inhibited the extraction of collagen from chicken bone, but had little effect on the extraction of calf bone collagen. The heterogeneity of the bone gelatin from both species on disc electrophoretic analysis suggested that peptide bonds had been cleaved in some of the collagen chains during exposure to formic acid, thus facilitating the solubilization of the bone collagen as the gelatin. Analysis of the collagen extracted from chicken bone for reducible crosslinks indicated that a large proportion of these bonds had remained intact, in contrast to a previous finding that most of these crosslinks were destroyed in bone gelatin extracted by 4 M CaCl2, at pH 7.0. The stability of the major reducible crosslinks in bone collagen to severe acid conditions may explain in part some of its unique properties, such as its failure to swell or be solubilized in dilute acid, which distinguish it from soft tissue collagens.
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  • 32
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    Calcified tissue international 15 (1974), S. 173-179 
    ISSN: 1432-0827
    Keywords: Bone ; Strength ; Tension ; Compression
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract A simple method is described for visualising regions of bone that have yielded in tension. The appearance of such regions is quite different from that of regions that have yielded in compression. The significance of these findings is discussed.
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  • 33
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    Calcified tissue international 15 (1974), S. 189-199 
    ISSN: 1432-0827
    Keywords: Bone ; Densitometry ; X-ray ; Radiation ; Specific gravity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract X-ray and γ-radiation techniques for evaluating bone density under field conditions in cattle and sheep were investigated. The best results were obtained from measurements of the density of radiographs of tibial tarsal bones of sheep and from the absorption of γ-radiation of the tibial tarsal bones of sheep and the fibular tarsal bones of cattle. The γ-radiation techniques may be carried out rapidly under field conditions (up to 30 animals an hour) and bone density can be estimated with a standard error of 0.042–0.046 SG units.
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  • 34
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    Calcified tissue international 15 (1974), S. 181-188 
    ISSN: 1432-0827
    Keywords: Biopsy ; Bone ; Calcium ; Phosphorus ; Specific gravity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract The specific gravities (SG) of bone samples taken from various parts of the skeleton of cattle and sheep were determined gravimetrically in an effort to establish which sites give the most reproducible and uniform results, so that between animals, or sequential within animals, comparisons may be made with maximum sensitivity. Samples obtained from the mandible of sheep and the rib of cattle and sheep were found to be too variable to be useful for most purposes. Best results were obtained using whole bones which are easily prepared, such as the tibial tarsal bones of cattle and sheep and the fibular tarsal bone of cattle. These bones gave within animal deviations of 0.012–0.024 SG units, when comparing left bone with right bone. Slightly higher values were obtained for coccygeal vertebrae from cattle and distal metacarpal condyles from sheep. SG was related to ash, calcium and phosphorus contents of coccygeal vertebrae of cattle and it is considered that, for survey work on the mineral status of the bones of cattle and sheep, the correlations are sufficiently high to make their determination unnecessary. This will enable radiation determined SG techniques to be applied to this type of work.
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  • 35
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    Calcified tissue international 16 (1974), S. 335-338 
    ISSN: 1432-0827
    Keywords: Fluoride ; Plasma ; Bone ; Age
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract Fluoride analyses were carried out on blood samples from fasting subjects and on iliac crest biopsies obtained at autopsy, using an ion-selective electrode. Correlation coefficients of 0.53 and 0.67 respectively were determined between plasma fluoride and age, and bone fluoride and age. The proportionate rates of increase of fluoride levels in plasma and bone with age and the similarity of the correlation coefficients suggest that the fasting plasma fluoride concentration is in equilibrium with bone fluoride.
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  • 36
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    Calcified tissue international 16 (1974), S. 305-313 
    ISSN: 1432-0827
    Keywords: Osteosarcoma ; Lyophilization ; Induction ; Bone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Abstract Bone formation was induced by iso- and home-implantation of lyophilized mouse osteosarcoma, in which an osteogenic activity is observed. The inducing factor is present exclusively in osteosarcoma, such as BF and Gardner, while not in non-osteogenic tumors, such as Ehrlich ascites tumor (2N & 4N) or mouse mammary carcinoma. The production of bone was rapid and extensive. It usually occurred within 21 days, and the time required for osteogenesis was almost the same as that reported in previous studies.
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  • 37
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    Cell & tissue research 148 (1974), S. 11-26 
    ISSN: 1432-0878
    Keywords: Dentine ; Bone ; Collagen structure ; Collagen mineralization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary It has been previously shown that the distances between the nuclei within the collagen bundles of mineralizing tissues were in good agreement with the repeat distances of the cross-banding pattern of collagen, which supports the assumption that the distances between the mineral deposits reflect to a good approximation the distances between nucleation centres on the collagen macromolecule. However, the lateral separation of the nuclei were significantly higher than the distances between close-packed triple helices. Recently a new model of collagen aggregation has been proposed in which the smallest morphological units are subfibrils (Ø approx. 39 Å) packed in tetragonal array. This led us to measure once again the lateral separation between a) close-packed calcium phosphate needles lying in bundles at (1) the mineralizing front of mantle dentine and (2) at the mineralizing front of rat tail bone, and b) between the uranyl-lead nuclei produced in the staining of rat tail tendon. The mean lateral distances separating these nuclei fell within the range of 39–47 Å, which is a little higher than the distances of 39 Å which separate the microholes between the subfibrils in the tetragonal packing model, which are regarded as the likely sites of nucleation. If, however, it is assumed that the forces generated during mineralization can cause the collagen fibres to swell, then the lateral separation of the nuclei and the distances between the microholes would correspond very closely.
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  • 38
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    International Journal of Chemical Kinetics 6 (1974) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 39
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    International Journal of Chemical Kinetics 6 (1974) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 40
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    International Journal of Chemical Kinetics 6 (1974), S. 245-256 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of N-phenylphthalamic acid and of N-phenylphthalimide hydrolysis in aqueous solutions of sulfuric acid has been studied. A reaction mechanism is proposed implying that unreactive forms of the reactant appear by protonization of the amide bond at the carbonyl oxygen and by dissociation of the o-carboxyl group (N-phenylphthalamic acid). Attack of the nonprotonized amide bond by the hydroxonium ion is suggested to be the rate-limiting step.
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  • 41
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    International Journal of Chemical Kinetics 6 (1974), S. 77-87 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Electronically excited oxygen atoms O(21D2) have been generated by the pulsed irradiation of ozone in the Hartley-band continuum and monitored photoelectrically in absorption by time-resolved attenuation of atomic resonance radiation at λ = 115.2 nm [O(31D2°) → O(21D2)]. Collisional quenching of the excited atom has been investigated for all the noble gases, and the first absolute values for the second-order deactivation rate constants are reported. The resulting rate data are discussed in terms of a curve-crossing mechanism based on existing spectroscopic data for the noble gas oxides. The absolute rate constants are compared with previous relative rate data for the deactivation of O(21D2) by the noble gases.
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  • 42
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    International Journal of Chemical Kinetics 6 (1974) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 43
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    International Journal of Chemical Kinetics 6 (1974), S. 297-308 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constant for the reaction I(2P1/2) + CH3I → I2 + CH3 has been reevaluated taking into account both collisional deactivation of excited iodine atoms and loss of I2 by I2 + CH3 → I + CH3I. The reevaluation is based upon data obtained (R. T. Meyer), J. Chem. Phys., 46, 4146 (1967) from the flash photolysis of CH3I using time-resolved mass spectrometry to measure the rate of I2 formation. Computer simulations of the complete kinetic system and a closed-form solution of a simplified set of the differential equations yielded a value of 6(± 4) × 106 1./mole-sec for the excited iodine atom reaction in the temperature region of 316 to 447 K. A slight temperature dependence was observed, but an activation energy could not be evaluated quantitatively due to the small temperature range studied. An upper limit for the collisional deactivation of I(2P1/2) with CH3I was also determined (2.4 × 107 1./mole-sec).
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  • 44
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Competitive studies of the reactions of ground-state oxygen atoms, generated by mercury-photosensitized decomposition of nitrous oxide, have been carried out with ethylene and all the fluoroethylenes using 2-(trifluoromethyl)-propene as reference compound. From measurements at 25°C and 150°C relative rate constants have been determined and used to calculate the Arrhenius parameters shown in the following table: TextOlefin\documentclass{article}\pagestyle{empty}\begin{document}$$\frac{{A_{{\rm olefin}} }}{{A_{{\rm 2TFMP}} }}$$\end{document}ΔERef\documentclass{article}\pagestyle{empty}\begin{document}$$\frac{{A_{{\rm olefin}} }}{{A_{{\rm C}_{\rm 2} {\rm H}_{\rm 4} } }}$$\end{document}ΔEC2H4CH2—CH21.10-1.18(1.0)(0)CH2—CHF1.030.840.942.02CH2—CF20.711.490.652.67CHF—CHF (cis-)1.231.921.123.10CHF—CHF (trans-)1.400.791.271.97CF2—CHF1.060.000.961.22CF2—CF20.86-3.220.78-2.04ΔERef = Eolefin - E2TFMP and ΔEC2H4 = Eolefin - EC2H4. Units are kJ/mole.The results are compared with corresponding data for other atoms and radicals, and discussed in terms of the electronic changes produced in the double bond by fluorine substitution, and in relation to the nature of the transition state.
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  • 45
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    International Journal of Chemical Kinetics 6 (1974), S. 467-479 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nucleophilic substitution reactions in the alkyl halides, RX + Y- → RY + X-, proceeding in polar media are considered on the basis of the theory presented in Part A. It is shown that the solvent reorganization energy is the main part of the activation energy for this processes. According to calculations performed, the values of the solvent reorganization energy equal ∼2.5-3 eV for H2O and ∼ 1.8-2.3 eV for acetone. From experimental data on the kinetic isotope effect, an estimate for the splitting of nonadiabatic terms and for the slope of the potential curve v′ of the intermolecular interaction between halide ion and methyl halide near transition configuration is made. Further, the parameter v′ is used for calculating the activation entropy of substitution reactions in the methyl halides. Theoretical activation energies and activation entropies agree with experimental values. In the framework of theory presented an interpretation of change of Ea and the preexponential factor with the type of alkyl halide is given.
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  • 46
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    International Journal of Chemical Kinetics 6 (1974), S. 371-382 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the thermal decomposition of diallylamine to propylene and prop-2-enaldimine have been studied in the gas phase in presence of an excess of methylamine over the temperature range of 532.7 to 615.6°K, using a static reaction system. Methylamine reacted with the unstable primary product prop-2-enaldimine, forming the thermally stable N-methyl prop-2-enaldimine.First-order rate constants, based on the internal standard technique, fit the Arrhenius relationship log k(s-1) = (11.04 ± 0.13) - (37.11 ± 0.33 kcal/mole)/2.303 RT. They were independent on the initial total pressure (46-340 torr), the initial pressure of diallylamine (9.2-65 torr), or methylamine as well as the conversion attained. Despite an apparent surface sensitivity, the reaction is essentially homogeneous in nature as demonstrated by experiments carried out in a packed reaction vessel.The observed activation parameters for the title reaction together with those observed earlier for triallylamine and allylcyclohexylamine are consistent with the proposed concerted reaction mechanism involving a cyclic 6-center transition state. The observed substituent effects suggest a nonsynchronous mode of bond breaking and bond formation.
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  • 47
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    International Journal of Chemical Kinetics 6 (1974) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 48
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    International Journal of Chemical Kinetics 6 (1974), S. 457-466 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Activation energies for substitution reactions of the type AC + B → A + CB, occurring in polar media and characterized by an abrupt change of the term along two coordinates have been calculated within the framework of the quantum-mechanical theory of chemical reactions. In the case of nonadiabatic processes, the transmission coefficient and activation energy for these reactions are expressed in terms of characteristic parameters of the medium (reorganization energy, effective frequency of solvent fluctuation polarization) and the potential energy curves for intermolecular interactions between the reactants (AC and B) and between the products (A and BC).
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  • 49
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of ethylallylether (EAE) has been studied in the gas phase over the temperature range of 560-648°K. Propylene and acetaldehyde are the only reaction products observed. The reaction is apparently homogeneous in nature and independent of the pressure of EAE and of added foreign gases. The experimetally determined first-order rate constants, using the internal standard technique, fit the Arrhenius relationship log k(s-1) = 11.84 ± 0.29 - (43.57 ± 0.77 kcal/mole)/2.303RT. Independently the same rate constants are obtained, based on the amounts of products formed. The observed activation parameters are in general agreement with expectations based on the concept of a 6-center 1,5-H-shift retro-“ene” reaction mechanism, and they agree with previous results obtained for the similar reactions involving alkylallylamines and olefins.
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  • 50
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    International Journal of Chemical Kinetics 6 (1974), S. 453-456 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A competitive method involving the direct measurement of radical concentrations by EPR spectroscopy has been used to show that in solution at 25°C the rate constants for the bimolecular self-reactions of ethyl, isopropyl, tert-butyl, cyclopentyl, and trichloromethyl are all approximately equal, as had been indicated previously by direct measurement of the rate constants for decay of these radicals.
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  • 51
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    International Journal of Chemical Kinetics 6 (1974), S. 507-516 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Predictions of the “redox” and “complex” schemes for the Fe3+ catalyzed decomposition of H2O2 have been compared with published and new experimental data by numerical integratior of the appropriate complete sets of differential equations. Apparent discrepancies for the redox scheme at high Fe3+/H2O2 ratios are shown to disappear in the complete treatment, and inconsistencies of the complex scheme with both kinetic data and spectroscopic measurements are pointed out.
    Additional Material: 7 Ill.
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  • 52
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    International Journal of Chemical Kinetics 6 (1974), S. 531-543 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of reactant self-heating or cooling upon rate data is considered, and three approaches to the problem of obtaining valid kinetic parameters are described in detail. A comparison of these approaches emphasises the need to assess and allow for thermal effects during the initial planning of kinetic experiments if satisfactory results are to be acquired. An integrated rate expression is given for use with nonisothermal data, and is used to provide correction factors for rate constants which have been derived without allowance for thermal effects.
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  • 53
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    International Journal of Chemical Kinetics 6 (1974), S. 553-565 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of O(3P), prepared from the Hg photosensitization of N2O, with C2HCl3 was studied at 25°C. The products of the reaction in the absence of O2 were CO, CHCl3, and polymer (as well as N2 from the N2O). The quantum yields of CO and CHCl3 were 0.23 ± 0.01 and 0.14 ± 0.05, is respectively independent of reaction conditions. The reaction mechanism is with k14a/k14 = 0.23, where k14a + k14b. Most of the HCl and CCl2 combine to form CHCl3, but some other products must also be formed to account for the difference in the CO and CHCl3 quantum yields. The C2HCl3O* adduct polymerizes without involving additional C2HCl3 molecules, since the quantum yield of C2HCl3 disappearance, —Φ{C2HCl3}, was about 1.0 at high values of [N2O]/[C2HCl3]. The rate coefficient for the reaction of O(3P) with C2HCl3 is 0.10 that for the reaction of O(3P) with C2F4.In the presence of O2 the free radical chain oxidation occurs because of the reaction The main product is CHCl2CCl(O) with smaller amounts of CO and CCl2O, and some CO2. The chain lengths were long and values of — Φ {C2HCl3} up to 90 were observed.
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  • 54
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    International Journal of Chemical Kinetics 6 (1974), S. 587-595 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the decay of hydroxyl radicals in the presence of excess acetylene were studied at pressures in the vicinity of 1 torr and at ambient temperature in a tubular discharge-flow reactor. Hydroxyl radicals were produced by the reaction of atomic hydrogen with nitrogen dioxide, H + NO2 → OH + NO. The concentration of hydroxyl was followed by line absorption photometry at 308.939 nm and 308.328 nm. Second-order rate coeffcients were determined in two sets of experiments. The initial concentration ratio [C2H2]0/[OH]0 was in the range of 2.3 to 13.2 in the first set, and 14 to 125 (owing to greater hydroxyl detection sensitivity) in the second set. Values of the second-order rate coefficient obtained were nk5 = (2.9 ± 0.3) × 10-13 cm3/molec-sec in the first set, and nk5 = (2.1 ± 0.6) × 10-13 cm3/molec-sec in the second set, where n is the stoichiometric coefficient of OH. A value of the bimolecular rate constant k5 = (2.0 ± 0.6) × 10-13 cm/molec-sec is consistent with both sets of data, as well as an earlier determination.
    Additional Material: 4 Ill.
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  • 55
    Electronic Resource
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 56
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    International Journal of Chemical Kinetics 6 (1974), S. 631-641 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of t-butylmethyl ether has been studied using the VLPP technique. The recommended Arrhenius parameters for the molecular elimination, reaction (1), are A(800°K) = 101 3, 9 sec-1 and Ea (800°K) = 59.0 ± 1.0 kcal/mole. No radical reactions occur under the conditions used. These parameters are in good agreement with earlier experimental work and with theoretical estimates of both A and E.
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  • 57
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    International Journal of Chemical Kinetics 6 (1974), S. 829-848 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chemical reactions of SO2(3B1) molecules with cis- and trans-2-butene have been studied in gaseous mixtures at 25°C by excitation of SO2 within the SO2(3B1) → SO2(+, 1A1) ‘forbidden’ band using 3500-4100-Å light. The initial quatum yields of olefin isomerization were determined as a function of the [SO2]/[2-butene] ratio and added gases, He and O2. The kinetic treatment of these data suggests that there is formed in the SO2(3B1) quenching step with either cis- or trans-2-butene, some common intermediate, probably a triplet addition complex between SO- and olefin. It decomposes very rapidly to form the 2-butene isomers in the ratio [trans-2-butene]/[cis-2-butene] = 1.8. In another series of experiments SO2 was excited using a 3630 ± 1-Å laser pulse of short duration, and the SO2(3B1) quenching rate constants with the 2-butenes were determined from the SO2(3B1) lifetime measurements. The rate constants at 21°C are (1.29 ± 0.18) × 1011 and (1.22 ± 0.15) × 1011 l/mole·sec with cis-2-butene and trans-2-butene, respectively, as the quencher molecule. Within the experimental error these quenching constants equal those derived from the quantum yield data. Thus the rate-determining step in the isomerization reaction is suggested to be the quenching reaction, presumably the formation of the triplet SO2-2-butene addition complex. In a third series of experiments using light scattering measurements, it was found that the aerosol formation probably originates largely from SO3 and H2SO4 mist formed following the reaction SO2(3B1) + SO2 → SO3 + SO(3Σ-). Aerosol formation from photochemically excited SO2-olefin interaction is probably unimportant in these systems and must be unimportant in the atmosphere.
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  • 58
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    International Journal of Chemical Kinetics 6 (1974), S. 887-891 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decaying absorption of CH3 radicals at 216.4 nm has been followed over more than three half-lives using a photoelectric split-beam kinetic spectrometer. The rate constant for recombination kr was found to be (5.60 ± 0.76) × 10-11 cm3/molecule·s.
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  • 59
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    International Journal of Chemical Kinetics 6 (1974), S. 899-920 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Singlet methylene was reacted with cyclopentadiene to give chemically activated bicyclo[3.1.0]hex-2-ene (BCH). The rate of isomerization of BCH to 1,4-cyclohexadiene, 1,3-cyclohexadiene, cis-1,3,5-hexatriene, and l-methylcyclopentadiene is compared with calculated rate constants using the RRKM theory and measured or estimated thermal Arrhenius parameters. Subsequent isomerizations of the C6H8 products are also measured and calculated. These include 1,4-cyclohexadiene to benzene and the reversible reactions between 1,3-cyclohexadiene, cis-1,3,5-hexatriene, and trans-1,3,5-hexatriene. The results provide new data for several of these reactions which have not been observed in thermal studies. Agreement between the observed and calculated rates using the strong collision assumption is satisfactory except for the trans-1,3,5-hexatriene to cis-1,3,5-hexatriene reaction.
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  • 60
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    International Journal of Chemical Kinetics 6 (1974), S. 813-828 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Study of the reaction by very-low-pressure pyrolysis (VLPP) in the temperature range of 550-850°K yields for the high-pressure Arrhenius parameters \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }\,k_{\rm 1} = (15.6 \pm 0.5) - (36.0 \pm 1.0)/\theta {\rm \,(sec}^{{\rm - 1}})$$\end{document} where θ = 2.303RT in kcal/mole. These in turn yield for the high-pressure second-order recombination of tBu + NO, k-1 = (3.5 ± 1.7) × 109 1./mole·sec at 600°K. For the competing reaction l./mole·sec and E4 ≥ 4.2 kcal/mole. The bond dissociation energy DHo (tBu-NO) was determined to be (39.5 ± 1.5) kcal/mole, both from the equilibrium constant and from the activation energy of reaction (1), obtained from RRKM calculations. A ‘free-volume’ model for the transition state for dissociation is consistent with the data. A limited study of the system at 8-200 torr showed an extremely rapid inhibition by products and a very complex set of products.
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  • 61
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    International Journal of Chemical Kinetics 6 (1974), S. 875-876 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 62
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    International Journal of Chemical Kinetics 6 (1974), S. 893-897 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal isomerization of 1,1-divinylcyclopropane has been investigated in the gas phase in the temperature range of 238 to 288°C and for pressures in the range of 4 to 12 torr. The isomerization to 1-vinylcyclopentene is homogeneous and kinetically first order and almost certainly unimolecular. The rate constants yield the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }k({\rm s}^{ - 1} {\rm)} = 13.53 \pm 0.13 - (42.45 \pm 0.33{\rm \,kcal/mole})/RT\,{\rm In 10}$$\end{document} or \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }k({\rm s}^{ - 1} {\rm)} = 13.53 \pm 0.13 - (117.6 \pm 1.4{\rm \,kJ/mole})/RT\,{\rm In 10}$$\end{document} The assumption of a similar transition state for this isomerization with that of l-methyl-l-vinylcyclopropane leads to a value for an alkylpentadienyl radical stabilisation energy of 19.2 ± 1.6 kcal/mole (80.4 ± 6.7 kJ/mole), and this value is compared with other estimates.
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  • 63
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    International Journal of Chemical Kinetics 6 (1974), S. 15-28 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidation of inositol by quinquevalent vandadium in acid medium is a first-order reaction both in vanadium (V) and inositol. The stoichiometry of the reaction is consistent with the use of two equivalents of vanadium (V) per mole of inositol with the formation of one mole of inosose. The reaction is catalyzed both by sulfuric and perchloric acid, but the rate is faster in sulfuric acid than in perchloric acid. In 1M-6M perchloric acid solutions the reaction has shown a variable order in H+, but in solutions of 2M-5M sulfuric and perchloric acid of constant ionic strength, the rate has a linear dependence on [H+]2. There is also a linear correlation between the rate and bisulfate ions in sulfuric acid at constant hydrogen ion concentration. The energy of activation is found to be 19 kcal/mole and a negative entropy value of - 14 e.u. A suitable mechanism, consistent with the kinetics in 2M-5M acid solutions, is suggested and the values of various rate constants are evaluated.
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  • 64
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Very strong laser emission at 5 μm was detected when SO2 and CHBr3 were flash photolyzed in the vacuum ultraviolet (λ ≥ 165 nm) in the presence of a large amount of diluent (SF6, He, or Ar). About 110 vibration-rotation transitions ranging from Δv = 18 → 17 to 3 → 2, except 16 → 15, were identified. The primary reactions leading to the CO stimulated emission are as follows: The product analysis results and the variation of laser intensity with flash energy and SO concentration indicate that the following side reactions are also occurring. Addition of a small amount of O2 enhances the laser output by both eliminating these side reactions and simultaneously producing vibrationally excited CO via reaction (8), which has been previously shown to generate CO stimulated emission. The effects of various reactive (NO and H2) and inert (He, Ar, SF6, CO, N2, N2O, and CO2) gases have been examined. All additives (P ≤ 20 torr), except NO and H2, increase the total laser output. N2O enhances the power most efficiently, whereas CO, N2, and CO2 are less effective and have similar efficiencies. The enhancement of the laser intensity by these near-resonant gases is ascribed to the depletion of CO population at lower levels which thus increases the rates cascading from higher levels. NO and H2 quench the laser output by chemically reducing the concentration of the CH radical.
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  • 65
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    International Journal of Chemical Kinetics 6 (1974), S. 61-75 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A kinetic study of lead atoms in the spin orbit states, Pb(63P1) and Pb Pb(63P2), 0.969 and 1.320 eV, respectively, above the 63P0 ground state, has been carried out by atomic absorption spectroscopy. The electronically excited lead atoms were generated by the pulsed irradiation of lead tetraethyl and monitored photoelectrically by time-resolved attenuation of resonance radiation. The decay of the two atomic states has been studied in the presence of He, Ar, H2, D2, N2, O2, CO, NO, CO2, N2O, CH4, C2H4, C2H2 CF4, SF6, and PbEt4, and rate constants for the collisional quenching by these gases are reported. The resulting data are compared with those for the deactivation of other atomic spin orbit states of comparable energy. In general, the higher energy state, Pb(63P2), is found to be deactivated more rapidly. It would appear that the magnitude of the electronic energy to be transferred on collision governs the rates of quenching, at least where a weak interaction potential is involved, and that for most gases, deactivation of Pb(63P2) proceeds via Pb(63P1).
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  • 66
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation and characterization of the iron(II) complex of the hexadentate Schiff base ligand NN‴-bis-[α-(2-pyridyl)benzylidene]triethylenetetramine are reported. Kinetic patterns and rate constants for aquation of this complex, and for its reactions with hydroxide, cyanide, and peroxodisulphate have been determined. Activation parameters for the reaction with cyanide, in aqueous solution, are ΔH
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  • 67
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    International Journal of Chemical Kinetics 6 (1974), S. 169-228 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methods are discussed for the production and detection of the hydroperoxyl radical for use in gas phase kinetic studies. Rate constants for gas phase reactions of the hydroperoxyl radical with itself, H2, H2O, CO, NO, SO2, O3, C2H6, C3H8, i-and n-C4H10, C2H4, i-C4H8, HCHO, C2H5CHO, n-C3H7CHO, Br, O, OH, and H are critically evaluated. Recommended or estimated rate constant expressions with associated error limits are given applicable over specified temperature ranges (normally 300-1000°K). The reactivity of HO2 compared with OH, O, H, F, Cl, Br, CH3, and CH3O is presented in tabular form and the implications for atmospheric chemistry are discussed.
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  • 68
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    International Journal of Chemical Kinetics 6 (1974), S. 257-263 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of C6F5I has been studied by the toluene carrier method over the temperature range of 900-978°K with contact times of 0.4-2.0 seconds and total pressures of 11.2-19.5 torr. Percent decomposition ranged from 8.6 to 97.7%. With toluene-to-C6F5I molar ratios of greater than 150, 85-100% of the C6F5 released abstracts a hydrogen atom from toluene to produce C6F5H. No significant quantities of I2 were observed and the only major gaseous product was HI. Within the limits of the experimental method the decomposition of C6F5I was first order and homogeneous.Least squares analysis of log k1 and 103/T(C6F5I → C6F5 + I) values gives \documentclass{article}\pagestyle{empty}\begin{document}$${\rm log}\,k_1 ({\rm s}^{- 1}) = 15.9 - 69,200/4.576T $$\end{document} while a weighted line of best fit yields. \documentclass{article}\pagestyle{empty}\begin{document}$${\rm log}\,k_1 ({\rm s}^{- 1}) = 15.4 - 67,000/4.576T$$\end{document} Based on this latter equation D[C6F5—I] at 298°K is estimated as 66.2 kcal/mole.
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  • 69
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    International Journal of Chemical Kinetics 6 (1974), S. 265-277 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gamma-radiation-induced free radical chain reaction in solutions of C2Cl3F in cyclohexane (RH) was investigated over a temperature range of 87.5-200°C. The following rate constants and rate constant ratios were determined for the reactions: \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {{\rm (2a)}} & {{\rm R} + {\rm C}_{\rm 2} {\rm Cl}_{\rm 3} {\rm F} \to {\rm RCClFCCl}_{\rm 2}} \\ \end{array}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {(2{\rm b})} & \to \\ \end{array}{\rm RCCl}_{\rm 2} {\rm CClF}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c}{{\rm (3a)}} & {{\rm RCClFCCl}_{\rm 2} \to {\rm RCF}}\\ \end{array}{\raise1pt\hbox{$\Relbar \kern-4pt{\Relbar}$}}{\rm CCl}_{\rm 2} + {\rm Cl}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {{\rm (4a)}} & {{\rm RCClFCCl}_{\rm 2} + {\rm RH} \to {\rm RCClFCCl}_{\rm 2} {\rm H} + {\rm R}} \\ \end{array}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }k_{2a} ({\rm mole}^{{\rm - 1}} 1.\,{\rm sec}^{{\rm - 1}}) = (8.64 \pm 0.35) - (6.38 \pm 0.41)/\theta ^1$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }k_{{\rm 2b}} /k_{{\rm 2a}} = (- 0.03 \pm 0.15) - (2.39 \pm 0.28)/\theta$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm (}k_{3{\rm a}} /k_{4{\rm a}})({\rm mole}\,1.^{{\rm - 1}}) = (6.17 \pm 0.10) - (10.14 \pm 0.18)/\theta$$\end{document} In competitive experiments in ternary solutions of C2Cl4 and C2Cl3F in cyclohexane the rate constant ratio k2c/k2a was determined \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {{\rm (2c)}} & {{\rm R} + {\rm C}_{\rm 2} {\rm Cl}_{\rm 4} \to {\rm RC}_{\rm 2} {\rm Cl}_{\rm 4}} \\ \end{array}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }k_{{\rm 2c}} /k_{{\rm 2a}} = (0.13 \pm 0.06) - (1.20 \pm 0.12)/\theta$$\end{document} By comparing with previous data for the addition of cyclohexyl radicals to other chloroethylenes it is shown that in certain cases the trends in activation energies for cyclohexyl radical addition can be correlated with the C—Cl bond dissociation energies in the adduct radicals.
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  • 70
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    International Journal of Chemical Kinetics 6 (1974), S. 323-336 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The substitution of N-alkyl substituted ethylenediamines for chloride ions in the rapidly equilibrating system \documentclass{article}\pagestyle{empty}\begin{document}$${\rm PdCl}_{\rm 4} ^{{\rm 2 - }} {\rm + H}_{\rm 2} {\rm O}\rightleftharpoons{\rm PdCl}_{\rm 3} ({\rm H}_2 {\rm O)}^{\rm - } + {\rm Cl}^{\rm - }$$\end{document} has been investigated in aqueous acid medium. The kinetic data can be accommodated by the general rate law \documentclass{article}\pagestyle{empty}\begin{document}$$k_{{\rm obs}} = \left\{ {\frac{k}{{\left[{{\rm H}^{\rm + }} \right]}} + \frac{{k'}}{{\left[{{\rm H}^{\rm + } } \right]\left[{{\rm Cl}^{\rm - } } \right]}}} \right\}\left[{{\rm N}_{\rm n} {\rm N}_{\rm m} {\rm en}} \right]_{{\rm total}}$$\end{document} where n = 0, 1, or 2 and m = 0, 1, or 2, depending on whether none, one, or two methyl groups are attached to the two nitrogen atoms of ethylenediamine. Reaction with the most heavily substituted ethylenediamine, namely, N2N2en discloses a change of the mentioned rate law to \documentclass{article}\pagestyle{empty}\begin{document}$$k_{{\rm obs}} = \left\{ {\frac{{k''}}{{\left[{{\rm H}^{\rm + } } \right]}} + \frac{{k'''\left[{{\rm Cl}^{\rm - } } \right]}}{{\left[{{\rm H}^{\rm + } } \right]}}} \right\}\left[{{\rm N}_{\rm 2} {\rm N}_{\rm 2} {\rm en}} \right]_{{\rm total}}$$\end{document} on going from a lower to a higher chloride ion concentration range. This change in the mathematical form of the rate law can be explained in terms of an ion-pair association of N2N2enH+ and free chloride ions.
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  • 71
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    International Journal of Chemical Kinetics 6 (1974), S. 383-394 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An inhibitor method for measuring the initiation rate is proposed for the system Fe3+ + H2O2. C(NO2)4 was used as inhibitor. The number of chains terminated by one C(NO2)4 molecule was estimated in specific photochemical experiments and found to be unity. The initiation appeared to involve two processes. The first is proportional to the first power of ferric ion concentration, and the second to the second power. The rate constants and activation energies of these processes are determined. Allowance for the second initiation process permitted qualitative and quantitative description of various reported data on H2O2 decomposition rates over a wide range of Fe3+, H2O2, and H+ concentrations.
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  • 72
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    International Journal of Chemical Kinetics 6 (1974), S. 493-506 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of the addition of hydrogen chloride on the photolysis of carbon tetrachloride in the presence of cyclohexane has been investigated in a companion paper. The data enable the rate constant ratio k8/(k5)1/2 to be determined. Since k-8 is well established, k5 can be estimated from known thermochemical data. The validity of the thermochemical derivation is checked by applying it to trifluoromethyl radicals. The photolysis of bromotrichloromethane and carbon tetrachloride in the presence of hydrogen chloride has been investigated over a range of temperatures. From these results and assuming reaction (5) has no activation energy, Arrhenius parameters for reaction (8) have been determined: The activation energies for the reaction of methyl, trichloromethyl, and trifluoromethyl radicals with hydrogen chloride are compared, and at first sight surprising results are rationalized in terms of relative electronegativity.
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  • 73
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    International Journal of Chemical Kinetics 6 (1974), S. 527-530 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Measurements of rates of oxygen absorption and steady-state peroxy radical concentrations for the autoxidation of tetralin in the presence of tert-butyl hydroperoxide have shown that the rate constant for reaction of the tert-butylperoxy radical with tetralin at 60°C is approximately 11.0 M-1 s-1. This rate constant is about a factor of 4 larger than the value recently reported by Niki, Okayasu, and Kamiya for this reaction.The present work emphasizes that great care should be taken when the hydroperoxide method is used to estimate cross-propagation rate constants for a substrate as reactive as tetralin at a temperature as high as 60°C.
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  • 74
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    International Journal of Chemical Kinetics 6 (1974), S. 567-572 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition of acetylenedicarboxylic acid in acetophenone was studied in the temperature range of 100-130°C. The rate constants and activation parameters for the consecutive pair of first-order steps (each yielding carbon dioxide) were calculated. Hydrogen kinetic isotope effects were also studied. Comparisons were made with the decompositions of oxalic acid and malonic acid. An intramolecular H—C transfer is believed to be the main part of the reaction coordinate in addition to the C—C bond breaking.
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  • 75
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    International Journal of Chemical Kinetics 6 (1974), S. 777-786 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chloroethanes react with aqueous caustic to yield either elimination or substitution products. The reaction rates were measured for the dichloroethanes, trichloroethanes, tetrachloroethanes, and pentachloroethane between 283 and 353°K. The constants of HCl eleminations referring to the rate equation \documentclass{article}\pagestyle{empty}\begin{document}$$r = k[{\rm OH}^{\rm - }][{\rm dissolved \,substrate]}$$\end{document} are given by \documentclass{article}\pagestyle{empty}\begin{document}$${\rm 1,2 - C}_{\rm 2} {\rm H}_{\rm 4} {\rm Cl}_{\rm 2} {\rm }\,k = 10^{10.99 \pm 0.03} \exp (- 23,000 \pm 50RT)$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$${\rm 1,1,2 - C}_{\rm 2} {\rm H}_{\rm 3} {\rm Cl}_{\rm 3} {\rm}\,k = 10^{13.99 \pm 0.03} \exp (- 22,400 \pm 50/RT)$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$${\rm 1,1,1,2 - C}_{\rm 2} {\rm H}_{\rm 2} {\rm Cl}_{\rm 4} {\rm }\,k = 10^{15.45 \pm 0.14} \exp (- 25,800 \pm 210/RT)$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$${\rm 1,1,2,2 - C}_{\rm 2} {\rm H}_{\rm 2} {\rm Cl}_{\rm 4} {\rm }\,k = 10^{16.40 \pm 0.05} \exp (- 22,550 \pm 70/RT)$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$${\rm C}_{\rm 2} {\rm HCl}_{\rm 5} {\rm }\,k = 10^{12.50 \pm 0.08} \exp (- 15,200 \pm 110/RT)$$\end{document} all rate constants being in 1./mole·s and R in cal/mole· deg.With ethyl chloride, 1,1-dichloroethane, and 1,1,l-trichloroethane, the elimination is not observed and a slow substitution takes place. The influence of chlorine substituents on both sides of the molecule on mechanism and rate parameters is discussed.
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  • 76
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The occurrence of anchimeric assistance in the vapor-phase thermolysis of anti- and syn-7-acetoxy-7-methylnorbornene and 7-acetoxy-7-methylnorborane has been investigated. The relative rates of thermolysis were found to be 1.9, 0.87, and 1.0, respectively. The nature of the transition state for ester thermolysis is discussed in light of the small amount of anchimeric assistance found in the thermolysis of the anti-isomer.
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  • 77
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    International Journal of Chemical Kinetics 6 (1974), S. 877-885 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The heats of formation of C3 and C4 alkyl nitrites (RONO) have been determined via their heats of combustion by bomb calorimetry, thereby providing a complete set of values of ΔHºf for C1-C4 alkyl nitrites. The experimental values are in excellent agreement with values derived from group additivity rules. For branched compounds these calculations involve corrections for gauche interactions. In these cases, the gauche interactions are reflected in the activation energies E1 determined by recent kinetic studies, required for breaking the RO-NO bond. The heats of formation of the alkoxy radicals involved together with ΔHºf(NO) = 21.6 kcal/mole leads to the result D(RO-NO) = 41.5 ± 1 kcal/mole. The concordance between D(thermochemical) and D(kinetic), unlike previous kinetic studies, implies that E2 = 0 ± 1 kcal/mole.
    Additional Material: 10 Tab.
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  • 78
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    International Journal of Chemical Kinetics 6 (1974), S. 337-357 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute values of the rate constants for the reaction of hydrogen atoms with cyclic olefins in the gas phase have been measured in a discharge-flow system under 3.5, 16, and 22 torr Ar at 23°C. The attenuation of hydrogen atom concentration in the reaction tube in the presence of a large excess of olefin was measured with an ESR spectrometer, and the products were analyzed by gas chromatography. Cyclic C6 hydrocarbons were the only significant products obtained when the hydrogen atom concentration was 2.6 × 10-10 mole/1., the olefin concentration was in the range of 9 to 22 × 10-8 mole/1., and the pressure was 16 torr Ar. The values for the rate constants for reaction with cyclohexadiene-1,3, cyclohexadiene-1,4, and cyclohexene are, respectively, (9 ± 2) × 108, (12 ± 1) × 108, and (6 ± 1) × 108 l./mole-sec, and they are not changed significantly by a sixfold change in total pressure. The fraction of the total interaction that proceeds by addition is 84% in the cyclohexadiene-1,3 system, but only 18% in the cyclohexadiene-1,4 system, and the cyclohexadienyl radical is therefore the dominant radical species in the latter system. The pattern of interaction between the hydrogen atom and the cyclohexadienyl radical was determined, and comprises 65% of disproportionation, and 13% and 23% of combination to yield cyclohexadiene-1,3 and cyclohexadiene-1,4, respectively. These results are consistent with the general patterns of reactivity emerging from studies of the reactions between free radicals and olefins in related systems.
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  • 79
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    International Journal of Chemical Kinetics 6 (1974), S. 395-400 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Different possible mechanisms for the gas phase reaction of formation of bromine chloride from bromine and chlorine are discussed. The rate of the reaction has been deduced from photometric measurements in conventional static reactors of surface-to-volume ratio ranging between 0.6 and 3 cm-1, at temperatures between 51 and 113°C. Experimental data show that (1) the observed reaction is predominantly heterogeneous, and (2) the homogeneous reaction must proceed by an atomic chain mechanism initiated by Br atoms.
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  • 80
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    International Journal of Chemical Kinetics 6 (1974), S. 417-428 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reaction between ozone and allene (A) were studied in the range of 226 to 325°K in the gas phase. Initial O3 pressures varied from 0.01 to 0.7 torr and allene pressures varied from 0.05 to 6 torr. At the higher initial O3 pressures the most important product was O2 followed by CO, H2O, CO2, and C2H4. Oxygen balances averaging about 110% were obtained, which implies that no important oxygenated products were missed. However, carbon balances were only about 50% and hydrogen balances were even less, so that unidentified hydrocarbons were presumably formed. The rate law found was - d[O3]/dt = k1[O3][A] + k2a[O3]2[A]/[O3]0 where log k1(M-1sec-1) = 6.0 ± 0.7 - (5500±1000)/2.30RT and log k2a(M-1sec-1) = 6.9 ± 0.7 - (6200 ± 800/2.30RT). A mechanism is proposed which accounts for the rate law and the observed stoichiometry of O2 formed-O3 used. This involves a heterogeneous catalyzed decomposition of O3. The rate constant k1 is identified with the primary addition reaction A + O3 → AO3, and this rate constant is compared with those from other O3 addition reactions.
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  • 81
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    International Journal of Chemical Kinetics 6 (1974), S. 401-416 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using the technique of flash photolysis-resonance fluorescence, absolute rate constants have been measured for the reaction H + O2 + M → HO2+M over a temperature range of 220-360°K. Over this temperature range, the data could be fit to an Arrhenius expression of the following form: \documentclass{article}\pagestyle{empty}\begin{document}$$k_{{\rm Ar}} = (6.75{\rm } \pm {\rm }1.1){\rm } \times {\rm }10^{ - 33} \exp {\rm }[685{\rm } \pm {\rm }128{\rm cal/mole]/}RT$$\end{document} The units for kAr are cm6/mole-s. At 300°K the relative efficiencies for the third-body gases Ar:He:H2:N2:CH4 were found to be 1.0:0.93:3.0:2.8:22. Wide variations in the photoflash intensity at several temperatures demonstrated that the reported rate constants were measured in the absence of other complex chemical processes.
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  • 82
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    International Journal of Chemical Kinetics 6 (1974), S. 481-492 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis of azocyclohexane, carbon tetrachloride, and cyclohexane at 360 nm has been investigated over a wide temperature range. At moderate temperatures a chain reaction ensues from which the following approximate rate constants could be determined assuming 2CCl3. → C2Cl6, k5 = 109.7 (303-673K): The really striking feature of the results is that they show that termination in bicyclohexyl [reaction (7)] is extremely slow: The root-mean-square rule for estimating the cross-combination rate is also followed.The photolysis of carbon tetrachloride and cyclohexane at 250 nm has also been investigated. The reaction is complicated by the occurrence of two concurrent photolytic processes, the main one yielding trichloromethyl radicals and chlorine atoms, and the subsidiary one yielding dichlorocarbene and molecular chlorine. Nonetheless the results from this reaction can be interpreted in the medium temperature range 360-430K, where long chains are present, in terms of the rate constants derived from the azocyclohexane system.
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  • 83
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    International Journal of Chemical Kinetics 6 (1974), S. 517-526 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photochemistry of 1,1,1-trifluoromethylazomethane has been partially characterized. The quantum yield for N2 formation from photolysis at 366 nm and room temperature was unity at low pressure and decreased to 0.5 at 630 torr. At room temperature the principal products were C2H6, C2F6, CH3CF3 (or CH2CF2 + HF at reduced pressures), plus substituted hydrazines, which mainly arise from addition of CF3 to the parent followed by combination of these radicals with CH3 or CF3. These fluorinated methyl hydrazine products detract from the general utility of CF3-N2-R compounds as sources for simultaneous study of the chemistry of CF3 and R radicals. At room temperature the hydrazine products accounted for more than 50% of the total yield; however, these products can be reduced by lowering the temperature and at 195°K their yields are negligible. The quantum yield for intramolecular (direct) formation of CH3CF3 + N2 was shown to be ≤0.002.
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  • 84
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    International Journal of Chemical Kinetics 6 (1974), S. 545-552 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The addition of propene to cyclohexa-1,3-diene has been studied between 512 and 638°K at pressures between 70 and 640 torr. The products are endo- and exo-5-methylbicyclo [2.2.2] oct-2-ene, and their formations are second order. The rate constants (in 1./mole-sec) are given by \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} k_{{\rm endo}} = - (26070 \pm 80)/4.576T + (5.74 \pm 0.03)$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} k_{{\rm exo}} = - (30090 \pm 80)/4.576T + (6.66 \pm 0.03)$$\end{document} The results are discussed in terms of a biradical mechanism.
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  • 85
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    International Journal of Chemical Kinetics 6 (1974), S. 725-739 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of ozone with simple olefins have been studied between 6 and 800 mtorr total pressure in a 220-m3 reactor. Rate constants for the removal of ozone by an excess of olefin in the presence of 150 mtorr oxygen were determined over the temperature range 280 to 360° K by continuous optical absorption measurements at 2537 Å. The technique was tested by measuring the rate constants k1 and k2 of the reactions (1) NO + O3 → NO2 + O2 and (2) NO2 + O3 rarr; NO3 + O2 which are known from the literature. The results for NO, NO2, C2H4, C3H6, 2-butene (mixture of the isomers), 1,3→butadiene, isobutene, and 1,1 -difluoro-ethylene are 1.7 × 10-1 4 (290°K), 3.24 × 10-17 (289°K), 1.2 × 10-1 4 exp (-4.95 ± 0.20/RT), 1.1 × 10-1 4 exp (-3.91 ± 0.20/RT), 0.94 × 10-1 4 exp ( -2.28 ± 0.15/RT), 5.45 ± 10-1 4 exp ( -5.33 ± 0.20/RT), 1.8 ×10-17 (283°K), and 8 × 10-20 cm3/molecule ·s(290°K). Productformation from the ozone-propylene reaction was studied by a mass spectrometric technique. The stoichiometry of the reaction is near unity in the presence of molecular oxygen.
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  • 86
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    International Journal of Chemical Kinetics 6 (1974), S. 773-776 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 87
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    International Journal of Chemical Kinetics 6 (1974), S. 801-811 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of added nucleophiles (methanol and 1,4-butanediol) on the steady-state kinetics of α-chymotryptic hydrolysis of a series of N-acetyl-L-amino acid methyl esters, R-CH(NHCOCH3)C(O)OCH3, has been studied. As a result, the rate and equilibrium constants of the ‘elementary’ steps of the enzyme process have been determined.It has also been demonstrated how the free energy-reaction coordinate profile changes if the structure (the size of the hydrocarbon chain) of the ‘chemically inert’ substrate fragment R is varied. The effects observed can be described by the following equation: where ΔGs and ΔGa are the free energies of formation of metastable intermediates, i.e., the enzyme-substrate complex and the acylenzyme, respectively, ΔG2≠ and ΔG3≠ are the free energies of activation for the chemical steps, i.e., enzyme acylation and acylenzyme hydrolysis, respectively; and ΔGtrans(R) is the free energy of transfer of substrate group R from water into a nonaqueous solvent.To explain the results obtained, a mechanism for enzyme-substrate interaction is suggested according to which the potential free energy of sorption of substrate group R on the enzyme is 2 ΔGtrans(R). Such a high gain in the free energy of hydrophobic interaction may only be realized if (a) in the free enzyme the sorption region has a thermodynamically unfavorable contact with the aqueous medium, and (b) water is forced out of the active center as a result of the hydrophobic interaction of substrate group R with the enzyme. Such a model is in agreement with the published x-ray data on the structure of the crystalline enzyme.The kinetic experiment has proved that not all the potential free energy of sorption is realized as binding force. Thus the true free energy of the binding of substrate group R with the protein does not exceed half the maximum value, both in the enzyme-substrate complex and acylenzyme.
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  • 88
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A step perturbation (concentration-jump or solvent-jump) relaxation method is described for studying the rates of fast reactions, using nontransient observation in a steadystate flow system. Therelaxation time is determined from a single measurement of an integrated relaxation amplitude. Remeasurement of the rate of dimerization of aqueous rhodamine B is reported.
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  • 89
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    International Journal of Chemical Kinetics 6 (1974), S. 753-761 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Shock tube experiments on the decay of OH-radical concentration after shock-initiated combustion of H2:O2:Ar = 10:1:89 mixtures were analyzed to give the rate constant 1 × 1015 cm6mol-2s-1for the reaction H + H + Ar = H2 + Ar overthe temperature range 1300 to 1700 K.
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  • 90
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    International Journal of Chemical Kinetics 6 (1974) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 91
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chemically activated acetyl radicals, with an excitation energy of 78 kJ/mole, were formed by the addition of methyl radicals to carbon monoxide. At 273·K the pressure required to stabilize one half of the excited radicals was 500 torr. From measurements of the acetyl radical yield at pressures in the range of 700-2100 torr, and at temperatures in the range of 260-413 K, extrapolations to infinite pressure yielded kinetic parameters for the addition of methyl radicals to carbon monoxide, and for the thermal decomposition of acetyl radicals. The rate constants were found to be log k[cm3 / (mole·s)] = 11.2-25(kJ/mole/2.3) RT, and log k(s-1) = 13.5-72 (kJ/mole)/2.3RT, respectively. Estimated thermochemical properties of the acetyl radical are ΔHfº = -17 kJ/mole and Sº = 262 J/K°mole.
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  • 92
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    International Journal of Chemical Kinetics 6 (1974), S. 945-949 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 93
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Time-resolved measurements of the oxygen atom concentration during shock-wave initiated combustion of low-density (25 ≤ p ≤ 175 kPa) H2—O2—CO—CO2—Ar mixtures have been made by monitoring CO + O → CO2 + hv (3 to 4 eV) emission intensity, calibrated against partial equilibrium conditions attained promptly at H2:O2 = 1. Significant transient excursions (“spikes”) of [O] above constant-mole-number partial-equilibrium levels were found from 1400 to 2000°K for initial H2:O2 ratios of 16 and 10 and below ± 1780°K for H2:O2 = 6; they did not occur in this range for H2:O2 ± 4. Numerical treatment of the H2—O2—CO ignition mechanism for our conditions showed [O] to follow a steady-state trajectory governed by large production and consumption rates from the reactions with a pronounced maximum in the production term ka[H][O2]. The measured spike concentration data determine kb/ka = 3.6 ± 20%, independent of temperature over 1400 ≤ T ≤ 1900°K, which with well-established ka data yields \documentclass{article}\pagestyle{empty}\begin{document}$$k_{\rm b} {\rm = 2}{\rm .2 } \times 10^{14} \exp (- 57.5(kJ)/RT){\rm cm}^{\rm 3} /{\rm mole} \cdot {\rm s}$$\end{document} This result reinforces the higher of several recent combustion-temperature determinations, and its correlation with results below 1000°K produces a distinctly concave upward Arrhenius plot which is closely matched by BEBO transition state calculations.
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  • 94
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    International Journal of Chemical Kinetics 6 (1974), S. 29-37 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The following net processes occur in a system containing chlorine and hydrogen bromide: \documentclass{article}\pagestyle{empty}\begin{document}$$(1)\begin{array}{*{20}c} {} & {} \\ \end{array}{\rm Cl}_{\rm 2} + {\rm HB}r \to {\rm BrCl + HCl}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$(2)\begin{array}{*{20}c} {} & {} \\ \end{array}{\rm BrCl + HB}r \to {\rm Br}_{\rm 2} {\rm + HCl}$$\end{document} These reactions have been followed spectrophotometrically in a gas phase stopped flow apparatus. The first two reactions are strongly surface catalyzed on untreated glass or quartz, but are much slower if the cell surface has been covered with silicone and photochlorinated. Rates in such systems are first order in each reactant, and comparable limiting rate constants have been obtained in cells with different methods of preparing the surfaces and with different surface-to-volume ratios. These experimental rate constants must be equal to or greater than those of the homogeneous bimolecular reactions. Then limiting rate constants at 35°C in liters per mole per second are k1 ≤ 0.8, k 2 ≤ 15, and k3 ≤ 0.04. Reactions of HI with Cl2, Br2, and ICl are all much faster than reaction (2). These observations and those of other diatomic molecule reactions can be rationalized if halogen and hydrogen halide molecules react through a transition state in which the hydrogen atom is near the center of a triangle of three halogen atoms.
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  • 95
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    International Journal of Chemical Kinetics 6 (1974), S. 89-102 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Flash photolysis of 2,4,6-trinitrotoluene solutions (TNT) indicates a photochemically induced isomerization leading to the aci-quinoid isomer with an absorption maximum at 460 nm in nonpolar solvents, or the conjugate base of the aci-quinoid isomer with absorption maxima at 500, 540, and 630 nm in polar solvents. Both species, the quinoid isomer and the conjugate base, have transient existence and their identification was based on detailed spectroscopic and kinetic studies presented here. The magnitude of the negative charge on the transient conjugate base was determined with salt effect experiments and found to be equal to unity.
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  • 96
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    International Journal of Chemical Kinetics 6 (1974), S. 103-110 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the alkaline hydrolysis of five diol monoesters and related esters in aqueous DMSO, aqueous acetone, and aqueous ethanol are reported. A novel solvent dependency of the reactivity pattern of the various esters is noticed. The results are explained on the basis of an internal stabilization of the transition state and the influences of the various solvent systems on such transition states. It is suggested that such dipolar aprotic-protic solvent influences on reaction rates can be used as a criterion in the assessment of anchimeric assistance in such reactions.
    Additional Material: 7 Tab.
    Type of Medium: Electronic Resource
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  • 97
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 111-123 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The exponential relaxation of CH3, produced by the reaction O + C2H4 → CH3 + HCO, to its steady-state concentration was quantitatively monitored after the reactants were mixed. The relaxation profiles yield the rate constant of the reaction O + CH3 → H2CO + H equal to (1.85 ± 0.28) × 10-10 cm3/molecule-sec at 300°K. Ancillary experiments yielded values for the rate constant for the reaction of O atoms with C2H4 at 300°K, the average of which is 7.7 × 10-12 cm3/molecule-sec. The experimental technique, which employs a fast-flow reactor coupled to a photoionization mass spectrometer, is described in detail and its potential discussed.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 98
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 39-50 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reaction between Mg2+ and Eriochrome-Black-T (EBT) has been investigated in the pH range between 7.05 and 9.0, in the presence of 12% ethanol. The reaction is found to consist of two parallel paths, one involving the tervalent unprotonated ligand, and one its monoprotonated form. The rate constant for the unprotonated ligand has a “normal” value, whereas that for the protonated form is much lower. The numerical value of the rate constant for the unprotonated ligand obtained from results at a magnesium concentration of 10-3M and a pH up to 9.0 is, however, inconsistent with that obtained from results at [Mg2+] = (1 to 4) × 10-3M and pH up to 8.1. This can be explained, at least partially, if we assume the intermediate MgHD to lose its proton not only to H2O, but also to other bases present in the solution.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 99
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 279-290 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oxidation of tetralin in the presence of tert-butyl hydroperoxide and tetralyl hydroperoxide, initiated with azobisisobutyronitrile, was studied at 60°C in order to examine the complications involved in the hydroperoxide method devised by Howard and Ingold. From literature data on absolute rate constants and our rates of oxidation, cross termination rate constants and contributions of each elementary propagation and termination step were computed. It was confirmed that this method was quite useful in determining the cross propagation rate constant, but it was also demonstrated that the rate of oxidation should be measured at very low conversion and with quite high concentrations of hydroperoxide, especially when the peroxy radical derived from the added hydroperoxide has a much lower termination rate constant than that from the oxidizing substrate.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 100
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 51-59 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constants for the replacement of water from the inner-coordination shell of Co(NH3)5OH23+, I, by dimethyl sulfoxide (DMSO) as DMSO gradually replaced water in the solvation shell of I were found to approach, and finally equal, the water-exchange rate constant of I in aqueous media in accordance with expectation for a dissociative mechanism. Also the rate constants for the replacement of DMSO from the innercoordination shell of Co(NH3)5DMSO3+, II, by water as water replaced DMSO in the solvation shell of II were found to approach, and approximately equal, the DMSO-exchange rate constant for II in liquid DMSO in accordance with expectation for a dissociative mechanism.The DMSO-exchange rate constant for II in liquid DMSO was determined and found to be equal to (3.6 ± 0.8) × 10-4 sec-1 at 45°C.The dissociation quotient, [II] [NO3-]/[Co(NH3)5NO32+], was found to be equal to 0.28 ± 0.11 M at 45°C by NMR methods. The pseudo first-order rate constants for anation of II by NO3- and the solvation of Co(NH3)5NO3 2+ by DMSO were determined at various temperatures.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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