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991.
T. M. Gorrie S. Kalyana Raman H. K. Rouette Heinrich Zollinger 《Helvetica chimica acta》1973,56(1):175-195
An NMR. investigation of the state of formaldehyde in acidic solutions has been carried out. Solutions of DCl/D2O/CD3COOD containing two sources of formaldehyde, i.e. paraformaldehyde (I) and trioxane (II), were used for this purpose. In systems I and II the effect of various D2O/CD3COOD ratios, at a constant DCl concentration, was studied, while for II the effect of changing DCl concentration was also investigated. The results show that in aqueous solution, formaldehyde exists primarily as the monomeric and linear oligomeric forms of methylene glycol. Reducing the amount of D2O (at constant DCl concentration), while increasing the CD3COOD content, results in an increase in the polymeric species and in trioxane. In addition, substitution of water by acetic acid results in systems that are catalytically more active than aqueous solutions of the same hydrochloric acid concentration. Along with the usual polymer-monomer equilibria which exist in such solutions, side reactions of methylene glycol with the hydrochloric acid present also occur to a small extent, e.g. acetylation, substitution of OH by Cl and the Cannizzaro reaction. It is suggested that these findings will result in a better understanding of the formaldehyde crosslinking reactions in cotton cellulose. 相似文献
992.
Mechanism for polymerization of ε-caprolactam in the presence of both sodium and aluminum caprolactamate was investigated at 171°C. The role of Al(Cap)3 as an initiator was revealed. The apparent rate constant of propagation reaction decreased with the increase in the concentration of Al(Cap)3, as the two different metal salts interact even at 171°C. The activation energy of the overall polymerization reaction with this catalyst system was estimated to be 41.18 kcal/mole. 相似文献
993.
VIVIENNE E. REEVE GAVIN E. GREENOAK PAUL J. CANFIELD CHRISTA BOEHM-WILCOX CLIFFORD H. GALLAGHER 《Photochemistry and photobiology》1989,49(4):459-464
Epidermal urocanic acid has been postulated to be the mediator of the specific state of immunosuppression induced by UV irradiation, by which UV-initiated tumour cells are able to evade normal recognition and can survive to grow progressively into malignant tumours. These experiments demonstrate that topical application of UV-irradiated urocanic acid systemically suppresses the contact type hypersensitivity response to oxazolone in hairless mice. In addition, topically applied urocanic acid markedly increases the overt tumour yield and the degree of malignancy in hairless mice exposed chronically to daily minimally erythemal doses of simulated solar UV light. Topical urocanic acid also increases the number of latent UV-initiated tumours, detectable by croton oil promotion. Therefore UV photoproducts of urocanic acid can both systemically suppress contact hypersensitivity in the epidermis, and also enhance early survival of UV-initiated tumour cells resulting in augmentation of UV photocarcinogenesis. 相似文献
994.
The percutaneous absorption of ketoprofen (KPF) from gel patches containing d-limonene and ethanol was investigated in rats. Plasma levels of KPF varied with the kind of polymers which constitute the gel patch, and the highest level was observed when the copolymer of ethylacrylate (EA) and diethyleneglycolmethacrylate (DEGMA) was used as a vehicle. The amount of KPF permeating through the rat skin from the gel patch was well correlated with that of ethanol. Permeations were enhanced with increase in the amount of d-limonene distributed from the vehicle to the skin tissue. The amount of d-limonene accumulated in the skin varied greatly with the kind of polymers; the highest accumulation was observed with the EA-DEGMA copolymer, and decreased with increasing affinity of d-limonene to the polymers. The reason EA-DEGMA copolymer showed the highest percutaneous absorption of KPF from gel patches containing d-limonene may be the hydrophilic nature of this polymer which showed the lowest affinity to d-limonene. 相似文献
995.
It is possible to synthesize OGaF in an argon matrix by co-condensation of GaF with O atoms. The stretching vibrations of this compound are found at 943 and 690 cm−1 (16O69GaF). An exact calculation of the force field is possible with the aid of the observed 16O/18O and 69Ga/71Ga shifts. The following force constants are found: f(GaO) = 6.32; f(GaF) = 4.69; f(GaO/GaF) = −0.1 [102Nm−1] 相似文献
996.
The method proposed for the evaluation of statistical weights in paper I, and the three-state model [alpha-helical (alpha), extended (epsilon), and other (c) states] formulated in paper II, have been used to develop a procedure to predict the backbone conformations of proteins, based on the concept of the predominant role played by shortrange interactions in determining protein conformation. Conformational probability profiles, in which the probabilities of formation of three consecutive alpha-helical conformations (triad) and of four consecutive extended conformations (tetrad) have been defined relative to their average values over the whole molecule, are calculated for 19 proteins, of which 16 had been used in paper I to evaluate the set of statistical weights of the 20 naturally occurring amino acids. By comparing these conformational probability profiles to experimental x-ray observations, the following results have been obtained: 80% of the alpha-helical regions and 72% of the extended conformational regions have been predicted correctly for the 19 proteins. The percentage of residues predicted correctly is in the range of 53 to 90% for the alpha-helical conformation and in the range of 63 to 88% for the extended conformation for the 19 proteins in the two-state models [alpha-helical (alpha) and other (c) states, and extended (epsilon) and other (c) states]. In the three-state model, the percentage of residues predicted correctly is in the range of 47% to 77 for 19 proteins. These results suggest that the assumption of the dominance of short-range interactions, on which the predictive scheme is based, is a reasonable one. The present predictive method is compared with that of other authors. 相似文献
997.
Lifetimes of Hg(3P0) complexes were determined by simultaneous observation of Hg(3P0) optical absorption and complex emission, using a modulation technique and phase sensitive detection. The lifetimes of the mercury complexes with methanol, (1.4 ± 0.7) × 10-8 s, and water, ? 8 × 10-8 s, were found to be much shorter than reported in earlier work. For the ammonia complex, however a lifetime was measured which is in good agreement with previous determinations. Reasons for the large errors in earlier work where the methanol and water complex lifetimes were determined from complex emission data alone are discussed, and these data are reinterpreted. In the reaction rate of Hg(3P0) with methanol no detectable contribution from the termolecular process Hg(3P0) + 2CH3OH → (Hg·CH3OH)* + CH3OH could be observed. 相似文献
998.
Zusammenfassung Die Abhängigkeit der Struktur des o-Hydroxymandelsäurelactons von Lösungsmittel und Temperatur wird mit Hilfe IR- und NMR-spektroskopischer Methoden nachgewiesen.
The temperature and solvent dependence of the structures of 2-hydroxymandelic acid lactone and dioxindole have been shown by IR and NMR spectroscopy.相似文献
999.
K. H. Beckmann 《Angewandte Chemie (International ed. in English)》1968,7(3):161-171
Measurement of the state of polarization of reflected light (ellipsometry) permits the determination of the thickness and refractive index of thin layers formed on a surface. The IR absorption spectra of such thin layers, which can be measured by means of internal reflection spectroscopy (IRS), provide information about their chemical composition. These methods have been used to study adsorption processes and the formation of reaction layers at semiconductor interfaces, and may also be used for measurements of free charge carriers in the space-charge region and in surface states. Results of such investigations are given in this article. 相似文献
1000.
H. Kindl G. J. Kremlicka O. Hoffmann-Ostenhof 《Monatshefte für Chemie / Chemical Monthly》1966,97(6):1783-1786
Zusammenfassung Die Bildung und das Vorkommen von Cycliten inThuja occidentalis wurden mit Hilfe der Methode der Photoassimilation in einer Atmosphäre von14CO2 untersucht. Nebenmyo-Inosit, Sequoyit,d-chiro-Inosit undd-Pinit wurde auchl-Leucanthemit (l-1,2,4/3-Cyclohexentetrol), ein Cyclit, der bisher nur als Inhaltsstoff mehrerer Angiospermae bekannt ist, nachgewiesen. Das Vorkommen vonl-Leucanthemit konnte auch inPinus austriaca sichergestellt werden. Methoden zur Isolierung vonl-Leucanthemit ausThuja occidentalis wurden ausgearbeitet.
The formation and the occurrence of cyclitols inThuja occidentalis has been studied, using the method of photoassimilation in an atmosphere of14CO2. Besidesmyo-inositol, sequoyitol,d-chiro-inositol, andd-pinitol, alsol-leucanthemitol (l-1,2,4/3-cyclohexentetrol), a cyclitol which so far has only been found in Angiospermae, was identified. The occurrence ofl-leucanthemitol could also be established inPinus austriaca. Methods have been elaborated which permit the isolation ofl-leucanthemitol fromThuja occidentalis.相似文献