The technique of microozonolysis followed by gas chromatography has been used to determine the amount of 1,2-structures occurring as 1,4–1,2–1,4 sequences in n-butyl-lithium-initiated polybutadienes. The product obtained from the ozonolysis of these sequences, 3-formly-1,6-hexanedial, was directly proportional to the 1,2 (vinyl) content of the polymers as measured by infrared or NMR spectroscopy. An unusual ozonolysis product, 4-octene-1,8-dial, has been found in the ozonolysis products of high-1,4 poly-butadienes. Ozonolysis has also been used to determine alternating structures in propylene-butadiene copolymers. The product obtained from ozonolysis of such structures is 3-methyl-1,6-hexanedial. Ozonolysis of a polyisoprene containing equal amounts of 1,4 and 3,4 structures indicated it to have a nonalternating structure with long blocks of 1,4-isoprene units. Gas chromatographic separation was accomplished by using sucrose acetate isobutyrate with Carbowax 20M as the liquid phase. Retention times were established by using model compounds where possible. 相似文献
The diphosphate ester (ThDP) of thiamin (vitamin B1) is an important cofactor of enzymes within the carbohydrate metabolism. The initial reaction step shared by all ThDP-dependent enzymes is the deprotonation of the C2–H of the thiazolium ring. The replacement of the 4′-amino group by a hydroxyl one in the pyrimidine ring leads to the oxy-ThDP analogue which is known as an antagonist in thiamin catalysis.
Ab initio and DFT calculations on the MP2/6-31G* and B3LYP/6-31G* level were performed to study the proton relay function in thiamin and oxythiamin systems. Both MP2 and B3LYP calculations show significant differences of the reaction coordinate of the ylide formation in the systems. Tautomers, protonated and deprotonated species of both systems show different trends regarding their stability. The influence of correlation effects on the results is discussed by comparison with the HF-SCF/6-31G* data. Frequency calculations on the B3LYP/6-31G* level were performed to characterize the minima and transition state structures, respectively. 相似文献
The NMR spectra of a series of five 3-pyridinols in dioxane and dimethyl sulfoxide have been correlated with electron densities calculated by the Extended Hückel MO method. The data were found to fit a straight line of the form y=ax+b. The effects of hydrogen-bonding between pyridinol molecules on the correlation have been considered, and they have been estimated quantitatively for 6-methyl-3-pyridinol via Extended Hückel Calculations on a hydrogen-bonded model.
Zusammenfassung Die Kernresonanzspektren von fünf 3-Pyridinolen in Dioxan und Dimethylsulfoxyd wurden mit den Elektronendichten aus dem erweiterten Hückelverfahren korreliert, und zwar ergibt sich eine lineare Beziehung. Der Einfluß von intermolekularen Wasserstoffbrücken ist für einen Fall (die 6-Methyl-Verbindung) durch EHT-Rechnungen festgestellt und in den übrigen Fällen geschätzt worden.
Résumé Les spectres NMR d'une série de cinq 3-pyridinols dans le dioxane et le diméthyle-sulfoxyde ont été corrélés avec les densités électroniques calculées par la méthode de Hückel Etendue. Les données se placent correctement sur une droite y=ax+b. Les effets de la liaison hydrogène entre les molécules de pyridinol ont été envisagés et estimés quantitativement pour le 6-méthyl-3-pyridinol par des calculs EHT sur un modèle à liaison hydrogène.
Removal of CuI from Cu(2)P(1.8)As(1.2)I(2) results in a novel P--As allotrope. Although the product is X-ray amorphous, lattice fringes are observed in the transmission electron micrographs with spacings reflecting the diameter of the linear pnicogen polymer in Cu(2)P(1.8)As(1.2)I(2), suggesting the pnicogen chains remain intact upon loss of CuI. The straight needles present in Cu(2)P(1.8)As(1.2)I(2) appear to be kinked in the P--As phase due to lattice mismatch between the liberated polymers, ultrasonic treatment, or a combination of these effects. This new P--As modification is semiconducting with a band gap of 1.05 eV. 相似文献
Polycrystalline Cu3P was successfully prepared under a wide variety of solvothermal conditions. The reaction of red phosphorus with several copper sources (copper metal, copper (I) iodide, copper (I) chloride and copper (II) chloride) at 150-200 °C for 1-2 days in water produced Cu3P. Products were examined with powder X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy. Thermal analyses and optical spectroscopy were also performed. A detailed list of reaction conditions, products and impurity phases (where applicable) are reported. 相似文献
LetM be a multiplicative set with 1M andmnM if and only ifmM,nM for (m,n)=1. It is shown by elementary means that there exists the asymptotic density of the setM(M–1) for every multiplicative setM. The density is positive if and only ifM possesses a positive density and 2M for some . This result is slightly generalized to sums over multiplicative functionsf with |f|1. 相似文献
The substrate scope of a steroid monooxygenase (STMO) from Rhodococcus rhodochrous DSM 43269 was investigated for a large range of different ketone substrates. These studies revealed that this enzyme not only oxygenates steroids, but also ketone moieties of a series of other open-chain ketones, such as cyclohexyl methyl ketone, cyclopentyl methyl ketone, and 3-acetylindole. Furthermore, the STMO catalyzed the oxygenation of cyclobutanone derivatives. Comparative biotransformations with recombinant Escherichia coli resting cells harboring the STMO, the cycloalkanone monooxygenase (CAMO) from Cylindrocarpon radicicola or the cyclohexanone monooxygenase (CHMO) from Acinetobacter calcoaceticus revealed that the STMO is enantiodivergent compared to the CHMO-type. Moreover, the STMO resulted in a higher enantiomeric excess of the product lactones compared to the known BVMOs of the same enantiopreference, such as cyclopentanone monooxygenases. 相似文献