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21.
The resonance Raman spectra of tris(acetylacetonatoiron(III)) and ruthenium(III) complexes in various solvents and in water-acetonitrile (W-AN) mixtures were measured. The resonance Raman spectra of both complexes indicated peaks near 460 and around 1580 cm–1. Thev(C-O) peak (around 1580 cm–1) is shifted to low frequency with an increase in the dielectric constant T of the solvents, whereas thev(M-O) (M=Fe and Ru, near 460 cm–1) are constant, independent of T. It implies that the C-O bond in the acac– ligand is lengthened by the polarizability effect of the solvents, while both the Fe-O and Ru-O bonds, which are located in the inside of the complexes, are not influenced by the solvents indicating that the interaction does not depend on the properties of individual solvent molecules but on those of the aggregate. 相似文献
22.
I. Yamamoto M. Nishii E. Tokuoka T. Handa K. Miyajima 《Colloid and polymer science》1997,275(7):627-633
We evaluated the hydrolysis of egg yolk phosphatidylcholine (PC) by phospholipase D from Streptomyces chromofuscus (PLD) in small unilamellar vesicles (SUV) in presence of 50 μM Ca2+. After initial choline production (hydrolysis of 1.5% of the PC at the outer leaflets of the vesicle bilayers), the hydrolysis
was reduced to 5% of the initial velocity. The kinetic behavior in SUV of premixed PC and a low percentage of the hydrolysis
product, phosphatidic acid (PA), was similar to that of PC SUV. The reduced velocity disappeared when the membrane structure
was disintegrated by means of a nonionic surfactant. In the retardation phase, the partially hydrolyzed vesicles (postsubstrates)
had much higher affinity for PLD than fresh PC SUV. These results indicated that small clusters of the product, PA, at the
vesicle surface were responsible for the reduced velocity of hydrolysis.
The initial velocity increased in a biphasic manner with the substrate concentration. At a PC concentration range up to 4 mM,
the experimental data fit Michaelis–Menten kinetics. At concentrations above 6 mM, the velocity again markedly increased.
Negatively charged mixed vesicles of PC and PA did not have such kinetics. Furthermore, adding PC SUV to the postsubstrates,
where the fraction of free PLD was less than 0.05, induced steep choline production. These results showed that PLD bound to
vesicles had higher activity than free PLD. We speculated that PLD bound to vesicles collided with and was directly transferred
to PC SUV when the fraction of free PLD in aqueous medium was very small.
Received: 5 November 1996 Accepted: 26 February 1997 相似文献
23.
Ionic discotic liquid crystals: synthesis and characterization of pyridinium bromides containing a triphenylene core 总被引:1,自引:0,他引:1
Five novel pyridinium salts tethered with hexaalkoxytriphenylene molecules were synthesized by the quaternization of pyridine with ω-bromo-substituted triphenylene derivatives. Their chemical structures were determined by 1H NMR, 13C NMR, IR, UV spectroscopy and elemental analysis. The thermotropic liquid crystalline properties of these salts were investigated by polarizing optical microscopy and differential scanning calorimetry. These triphenylene-based pyridinium salts with bromide as counterion were found to be mesomorphic over a wide temperature range. 相似文献
24.
Thermal decomposition of ammonium tris (malonato) ferrate (III) tetrahydrate, i. e. (NH4)3[Fe(CH2C2O4)3]·4H2O has been studied up to 973 K in static air atmosphere employing Mössbauer and infrared spectroscopies, and non-isothermal techniques (TG, DTG, DTA). The anhydrous complex decomposes into an iron (II) intermediate at 453 K. The iron (II) species on further heating is reoxidized to -Fe2O3 as the final thermolysis product. An increase in particle size of -Fe2O3 with increasing decomposition temperature has been observed. The results are compared with the analogous oxalate complex. 相似文献
25.
I.J. Galpin F.E. Hancock B.K. Handa A.G. Jackson G.W. Kenner R. Ramage B. Singh 《Tetrahedron》1979,35(23):2791-2794
Combination of the protected peptide fragments 1–16, 17–26 and 27–37 to yield the 1–37 portion of a lysozyme analogue is described. The fragments were combined using DCCI with the addition of HONSu, and the products purified mainly by gel filtration. 相似文献
26.
Anand R Puri SC Verma N Handa G Khajuria RK Gupta VK Suri OP Qazi GN 《Journal of chromatographic science》2003,41(8):444-446
The present work describes isolation of bioactive lipophilic constituent [namely, hyperforin from St. John's wort (Hypericum perforatum L.)], of approximately 98% purity by semipreparative high-performance liquid chromatography (LC). The extraction, isolation, and analysis of the collected compound is performed without the use of antioxidants and inert gas atmospheres at all the stages. Hyperforin, separated isocratically on a 12microm semiprep column, is obtained in high purity, lyophilized after the removal of the organic phase, and preserved at a low temperature. The purity of the collected marker compound is estimated by the use of LC-mass spectrometry and spectroscopic techniques. 相似文献
27.
Sandeep K. Ginotra 《Tetrahedron》2006,62(15):3573-3581
Copper complexes of chiral tridentate pybox ligands synthesized using a modified procedure have been studied as catalysts for the enantioselective allylic oxidation of olefins. A variety of olefins have been used in this reaction. Using 5 mol% of a Cu(II) complex of the tridentate pybox ligand, phenylhydrazine, and tert-butyl perbenzoate as oxidant in acetone, optically active allylic benzoates were obtained up to 94% ee in few hours. It was also observed that the use of molecular sieves in the reaction did not alter the enantioselectivity. Temperature was found to be very crucial in rate of the enantioselective allylic oxidation of olefins. Using EPR spectra, it has been shown that the Cu(II) species is reduced to Cu(I) by phenylhydrazine and phenylhydrazone, but the reduction with the former is faster in comparison to the latter. It was concluded that the rate enhancement was not specific to the presence of phenylhydrazine or phenylhydrazone, but both were equally responsible provided acetone was used as a solvent. 相似文献
28.
T Fujii J Hirayama H Kanai T Kobayashi K Handa S Kusama M Miyazawa K Yano M Takizawa 《Radioisotopes》1979,28(3):157-162
RI-angiography with 99mTcO4- was carried out using a scintillation camera with a digital minicomputer for the purpose of imaging of bronchial blood flow in various lung diseases, and as application of dual radioisotope techniques, other imagings such as tumor imaging with 197HgCl2 or 67Ga-citrate and/or perfusion imaging with 99mTc-MAA, were performed simultaneously in patients remaining the same position, too. The image as a iso-count map extracted out of the image of 197HgCl2, 67Ga-citrate or 99mTc-MAA, was superimposed to the brightness image of RI-anigogram (aortic phase). By these procedures, the image of bronchial blood flow were obtained in some patients with lung cancer, pulmonary tuberculosis, lung abscess, and chronic bronchitis. The dual radioisotope techniques using RI-angiography and the other imaging were useful to make isotope diagnosis of lung diseases more reliable, and the image superimposition methods using RI-angiogram and the image of tumor or perfusion, were useful to improve anatomic orientation of the former. 相似文献
29.
M. A. Desando Y. P. Handa R. E. Hawkins C. I. Ratcliffe J. A. Ripmeester 《Journal of inclusion phenomena and macrocyclic chemistry》1990,8(1-2):3-16
The structure I clathrate hydrate of carbon monoxide has been studied using dielectric measurements and13C NMR spectroscopy. Broad, weak dielectric absorption curves with maxima at 2.2–3.8 K yieldE
a
= 0.14 kJ mol–1 for the average Arrhenius activation energy associated with the reorientation of the low polarity guest. Except for H2S this represents the fastest reorienting polar guest known among the clathrate hydrates. The low temperature dielectric absorption curves can best be fitted with a Cole-Davidson asymmetric distribution of relaxation times and activation energies (with = 0.06 at 4 × 106 Hz), which at 107 Hz has been resolved into a double symmetric distribution of discrete relaxation times for CO in the small and large cages. The cross-polarization magic angle spinning13C NMR spectra indicate identical chemical shifts for CO in the small and large cages, in contrast to other hydrates. The static spectra show that the CO molecules undergo anisotropic reorientation in the large cages and that there is still considerable mobility at 77 K. One possible model for the anisotropic motion has the CO rapidly moving among sites over each of the 14 faces of the cage with the CO axis orientated towards the cage centre. The cage occupancy ratio at 220 K,
s/
L = 1.11, indicates slightly greater preference of CO for the small cage.Dedicated to Dr D. W. Davidson in honor of his great contributions to the sciences of inclusion phenomena. 相似文献
30.
The surface pressure-molecular area curve of the mixed monolayer of 16-(9-anthroyloxy) palmitic acid (16AP) and fatty acid (palmitic or stearic acids) showed various kink points which indicated the phase transitions of the monolayer. On the basis of the surface phase rule, the phase diagrams of the mixed monolayer were elucidated. The bifunctional molecule, 16AP, takes two orientations in a monolayer state, that is, horizontal and vertical ones. Horizontally oriented 16AP and vertically oriented fatty acid form a mixed monolayer but this exhibits deviation from the ideal mixing, which was interpreted in terms of the surface regular solution theory. On the other hand, the 16AP molecule in the vertical state was found to be immiscible with the fatty acid molecule in a monolayer de spite both molecules being vertical to the surface and parallel to each other. This was caused by the participation of the 9-anthroyloxy moiety of 16AP in the interaction of 16AP and fatty acid in the hydrophobic region of the monolayer. 相似文献