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131.
Transmission gratings of holographic polymer-dispersed liquid crystals (HPDLC) are prepared under controlled reaction conditions by adding various amounts of chain-transfer agent (CTA). The resulting films have a higher gel content with lower cross-link density, less dark reaction, less grating shrinkage with much smoother LC/polymer interfaces, smaller induction period, and fast saturation of diffraction efficiency, which shows a maximum of 95 % with 1 % CTA. An optimum LC content of 35 % is verified on the basis of morphology and reaction kinetics. 相似文献
132.
STUDIES OF ELECTRON SPIN RESONANCE ON BILIRUBIN FREE RADICALS 总被引:1,自引:0,他引:1
The nature of ESR signals derived from bilirubin-Ⅸα has been studied by focusing onthe samples treated with free radical generating and inhibiting systems, i.e. X-XOD, Fe/EDTA, SOD, mannitol/ascorbate, CO, KCN, etc. In all the cases, the stable signals comprisethose originated from semiquinone radical (g = 2.0012) and superoxide free radical (g_∥=2.041, g_⊥= 2.0040). The superoxide is shown binding with certain metal ions chelated bybilirubin. The free radical scavengers are able to destroy these radicals. The kinetic curveof the regeneration of bilirubin radicals has been determined and the reaction follows azero order mechanism. It is likely that both the physiological and toxic actions of bilirubinare related to the characters of its free radicals. Bilirubin is discussed as "active oxygensink" in mammalians. 相似文献
133.
134.
We developed a new method to measure the average aggregation number of large rod-like micelles using static fluorescence self-quenching of a solubilized fluorophore. The method is based on the increase of self-quenching of micelle-solubilized pyrene through excimer formation. We consider the effect of random distribution of pyrene in micelles and the micellar size distribution. The measured average aggregation <n> M is based on a new M-weighted raging similar to our exponential-weighted averaging in the transient decay method. We apply this method to study the effect of a large concentration of salt on the average aggregation behavior of sodium dodecyl sulfate (SDS) and cetyle tetraammonium bromide (CTAB). The sizes increase with increasing ionic concentrations. For SDS, we used the thermodynamic model developed by Missel et al. to calculate < n > M which we compare with experimental results. 相似文献
135.
The recombination kinetics of spin-correlated radical pairs (RPs) with three nonequivalent magnetic nuclei were calculated
under conditions of enforced encounters between radicals at time-independent frequency ndif. The simplest two-position model of a RP was used, which includes two states (contact state and distance-separated state)
of the RP, differing in magnitude of isotropic spin-spin exchange interaction between radicals. The calculated kinetic curves
were treated in terms of a three-exponential model. The dependences of corresponding rate constants (k
rec) on ndif, external magnetic field strength (B
0), and intensity, A
eff, of isotropic hyperfine coupling (HFC) were obtained. The k
rec-vs.-ndif or k
rec-vs.-viscosity (ndif varies simultaneously with the inverse lifetime of the contact state) plots pass through maxima whose positions are shifted
from the ndif region near the A
eff value at B
0 = 0.5 G toward high ndif values with an increase in B
0. At ndif ≫ A
eff, the k
rec-vs.-B
0 plots pass through maxima in the region B
0 = A
eff. The calculated dependences are compared with experimental data on recombination of biradicals. The results of calculations
show that the experimentally observed maxima on the k
rec-vs.-B
0 or k
rec-vs.-ndif plots can be due to peculiar features of the spin dynamics induced by the hyperfine coupling rather than the exchange interaction
effects, as is commonly accepted.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1103–1110, May, 2005. 相似文献
136.
The magnetic interactions in a new series of isostructural imino nitroxide radical lanthanide(III) complexes, [Ln(hfac)3(IM2py)] (Ln = Gd–Yb: IM2py = 2-(2′-pyridyl)-4,5-dihydro-4,4,5,5-tetramethyl-1H-imidazoline-1-oxy; hfac = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione), are examined by considering the intrinsic paramagnetic contribution of the Ln(III) ion from the corresponding [Ln(hfac)3(pybzim)] with a diamagnetic pybzim(2-(2-pyridyl)benzimidazole) ligand; the Ln(III)–IM2py interaction being antiferromagnetic for the 4f7 to 4f13 Ln(III) complexes and negligibly small for the other complexes. This series is the first example reverse to the previous cases for the series of Ln–Cu or Ln–aminoxyl(NIT) radical (4,5-dihydro-4,4,5,5-tetramethyl-1H-imidazoline-3-oxide-1-oxy) complexes, other than only a few examples of semiquinone Ln complexes. This reverse nature of the magnetic interaction, as compared with the NIT complexes, validates the empirical approach by O. Kahn et al. [Inorg. Chem. 38 (1999) 3692; J. Am. Chem. Soc. 122 (2000) 3413] in the spin-coupled systems for a series of Ln(III) complexes. 相似文献
137.
The use of the reverse atom transfer radical polymerization (RATRP) to end-functionalize poly(methyl methacrylate) (PMMA) with fullerenes, e.g. C60 and C70 was described in this paper. The Cl-terrninated PMMA was prepared via RATRP with designed molecular weight and narrow molecular weight distributions, and then directly used to react with fullerenes to produce C60(C70) terminated PMMA polymers in the presence of CuBr/Cu/bipy or FeCl2/bipy catalysts. The resultant polymers exhibit good solubility in some common organic solvents, e.g. THF, CHCl3 and toluene, and were well structurally characterized by a variety of physical techniques. 相似文献
138.
D. Tirzite A. Krauze A. Zubareva G. Tirzitis G. Duburs 《Chemistry of Heterocyclic Compounds》2002,38(7):795-800
The alkylation of 3-cyano-1,4-dihydropyridine-2(3H)-thiones or the condensation of an aromatic aldehyde, cyanothioacetamide, acetylacetone, and methyl iodide in the presence of piperidine has given a series of novel 5-acetyl-2-alkylthio-4-aryl-6-methyl-1,4-dihydropyridine-3-carboxylic acid nitriles. A compound was obtained from 3,5-di(tert-butyl)-4-hydroxybenzaldehyde in the molecule of which were combined the active part of the antioxidant ionol and a 1,4-dihydropyridine ring. It was found that, among the compounds synthesized, the highest antiradical activity occurred in a compound having two hydroxyl groups in the 4-phenyl substituent. 相似文献
139.
The reaction of diethyl 3-ethoxycarbonyl-2-methyl-2-propenylphosphonate (1a) with 3-methylbutanal (2) in heterogeneous MOH (solid)-benzene systems in the presence of 5–10 mol.% of benzyltriethylammonium chloride (BTEAC) gives the reaction product (3) with a higher, for M=K, or lower, for M=Li, ratio of 2E,4E and 2Z,4E-stereoisomers than that observed in the absence of BTEAC. Tetrabutylammonium bromide (TBAB) as a catalyst of the reaction1a + 2 3 in the system KOH (solid)-wet benzene leads to a higher [2E,4E-3][2Z,4E-3] ratio than BTEAC; this ratio grows from 4456 without TBAB to 8020 at 100 mol.% of TBAB. In the latter case the stereochemical outcome of the reaction is similar to that obtained when tetrabutylammonium hydroxide in dry benzene is used as the deprotonating agent. The corresponding diisopropyl phosphonate (1b) and 3,7-dimethyloctanal (4a) interact in the system KOH (solid)-wet benzene-TBAB to give hydroprene (5) containing 88 % of the 2E,4E-isomer (5a) while in the case of 1 equiv. of [(n-Bu4)N]OH in dry benzene the content of5a is 92 %. Diisopropyl 3-isopropoxycarbonyl-2-methyl-2-propenylphosphonate (1c) and 7-methoxy-3,7-dimethyloctanal (4b) under either of these conditions afford methoprene (6) containing 93 % of the 2E,4E-isomer.Part 6, see ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1094–1098, June, 1993. 相似文献
140.
Xin-hua Wan Hui-lin Tu Ying-feng Tu Dong Zhang Ling Sun Qi-feng Zhou Yu-ping Dong Mao Tang Department of Polymer Science & Engineering College of Chemistry Peking University Beijing China Department of Materials & Chemical Engineering Beijing Institute of Technology Beijing China 《高分子科学》1999,(2):189-192
The first TEMPO-mediated "living" free radical polymerization of liquid crystallinemonomer, 2, 5-bis[(4-methoxyphenyl)oxycarbonyl]styrene(MPCS), was carried out at 130℃ withBPO as an initiator. The molecular weight of the polymer can be varied from rather low values to highvalues while maintaining narrow polydispersity. It was observed that the polymerization of MPCSproceeded much faster than that of styrene. A tentative explanation for this fast polymerization wassuggested. 相似文献