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141.
During nitroxide-mediated polymerization (NMP) in the presence of a nitroxide R2(R1)NO*, the reversible formation of N-alkoxyamines [P-ON(R1)R2] reduces significantly the concentration of polymer radicals (P*) and their involvement in termination reactions. The control of the livingness and polydispersity of the resulting polymer depends strongly on the magnitude of the bond dissociation energy (BDE) of the C-ON(R1)R2 bond. In this study, theoretical BDEs of a large series of model N-alkoxyamines are calculated with the PM3 method. In order to provide a predictive tool, correlations between the calculated BDEs and the cleavage temperature (T(c)), and the dissociation rate constant (k(d)), of the N-alkoxyamines are established. The homolytic cleavage of the N-OC bond is also investigated at the B3P86/6-311++G(d,p)//B3LYP/6-31G(d), level. Furthermore, a natural bond orbital analysis is carried out for some N-alkoxyamines with a O-C-ON(R1)R2 fragment, and the strengthening of their C-ON(R1)R2 bond is interpreted in terms of stabilizing anomeric interactions. 相似文献
142.
Xianfeng?You Feng?Chen Jinlong?ZhangEmail author 《Journal of Sol-Gel Science and Technology》2005,34(2):181-187
TiO2 powders were prepared by sol–gel template method and calcined under different conditions. XRD, BET and TEM were used to characterize the TiO2 powders obtained. The photocatalytic activity of TiO2 was investigated by the degradation of methyl orange. It was found that TiO2 powder has the highest photocatalytic activity at a calcination temperature of 673 K. The effects of physical properties such as surface area, crystallinity and crystal phase on the photocatalytic activity of TiO2 were discussed. 相似文献
143.
Rongbiao?WangEmail author Herbert?Schmiedel Bernd-Reiner?Paulke 《Colloid and polymer science》2004,283(1):91-97
Isothermal titration calorimetry (ITC) measurements of the mixture of the cationic surfactant cetyl trimethyl ammonium bromide (CTAB) with negatively charged, hairy copolymer latices (poly-(2,3-epoxypropylmethacrylate-co-methacrylic acid) in different ratio) at high water excess indicate a monomer adsorption mechanism of CTAB by the polymer particles. The number of adsorbed CTAB molecules at saturation corresponds approximately to the number of negative elementary charges bound at the surface of the latices. The mixing enthalpy is the sum of demicellization and sorption enthalpies. At 25 °C for CTAB the demicellization enthalpy amounts to 10 kJ/mol, whereas the adsorption enthalpy varies from –7 kJ/mol (surface charge density of the latices
=–0.37 C/m2) to +3 kJ/mol (=–0.085 C/m2). The hydrodynamic radius
RH of the latex particles upon titration of cationic detergent and salt (NaBr) decreases by about 2 nm until the onset of aggregation near the isoelectric point. Titration of nonionic or anionic detergents has much less influence on the hydrodynamic radius and produces no measurable adsorption heat. The results are consistent within a model of latex particles with extended negatively charged polymer chains interacting predominantly via Coulombic forces with detergents. 相似文献
144.
Veronica?StigssonEmail author G?ran?Kloow Ulf?Germg?rd Niclas?Andersson 《Cellulose (London, England)》2005,12(4):395-401
Controlling the reduction in molecular weight of the cellulose chains is essential in the production of carboxymethyl cellulose
(CMC). Such a reduction can be achieved by the addition of cobalt during the process of cobalt(II) ions, which act as a catalyst
for oxidative cleavage, and the influence thereof has been studied under a variety of conditions. This study has resulted
in a model that summarises the effects of the added amount of cobalt, the time for the cobalt reaction, the temperature in
the mercerisation stage of the CMC-manufacturing process and finally the effect of the temperature in the etherification stage.
It is shown that it is important for cobalt to be present during the mercerisation stage in order to achieve the desired viscosity. 相似文献
145.
Let {ø n (dμ)} be a system of orthonormal polynomials on the unit circle with respect to a measuredμ. Szegö's theory is concerned with the asymptotic behavior ofø n (dμ) when logμ′∈L 1. In what follows we will discuss the asymptotic behavior of the ratioø n (dμ 2)/ø n (dμ 1) on the unit circle whendμ 1 anddμ 2 are close in a sense (e.g.,dμ 2=gdμ 1, where g≥0 is such thatQ(e it )g(t) andQ(e it )/g(t) are bounded for a suitable polynomialQ) and μ 1 ′ >0 almost everywhere or (a somewhat weaker requirement) lim n→∞Φ n (dμ 1,0)=0 for the monic polynomial Φ n . The asymptotic behavior of the same fraction outside the unit circle was discussed in an earlier paper. 相似文献
146.
Kimmo Smolander Risto J?rnstr?m Annika Sajalinna 《Fresenius' Journal of Analytical Chemistry》1989,335(4):392-394
Summary The matric effect of boric acid was investigated in the determination of iron in the primary circuit coolant water of nuclear power plants by furnace atomic absorption spectrometry. The effect of boric acid was of particular interest. The method was applied during refuelling and maintenance periods and the results were used to interpret the chemical changes in the water.
Einfluß von Borsäure auf die Bestimmung von Eisen in Reaktorkühlwasser durch GF-AAS相似文献
147.
The title compound, (isopropylxanthato)(phenyl)mercury(I), was synthesized and characterized by elemental analysis, IR and thermogravimetric analysis. Density functional theory (DFT) method calculations were performed at B3LYP/CEP-121G and B3LYP/CEP-31G levels of theory, respectively. Vibrational frequencies were predicted, assigned, compared with the experimental values, and they are supported each other. The calculated results show that the strength of bond Hg—C is stronger than that of Hg—S, which is good agreement with the experimental data. The calculations of the second order optical nonlinearity and electronic absorption spectra are also performed. 相似文献
148.
Host-guest complexes of cucubit[8]uril with phenanthrolines and some methyl derivatives 总被引:1,自引:0,他引:1
DAY Anthony I 《中国科学B辑(英文版)》2005,48(4):305-314
Cucurbituril a molecular container (or host) has a rigid hollow interior cavity which is large enough to accommodate, one or more, smaller molecules (or guests). The cavity is accessible through two carbonyl portal openings. Molecules or guests enter the … 相似文献
149.
150.
This paper reports the results of a variety of experiments carried out for understanding the solvation behavior of potassium thiocyanate in methanol–water mixtures. Electrical conductivity, speed of sound, viscosity, and FT-Raman spectra of potassium thiocyanate solutions in 5 and 10% methanol–water (w/w) mixtures were measured as functions of concentration and temperature. The conductivity and structural relaxation time suggest the ion–solvent and solvent-separated ion–ion associations increase as the salt concentration increases in the mixtures. The Raman band shifts due to the C–O stretching mode of methanol for the solvent mixtures reveal the formation of methanol–water complexes. The significant changes in the Raman bands for the C–N, C–S and O–H stretching modes indicate the presence of SCN−−solvent interactions through the N-end, “free” SCN− and the solvent-shared ion pairs as potassium thiocyanate is added to the methanol–water mixtures. The relative changes corresponding to H–O–H bending and C–O stretching frequencies indicate that K+ is preferentially solvated by water in these solvent mixtures. The appearance and increase of the intensity of a broad band at ≈940 cm−1 upon salt addition was attributed to the SCN−–H2O–K+ solvent-shared ion pairs. No Raman spectral evidence for K+(H2O)n species was observed. The preferential solvation of K+ and SCN− in the methanol−water mixtures was verified by the application of the Kirkwood−Buff theory of solutions. This theory confirms that K+ is strongly preferentially solvated by water, whereas SCN− is preferentially solvated by the methanol component. 相似文献