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251.
广义的荧光猝灭系指所有能使荧光强度降低的物理和化学过程,但通常涉及的主要有动态猝灭和静态猝灭,二者均遵从Stern-Volmer方程,但由于猝灭作用本质不同,它们在荧光寿命变化、温度效应及吸收光谱等方面表现出差异可资区别.本文通过稳态荧光强度变化和荧光衰减速率的比较研究了具有不同烷基链长的十四烷基苄基二甲基氯化铵(Zeph)和苄基三甲基溴化铵(TMBA)对芘的荧光猝灭,并基于电导实验结果以及猝灭剂全反式构象从理论上计算了Zeph和TMBA的猝灭速率常数,讨论了荧光猝灭的性质和长链分子的构型。 相似文献
252.
Two separate peaks are observed for narrow polymer standards in both isocratic and gradient HPLC. One peak appears around the solvent front (the "solvent-plug peak" or "breakthrough peak"), whereas the second peak is retained significantly--or even highly. Although the effect has been observed many times before, it has never been rigorously explained. In this paper we provide a detailed explanation for the breakthrough peak. The two completely separate peaks are demonstrated not to represent to different fractions of the sample (e.g., the low- and high-molecular-mass parts of the distribution). Both peaks are representative of the entire polymeric sample for narrow polymer standard. Because the amount of the polymer in the breakthrough peak may vary, the quantitative analysis of the polymers by LC is jeopardized. The effects of the sample solvent, the (initial) mobile phase composition, the injection volume, the injected sample concentration, the column temperature, and the analyte structure and molecular mass on the breakthrough peak were investigated in LC experiments involving standards of polystyrene and poly(methyl methacrylate). Three necessary and sufficient conditionsare suggested for the breakthrough phenomenon to be observed. Recommendations to avoid the breakthrough phenomenon are given, culminating in a structured method for selecting the best possible sample solvents. 相似文献
253.
Raman mapping and in situ SERS spectroelectrochemical studies of 6-mercaptopurine SAMs on the gold electrode 总被引:1,自引:0,他引:1
Yang H Liu Y Liu Z Yang Y Jiang J Zhang Z Shen G Yu R 《The journal of physical chemistry. B》2005,109(7):2739-2744
The self-assembled monolayers (SAMs) of 6-mercaptopurine (6MP) were formed at the roughened polycrystalline gold surfaces in acid and alkaline media. The time-dependent Raman mapping spectral analysis in conjunction with the quantum calculations for the vibrational modes using ab initio BLYP/6-31G method suggested that both of the resulted 6MP SAMs adopted the same adsorption mode through the S atom of pyrimidine moiety and the N7 atom of the imidazole moiety anchoring the gold surface in a vertical way. The in situ surface-enhanced Raman scattering spectroelectrochemical experiment was conducted to examine the stability of the SAMs at various bias potentials. It was found that the detaching process of the 6MP SAMs from the surface involved one electron reduction as the voltage was applied at ca. 0.7 V vs a standard calomel electrode. 相似文献
254.
XinZHANG DeHuaHE QiJiangZHANG BoQingXU QiMingZHU 《中国化学快报》2003,14(10):1066-1069
Comparatively high CH3OH selectivity (60.0%) and yield (6.7%) were obtained on MoOx/(LaCoO3 Co3O4) catalysts in selective oxidation of methane to methanol using molecular oxygen as oxidant. The interaction between MoOx and La-Co-oxide modified the molecular structure of molybdenum oxide and the ratio of O^-/O^2- on the catalyst surface, which controlled the catalytic performance of MoOx/(LaCoO3 Co3O4) catalysts. 相似文献
255.
256.
The α-diazophosphonate was added to aryl (N-tosyl)imine to give β-aryl β-(N-tosyl)amino α-diazophosphonates, which were further subjected to TsOH-catalyzed diazo decomposition to yield α-aryl β-(N-tosyl)enaminophosphonates through 1,2 aryl migration. The α-aryl β-(N-tosyl)enamino phosphonates were hydrogenated to give α-aryl β-(N-tosyl)amino phosphonates. 相似文献
257.
在色谱微反流动法实验装置上考察了负载Sm2O3对CuOγAl2O3催化剂CO氧化活性的影响,并运用X射线衍射(XRD)、程序升温还原(TPR)及程序升温脱附(TPDMS)技术研究了Sm2O3对CuOγAl2O3催化剂的物相结构、氧化还原特性及表面氧的脱附与恢复行为的影响。结果表明,负载适量的Sm2O3对CuOγAl2O3催化剂表面氧的脱出与恢复有促进作用,可使部分γAl2O3相变成γAl2O3和θAl2O3的混合型。负载适量的Sm2O3能改善催化活性,而负载过量的Sm2O3则使CuO催化剂上CuO的晶粒增大,从而对催化活性起了抑制作用。 相似文献
258.
粘度法预测聚乙二醇/壳聚糖体系的相容性 总被引:4,自引:0,他引:4
甲壳素在自然界的含量很大,仅次于纤维素,是一种颇具应用潜力的天然高分子.可由甲壳素经脱酸基化制得壳聚糖.由于其分子中存在氨基,因此能溶解干酸性水溶液中,并以聚电解质的形式存在,近来用壳聚糖制得的纤维膜应用于药物、食品等的分离和纯化、污水的处理,分离效果好,且不带入任何化学杂质.在壳聚糖纤维膜制作及与纤维的混纺过程中,都要探讨它与其它相应高聚物的相容性[1].我们以相容的壳聚糖(chitosan)/聚乙二醇(PEG)体系为例,采用粘度法讨论其分子间的相互作用,并预测它们的相容性.壳聚糖的基本结构为1实验部分1.1… 相似文献
259.
5-氟尿嘧啶-1-乙酸合铜(Ⅱ)的合成及其与DNA的作用 总被引:1,自引:0,他引:1
The 5-fluorouracil-1-acetic acid (5FuAA) and its Cu(Ⅱ) complex (5FuAACu) were synthesized and the date for the crystal complex was obtained. The interaction of 5-fluorouracil-1-acetic acid (5FuAA) and its Cu(Ⅱ) complex (5FuAACu) with DNA was also investigated by using spectral, viscometric, electrochemical and agarose gel electrophoresis methods. The results of interaction with DNA suggest that both 5FuAA and 5FuAACu can bind to DNA in a static electricity attraction mode. But the attraction of 5FuAACu is greater than that of 5FuAA. 相似文献
260.
According to the new method of preparing core-shell nanospheres developed by our group, by using two monomers, 2-hydroxypropyl
methacrylate(HPMA) and vinyl acetate(VAc), two kinds of core-shell nanospheres with poly(ɛ-caprolactone) (PCL) as the core
and crosslinked poly(2-hydroxypropyl methacrylate) (PHPMA) or poly(vinyl acetate) (PVAc) as the shell were successfully prepared
under similar conditions. After degrading the PCL cores of the two kinds of nanospheres by lipase, the corresponding crosslinked
poly(methyl acrylic acid) hollow spheres and crosslinked poly(vinyl alcohol) hollow spheres were obtained. Results indicate
that the new method we proposed for preparing core-shell polymeric nanospheres via in-situ polymerization can be generalized to a certain extent, and it is suitable for many systems provided the monomer used is soluble
in water, while its corresponding polymer is insoluble in water.
Translated from Chemical Journal of Chinese University, 2006, 27(9): 1762–1766 [译自: 高等学校化学学报] 相似文献