Oxidation of Low-Density Lipoproteins in the Presence of a Fullerene-Containing Silica Gel

The results of a study on the oxidation of low-density lipoproteins (LDLs) in the presence of a fullerene-containing silica gel in the sorbent phase (a solid stationary phase) and in the phase of an LDL solution (a liquid mobile phase) are presented. It was found that the main distinctive feature of the process of LDL oxidation in the presence of a fullerene-containing silica gel consists in its heterogeneity; that is, the oxidation simultaneously occurs in both of the phases. In this case, the effect of the oxidation process in a solid phase on the kinetics in a liquid phase can be described in terms of the nonuniform distribution of reactant concentrations in the phases of the system and the formation of a donor–acceptor complex. It was found that the concentration of oxidation products is an exponential function of LDL concentration; this fact is indicative of a free-radical chain mechanism of the LDL oxidation reaction in the presence of the sorbent. This relationship was described by an empirical equation, which is the same for either of the phases, and the parameters of this equation have precise physical meanings. It was found from calculations that both the formation of donor–acceptor complexes and the nonuniform distribution of LDL in the two-phase system are responsible for a considerable difference between the kinetics of sorbent-initiated LDL oxidation in the sorbent phase and the solution phase.     

Oxidation of Sulfides with Pyridinium Tribromide in the Presence of Hydrated Silica Gel

A variety of sulfides have been oxidized to sulfoxides utilizing pyridinium tribromide in the presence of hydrated silica gel in a non‐aqueous media. A combination of pyridinium tribromide and hydrated silica gel releases molecular bromine slowly in the reaction, affecting the oxidation. Hydrated silica gel also promotes decomposition of the bromosulfonium intermediate to the product. This procedure employs non‐aqueous media for the first time in such a reaction.     

在氢化钙-硅胶存在下的烯丙醇催化不对称环氧化

自从 Sharpless 不对称环氧化被发现以来,这个反应已被广泛地应用于手性天然产物的合成。最近,Sharpless 及其同工作者又将原方法中使用的等摩尔量四异丙氧基钛和酒石酸酯减少到催化量,并加入3(?)或4(?)分子筛。这一改进可减少敏感性环氧醇产物的破环,使产物易于分离。从而使这个方法变得更为经济简便。我们曾报道过的改良 Sharpless     

稀土β-二酮类配合物掺杂硅胶的光声光谱及荧光光谱研究

用Ｓｏｌ－Ｇｅｌ过程制备了一系列稀土β－二酮类配合物掺杂的ＳｉＯ２凝胶，测量了这些掺杂ＳｉＯ２凝胶的光声光谱，与固体配合物相比，掺杂ＳｉＯ２凝胶的光声光谱吸收峰发生蓝移，荧光发射峰发生红移。从无辐射跃迁角度研究了掺杂凝胶的Ｅｕ－β二酮类配合物的分子内能量传递模型。     

Room Temperature Catalytic Aromatization of Hantzsch 1,4-Dihydropyridines by Sodium Nitrite in the Presence of Acidic Silica Gel

Summary. Various alkyl, aryl, and heterocyclic Hantzsch 1,4-dihydropyridines were converted to the corresponding pyridines in excellent yields and short times using sodium nitrite in the presence of a catalytic amount of acidic silica gel at room temperature.     

Use of Different Salt Solutions in Salting-Out TLC of Co(III) Complexes on Silica Gel

Saturated aqueous solutions of 28 different salts have been studied as a potential mobile phases for salting-out thin-layer chromatography, on silica gel, of a series of four mixed bis-aminocarboxylato cobalt(III) complexes. In addition, by linear regression analysis of chromatographic data obtained for fifteen mixed aminocarboxylato Co(III) complexes (four series) with solutions of ammonium chloride, three alkali metal chlorides, and four alkaline earth metal chlorides, four linear dependences previously established on different adsorbents with (NH₄)₂SO₄ solutions were confirmed. The qualities of the separations achieved with the salts were compared and Li⁺, Mg²⁺, and Ca²⁺ chlorides are proposed as the most suitable.     

两种红光铱配合物的合成和电致发光性能研究

以二(二苯基磷酰)胺(Htpip)作为辅助配体,与主配体2-(2,4-二氟苯基)异喹啉和2-(4-三氟甲基苯基)异喹啉合成了红光铱磷光配合物Ir(dfpiq)2tpip和Ir(tfmpiq)2tpip并得到了晶体结构。在CH2Cl2中发射光谱主要是MLCT发射,峰位置分别为622和600 nm,量子效率分别为15%和17%,而HOMO/LUMO能级分别是-4.80/-2.58和-4.73/-2.57 eV。在1150~1300(V·cm-1)1/2电场范围,Ir(dfpiq)2tpip的电子迁移率为6.61~8.49×10-6cm2·V-1·s-1,Ir(tfmpiq)2tpip的电子迁移率为6.08~6.61×10-6cm2·V-1·s-1。ITO/TAPC(60 nm)/Ir-complex(15wt%):CBP(50 nm)/TPBi(60 nm)/LiF(1 nm)/Al(100 nm)中基于Ir(dfpiq)2tpip的器件最大安培效率和功率效率分别为4.71 cd·A-1和1.82 lm·W-1,12.0 V时达到的最大亮度为18 195 cd·m-2。基于Ir(tfmpiq)2tpip的器件最大安培效率和功率效率分别为3.47 cd·A-1和1.51 lm·W-1,12.4 V时达到的最大亮度为14 676 cd·m-2。     

窄光谱磷光配合物的设计及电致发光性能

通过对螯合配体及辅助配体的设计与筛选, 构筑了一种全新的天蓝光铱金属配合物(MeFPyPy)₂Ir(dipcMePy)(简称MFPMP), 实现了三重态配体中心、 三重态金属-配体电荷转移和/或三重态配体-配体电荷转移跃迁类型混合比例较优化的发光过程. 以MFPMP作为发光体的磷光有机电致发光器件实现了半峰宽为52 nm, 最大发光波长为476 nm的窄光谱、 单峰型、 高亮度、 高效率天蓝光发射, 并在1000 cd/m²的实用亮度下保持了25%以上的外量子效率(EQE), 与目前报道的最高水平有机电致发光器件性能相当. 本工作为进一步开发色纯度更高、 更具有实用性的磷光配合物发光材料提供了一条可行的途径.     

Selective Oxidation of Aryl Ketones to a-Diketones with 4-Aminoperoxybenzoic Acid Supported on Silica Gel in Presence of Air

4-Aminoperoxybenzoic acid supported on silica gel in presence of air was found to be a selective and convenient oxidant for the oxidation of methylene groups in aryl ketones to convert them to -diketones.     

Kinetics of the Interaction of O2 with Mo(V) Oxo Complexes on Silica Gel in Outer-Sphere Electron Transfer

The kinetics of the interaction of Mo⁵⁺ oxo complexes on SiO₂ with dioxygen distributed among the gas phase, silica gel, and complexes was examined using the relationship between the reaction rate constants k _e and rate constant for substrate consumption k _m in a closed reactor. The kinetic criteria are given for selection of the mechanism for the photochemical and thermal reactions with a collisional or equilibrium intermediate.     

阴、阳离子表面活性剂混合体系在硅胶/水及硅胶/矿化水界面上的吸附

研究阴、阳离子表面活性剂混合体系(十二烷基氯代吡啶,辛基磺酸钠,辛基三乙基溴化铵/十二烷基苯磺酸钠)在硅胶,纯水和硅胶,矿化水界面上的吸附作用,探讨阴(阳)离子表面活性剂的存在对阳(阴)离子表面活性剂吸附作用的影响．结果表明,阴离子表面活性剂的存在基本不影响阳离子表面活性剂在带负电固体表面的吸附;而阳离子表面活性剂的存在却使本来吸附量就不大的阴离子表面活性剂在带负电的固体表面上不再吸附．在矿化水中阳离子表面活性剂的吸附量比在纯水中明显降低．从硅胶表面吸附机制解释了所得结果．     

Synthesis of Monolithic Silica Gel in Alkaline Medium

The influence exerted by the basicity and nucleophilicity of a number of organic amines on the formation of a monolithic silica gel by the organic sol-gel method was studied.     

Formation of Hierarchical Pore Structure in Silica Gel

By inducing a phase separation parallel to the sol-gel transition of alkoxy-derived silicate systems, gels with well-defined macroporous structure can be prepared. Depending on the post-gelation treatment such as aging and solvent exchange, the final pore structure in the nanometer range of dried and heat-treated gels exhibits a considerable variation. With an aim of completely controlling the hierarchical pore structure in the discrete size ranges of nanometers and micrometers, systematic experimental studies have been performed. The macroporous nature of the wet gels allows an efficient solvent exchange process compared with conventional gels only with mesopores. In addition, the surface chemistry of the wet gel skeleton affects the mesopore formation process by the solvent exchange to a great extent. The median size of mesopores larger than 5 nm can be controlled by adjusting the basic solvent exchange conditions such as pH value, temperature and bath ratio for any kind of macroporous silica gel. On the other hand, the control of pore volume independent of the mesopore size is possible only in the system incorporated with the micelle-forming surfactant. Some examples of the effects of controlled mesopores on the analytical performance of monolithic-type chromatographic columns are also presented.     

铕配合物电致发光研究进展

稀土铕配合物电致发光研究已经进入了一个关键阶段。本文在综述近年来铕配合物光致发光和电致发光研究现状的基础上，从铕配合物材料设计和器件结构优化的角度，讨论了影响其电致发光性能的几个重要因素。针对存在的铕配合物挥发性和热稳定性的问题提出了一些可能的解决办法，如通过提高阴离子配体或中性配体的挥发性来改善铕配合物整体挥发性能；修饰中性配体，增强其与铕离子的键合能力，提高配合物的热稳定性。     

Biocatalytic Gelation of Silica in the Presence of a Lipase

The effect of the lipase from Burkholderia cepacia (previously known as Pseudomonas cepacia) on the gelation kinetics and gel structure was examined on a type of silica aerogel made from a mixture of methyltrimethoxysilane and tetramethoxysilane. For this purpose, gels were made with increasing concentrations of lipase in otherwise constant other conditions (pH, water and Si precursors concentrations). It was found that the enzyme accelerated the gelation kinetics, hence was participating in some way to the hydrolysis of the silica precursor. The structure of the gel was simultaneously modified to produce an increasing proportion of Q⁴ silicon sites.     

Oxidation of Aromatic Amines to Quinones by Iodic Acid under Microwave Irradiation in the Presence of Montmorillonite K10 and Silica Gel

Summary. A variety of aromatic amines are oxidized to their corresponding quinones in excellent yields by supported iodic acid under microwave irradiation and solvent free conditions.     

Oxidation of Aromatic Amines to Quinones by Iodic Acid under Microwave Irradiation in the Presence of Montmorillonite K10 and Silica Gel

A variety of aromatic amines are oxidized to their corresponding quinones in excellent yields by supported iodic acid under microwave irradiation and solvent free conditions.