硫增感的敏化中心和潜影中心的氧化还原性能的研究

本文采用Reinders的氧化还原缓冲液的方法研究硫敏化的立方体卤化银微晶的敏化中心和潜影中心的氧化还原性能.实验结果表明:1)Reinders的氧化还原缓冲液的方法,不仅可用于研究潜影中心,也可用于研究敏化中心;2)本实验条件下的硫化银敏化中心的氧化还原电位约略负于－220 mV(相对于饱和甘汞电极),潜影中心的氧化还原电位值是介于－220 mV与－190 mV之间(相对于饱和甘汞电极);3)潜影中心的氧化还原活性较敏化中心大得多.     

ZnHZSM－5上脱氢环化芳构化过程的探讨

以正己烷、环己烷、甲基环戊烷、１－己烯和环己烯等分子探针反应，考察了单Ｂ酸型ＨＺＳＭ－５、Ｚｎ－Ｌ酸型ＺｎＮａＺＳＭ－５和双中心型ＺｎＨＺＳＭ－５（Ｂ酸和Ｚｎ－Ｌ酸）催化剂的性能，探讨了Ｂ酸中心和Ｚｎ－Ｌ酸中心在芳构化过程中的作用．实验结果表明，Ｂ酸中心有利于环化，Ｌ酸中心有利于脱氢芳构化．单具Ｂ酸或Ｚｎ－Ｌ酸中心催化剂上，直链烃分子的芳构化性能较差，当两种中心同时存在时，双功能互相促进，加快芳构化过程．文中还对Ｃ６分子脱氢环化芳构化过程进行了讨论     

V Centers and Hole-Photostimulated Luminescence of BaFCl Crystal

V centers (hole centers) and hole-photostimulated luminescence of BaFCl crystal are reported for the first time. The absorption bands of V1, V2 and V3 centers are peaking at 205, 238 and 355 nm respectively. V2 center creation by X-irradiation and decay during photostimulated luminescence process are synchronousl with that of F center. This indicates that V centers play the same roles as F centers in X-ray storage and photostimulated luminescence processes.     

A Rule to Design High Spin Molecules with Hetero spin Centers

ＩｎｔｒｏｄｕｃｔｉｏｎＨｉｇｈｓｐｉｎｍｏｌｅｃｕｌｅｓｈａｖｅａｔｔｒａｃｔｅｄｍｕｃｈｉｎｔｅｒｅｓｔ,ｂｅｃａｕｓｅｔｈｅｙｃａｎｂｅｓｅｒｖｅｄａｓｔｈｅｂｕｉｌｄｉｎｇｂｌｏｃｋｆｏｒｍａｇｎｅｔｉｃｍａｔｅｒｉａｌｓ［１－２］．ＩｔｉｓｓｕｇｇｅｓｔｅｄｂｙＦｕｋｕｔｏｍｅ［３］ａｎｄＤｏｕｇｈｅｒｔｙｅｔａｌ．［４］ｔｈａｔｔｈｅｈｉｇｈｓｐｉｎｍｏｌｅｃｕｌｅｓｃａｎｂｅｄｉｖｉｄｅｄｉｎｔｏｔｗｏｃｏｍｐｏｎｅｎｔｓ：ｔｈｅｓｐｉｎ－ｃｏｎｔａｉｎｉｎｇ（ＳＣ）ｆｒａｇｍｅｎ…     

Formation of Specific Configurations at Stereogenic Nitrogen Centers upon Their Coordination to Zinc and Mercury

The coordination of (R,R)-tetramethylcyclohexane-1,2-diamine derivatives with stereogenic nitrogen centers to zinc and mercury halides is investigated. It is shown that the resulting complexes display one specific configuration at the stereogenic nitrogen centers. This fact is unusual due to the fast inversion of nitrogen centers but highly desirable as the stereoinformation of the ligands is brought closer to the metal centers of the potential catalysts. A combination of NMR studies and quantum chemical calculations gives insight into the selective formation of one specific configuration at the stereogenic nitrogen centers of the zinc complexes.     

<Emphasis Type="Italic">Ab initio</Emphasis> calculation of the hydration of organic cations and their associates with amines on the surface of kaolinite

It was shown, by ab initio calculations of the characteristics of hydrophilic centers formed on the surfaces of organosubstituted kaolinites with equivalent and superequivalent modifications, that superequivalent modifications of the mineral surface with octadecylammonium chloride, i.e. blocking the hydrophilic centers of the ionic-adsorbed cationic surface-active substance with the molecular adsorbed amine, led to the redistribution of the electron density close to these centers, in particular to the decrease in the effective charge at the hydrophilic centers. The calculated structures and energetics of nanostructures formed by the adsorption of water molecules at such hydrophilic centers showed that such redistribution decreases the energy of their interaction with water, which resulted from theoretical decrease in the energetic effects of hydration of the centers effectively agreed with the experimental values of the heats of adsorption. It was shown that for such adsorbtion systems the energetics were suitable for the formation in the region of the adsorption centers of cyclic structures of water.     

X射线诱导BaFCl:Eu2+光激励发光过程的新观察

本文研究了ＢａＦＣｌ：Ｅｕ＾２＾＋光激励发光（ＰＳＬ）对Ｘ射线剂量的响应关系，光激励发光的衰减规律，以及色心的形成与转型。除了简单的Ｆ心之外，我们还发现了Ｆ心的缔合中心，它们的吸收带位于７００－９５０ｎｍ。连续光激励Ｆ心时，光激励发光呈指数型衰减，而光激励发光（ＴＳＬ）也显现类似的衰减规律。光激励Ｆ缔合中心时，伴随着光激励发光还可能有一些无辐射跃迁过程的产生，例如色心的分解，转型和解离电子的再捕获     

金在铱内敏的直接正像乳剂中的作用

制备依内敏的AgBr立方体乳剂,乳剂被二氧化硫脲和三氯化金灰化。实验表明:有金存在时灰化乳剂,灰化中心优先在颗粒表面形成;金不存在时,则灰化中心优先在颗粒内部形成。用Na₁S₂O₃溶液刻蚀乳剂,得到了灰化中心在乳剂颗粒体相中的分布曲线。当二氧化硫脲量小,加金灰化时,灰化中心分布在颗粒表面和次表面;当二氧化硫脲量大,加金灰化时,灰化中心分布在颗粒体相中,但由表到里,灰化中心越来越少;当二氧化硫脲量大,不加金灰化时,灰化中心主要分布在颗粒中层部分。对加金灰化的乳剂来说,由于颗粒内部没有灰化中心竞争光生空穴,有大量的光生空穴破坏颗粒表面的灰化中心,因而可以获得高感直接正像乳剂。     

氧化铝基COS、CS_2水解催化剂表面碱性和催化作用

进行了３种氧化铝基催化剂上ＣＯ２的ＴＰＤ和ＣＯＳ、ＣＳ２的水解活性研究．结果表明，催化剂表面碱性中心类型、强度和数目是不相同的；Ｋ２Ｏ和Ｐｔ的负载能提高弱碱性中心的数目和强度，同时能显著提高ＣＯＳ、ＣＳ２的水解转化率．关联第一类ＣＯ２脱附活化能和峰面积与ＣＯＳ水解反应活化能和速率常数，发现呈线性关系，说明弱碱性中心是ＣＯＳ催化水解的活性中心．关联第一、二两类ＣＯ２脱附峰面积与ＣＳ２水解速率常数，指出弱、次弱两类碱性中心均参与了ＣＳ２催化水解．催化剂表面上能量的分布是不均匀的．     

氧化铝基催化剂上羰基硫和二硫化碳的水解研究 I.COS和CS_2的水解活性研究

在温度３０～１４０Ｃ空速１０００～５０００ｈ１和常压下，利用固定床反应器测定了三种氧化铝基催化剂上ＣＯＳ和ＣＳ２的水解活性。结果表明，ＣＯＳ和ＣＳ２水解反应速率与其浓度呈一级。低温时三种催化剂上ＣＯＳ和ＣＳ２表观反应活化能依次分别为５７．８０及５２．５０，４４．７１及５５．５３，３８．７０及３５．０ｋＪ／ｍｏｌ。三种催化剂中，负载Ｋ２Ｏ和Ｐｔ的催化剂具有较好稳定性和最高活性。     

1-辛烯Ziegler-Natta聚合的活性中心多分散性——分子量分布及动力学的研究

 本文通过对TiCl₃-Al(C₂H₅)₃聚合1-辛烯产物的双峰型分子量分布曲线用Schulz函数进行拟合、分峰处理,发现这种双峰型分布中的高分子量峰部分由一种活性中心生成,低分子量峰部分则由至少两种活性中心生成.将不同转化率时聚辛烯的分子量分布分峰拟合数据与聚合速率、活性中心数等测定数据相结合,得到了高分子量和低分子量两部分产物相应的活性中心上各自的动力学参数(增长速率常数、活性中心数、链转移常数等)及各自的聚合速率曲线,从而证实了多种活性中心的存在、它们催化特性的差异及与聚合物分子量分布增宽的关系.     

1-辛烯Ziegler-Natta聚合的活性中心多分散性——分子量分布及动力学的研究

本文通过对TiCl_3-Al(C_2H_5)_3聚合1-辛烯产物的双峰型分子量分布曲线用Schulz函数进行拟合、分峰处理,发现这种双峰型分布中的高分子量峰部分由一种活性中心生成,低分子量峰部分则由至少两种活性中心生成.将不同转化率时聚辛烯的分子量分布分峰拟合数据与聚合速率、活性中心数等测定数据相结合,得到了高分子量和低分子量两部分产物相应的活性中心上各自的动力学参数(增长速率常数、活性中心数、链转移常数等)及各自的聚合速率曲线,从而证实了多种活性中心的存在、它们催化特性的差异及与聚合物分子量分布增宽的关系.     

光生电子和由还原剂提供的电子在卤化银颗粒中性能的比较

本文研究了光生电子和还原剂提供的电子在卤化银晶体中的行为。光灰化和还原剂灰化生成的灰雾中心的位置不同。光灰化时灰雾中心优先在卤化银颗粒内部形成,表明光生电子可以直接进入卤化银晶体的导带。还原灰化时内部灰雾中心只有在灰化剂量足够多时才形成,而且滞后于表面灰雾中心的形成,表明还原剂提供的电子虽然可以进入卤化银的导带,但它们进入导带的方式与光生电子不同。     

Kinetics of propylene and ethylene polymerization reactions with heterogeneous ziegler-natta catalysts: Recent results

The article discusses recent results of kinetic analysis of propylene and ethylene polymerization reactions with several types of Ti-based catalysts. All these catalysts, after activation with organoaluminum cocatalysts, contain from two to four types of highly isospecific centers (which produce the bulk of the crystalline fraction of polypropylene) as well as several centers of reduced isospecificity. The following subjects are discussed: the distribution of active centers with respect to isospecificity, the effect of hydrogen on polymerization rates of propylene and ethylene, and similarities and differences between active centers in propylene and ethylene polymerization reactions over the same catalysts. Ti-based catalysts contain two families of active centers. The centers of the first family are capable of polymerizing and copolymerizing all α-olefins and ethylene. The centers of the second family efficiently polymerize only ethylene. Differences in the kinetic effects of hydrogen and α-olefins on polymerization reactions of ethylene and propylene can be rationalized using a single assumption that active centers with alkyl groups containing methyl groups in the β-position with respect to the Ti atom, Ti-CH(CH₃)R, are unusually unreactive in olefin insertion reactions. In the case of ethylene polymerization reactions, such an alkyl group is the ethyl group (in the Ti-C₂H₅ moiety) and, in the case of propylene polymerization reactions, it is predominantly the isopropyl group in the Ti-CH(CH₃)₂ moiety. Published in Russian in Vysokomolekulyarnye Soedineniya, Ser. A, 2008, Vol. 50, No. 11, pp. 1911–1934. The text was submitted by the authors in English.     

Sabatier效应机理的研究

通过对核壳乳剂以及均质乳剂潜影分布和sabatier效应的研究,提出了产生Sabatier效应的可能机理:第一次曝光产生的表面潜影吸附了显影剂负离子以后变成空穴捕获中心而在第二次曝光时被漂白造成影像反转;卤化银颗粒上必须同时有足够的表面敏化中心和足够的内部敏化中心,两者应相匹配。利用这个机理可以解释许多有关Sabatier效应的实验现象。     

Chemistry at corners and edges: generation and adsorption of H atoms on the surface of MgO nanocubes

We used UV light to generate site-selective O- hole centers at three-coordinated corner oxygen sites on MgO nanocubes. These highly reactive O- radicals split H2 homolytically and, in the course of this reaction, become hydroxylated and produce hydrogen atoms. The hydrogen atoms adsorb predominantly at cube edges and dissociate into surface-trapped electrons and protons. We propose that the experimentally observed (H+)(e-) centers are formed adjacent to the hydroxyl groups generated in the homolytic splitting process and can be defined as (H+)3C...(e-)(H+)NC centers where 3C and NC refer to the coordination numbers of the corresponding hydroxylated oxygen sites. Our ab initio embedded cluster calculations reveal that the electronic properties of (H+)3C...(e-)(H+)4C centers situated along MgO nanocube edges are consistent with both the electron-paramagnetic-resonance signal parameters and the reported optical-absorption properties. The transformation of corner O- centers into the (H+)3C...(e-)(H+)NC-type centers prevents their recombination with electronic surface centers and, hence, significantly alters the electronic structure of MgO nanocubes by introducing shallow electron traps.     

Polymerization Kinetics of Propylene with the MgCl_2-Supported Ziegler-Natta Catalysts——Active Centers with Different Tacticity and Fragmentation of the Catalyst

The catalytic activity and stereospecificity of olefin polymerization by using heterogeneous TiCl_4/MgCl_2 Ziegler-Natta(Z-N) catalysts are determined by the structure and nature of active centers, which are mysterious and fairly controversial. In this work, the propylene polymerization kinetics under different polymerization temperatures by using Z-N catalysts were investigated through monitoring the concentration of active centers [C*] with different tacticity. SEM was applied to characterize the catalyst morphologies and growing polypropylene(PP) particles. The lamellar thickness and crystallizability of PP obtained under different polymerization conditions were analyzed by DSC and SAXS. The PP fractions and active centers with different tacticity were obtained with solvent extraction fractionation method. The catalytic activity, active centers with different tacticity and propagation rate constant k_p, fragmentation of the catalyst, crystalline structure of PP are correlated with temperature and time for propylene polymerizations. The polymerization temperature and time show complex influences on the propylene polymerization. The higher polymerization temperature(60 ℃) resulted higher activity, k_p and lower [C*], and the isotactic active centers C_i* as the majority ones producing the highest isotactic polypropylene(iPP) components showed much higher k_p when compared with the active centers with lower stereoselectivity. Appropriate polymerization time provided full fragmentation of the catalyst and minimum diffusion limitation. This work aims to elucidate the formation and evolution of active centers with different tacticity under different polymerization temperature and time and its relations with the fragmentation of the PP/catalyst particles, and provide the solutions to the improvement of catalyst activity and isotacticity of PP.     

Electron paramagnetic resonance and scanning tunneling microscopy investigations on the formation of F(+) and F(0) Color centers on the surface of thin MgO(001) films

The formation of surface color centers (F(S) centers) by electron bombardment of thin MgO(001) films is investigated using electron paramagnetic resonance and low-temperature scanning tunneling microscopy. At low electron doses both techniques indicate the formation of singly occupied color centers (F(S)(+)), whereas at high electron doses the doubly occupied type (F(S)(0)) is dominant. It is suggested that with increasing electron dose F(S)(+) centers are transformed into F(S)(0). Tunneling spectra of individual F(S)(0) centers reveal a large distribution of energetic positions of occupied and unoccupied states, which is caused by local variations of the coordination number of the defects and explains the broad signals usually detected with integrating spectroscopic techniques.     

Oxygen chemisorption on the PbS(001) surface: Quantum-chemical modeling

The structure and stability of local centers involving a different number of oxygen atoms on the surface of crystalline lead sulfide (001) were calculated in the framework of the cluster approach by the hybrid density functional theory B3LYP method. The trends of the formation of such centers and changes in the core electron binding energies for the sulfur and lead atoms constituting these centers were considered.     

Triplet Energy Transfer between the Primary Donor and Carotenoids in Rhodobacter sphaeroides R-26.1 Reaction Centers Incorporated with Spheroidene Analogs Having Different Extents of π-Electron Conjugation

Abstract— Three carotenoids, spheroidene, 3,4-dihydrospheroidene and 3,4,5,6-tetrahydrospheroidene, having 8, 9 and 10 conjugated carbon-carbon double bonds, respectively, were incorporated into Rhodobacter (Rb.) sphaeroides R-26.1 reaction centers. The extents of binding were found to be 95±5% for spheroidene, 65±5% for 3,4-dihydrospheroidene and 60±10% for 3,4,5,6-tetrahydrospheroidene. The dynamics of the triplet states of the primary donor and carotenoid were measured at room temperature by flash absorption spectroscopy. The carotenoid, spheroidene, was observed to quench the primary donor triplet state. The triplet state of spheroidene that was formed subsequently decayed to the ground state with a lifetime of 7.0±0.5 μs. The primary donor triplet lifetime in the Rb. sphaeroides R-26.1 reaction centers lacking carotenoids was 60±5 μs. Quenching of the primary donor triplet state by the carotenoid was not observed in the Rb. sphaeroides R-26.1 reaction centers containing 3,4-dihydrospheroidene nor in the R-26.1 reaction centers containing 3,4,5,6-tetrahydrospheroidene. Triplet-state electron paramagnetic resonance was also carried out on the samples. The experiments revealed carotenoid triple-state signals in the Rb. sphaeroides R-26.1 reaction centers incorporated with spheroidene, indicating that the primary donor triplet is quenched by the carotenoid. No carotenoid signals were observed from Rb. sphaeroides R-26.1 reaction centers incorporating 3,4-dihydrospheroidene nor in reaction centers incorporating 3,4,5,6-tetrahydrospheroidene. Circular dichroism, steady-state absorbance band shifts accompanying the primary photochemistry in the reaction center and singlet energy transfer from the carotenoid to the primary donor confirm that the carotenoids are bound in the reaction centers and interacting with the primary donor. These studies provide a systematic approach to exploring the effects of carotenoid structure and excited state energy on triplet transfer between the primary donor and carotenoids in reaction centers from photosynthetic bacteria.