Electron transfer reactions of nickel(III) and nickel(IV) complexes

This review narrates the electron transfer reactions of various nickel(III) and nickel(IV) complexes reported during the period 1981 until today. The reactions have been categorized mainly with respect to the type of nickel complexes. The reactivity of nickel(III) complexes of macrocycles, 2,2′-bipyridyl and 1,10-phenanthroline, peptides and oxime–imine, and of nickel(IV) complexes derived from oxime–imine, oxime and miscellaneous ligands with various organic and inorganic electron donors have been included. Kinetic and mechanistic features associated with such interactions have been duly analyzed. The relevance of Marcus cross-relation equations in the delineation of the electron transfer paths has also been critically discussed.     

A complete active-space self-consistent-field study on cubic N8

Summary Complete Active-Space Self-Consistent-Field (CAS-SCF) calculations for cubic N₈ are presented. We studied the N₈↔4N₂ reaction inD _4h symmetry and found its energy release and activation barrier with three different atomic basis sets. The energy release for this reaction is predicted to be around 526 kcal/mol, while the energy barrier to dissociation is estimated about 159 kcal/mol. These results are in substantial agreement with previousab initio estimates. The authors of this paper have agreed to not receive the proofs for correction.     

低密度聚乙烯光引发交联机理——Ⅱ.BNB自旋捕捉ESR研究

在光引发剂二苯甲酮(BP)存在下,紫外光辐照低密度聚乙烯(LDPE)所形成的自由基中间体已被自旋捕捉剂2,4,6-三特丁基亚硝基苯(BNB)所捕捉,其自旋加合物自由基已为电子自旋共振(ESR)所特征。现已检测和鉴定到二种自旋加合物:一种是叔碳自由基;另一种是仲碳自由基。它们分别是由BP的激发三重态从LDPE链的支化点和亚甲基团上夺氢所形成的自由基中间体同自旋捕捉剂BNB反应生成的。上述的证据表明:LDPE的光引发交联点主要发生在叔碳和仲碳原子上,且H-型交联点占主导地位。     

钢中Si、Mn的电子探针定量分析与标样

采用特制的Fe-Si、Fe-Mn合金系列标样，用电子探针测定了钢或铁基合金中低含量的Si和Mn元素、与用纯元素作标样、经ZAF修正的结果相比较，提高了分析准确度．     

Studies on the self-assembly behavior of the amphiphilic block copolymer of PSt-b-PAA in apolar solvents with polar fluorescent probe

The block copolymer of polystyrene-b-poly(butyl acrylate) (PSt-b-PBA) with a well-defined structure was synthesized by atom transfer radical polymerization (ATRP); its structure was characterized, and the living polymerization was also validated by gel permeation chromatography, Fourier transform infrared, and ¹H NMR measurements. Then, the amphiphilic block copolymer of polystyrene-b-poly(acrylic acid) (PSt-b-PAA) has been prepared by hydrolysis of PSt-b-PBA, and copolymers of PSt-b-PAA with longer PSt blocks and shorter PAA blocks were obtained by controlling the conditions of ATRP polymerization. The reversed micelle solution of PSt-b-PAA in toluene was prepared by using the single-solvent dissolving method, and the reverse micellization behavior of PSt-b-PAA in toluene was mainly investigated in this paper. The fluorescent probe technique was used by using polar fluorescence compound N-(1-Naphthyl)ethylenediamine dihydrochloride (NEAH) as a polar fluorescent probe to study the reverse micellization behavior of PSt-b-PAA. It was found that the reverse micellization behaviors of PSt-b-PAA in toluene can be clearly revealed by using NEAH as a polar fluorescence probe, and the critical micelle concentrations (cmcs) can be well displayed. The experimental results showed that the self-assembling behavior of PSt-b-PAA in toluene depends apparently on the microstructure of the macromolecules and is also influenced by the temperature. For the copolymers of PSt-b-PAA with the same length of hydrophobic PSt blocks, the copolymer with a longer hydrophilic block PAA has lower cmc, and at higher temperature, the copolymer has lower cmc.     

铕离子探针研究Al2O3的相变过程

氧化铝具有许多重要的工业用途，而制备高热稳定活性氧化铝的技术也在不断地发展[1，2]，因此，研究其高温烧结下的相变过程很有意义．离子深法作为新型测试手段，已成功地用于生物大分子结构与功能研究方面［‘］，而在固体材料测试中的应用尚未见报道．我们以EU’“作为荧光探针，并结合＊＊D和＊nR研究了川对。在不同烧结温度下的相变过程．1实验部分样品的制备采用复盐分解法．先将Elf刀s用高纯硝酸溶解定容．以占AlzO。重量1％的量加入到硫酸铝锭溶液中，进行超声处理，冷冻干燥．再依次登于900”C、1000C、1100C、1200C的高温炉…     

有机溶剂与水溶液引入电感耦合等离子体电子密度和电子温度轴向分布的比较

为了研究有机ICP最佳分析条件与水溶液ICP明显不同的原因,本文在不同的等离子体操作条件下测量了Hβ486.133nm Stark变宽,分别计算了有机溶剂和水溶液引入1CP轴向的n_e和Te值,并进行了比较。有机溶剂引入ICP时,在固定的功率,观测高度及载气流量下其轴向ne和Te均比用水溶液引入时低一些。有机ICP的优异分析性能只有在比水溶液ICP有较高的入射功率和较低的载气流量条件下才能展现出来。     

How electrons guard the space: shape optimization with probability distribution criteria

Efficient formulas for computing the probabilities of finding exactly electrons in an arbitrarily chosen volume ³ for Hartree–Fock wavefunctions are presented. These formulas allow the use of shape optimization techniques, such as level set methods, for optimizing with respect to various criteria involving such probabilities. The criterion defined as the difference between the Hartree–Fock and the independent-particle model probabilities of finding electrons in stresses the quantum effects due to the Pauli principle. We have implemented a 2D level set method for optimizing this criterion in order to study spatial separation of electron pairs in linear molecules. The method is described and the illustrative example of the BH molecule is reported.Contribution to the Jacopo Tomasi Honorary Issue     

基于硫化镉纳米团簇标记DNA电化学传感的研究

合成了表面具有自由羧基的硫化镉纳米团簇，以乙基-（3-二甲基丙基）碳二 亚胺盐酸盐为偶联活化剂，将其标记于人工合成的5'端氨基修饰的寡聚核苷酸片段 上，制备成CdS纳米团簇标记DNA探针，该寡聚核苷酸片段与大肠杆菌肠毒素基因相 关。在一定的条件下，使基与固定晨玻碳电极表面的待测DNA序列进行杂交反应， 利用阳极溶出示差脉冲伏安法（ASDPV）间接测定Cd的量，实现对互补、非互补 DNA片段的识别和电化学检测，从而对大肠杆菌肠毒素基因片段识别和检测。     

聚电解质溶液中2.6-ANS探针的荧光谱研究

本文合成了2.6—ANS荧光探针分子,并在含有不同外加盐的NaPSS溶液中测定了探针的荧光发射光谱。结果表明:探针的荧光强度随Cs增大而增大,而探针光谱的最大发射波长和半波宽度随Cs增大而减小。当Cs达到一定值时,荧光谱参数与Cs关系曲线出现转折点,此时聚离了链以“类胶束”状态存在。