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951.
952.
The localized molecular orbitals and their energy levels for the clusters [Fe3S4(SH)3]2–, [(HS)3Fe3S4·Ni(PH3)]2–, [Mo3S4(OH2)9]4+, and [Mo3S4·Ni]4+ have been calculated by mean of the Edmiston-Ruedenberg energy localization technique under the CNDO/2 approximation in order to reveal the resemblance between [Fe3S4]+ and [Mo3S4]4+ in the geometrical configurations and the addition reactivities with heterometal atoms. It is shown that in these two cluster species with core {M
3(3-S)(-S)3} of similar structure (M = Mo, Fe) there exist three synergically connected three-centered two-electron (M-S-M) -bonds around the puckered six-membered {M3S3} rings on account of delocalization of a lone electron pair on each bridging S atom; these (M-S-M) -bonds are thus capable of forming cubane-like heterometal clusters with intruder metal atoms through the ( M) bonding. It is therefore seen that unlike the [Mo3S4]4+ with appreciable bonding between the Mo atoms, the extra d-electrons on the metal atoms in the [Fe3S4]+ cluster are localized on the Fe atoms, exhibiting an electronic structure significantly different from that of the [Mo3S4]4+ cluster. 相似文献
953.
Tao Liu Yong-Gang Wei Qi-Hua Wu Qing-Xiang Guo 《Research on Chemical Intermediates》2005,31(9):833-844
A series of adamantanamine-(OCH2CH2)n-phenothiazine (n = 0, 1, 2, 3) electron donors was synthesized. Photoinduced electron transfer was observed in the supramolecular complex
of the phenothiazine derivatives with p-nitrobenzoyl-β-cyclodextrin (NBCD) through binding of the adamantyl group by the NBCD cavity, which is stabilized clearly via hydrophobic interactions in aqueous solution. Detailed Stern–Volmer constants were measured and they were partitioned into
dynamic Stern–Volmer quenching constants and static binding constants. The results revealed an efficient electron transfer
process inside the supramolecular systems compared to that controlled by diffusion. This observation also indicates that the
chain length will influence the electron transfer efficiency of a supramolecular donor–acceptor system. 相似文献
954.
As bio‐inspired chemical model of the oxygen‐evolving complex (OEC) in photosystem II, a new tyrosine‐modified corrole ligand 3 and its high‐valent copper and manganese complexes 3a and 3b were synthesized and characterized. The copper complexes 1a and 2a of corrole 1 and 2 were also prepared for comparison. The emission property indicates that the emission of ligands 2 and 3 is located at 670 nm, but no emission is observed for their metal complexes due to its suppression by the metal center. The electrochemical study shows that 3a might dimerize at the first two reversible oxidations, a behavior which was not observed in the case of 1a and 2a . The corrolato manganese(IV) complex 3b shows one reversible reduction and one quasireversible oxidation at ?0.17 and 0.77 V vs. Ag/Ag+, respectively. 相似文献
955.
Nd-Fe-B磁体烧结过程晶粒长大行为的研究 总被引:4,自引:0,他引:4
定量描述了Nd-Fe-B磁体烧结过程晶粒长大行为,分析了烧结温度、烧结时间、合金粉末粒度及其分布对烧结过程晶粒长大的影响,讨论了烧结过程晶粒长大机制。在Nd-Fe-B磁体烧结过程开始之后的0—1h时间区段,晶粒长大迅速;随着烧结时间的延长,晶粒长大速度减小。合金粉末平均粒度增大,或者合金粉末粒度分布范围增宽,显著促进Nd-Fe-B磁体烧结过程中晶粒的长大。在Nd-Fe-B磁体的烧结过程中,存在两类晶粒长大机制,即Nd2Fe14B颗粒的溶解与析出、Nd2Fe14B颗粒的并合与长大。Nd2Fe14B颗粒的并合与长大不仅使磁体的平均晶粒尺寸增大,也使晶粒尺寸分布范围增宽,是烧结Nd-Fe-B磁体显微组织中出现异常大晶粒的根本原因。 相似文献
956.
Jia-you Shu Mo Zhu Yi Shu Qi-jun Liu Tong Li 《高分子科学》2006,(4):395-401
The new chelate resins, abbreviated as PNBMZs and PBBMZs based on epoxide polymer, were synthesized by polycondensation of N,N-diglycidyl-4-glycidyloxyaniline or 1,4-bis(2,3-epoxypropyl)benzene with the primary amine group of 1,3-bis(benzimidazol-2yl)propylamine (BBPAH). The ion exchangers contain 2.71-3.23 mmol of the ligand contents per gram of the resin. Batch extraction capacities were determined for the metal chloride salts in buffer solutions in the pH range from -1 to 6.0. The chelate resins were very selective for Cu^2+, Zn^2+, Cd^2+ in the presence of other divalent transition metal ions. The maximum uptake capacities of PNBMZ (synthetic molar ratio = 1:1.5) under non-competitive condition were found to be 0.94 mmol/g for Cu^2+ at pH = 2, 1.3 mmol/g for Cd^2+ at pH = 1 and 1.75 mmol/g for Zn^2+ at pH = -1 respectively. While in the case of PBBMZ, it was 1.39 mmol/g for Cd〉 at pH = 1. The metal-uptake behaviors for both of them showed strong pH dependence, and their extraction capacities increase with decreasing pH. The uptake of Cu^2+ by the resin PNBMZs at pH = 1 was found to be rather fast with t1/2 = 18 min. Metal-uptake experiments under competitive conditions also confirm that the chelate resins have a high selectivity for Cu^2+, Zn^2+, Cd^2+ and the contrary pH dependence. 相似文献
957.
纳米CoHCF修饰电极的制备及其对血红蛋白的电化学测定研究 总被引:1,自引:0,他引:1
A cobalt hexacyanoferrate (CoHCF) nanoparticle (size ca. 60 nm) chemically modified electrode (CME) was fabricated and the electrochemical behavior of hemoglobin (Hb) at this nanosized CoHCF CME was studied. In comparison with a bare glassy carbon electrode (GCE) and a general CoHCF CME electrodeposited in a traditional manner, the present nanosized CoHCF CME performed efficiently electrocatalytic reduction for Hb with relatively high sensitivity, stability, and longlife, Combined with liquid chromatography (LC), the nanosized CoHCF CME was used as the electrochemical detector of Hb in the established flow injection analysis-electrochemical determination (FIA-ECD) system. The peak current was a linear function of concentrations in the range from 2.5×10^-8 to 5.0×10^-6mol/L for Hb, with detection limit of 1.4×10^-8 mol/L. The FIA-ECD system has been successfully applied to assess the Hb content of clinic blood samples with advantages of sensitiveness, speediness, easy control and small sample-consumption. 相似文献
958.
本文描述了一个倾斜交叉、差分式激光热透镜光谱法。采用本方法可消除较高的溶剂空白的影响。文章讨论了调制频率和泵浦光功率对热透镜信号的影响,给出了检测Cu~(2+)的工作曲线,讨论了影响方法灵敏度的诸因素,提出了可能的改进方案。 相似文献
959.
A complete assignment of the 1H, 13C and 19F NMR spectra of 1,1,4,4-tetrafluoro-2-propylidene-3-methyl-6-tert-butyl-1,4-disila-5-cyclohexene 3, the product of the cycloaddition reaction between tetrafluorodisilacyclobutene 1 and cis, trans-2,4-hexadiene mediated by (n5-C5H5)Mn(CO)3, has been made by means of various 2D NMR chemical shift correlation methods and selective heteronuclear decoupling techniques. An analysis of the three bond 13C-1H coupling constants and two bond 13C-19F coupling constants and the molecular modeling results enabled the determination of the conformation and configuration of compound 3. The conformation of 3 provides insight into mechanistic details of the Mn-mediated cycloaddition. 相似文献
960.
The dependence of the frequency factor on the temperature (A=A
0
T
m) has been examined and the errors involved in the activation energy calculated from some integral methods without considering
such dependence have been estimated. Investigated integral methods are the Coats-Redfern method, the Gorbachev-Lee-Beck method,
the Wanjun-Yuwen method and the Junmeng-Fusheng method. The results have shown that the error in the determination of the
activation energy calculated ignoring the dependence of the frequency factor on the temperature can be rather large and it
is dependent on x=E/RT and the exponent m. 相似文献