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81.
The equilibrium geometries, electronic structures, as well as one- and two-photon absorption cross sections of a series of octupolar chromophores with Zn(2+) or Cu(+) as coordinate centers and 4,4'-bis(dibutylaminostyryl)-[2,2']-bis(bipyridyl) as ligands have been determined by using B3LYP/6-31G and ZINDO methods. These molecules are designed by controlled combination of two or three bipyridyl ligands with the metal centers. The results show that Zn(2+) is an effective template for the design of octupolar structures which enable it to form tetrahedral and octahedral coordinated complexes; while Cu(+) only exists in a tetrahedral coordinated complex, comparing the tetrahedral complex with Zn(2+) as the center with that of Cu(+) as the center, it is found that the complex with the Cu(+) center is a better two-photon absorption material than the former as far as the transparency/nonlinearity is concerned. Furthermore, for the same metal center of Zn(2+), both one- and two-photon absorptions of the tetrahedral complex are redshifted relative to those of the octahedral complex, is attributed to the spiroconjugation effect in the tetrahedral complex. Our theoretical findings are consistent with recent experimental observations and provide an important foundation for the design of improved transparency-nonlinearity two-photon absorption materials. 相似文献
82.
PengZHANG JiCunREN ZuoJunSHEN 《中国化学快报》2004,15(9):1091-1094
In this paper, we first presented a novel method for quantification of circulating DNA in human serum based on capillary zone electrophoresis with laser-induced fluorescence detection (CZE-LIF). The serum was digested by proteinase to release free DNA, and then CZE-LIF system was used for the quantification of total circulating DNA. This method was successfully used to quantify the circulating DNA levels in sera from healthy individuals and certain cancer patients.We found the significantly elevated circulating DNA levels in certain prostate cancer patients. Our results demonstrated that CZE-LIF system has good linearity, excellent sensitivity (0.5 ng/mL DNA),satisfactory reproducibility (RSDs in one day and between days were both less than 5%) and reliability, and is well suitable to the quantification of the circulating DNA in human serum or plasma. 相似文献
83.
A novel and practical procedure was developed for the abnormal Beckmann rearrangement of steroid 17-oximes. Treatment of the 17-oximes with TFA/CH(OMe)(3) in boiling THF for 2 h gives the corresponding 13,17-seco alkene nitrile products in unprecedented high yields (70-92%). Since the alkene nitriles can be subsequently converted into 18-norsteroids, this general method provides a highly efficient route to these biologically important compounds and, by extension, to other structurally related natural products. 相似文献
84.
羧甲基壳聚糖/聚乙烯醇/甘油环氧树脂蛇笼型复合螯合膜的制备及对金属离子的吸附性能 总被引:4,自引:0,他引:4
以交联甘油环氧树脂交联的聚乙烯醇(PVA)为笼树脂,羧甲基壳聚糖(CCTS)为蛇树脂制备了具有蛇笼结构的复合螯合膜,研究了其对Cu^2 、Ni^2 、Pb^2 、Fe^3 、Zn^2 ,Hg”^2 、Cd^2 等金属离子的吸附性能,研究表明,该树脂对Cu^2 、Ni^2 、Pb^2 有较好的吸附性能,其中PVA是对Cu^2 的吸附的主要贡献者,而CCTS则是在对Ni^2 的吸附中起主要作用。该树脂可以用于含Cu^2 废水的处理。 相似文献
85.
Xu X Zhao J Jiang D Kong J Liu B Deng J 《Analytical and bioanalytical chemistry》2002,374(7-8):1261-1266
A novel hydrogen peroxide biosensor was developed based on the immobilization of horseradish peroxidase (HRP) in a TiO(2) sol-gel matrix on an electropolymerized phenazine methosulfate (PMS) modified electrode surface. Such membranes are of interest due to their high surface area, biological compatibility, and ease of fabrication. HRP entrapped in the TiO(2) matix was stable and retained its activity to a large extent. Cyclic voltammetry and amperometric measurements were employed to demonstrate the feasibility of electron transfer between immobilized HRP and the glassy carbon electrode via electropolymerized PMS. The influence of various experimental parameters such as operating potential, pH, temperature, and stability was investigated for optimum analytical performance. The biosensor provided a wide linear calibration range from 4.0x10(-6) M to 1.0x10(-3) M, with a detection limit of 8.0x10(-7) M at a signal-to-noise ratio of 3. The sensor retained 80% of its original activity after two months of operation. 相似文献
86.
High-energy-density batteries are in urgent need to solve the ever-increasing energy storage demand for portable electronic devices, electric vehicles, and renewable solar and wind energy systems. Alkali metals, typically lithium(Li), sodium(Na) and potassium(K), are considered as the promising anode materials owing to their low electrochemical potential, low density, and high theoretical gravimetric capacities. However, the problem of dendrite growth of alkali metals during their plating/stripping process will lead to low Coulombic efficiencies, a short lifespan and huge volume expansion, eventually hindering their practical commercialization. To resolve this issue, a very effective approach is engineering the anodes on structured current collectors. This review summarizes the development of the alkali metal batteries and discusses the recent advances in rational design of anode current collectors. First, the challenges and strategies of suppressing alkali-metal dendrite growth are presented. Then the special attention is paid to the novel current collector design for dendrite-free alkali metal anodes. Finally, we give conclusions and perspective on the current challenges and future research directions toward advanced anode current collectors for alkali metal batteries. 相似文献
87.
The electrochemical carbon dioxide reduction reaction (CO2RR) offers a promising solution to mitigate carbon emission and at the same time generate valuable carbonaceous chemicals/fuels. Single atom catalysts (SACs) are encouraging to catalyze the electrochemical CO2RR due to the tunable electronic structure of the central metal atoms, which can regulate the adsorption energy of reactants and reaction intermediates. Moreover, SACs form a bridge between homogeneous and heterogeneous catalysts, providing an ideal platform to explore the reaction mechanism of electrochemical reactions. In this review, we first discuss the strategies for promoting the CO2RR performance, including suppression of the hydrogen evolution reaction (HER), generation of C1 products and formation of C2+ products. Then, we summarize the recent developments in regulating the structure of SACs toward the CO2RR based on the above aspects. Finally, several issues regarding the development of SACs for the CO2RR are raised and possible solutions are provided.The electrochemical carbon dioxide reduction reaction (CO2RR) offers a promising solution to mitigate carbon emission and at the same time generate valuable carbonaceous chemicals/fuels. 相似文献
88.
UB3LYP/6-31G(d) and ROMP2/6-311++G(d,2p) methods were used to calculate the Si-X bond dissociation energies (BDEs) of a number of para-substituted aromatic silanes (4-Y-C(6)H(4)-SiH(2)X, where X = H, F, Cl, or Li). It was found that the substituent effect on the Si-H BDE of 4-Y-C(6)H(4)-SiH(3) was small, as the slope (rho(+)()) of the BDE- regression was only 0.09 kJ/mol. In comparison, the substituent effect on the Si-F BDE of 4-Y-C(6)H(4)-SiH(2)F was much stronger, whose rho(+ )()value was -2.34 kJ/mol. The substituent effect on the Si-Cl BDE of 4-Y-C(6)H(4)-SiH(2)Cl was also found to be strong with a rho(+)() value of -1.70 kJ/mol. However, the substituent effect on the Si-Li BDE of 4-Y-C(6)H(4)-SiH(2)Li was found to have a large and positive slope (+9.12 kJ/mol) against. The origin of the above remarkably different substituent effects on the Si-X BDEs was found to be associated with the ability of the substituent to stabilize or destabilize the starting material (4-Y-C(6)H(4)-SiH(2)X) as well as the product (4-Y-C(6)H(4)-SiH(2)* radical) of the homolysis. Therefore, the direction and magnitude of the effects of Y-substituents on the Z-X BDEs in compounds such as 4-YC(6)H(4)Z-X should have some important dependence on the polarity of the Z-X bond undergoing homolysis. This conclusion was in agreement with that from earlier studies (for example, J. Am. Chem. Soc. 1991, 113, 9363). However, it indicated that the proposal from a recent work (J. Am. Chem. Soc. 2001, 123, 5518) was unfortunately not justified. 相似文献
89.
Eight tris(organotin)-substituted Keggin tungstosilicate heteropolyanions have been synthesized and characterized by elemental analysis, infrared and M?ssbauer spectroscopy, multinuclear NMR, and X-ray crystallography. The new anions contain alpha- or beta-SiW(9)O(34)(10)(-) moieties and are of two structural types, [(RSn)(3)(SiW(9)O(37))](7)(-) (R, isomer: Ph, alpha-, 1; n-Bu, alpha-, 2; Ph, beta-, 3; n-Bu, beta-, 4) and [(RSnOH)(3)(SiW(9)O(34))(2)](14)(-) (Ph, alpha-, 5; n-Bu, alpha-, 6; Ph, beta-, 7; n-Bu, beta-, 8). Crystals of Cs(4)H(3)[(PhSn)(3)(SiW(9)O(37))].8H(2)O (anion 3) are monoclinic, space group C2/c, with lattice constants a = 48.91(2) ?, b = 12.111(3) ?, c = 20.334(9) ?, beta = 102.30 degrees, and Z = 8. The anion has nominal C(3)(v)() symmetry and has a structure with three corner-shared WO(6) octahedra of the beta-Keggin anion replaced by three PhSnO(5) groups. Crystals of Cs(9)H(5)[(BuSnOH)(3)(SiW(9)O(34))(2)].36H(2)O (anion 6) are tetragonal, space group P&fourmacr;2(1)m, with lattice constants a = b = 29.005(4) ?, c = 13.412(4) ?, and Z = 4. The anion has the anticipated D(3)(h)() symmetry and contains three BuSnOH groups sandwiched between A,alpha-SiW(9)O(34)(10)(-) anions. 相似文献
90.
Petrassi HM Johnson SM Purkey HE Chiang KP Walkup T Jiang X Powers ET Kelly JW 《Journal of the American Chemical Society》2005,127(18):6662-6671
Transthyretin (TTR) amyloidogenesis requires rate-limiting tetramer dissociation and partial monomer denaturation to produce a misassembly competent species. This process has been followed by turbidity to identify transthyretin amyloidogenesis inhibitors including dibenzofuran-4,6-dicarboxylic acid (1). An X-ray cocrystal structure of TTR.1(2) reveals that it only utilizes the outer portion of the two thyroxine binding pockets to bind to and inhibit TTR amyloidogenesis. Herein, structure-based design was employed to append aryl substituents at C1 of the dibenzofuran ring to complement the unused inner portion of the thyroxine binding pockets. Twenty-eight amyloidogenesis inhibitors of increased potency and dramatically increased plasma TTR binding selectivity resulted. These function by imposing kinetic stabilization on the native tetrameric structure of TTR, creating a barrier that is insurmountable under physiological conditions. Since kinetic stabilization of the TTR native state by interallelic trans suppression is known to ameliorate disease, there is reason to be optimistic that the dibenzofuran-based inhibitors will do the same. Preventing the onset of amyloidogenesis is the most conservative strategy to intervene clinically, as it remains unclear which of the TTR misassembly intermediates results in toxicity. The exceptional binding selectivity enables these inhibitors to occupy the thyroxine binding site(s) in a complex biological fluid such as blood plasma, required for inhibition of amyloidogenesis in humans. It is now established that the dibenzofuran-based amyloidogenesis inhibitors have high selectivity, affinity, and efficacy and are thus excellent candidates for further pharmacologic evaluation. 相似文献