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41.
Wang C Zhu G Li J Cai X Wei Y Zhang D Qiu S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(17):4975-4982
We demonstrate a novel strategy for the preparation of mesoporous silica-supported, highly dispersed, stable metal and bimetal nanoparticles with both size and site control. The supporting mesoporous silica, functionalized by polyaminoamine (PAMAM) dendrimers, is prepared by repeated Michael addition with methyl acrylates (MA) and amidation reaction with ethylenediamine (EDA), by using aminopropyl-functionalized mesoporous silica as the starting material. The encapsulation of metal nanoparticles within the dendrimer-propagated mesoporous silica is achieved by the chemical reduction of metal-salt-impregnated dendrimer-mesoporous silica by using aqueous hydrazine. The site control of the metal or bimetal nanoparticles is accomplished by the localization of inter- or intradendrimeric nanoparticles within the mesoporous silica tunnels. The size of the encapsulated nanoparticles is controlled by their confinement to the nanocavity of the dendrimer and the mesopore. For Cu and Pd, particles locate at the lining of mesoporous tunnels, and have diameters of less than 2.0 nm. For Pd/Pt, particles locate at the middle of mesoporous tunnels and have diameters in the range of 2.0-4.2 nm. The Pd and Pd/Pt nanoparticles are very stable in air, whereas the Cu nanoparticles are stable only in an inert atmosphere. 相似文献
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43.
Caignan GA Deshmukh R Wilks A Zeng Y Huang HW Moënne-Loccoz P Bunce RA Eastman MA Rivera M 《Journal of the American Chemical Society》2002,124(50):14879-14892
The origin of the unusual regioselectivity of heme oxygenation, i.e. the oxidation of heme to delta-biliverdin (70%) and beta-biliverdin (30%), that is exhibited by heme oxygenase from Pseudomonas aeruginosa (pa-HO) has been studied by (1)H NMR, (13)C NMR, and resonance Raman spectroscopies. Whereas resonance Raman indicates that the heme-iron ligation in pa-HO is homologous to that observed in previously studied alpha-hydroxylating heme oxygenases, the NMR spectroscopic studies suggest that the heme in this enzyme is seated in a manner that is distinct from that observed for all other alpha-hydroxylating heme oxygenase enzymes for which a structure is known. In pa-HO, the heme is rotated in-plane approximately 110 degrees, so the delta-meso-carbon of the major orientational isomer is located within the HO-fold in the place where the alpha-hydroxylating enzymes typically place the alpha-meso-carbon. The unusual heme seating displayed by pa-HO places the heme propionates so that these groups point in the direction of the solvent-exposed heme edge and appears to originate in large part from the absence of stabilizing interactions between the polypeptide and the heme propionates, which are typically found in alpha-hydroxylating heme oxygenase enzymes. These interactions typically involve Lys-16 and Tyr-112, in Neisseriae meningitidis HO, and Lys-16 and Tyr-134, in human and rat HO-1. The corresponding residues in pa-HO are Asn-19 and Phe-117, respectively. In agreement with this hypothesis, we found that the Asn-19 Lys/Phe-117 Tyr double mutant of pa-HO exists as a mixture of molecules exhibiting two distinct heme seatings; one seating is identical to that exhibited by wild-type pa-HO, whereas the alternative seating is very similar to that typical of alpha-hydroxylating heme oxygenase enzymes and is related to the wild-type seating by approximately 110 degrees in-plane rotation of the heme. Furthermore, each of these heme seatings in the pa-HO double mutant gives rise to a subset of two heme isomeric orientations that are related to each other by 180 degrees rotation about the alpha-gamma-meso-axis. The coexistence of these molecules in solution, in the proportions suggested by the corresponding area under the peaks in the (1)H NMR spectrum, explains the unusual regioselectivity of heme oxygenation observed with the double mutant, which we found produces alpha- (55%), delta- (35%), and beta-biliverdin (10%). Alpha-biliverdin is obtained by oxidation of the heme seated similar to that of alpha-hydroxylating enzymes, whereas beta- and delta-biliverdin are formed from the oxidation of heme seated as in wild-type pa-HO. 相似文献
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45.
γ-[SiW10O36]8-夹心型稀土元素单取代多酸化合物的合成与表征 总被引:2,自引:0,他引:2
利用缺位填充法合成了12个γ-[SiW10O36]8-夹心型稀土元素单取代多酸化合物K13[Ln(SiW10O36)2]·nH2O(Ln=La3+,Ce3+,Pr3+,Nd3+,Sm3+,Eu3+,Gd3+,Tb3+,Dy3+,Ho3+,Er3+,Yb3+).通过元素分析确定其组成,由红外光谱、紫外-可见吸收光谱、循环伏安及室温磁化率测定结果确认稀土离子与γ-[SiW10O36]8-相配位;183WNMR及荧光光谱结果则表明,稀土离子处于2个γ-[SiW10O36]8-构成的八配位环境中,标题化合物具有夹心型D2d对称性结构. 相似文献
46.
Geise CM Wang Y Mykhaylova O Frink BT Toscano JP Hadad CM 《The Journal of organic chemistry》2002,67(9):3079-3088
The effect of aromatic substitution on the singlet-triplet energy gap in substituted phenyl(carbomethoxy)carbene (X-Ph-C-CO(2)CH(3), PCC) has been explored by time-resolved infrared (TRIR) spectroscopy and gas-phase computational methods. The ground state of para-substituted PCC is calculated to change from the triplet state in p-NO(2)-PCC (Delta G(ST) = 6.1 kcal/mol) to the singlet state in p-NH(2)-PCC (Delta G(ST) = -2.8 kcal/mol). The absence of solvent perturbation in the TRIR spectra of p-N(CH(3))(2)-PCC (which should have electronic properties similar to p-NH(2)-PCC) and parent PCC is consistent with their ground states lying > +/-2 kcal/mol from the next available electronic state, in line with the computational results. The observation of solvent perturbation in the TRIR spectra of p-OCH(3)-PCC and p-CH(3)-PCC implies that their ground states lie < +/-1 kcal/mol from their next available electronic state. This is in agreement with our computational results, which predict a gas-phase Delta G(ST) of -0.8 and 1.6 kcal/mol for p-OCH(3)-PCC and p-CH(3)-PCC as compared to Delta G(ST) values of -3.9 and -1.3 kcal/mol from polarizable continuum model (PCM) calculations with acetonitrile as a solvent. Gas-phase computational results for the meta- and ortho-substituted PCC species are also presented, along with selected linear free energy (LFE) relationships for the para and meta species. 相似文献
47.
改革工程光学实验教学,培养学生创新能力 总被引:3,自引:0,他引:3
通过分析工程光学实验教学体系和实验设置,讨论了将工程光学实验单立实验课,有独立的教学大纲,增加实验内容的设计性、综合性实验项目,使实验教学得到完善和发展,有利于提高学生的学习主动性和实验技能,有利于培养学生的创新能力。 相似文献
48.
Planck粒子、磁单极子和亚夸克超对称伴子的相互关联 总被引:2,自引:0,他引:2
用亚规范理论和焦-官亚夸克模型、Nambu模型,唯象地算出亚夸克的质量,发现亚夸克的超对称伴子质量与宇宙大爆炸后磁单极子的质量相等,经强作用修正后,所得结果与Plarck粒子质量仅差一个量级,现时粒子的超对称伴子大质量标度将从mT≈175 GeV一举延伸到mpl≈1.22×1019GeV广大空白区,深化了对宇宙早期物理规律的认识. 相似文献
49.
50.
随着计算机网络的飞速发展以及Internet相关技术的普遍应用,数据处理已经不再局限于网络中的某一台计算机上运行,而是要求所有计算机都参与到网络这一大环境中,这就需要基于智能化和网络化进程的移动代理技术来解决复杂、动态和分布式智能应用的问题.文章首先简要阐述软件代理和移动代理的一些基本知识,然后以目前常用的移动代理开发平台Aglet为例,详细讲述如何开发基于移动代理的网络应用程序. 相似文献