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81.
本文研究在盐酸介质中以三辛胺氮氧化物(分子式为(C_8H)O,简称TOO),萃取金(Ⅲ)的行为及其机理。用等温曲线、斜率、Job法、紫外光谱、摩尔电导、红外和核磁共振等方法确定了萃合物的组成,表明系由两个TOO分子和H~+发生氢键作用,并与AuCl形成离子缔合物,其组成可表述为[TON0…H~+…0NOT]AuCl_4-。 相似文献
82.
A model beta-hairpin dodecapeptide [EFGWVpGKWTIK] was designed by including a favorable D-ProGly Type II' beta-turn sequence and a Trp-zip interaction, while also incorporating a beta-strand unfavorable glycine residue in the N-terminal strand. This peptide is highly folded and monomeric in aqueous solution as determined by combined analysis with circular dichroism and 1H NMR spectroscopy. A peptide representing the folded conformation of the model beta-hairpin [cyclic(EFGWVpGKWTIKpG)] and a linear peptide representing the unfolded conformation [EFGWVPGKWTIK] yield unexpected relative deviations between the CD and 1H NMR spectroscopic results that are attributed to variations in the packing interactions of the aromatic side chains. Mutational analysis of the model beta-hairpin indicates that the Trp-zip interaction favors folding and stability relative to an alternate hydrophobic cluster between Trp and Tyr residues [EFGYVpGKWTIK]. The significance of select diagonal interactions in the model beta-hairpin was tested by rearranging the cross-strand hydrophobic interactions to provide a folded peptide [EWFGIpGKTYWK] displaying evidence of an unusual backbone conformation at the hydrophobic cluster. This unusual conformation does not appear to be a result of the glycine residue in the beta-strand, as replacement with a serine results in a peptide [EWFSIpGKTYWK] with a similar and seemingly characteristic CD spectrum. However, an alternate arrangement of hydrophobic residues with a Trp-zip interaction in a similar position to the parent beta-hairpin [EGFWVpGKWITK] results in a folded beta-hairpin conformation. The differences between side chain packing of these peptides precludes meaningful thermodynamic analysis and illustrates the caution necessary when interpreting beta-hairpin folding thermodynamics that are driven, at least in part, by aromatic cross strand interactions. 相似文献
83.
The hexamolybdenum cluster complex [Mo6(3-Cl)8(O2CMe)6]2–, 1 was isolated as the Bu4N+ salt in 71% yield from the reaction of (Bu4N)2[Mo6(3-Cl)8Cl6] with AgO2CMe in CH2Cl2 solvent. The compound was characterized by single crystal X-ray diffraction analysis. The cluster contains an octahedral arrangement of six molybdenum atoms with eight chloride ligands bridging the eight trianglar faces and six carboxylate ligands terminally coordinated through one oxygen atom to each of the six molybdenum atoms. Crystal data: space group =P21/n,a=10.713(3)Å,b=14.43(1)Å,c=21.919(4)Å, =94.37(2)°,Z=2, 1965 reflections,R=0.036. 相似文献
84.
Ning GL Li XC Munakata M Gong WT Maekawa M Kamikawa T 《The Journal of organic chemistry》2004,69(4):1432-1434
Phenyl-substituted cyclopentadienes are proved to form phenylated pyrylium cations in the presence of silver(I) perchlorate by insertion of an oxygen atom into the cyclopentadiene-ring. Three phenylated pyrylium compounds, [(Ph(5)C(5)O(+))(ClO(4)(-))](2)(CH(2)Cl(2)) (1), Ag(ClO(4))(H(2)O)(Ph(4)HC(5)O(+)) (ClO(4)(-)) (2), and (Ph(3)H(2)C(5)O(+))(ClO(4)(-)) (3) have been synthesized and characterized. A possible reaction pathway and formation mechanism of the pyrylium cation are proposed and discussed. 相似文献
85.
Ni^2—交换蒙脱石中的镍物种及焙烧温度影响研究 总被引:2,自引:0,他引:2
对一组自制Ni^2+交换蒙脱石样品中镍物种的存在在形及焙烧温度影响进行了TPR和XRD考察结果表明,样品中镍负载量等于或小于Ni^2+的交换量时,镍主要以难还原听可交换性阳离子Ni(OH)^q+x和易还原的自由态镍Ni(OH)2或NiO两种形式存在。 相似文献
86.
Using the mixture of cetyltrimethylammonium bromide (CTAB) and p‐Octyl polyethylene glycol phenyl ether (OP‐10) as templates, siliceous MCM‐48 materials can be synthesized with low molar ratio of CTAB to silica (0.139:1) and low concentration of mixed surfactants (ca.5%) and within a wide range of OP‐10/CTAB ratio (0.08?0.25). The materials were characterized by X‐ray powder diffraction, N2 adsorption/desorption isotherm, TEM, TG‐DSC and 29Si MAS NMR. Measurements indicated that the use of mixed surfactants allowed better condensation and higher ordering of the cubic mesostructure; at the same time, some properties of these materials were sensitive to the OP‐10/CTAB ratio. It was also found that the reduced pH of the gel which had been crystallized for a certain time gave a highly reproducible synthesis with a high silica yield (about 95%). Furthermore, the reaction mechanism of the synthesis is discussed in detail. 相似文献
87.
88.
Feng‐You Hao Yong‐Fang Zhao Xiao‐Gong Jing Xin‐Ying Li Feng‐Li Liu 《International journal of quantum chemistry》2007,107(6):1502-1507
Ab initio quantum chemical calculations have been performed on X2Cl? and X2Cl (X = C, Si, Ge) clusters. The geometrical structures, vibrational frequencies, electronic properties and dissociation energies are investigated at the Hartree–Fock (HF), Møller–Plesset second‐ and fourth‐order (MP2, MP4), CCSD(T) level with the 6‐311+G(d) basis set. The X2Cl (X = C, Si, Ge) and X2Cl? (X = Si, Ge) take a bent shape obtained at the ground state, while C2Cl? has a linear structure. The impact on internal electron transfer between the X2Cl and the corresponding anional clusters is studied. The three different types of electron affinities (EAs) at the CCSD(T) are reported. The most reliable adiabatic electronic affinities, obtained at the CCSD(T)/cc‐pvqz level of theory, are predicted to be 3.30, 2.62, and 1.98 eV for C2Cl, Si2Cl, and Ge2Cl, respectively. The calculated EAs of C2Cl and Ge2Cl are in good agreement with theoretical results reported. The correlation effects and basis sets effects on the geometrical structures and dissociation energies are discussed. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
89.
The monodisperse, macroporous poly(glycidyl methacrylate- co-ethylene dimethacrylate) beads were synthesized by a single-step swelling and polymerization method. Based on this media, a weak cation exchange (WCX) stationary phase for HPLC was synthesized by a new chemically modified method. The prepared resin has advantages for biopolymer separation, high column efficiency, low column backpressure, high protein mass recovery, and good resolution for proteins. The measured bioactivity recovery for lysozyme was 98+/-5%. The dynamic protein loading capacity of the WCX packings was 17.3 mg g(-1). The experimental results show that the synthesized WCX resin has very weak hydrophobicity. 相似文献
90.
Adaptive Constrained Control of Unknown Strict Feedback Nonlinear Systems With Dead Zone Input北大核心CSCD
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研究了具有死区输入的预设约束未知高阶严格反馈非线性系统的控制问题,提出了一种基于免疫函数的自抗扰预设漏斗约束自适应控制策略。首先,针对系统内部的未知问题,采用免疫函数与扩张状态观测器结合对系统内部未知项进行观测;其次,通过Lyapunov方法与漏斗控制相结合设计控制器,使得跟踪误差能够维持在预先设定的漏斗约束范围内;同时,利用双曲正切函数速率变化快这一特性设计自适应控制律,引入指令滤波器避免反步法中重复求导问题,分析证明了闭环系统所有信号的有界性。仿真实例表明了控制方法的有效性。 相似文献