Affinity capillary electrophoresis and quantum mechanical calculations applied to the investigation of hexaarylbenzene-based receptor binding with lithium ion

In this study, two complementary approaches, affinity capillary electrophoresis (ACE) and quantum mechanical density functional theory (DFT) calculations, have been employed for quantitative characterization and structure elucidation of the complex between hexaarylbenzene (HAB)‐based receptor R and lithium ion Li⁺. First, by means of ACE, the apparent binding constant of Li R ⁺ complex (K) in methanol was determined from the dependence of the effective electrophoretic mobilities of Li R ⁺ complex on the concentration of lithium ions in the 25 mM Tris/50 mM chloroacetate background electrolyte (BGE) using non‐linear regression analysis. Prior to regression analysis, the effective electrophoretic mobilities of the Li R ⁺ complex were corrected to reference temperature 25°C and constant ionic strength 25 mM. The apparent binding constant of the Li R ⁺ complex in the above methanolic BGE was evaluated as logK = 1.15±0.09. Second, the most probable structures of nonhydrated Li R ⁺ and hydrated Li R ⁺·3H₂O complexes were derived by DFT calculations. The optimized structure of the hydrated Li R ⁺·3H₂O complex was found to be more realistic than the nonhydrated Li R ⁺ complex because of the considerably higher binding energy of Li R ⁺·3H₂O complex (500.4 kJ/mol) as compared with Li R ⁺ complex (427.5 kJ/mol).     

Preparation and characterization of novel molecularly imprinted polymers based on thiourea receptors for nitrocompounds recognition

Molecularly imprinted polymers (MIPs) for the recognition of nitro derivatives are prepared from three different (thio)urea-bearing functional monomers. The binding capability of the polymers is characterized by a batch binding experiment. The imprinting factors and affinity constants (K) of the imprinted polymers exhibit the same tendency as the binding constants (K_a) of the functional monomers to the target substance in solution. Not only nitrofurantoin is efficiently bound by these MIPs but also a broad spectrum of other nitro compounds is bound with at the intermediate level, addressing that these (thio)urea-based monomers can be utilized to prepare a family of MIPs for various nitro compounds, which can be applied as recognition elements in separation and analytical application.     

基于结合位点的辅酶A结合蛋白家族的分类

发展了一种基于分子相互识别的蛋白质分类方法, 应用数据挖掘策略与统计学聚类, 根据辅酶A (coenzyme-A, CoA)结合蛋白的结合模式特征数据, 通过对比和分析多种分类方法对该体系的分类准确度, 对这类体内重要的蛋白进行了分类方法学研究, 选择了最优的两步聚类法. 本研究工作设计和建立了一个分类参数, 可以简洁有效地评价出各个结合特征的显著性与重要性, 并以此为依据从所有特征中筛选出决定性的特征变量. 研究结果所得到的CoA结合蛋白的三个分类, 都具有显著的氢键与疏水结合特征; CoA可以与多个生物活性关键氨基酸残基形成氢键作用. 这些相互作用的共性及分类上的差异, 说明了配体与不同受体相互作用过程中结合模式上的细微差别, 对于以CoA结合蛋白为靶点的选择性调控分子设计具有重要的参考意义与指导作用.     

铜镁铝三元水滑石的姜-泰勒效应

采用密度泛函理论(DFT),用CASTEP程序模块,对类水滑石(CuxMg3-xAl-LDHs,x=0-3)周期性模型进行几何全优化,通过分析各体系的结构参数、电子排布、氢键、Mulliken电荷布居、结合能,总结出体系中的姜-泰勒效应和结构稳定性规律.结果表明,姜-泰勒效应不仅存在于d轨道未排满的Cu2+中,在p轨道未排满的Mg2+中也可能存在,且未饱和的d、p轨道共同影响着金属离子姜-泰勒畸变的大小.在CuxMg3-xAl-LDHs(x=0-3)中,铝八面体和镁八面体分别以稳定的拉长的八面体形式存在.而随着Cu2+的增加,铜八面体逐渐从压扁的八面体向稳定的拉长的八面体形式转变,体系获得了逐渐增多的姜-泰勒稳定化能.总体上,随着Cu2+的增加,体系中姜-泰勒效应导致的畸变使主客体间的氢键和静电作用力均有减弱趋势,且体系的结合能绝对值逐渐减小,故体系稳定性下降.这有助于从理论上进一步认识含铜水滑石的姜-泰勒效应.     

A thermodynamic investigation on the binding of mercury ion with myelin basic protein at different temperatures

A thermodynamic study on the interaction of myelin basic protein with mercury ion was studied by using isothermal titration calonmetry,ITC,at 300.15,310.15 and 320.15 K in Tris buffer solution at pH 7.The enthalpies of MBP + Hg²⁺ interaction are reported and analysed in terms of the extended solvation model.It was found that MBP has two identical and non-cooperative binding sites for Hg²⁺ ions.The intrinsic dissociation equilibrium constants are 99.904,112.968 and 126.724μmol/L,and the molar enthalpy of binding are -11.634,-10.768 and -10.117kJ mol^-1 at 300.15,310.15 and 320.15 K,respectively.     

Spectrophotometric studies on the interactions of C.I. Basic Red 9 and C.I. Acid Blue 25 with hexadecyltrimethylammonium bromide in cationic surfactant micelles

Interactions between cationic dye-cationic surfactant and anionic dye-cationic surfactant systems were investigated in aqueous solutions using spectrophotometric method at 288.15, 298.15, 308.15 and 318.15 K. C.I. Basic Red 9 (BR9) and C.I. Acid Blue 25 (AB25) were used as cationic and anionic dyes, respectively, and hexadecyltrimethylammonium bromide (HDTMABr) was selected as cationic surfactant in this study. Although there was an interaction between the AB25 and the HDTMABr molecules, an interaction between the BR9 and HDTMABr did not occur due to the electrostatic repulsion forces. Binding constants and partition coefficients between the micellar and the bulk water phases for the AB25-HDTMABr system were calculated from the changes in absorbance values and the critical micelle concentrations at different temperatures. It was found that the values of binding constant and partition coefficient decreased with increasing temperature. Thermodynamic parameters (ΔG⁰, ΔH⁰ and ΔS⁰) were determined for the binding and partition processes of AB25-HDTMABr system. It was concluded from ΔG⁰ values that the binding of AB25 to HDTMABr occurred spontaneously. In addition, the binding and partition processes were exothermic.     

牛血清白蛋白与十二烷基硫酸钠作用的机理

利用电动势法得到了牛血清白蛋白(BSA)与十二烷基硫酸钠(SDS)相互作用的结合等温线. 通过四阶导数紫外光谱法和荧光光谱法研究了相互作用过程中芳香族氨基酸残基微环境极性的变化. 通过研究发现, 随着SDS浓度的逐渐增大, SDS在BSA上的平均结合数(v)逐渐增大, 色氨酸(Trp)残基所处微环境的极性在减弱后保持基本不变, 酪氨酸残基所处微环境的极性在明显增强后稍有减弱, 苯丙氨酸残基所处微环境的极性略有增强. 结果表明, 当v由0增大到14时, SDS主要结合在BSA的Trp-213附近并逐渐形成聚集体, 从而诱导BSA由结构域ⅡA 开始逐渐展开. 此后, SDS呈正协同作用的特点与BSA 结合, v急剧增大. 当v约为302 时, SDS在BSA上的结合基本达到饱和, BSA的构象趋于稳定.     

Magnetic and binding properties of metal-divacancy complexes at MgO (0 0 1) surface: DFT calculations

We have analyzed the magnetic and binding properties of Ni, Cr, Mo, and Pt metals deposited on the defect free and defect containing surfaces of MgO by means of density functional theory calculations and embedded cluster model. Clusters of moderate sizes with no border anions, to avoid artificial polarization effects, were embedded in the simulated Coulomb fields that closely approximate the Madelung fields of the host surfaces. Spin quenching occurs for Cr and Mo complexes at the defect free (terrace) surface, and Cr, Mo, and Pt complexes at the defect containing “pit” divacancy surface. The binding energies of the metals are significantly enhanced on the cationic vacancy end of the divacancy. The adsorption energies of the low spin states of spin quenched complexes are always greater than those of the high spin states. The metal-support interactions stabilize the low spin states of the adsorbed metals with respect to the isolated metals, but the effect is not always enough to quench the spin. The encountered variations in magnetic properties of free metals and of metal complexes are correlated with the energy gaps of the frontier orbitals. Spin contamination affect the adsorbate-substrate distances, Mulliken charges, Mulliken spin densities, natural charge, natural orbital population, and provide rationalization for the reported magnetic and binding properties. The electrostatic potential energy curves provide clearer understanding of the nature of magnetic and binding interactions. The magnetic and binding properties of a single metal atom adsorbed on a particular surface result from a competition between Hund's rule for the adsorbed metal, and the formation of a chemical bond at the interface.     

Optical properties of acceptor-exciton complexes in ZnO/SiO2 quantum dots

The binding energy E_b of the acceptor-exciton complex (A⁻,X) as a function of the radius (or of the impurity position of the acceptor) and the normalized oscillator strength of (A⁻,X) in spherical ZnO quantum dots (QDs) embedded in a SiO₂ matrix are calculated using the effective-mass approximation under the diagonalzation matrix technique, including a three-dimensional confinement of the carrier in the QD and assuming a finite depth. Numerical results show that the binding energy of the acceptor-exciton complexes is particularly robust when the impurity position of the acceptor is in the center of the ZnO QDs. It has been clearly shown from our calculations that these physical parameters are very sensitive to the quantum dot size and to the impurity position. These results could be particularly helpful, since they are closely related to experiments performed on such nanoparticles. This may allow us to improve the stability and efficiency of the semiconductor quantum dot luminescence which is considered critical.     

Adsorption of formaldehyde on the Fe site of clean and M (Ca, Sr and Ba) doped LaFeO3 (0 1 0) surface

The adsorption of formaldehyde (H₂CO) on the Fe site of clean and M²⁺ (Ca²⁺, Sr²⁺ and Ba²⁺) doped LaFeO₃ (0 1 0) surface have been investigated using the density functional theory (DFT) method. Calculation results show that the oxygen atom of the H₂CO molecule prefers to be adsorbed on the Fe site of the clean LaFeO₃ (0 1 0) surface. The adsorption of H₂CO could change the electronic properties of the LaFeO₃, indicating that the LaFeO₃ could be used as gas sensing material to detect the H₂CO gas. The analysis results of the DOS suggest that the bonding mechanism between the H₂CO molecule and the Fe site is mainly from the interaction between the Fe 3d and H₂CO 2p orbital. Comparing with the binding energy and the net charge-transfer, we find that the M²⁺ (Ca²⁺, Sr²⁺ and Ba²⁺) doping cannot improve the sensitivity of the LaFeO₃ to the H₂CO gas.