均三氮苯类除草剂结构与活性的理论研究

利用Gaussian03程序包中的B3LYP方法,选择6-31G基组对均三氮苯类除草剂及类似衍生物2-(4-溴苄氨基)-4-甲基-6-三氟甲基-1,3,5-三氮苯进行了量子化学计算,从理论上讨论了它们的空间结构、电子结构特征与活性的关系.计算结果表明:三氮苯环与N(7)和N(8)原子形成了共轭结构,分子活性大小与LUMO轨道的得电子能力以及在LUMO轨道中占主要成分的原子有重要关系.N(7)和N(8)连接单个具有推电子能力的基团,有利于生物活性的提高.对于2-(4-溴苄氨基)-4-甲基-6-三氟甲基-1,3,5-三氮苯中,N(8)和C(9)是重要的活性部位,和传统的均三氮苯类除草剂分子相比,与D1蛋白上不同的氨基酸残基发生了键合作用.     

A quantum scattering study of collinear state-testate reaction probabilities for the F + H2(v) → HF(v') + H system

A new quantum scattering approach (linear combination of arrangement channels-scattering wavefunction, LCAC-SW) proposed by Deng and his co-workers is used to calculate collinear state-to-state reaction probabilities for the F + H₂(v) → HF(v') + H system. Several interesting problems such M threshold energy, compound states and enhance by translational energy of the reactants and the vibration excitation of products are discussed and they are compared with other theoretical investigations reported in the literature. It is shown that the LCAC-SW approach is the successful one of quantum scattering methods.     

Quantum chemical calculations of the isomer shift in iron(II) complexes of 1,2,4-triazoles with a 1 A 1 ⇔ 5 T 2 spin transition

DFT calculations have been performed to determine the isomer shift for a series of iron(II) clusters with nitrogen-containing ligands which serve as models of coordination units in Fe(II) complexes with 1,2,4-triazoles possessing a ¹ A ₁ ? ⁵ T ₂ spin transition. Good agreement has been found between the theoretical and experimental values of the isomer shift for both low-and high-spin phases. Our calculations confirmed the hypothesis about relationship between the experimentally observed differences in the isomer shift for the low-spin phases of the complexes and variations of the Fe-N mean bond length.     

Fully quantum mechanical energy optimization for protein-ligand structure

We present a quantum mechanical approach to study protein-ligand binding structure with application to a Adipocyte lipid-binding protein complexed with Propanoic Acid. The present approach employs a recently develop molecular fractionation with a conjugate caps (MFCC) method to compute protein-ligand interaction energy and performs energy optimization using the quasi-Newton method. The MFCC method enables us to compute fully quantum mechanical ab initio protein-ligand interaction energy and its gradients that are used in energy minimization. This quantum optimization approach is applied to study the Adipocyte lipid-binding protein complexed with Propanoic Acid system, a complex system consisting of a 2057-atom protein and a 10-atom ligand. The MFCC calculation is carried out at the Hartree-Fock level with a 3-21G basis set. The quantum optimized structure of this complex is in good agreement with the experimental crystal structure. The quantum energy calculation is implemented in a parallel program that dramatically speeds up the MFCC calculation for the protein-ligand system. Similarly good agreement between MFCC optimized structure and the experimental structure is also obtained for the streptavidin-biotin complex. Due to heavy computational cost, the quantum energy minimization is carried out in a six-dimensional space that corresponds to the rigid-body protein-ligand interaction.     

碳点增强的Ru纳米颗粒复合材料用于碱性条件下高效电解水析氢

In the 21st century, hydrogen energy is a novel energy source. Its use is expected to mitigate the problems of environmental pollution and global warming caused by the excessive use of conventional fossil fuels. The hydrogen evolution reaction (HER) for water splitting has attracted considerable attention because of its environmental friendliness. To improve electrocatalyst performance and reduce operation cost, carbon-based metal hybrid materials exhibiting high efficiency and catalytic activity have been developed. Among them, carbon dots (CDs) have garnered significant research attention and have been widely applied in biosensing, bioimaging, and energy conversion/storage because of their facile synthesis, biocompatibility, tunable photoluminescence, excellent stability, and good electronic properties. CDs are widely used as carriers in the construction of electrocatalysts prepared from carbon-based metal hybrid materials. At present, it is believed that CDs exhibit excellent confinement effects, which can effectively inhibit the growth and agglomeration of metal nanoparticles, thereby preparing well-distributed carbon-based metal hybrid materials with a uniform and controllable size. However, the formation process of the small-molecule raw materials of CDs has not been elucidated. In this study, CDs and small-molecule raw materials from synthetic CDs were used as precursors to prepare nitrogen-doped CD-supported ruthenium nanoparticle (Ru@CDs) and small-molecule-supported ruthenium nanoparticle (Ru@Molecule) hybrid materials, respectively. The interaction between the small molecules and Ru in the process of CD formation and the effect on HER performance were explored. Moreover, we prepared different carriers such as metal organic frameworks(MOF), carbon nanotubes (CNTs), and graphene (GO)-supported ruthenium nanoparticle hybrid materials. Among them, Ru@CDs exhibited controllable size and excellent dispersibility and exhibited outstanding HER activity and good stability. Ru@CDs were found to require a low overpotential of 22 mV to reach a current density of 10 mA·cm⁻². Moreover, we observed the presence of an intermediate state between the molecules and CDs and demonstrated that the intermediate state exhibits no confinement effect. Furthermore, we found that with increasing calcination temperature, the intermediate state gradually changes to CDs. The unique spatial confinement between CDs and metal ions is key to the formation of monodisperse Ru nanoparticles. Our results confirmed that Ru@CDs serve as excellent HER catalyst supports. This work not only reveals the effect of the unique spatial confinement of CDs on the supported metals and their promoting effect on electrocatalytic activity but also provides guides the future development of CD-based metal hybrid electrocatalysts.     

Dialing in color with rare earth metals: facile photoluminescent production of true white light

Combining polymeric architectures with metal ions produces hybrid materials with extremely rich properties. We are studying polymers containing terpyridine in the side chain. In this report, the chelation of lanthanide ions, Eu³⁺, Tb³⁺, and Dy³⁺ resulted in metal functionalized copolymers that exhibited excellent emission of red, green, and blue light respectively. The polymer architecture easily allows incorporation of all three colors into the material, which leads to the facile production of true white light in solution or the solid state. Quantum efficiencies for the polymer systems were determined. The white light system had an efficiency of 5%. Various combinations of colors were achieved from the basic RBG colors by simply varying the metal ion ratios in the polymer backbone. This easy tuning of the color makes these systems attractive. Copyright © 2007 John Wiley & Sons, Ltd.     

Dynamic light-scattering analysis of the electrostatic interaction of hexahistidine-tagged cytochrome P450 enzyme with semiconductor quantum dots.

Currently, there is great interest in the development of methods suitable for determining the stoichiometry of biomolecules attached to nanoparticles. We describe the use of the dynamic light-scattering technique (DLS) to determine the stoichiometry of the protein cytochrome P450(BSbeta) attached to CdS and CdSe quantum dots (QDs). The enzyme-conjugated QDs have different diffusion characteristics compared to the QD and enzyme precursors, expressed in their size, scattering intensity as well as zeta-potential values. The significant enhancement of the scattering intensity of QDs observed upon conjugation with the P450(BSbeta) due to the refractive-index increment and the systematic variation in zeta potential resulting from charge neutralization of the anionic QDs by the cationic histidine-tagged P450(BSbeta) have been used for stoichiometry determination.     

水中矿物元素的ICP-MS分析

用ICP－MS对地下水、地表水和饮用水中的矿物元素进行了分析测定，实验证明用ICP－MS可以同时测定地下水，地表水和饮用水中矿物元素；该法灵敏度、精密度和准确度都能满足有关标准的要求，具有多元素同时分析，样品前处理简单，干扰少，测定快速，省事省力等优点。     

N,N-二(2-苯并咪唑亚甲基)甲胺高氯酸盐的晶体和电子结构

合成了三齿配体N,N-二(2-苯并咪唑亚甲基)甲胺(MN3)的高氯酸盐.对该化合物进行了元素分析、紫外和红外表征;采用X射线衍射方法测定了该化合物的晶体结构,依据晶体结构数据使用G98程序对配体(MN3)进行了量子化学计算.     

Vibrational analysis of 3-trifluoromethylphenol

The molecular geometry and molecular vibrations of 3-trifluoromethylphenol have been investigated by means of quantum chemical calculations and vibrational spectroscopy. The computations indicated the preference of the conformer with the OH hydrogen pointing in the direction of the trifluoromethyl group by 0.9 kJ/mol with respect to the anti conformer. FT-IR spectra of the vapour and CCl₄ solution as well as FT-IR and FT-Raman spectra of the pure liquid have been recorded in the range of 4000–150 cm⁻¹. The interpretation of the spectra was based on a scaled quantum mechanical (SQM) analysis for which the initial force field was calculated at the Becke3-Lee-Yang-Parr (B3LYP) DFT level supplemented with a 6-311++G** basis set. Using 11 scale factors refined in the present study an rms deviation of 7.6 cm⁻¹ between the experimental and SQM frequencies has been achieved. On the basis of the computations 40 of the total of 42 fundamentals of the title compound have been assigned.