高载酶量酶/酶免疫电极的制备及其电化学机理研究

本文利用扫描电镜和电化学方法确定了最佳镀铂电位,并进一步研究了酶电极和酶免疫电极在基体电极镀铂和未镀铂条件下的米氏常数、电化学反应速率常数和反应速度控制步骤。比较分析了生物电极的最佳实验条件。     

Revised mechanism of carboxylation of ribulose‐1,5‐biphosphate by rubisco from large scale quantum chemical calculations

Here, we describe a computational approach for studying enzymes that catalyze complex multi‐step reactions and apply it to Ribulose 1,5‐bisphosphate carboxylase–oxygenase (Rubisco), the enzyme that fixes atmospheric carbon dioxide within photosynthesis. In the 5‐step carboxylase reaction, the substrate Ribulose‐1,5‐bisphosphate (RuBP) first binds Rubisco and undergoes enolization before binding the second substrate, CO₂. Hydration of the RuBP.CO₂ complex is followed by C C bond scission and stereospecific protonation. However, details of the roles and protonation states of active‐site residues, and sources of protons and water, remain highly speculative. Large‐scale computations on active‐site models provide a means to better understand this complex chemical mechanism. The computational protocol comprises a combination of hybrid semi‐empirical quantum mechanics and molecular mechanics within constrained molecular dynamics simulations, together with constrained gradient minimization calculations using density functional theory. Alternative pathways for hydration of the RuBP.CO₂ complex and associated active‐site protonation networks and proton and water sources were investigated. The main findings from analysis of the resulting energetics advocate major revision to existing mechanisms such that: hydration takes place anti to the CO₂; both hydration and C C bond scission require early protonation of CO₂ in the RuBP.CO₂ complex; C C bond scission and stereospecific protonation reactions are concerted and, effectively, there is only one stable intermediate, the C3‐gemdiolate complex. Our main conclusions for interpreting enzyme kinetic results are that the gemdiolate may represent the elusive Michaelis–Menten‐like complex corresponding to the empirical K_m (=K_c) with turnover to product via bond scission concerted with stereospecific protonation consistent with the observed catalytic rate. © 2018 Wiley Periodicals, Inc.     

Mechanistic aspects on molecular structure formation of polymeric networks from diisocyanates with amidine compounds

Polymeric networks are produced by step‐growth polyaddition and co‐polyaddition reactions of 1‐ethylimidazoline in combination with various diisocyanates. Five aromatic, two aliphatic diisocyanates and a polyurethane prepolymer are used as particular reactant in N,N‐dimethylformamide as solvent at room temperature. Obviously, 1‐ethylimidazoline can serve as trifunctional monomer, which enables a crosslinking reaction with diisocyanates. Molecular structure elements of the polymeric networks were studied by solid state 13C‐NMR spectroscopy revealing that detailed molecular structure formations are determined whether aromatic or aliphatic diisocyanates are used. Quantum chemical calculations were used as supporting method to elucidate the complex reaction cascades. Hence, it can be shown that beside 3:1 stoichiometric structures 2:1 based structures are formed as well. These structures are observed as kinetically controlled products only when aromatic diisocyanate monomers are used. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 977–985     

“Click polyester”: Synthesis of polyesters containing triazole units in the main chain via safe and rapid “click” chemistry and their properties

Click Cu(I)‐catalyzed polymerizations of diynes that contained ester linkages and diazides were performed to produce polyesters (click polyesters) of large molecular weights [(～1.0–7.0 ) × 10⁴], that contained main‐chain 1,4‐disubstitued triazoles in excellent yields. Incorporation of triazole improved the thermal properties and magnified the even‐odd effect of the methylene chain length. We also found that, by changing the positions of the triazole rings, the thermal properties of the polyesters could be controlled. The use of in situ azidation was a safe reaction, as explosive diazides are not used. In addition, the microwave heating was found to accelerate the polymerization rates. This is the first study that has applied click chemistry for the synthesis of a series of polyesters. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4207–4218, 2010     

基于相关分析的LED路灯光强分布测试步距角优化研究

优化LED路灯光强分布测试系统的测试步距角可以较大程度地提高LED路灯测试的效率。选择不同的测试步距角对LED路灯的光强分布进行测试,将1°测试步距角所测得的路灯光强分布视为真值,采用相关分析的方法研究在较大步距角下所测得的路灯光强分布与真值之间的近似程度。研究结果显示,当相关系数要求在98%左右时,可以选择15°测试步距角对LED路灯的光强分布进行测试,相对于真值测试,在此步距下LED路灯的测试时间减少了98%以上,极大地提高了测试效率。     

以离子水合能解释离子选择电极响应机理

用相继切换不同浓度I^-试液的活度阶梯法研究了碘化银基离子选择电极（I^--ISE）的瞬时响应。随电位变化的离子水合自由能△Gh(I^-）显示出|△Gh（I^-）|越小，正活度阶民位跃迁越快而负活度阶梯电位变化越慢。将－△Gh(I^-）看作I（H2O）n^-与I^--ISE表面反应的活化能解释了这个现象。比起传统电位法，活度阶梯法的主要优点是ISEs响应非常快并且更灵敏，有可能实现小体积试液的快速分析。     

Synthesis of oligo(spiroketal)s by polycondensation of silyl ethers derived from naturally occurring myo‐inositol with 1,4‐cyclohexanedione

Oligo(spiroketal)s (OSKs) were synthesized from myo‐inositol, a naturally occurring cyclic compound bearing six hydroxyl groups. The successful synthesis of OSKs was achieved using silyl ethers 2 derived from 1,4‐di‐O‐alkylated myo‐inositol 1 as monomers, which underwent polycondensation with 1,4‐cyclohexanedione (CHD) at 0 °C in the presence of trimethylsilyl triflate as a catalyst. Because of the irreversible nature of the condensation reaction of silyl ethers with ketones, the resulting OSKs 7 had higher molecular weights than previously reported OSKs that were obtained by polycondensation of tetraols 1 with CHD, where backward hydrolysis of the ketal functions occurred. In addition, another series of OSKs, 8, were synthesized using silyl ethers 3 derived from 2,5‐di‐O‐alkylated myo‐inositol 6 , which are more symmetric monomers than silyl ethers 2 . Silyl ethers 3 underwent efficient polycondensation with CHD, whereas tetraol 6 did not, demonstrating that the derivation of such tetraols into the corresponding silyl ethers is a powerful strategy to access OSKs. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2407–2414     

Langmuir-Hinshelwood 动力学的有效实验条件

 使用 Langmuir-Hinshelwood (L-H) 动力学的学者大部分未注意到该动力学包含了所有吸附物种采用拟稳态假设的隐含条件, 因而他们通常忽视了确认实验条件是否允许采用拟稳态假设. 然而, 对于大部分气固催化反应, 拟稳态假设的成立需基于催化活性位浓度很小的前提. 对于催化活性位浓度高的反应体系, 其覆盖度较高的吸附物种不满足拟稳态假设. 因此, 在这种情况下通过实验测定的动力学常数没有物理意义, 而仅为该实验条件下的数学回归参数. 本文将活性位浓度小于最高反应气浓度的十分之一视为拟稳态假设成立的充分条件, 通过估算发现许多催化剂并不满足该条件.     

Free‐energy differences between states with different conformational ensembles

Multiple conformations separated by high‐energy barriers represent a challenging problem in free‐energy calculations due to the difficulties in achieving adequate sampling. We present an application of thermodynamic integration (TI) in conjunction with the local elevation umbrella sampling (LE/US) method to improve convergence in alchemical free‐energy calculations. TI‐LE/US was applied to the guanosine triphosphate (GTP) to 8‐Br‐GTP perturbation, molecules that present high‐energy barriers between the anti and syn states and that have inverted preferences for those states. The convergence and reliability of TI‐LE/US was assessed by comparing with previous results using the enhanced‐sampling one‐step perturbation (OSP) method. A linear interpolation of the end‐state biasing potentials was sufficient to dramatically improve sampling along the chosen reaction coordinate. Conformational free‐energy differences were also computed for the syn and anti states and compared to experimental and theoretical results. Additionally, a coupled OSP with LE/US was carried out, allowing the calculation of conformational and alchemical free energies of GTP and 8‐substituted GTP analogs. © 2013 Wiley Periodicals, Inc.