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     

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。     

气相色谱法测定车用汽油中含氧化合物和苯胺类化合物

利用中心切割技术和双毛细管色谱柱系统,采用两次进样的方式,建立了气相色谱测定车用汽油中含氧化合物和苯胺类化合物的分析方法。第一次进样分析,组分首先进入非极性DB-1色谱柱(30 m×0.32 mm×1.0μm),按沸点由低到高的顺序分离,通过电磁阀切换将沸点小于2-己酮的组分切割至强极性GS-OxyPLOT色谱柱(10 m×0.53 mm×10μm)或CP-Lowox色谱柱(10 m×0.53 mm×10μm),其余重烃组分通过阻尼柱进入FID检测器。在GS-OxyPLOT或CP-Lowox色谱柱上,烃类组分与含氧化合物分离并进入检测器检测,消除了大量的烃类组分对含氧化合物测定的影响。第二次进样分析,设定电磁阀切换时间为间-甲基苯胺从非极性色谱柱流出的时间,苯胺类化合物在GS-OxyPLOT或CP-Lowox色谱柱上与烃类和含氧化合物分离并进入检测器检测。以乙二醇二甲基醚为内标化合物进行内标法定量。实现了在一套系统上同时测定车用汽油中添加的甲基叔丁基醚(MTBE)、甲醇、甲缩醛、乙酸仲丁酯、乙酸乙酯、苯胺、邻/间/对-甲基苯胺和N-甲基苯胺的含量,各组分的检测范围为0.01%~10%(质量分数),回收率为86.0%~102.6%。该法可以为车用汽油的质量控制提供有效的检测手段。     

多个时间常数线性体系暂态响应方程参数的代数求解法

从线性条件出发,推导了含n个时间常数体系恒电位阶跃时暂态响应方程,并提出一套解析形为ΔI=ΔI_∞+sum from i=1 to n k_iexp(-t/τ_i)暂态方程各未知参数的代数解法。该方法可对未知体系时间常数个数进行判定,比起一般曲线拟合更加快速简便,且抗干扰能力较强。     

基于FHW的火箭发动机环境载荷评估

针对固体火箭发动机环境载荷的诸多不确定性,提出了环境载荷FHW量化评估算法.对比分析了火箭发动机的典型环境条件及其影响,采用熵值法确定了指标权重,基于FHW方法建立了火箭发动机的环境载荷评估模型,根据环境因素的分布特征给出评估指标的隶属函数,并获取其相应的灰色关联系数.算例验证了不同环境载荷因素对火箭发动机的影响程度,结果表明FHW评估策略和算法简单易行、精度高,在装备环境载荷量化评估中具有参考和应用价值.     

具有混合光滑性的Holder-Nikolskii-Wiener类在Lq(Rd)中的平均宽度（英文）

本文研究了具有混合光滑性的Holder-Nikolskii-Wiener类SrpqH在Lq(Rd)中的平均σ-K宽度(2≤q≤p<∞),得到了该量的弱渐近估计.     

On the Convergence of Descent Algorithms

It is proved that any cluster point of a sequence defined by a steepest descent algorithm in a general normed vector space is a critical point. The function is just assumed to be continuously differentiable. The class of algorithms we consider encompasses several choices such as the Cauchy steplength and the Curry steplength.     

Stabilized mixed finite element methods for the Navier‐Stokes equations with damping

In this paper, the stabilized mixed finite element methods are presented for the Navier‐Stokes equations with damping. The existence and uniqueness of the weak solutions are proven by use of the Brouwer fixed‐point theorem. Then, optimal error estimates for the H¹‐norm and L²‐norm of the velocity and the L²‐norm of the pressure are derived. Moreover, on the basis of the optimal L²‐norm error estimate of the velocity, a stabilized two‐step method is proposed, which is more efficient than the usual stabilized methods. Finally, two numerical examples are implemented to confirm the theoretical analysis.