Screening,Molecular Cloning,and Biochemical Characterization of an Alcohol Dehydrogenase from Pichia pastoris Useful for the Kinetic Resolution of a Racemic β‐Hydroxy‐β‐trifluoromethyl Ketone

The stereoselective synthesis of chiral 1,3‐diols with the aid of biocatalysts is an attractive tool in organic chemistry. Besides the reduction of diketones, an alternative approach consists of the stereoselective reduction of β‐hydroxy ketones (aldols). Thus, we screened for an alcohol dehydrogenase (ADH) that would selectively reduce a β‐hydroxy‐β‐trifluoromethyl ketone. One potential starting material for this process is readily available by aldol addition of acetone to 2,2,2‐trifluoroacetophenone. Over 200 strains were screened, and only a few yeast strains showed stereoselective reduction activities. The enzyme responsible for the reduction of the β‐hydroxy‐β‐trifluoromethyl ketone was identified after purification and subsequent MALDI‐TOF mass spectrometric analysis. As a result, a new NADP⁺‐dependent ADH from Pichia pastoris (PPADH) was identified and confirmed to be capable of stereospecific and diastereoselective reduction of the β‐hydroxy‐β‐trifluoromethyl ketone to its corresponding 1,3‐diol. The gene encoding PPADH was cloned and heterologously expressed in Escherichia coli BL21(DE3). To determine the influence of an N‐ or C‐terminal His‐tag fusion, three different recombinant plasmids were constructed. Interestingly, the variant with the N‐terminal His‐tag showed the highest activity; consequently, this variant was purified and characterized. Kinetic parameters and the dependency of activity on pH and temperature were determined. PPADH shows a substrate preference for the reduction of linear and branched aliphatic aldehydes. Surprisingly, the enzyme shows no comparable activity towards ketones other than the β‐hydroxy‐β‐trifluoromethyl ketone.     

异步热轧对钛合金Ti-6Al-4V微观组织及力学性能的影响

通过异步/同步热轧实验研究了异步热轧工艺对钛合金显微组织和力学性能的影响。实验表征了试样的显微组织、力学性能、断口形貌和微观取向。实验结果表明,复杂应变路径较之简单应变路径能更好的细化晶粒及同时提高强度和塑性,并且表层晶粒小于中心晶粒。异步轧制工艺相比同步轧制能更好获得细小晶粒。异步轧制试样的强度及塑性值高于同步轧制试样相应值,提高异步速比可提高强度及塑性值。异步轧制试样的塑性变形机制可能是滑移,而同步轧制试样塑性变形机制为滑移或孪晶。     

压电陶瓷作动器非对称迟滞建模与内模控制

压电陶瓷作动器被广泛应用于精密定位和控制中,但其本身存在的非对称迟滞非线性特性,严重影响了系统的定位和控制精度。针对这一问题,提出了一种基于广义Bouc-Wen模型的非对称迟滞建模方法,并利用差分进化算法辨识模型参数;基于所建的广义Bouc-Wen模型构建了其具有解析形式的迟滞逆模型,并设计了内模控制方案实现对压电陶瓷作动器的精密跟踪控制;最后在压电陶瓷作动器实验平台,对所提出的建模和控制方案进行了实验验证。对压电陶瓷作动器的建模结果表明,系统建模误差均小于0.051 0,比经典Bouc-Wen模型的建模误差降低约21%～46%;对100 Hz内幅值为20μm的期望位移信号的控制实验结果表明,所提出的控制方法具有良好的实时跟踪性能和跟踪控制精度。对100 Hz期望信号的跟踪控制均方根误差为0.491 6μm,相对误差为0.040 2μm,可以很好地满足实际工程需要。     

铱催化体系不对称合成手性药物中间体

考察了1,1-二苯基丙酮在手性双胺双膦配体与[IrHCl2(COD)]2组成的催化体系下不对称转移氢化合成(S)-(-)-1,1-二苯基-2-丙醇的反应,通过正交实验了考察了反应温度、n(底物):n(铱络合物)、n(铱络合物):n(手性配体)以及n(底物):n(KOH)对反应的影响。结果表明,在异丙醇中,利用该体系催化1,1-二苯基丙酮反应2小时后,反应产率可达97.85%,对映选择性(ee值)达到99.35%     

Construction of Chiral 2‐Substituted Octahydroindoles from Cyclic Ketones and Nitroolefins Bearing only One α‐Substituent

A dual catalytic system has been developed following the screening of a series of chiral primary amine catalysts and chiral phosphoric acid catalysts for the Michael addition of cyclic ketones to nitroolefins bearing only one α‐substituent. The resulting γ‐nitro ketones, which contain a substituent on the carbon connected to the nitro group, were formed in excellent yields (>80%) with high levels of stereoselectivity (up to 94:6 dr and 98% ee) when the reaction was performed in benzene at 0 °C with 10 mol% of the optimal amine/phosphoric acid combination (1:1) as a catalyst. Subsequent reduction of the nitro group followed by intramolecular reductive amination could afford optically active cis‐octahydroindole analogues bearing a non‐functional substituent at their 2‐position.

     

Enantioselective Titanium‐Catalyzed Cyanation Reactions of Carbonyl Compounds

This review surveys the recent developments in enantioselective titanium‐catalyzed cyanation reactions of carbonyl compounds, covering the literature since the beginning of 2008. It well demonstrates that this reaction constitutes an important tool in organic synthesis, still attracting a considerable interest due to the potential use of enantiopure cyanohydrins as natural products and useful synthetic intermediates in the synthesis of biologically active molecules. Abbreviations: Ac: acetyl; Ar: aryl; BINOL: 1,1′‐bi‐2‐naphthol; BINOLAM: bis(diethylaminomethyl)‐1,1‘‐binaphthol; Bn: benzyl; Cy: cyclohexyl; DFT: density functional theory; DMAP: 4‐(dimethylamino)pyridine; ee: enantiomeric excess; Naph: naphthyl; r.t.: room temperature; salen: 1,2‐bis(salicylidenamino)ethane; TADDOL: α,α,α′,α′‐tetraphenyl‐2,2‐dimethyl‐1,3‐dioxolane‐4,5‐dimethanol; TEA: trimethylamine; THF: tetrahydrofuran; TMS: trimethylsilyl; Tol: tolyl.

     

煤层气藏非对称水力裂缝直井产能评价

煤层具有非均值性较强、压裂裂缝展布不均匀、非对称分布等特点,目前缺少煤层非对称裂缝产能评价模型.针对上述问题,运用Langmuir等温吸附方程及Fick扩散定律描述煤层气藏中的吸附、解吸及扩散现象,引入特殊的拟时间函数解决考虑吸附解吸现象的物质平衡方程中非线性较强的问题,利用新定义的参数表征压裂过程中水力裂缝的非对称性...     

非径向对称随机向量的研究

本文利用过定点的Copula的最佳上、下界,构造了4个奇异Copula;证明了任意Copula与其生存Copula差的绝对值的上确界是三分之一;给出了度量随机变量非径向对称的方法;研究了最大非径向对称随机变量的性质及相关性度量的界。     

ZK60镁合金异步降温轧制显微组织与力学性能的演变（英文）

将异步降温轧制应用于制造沿轧制方向具有弱基面织构的细晶ZK60镁合金板。结果表明,多道次降温轧制可以显著改善显微结构的均匀性,细化晶粒尺寸。同时,在轧制过程中逐渐形成沿横向的纤维织构。重要的是,沿轧向的剪切变形使基面的c轴向轧向旋转,削弱沿此方向的基面织构。受这种显微结构变化的影响,由于连续的晶粒细化和柱面滑移的增加,沿横向的屈服强度持续增加,而由于应变硬化能力的下降,均匀伸长率下降。相反,沿轧向的基面织构的持续减弱大大抵消晶粒细化所带来的强化效果,从而导致屈服强度的轻微下降。     

基于反克隆机制的WSN区域密钥分发

针对无线传感网安全管理领域中存在的密钥生成困难、节点抗俘性能较差等不足,提出了一种基于反克隆机制的WSN区域密钥分发算法。首先,基于区域成型存在的簇头-簇节点的分层特性,采用反克隆机制进行节点层次认证,引入正交机制进行节点密钥分发,降低因簇头-簇成员节点信息交互不畅而导致的安全抖动风险。随后,采取密文非对称传输方式进行密钥冲激响应,通过逆向分发进一步降低密钥被破解的概率,减少安全确认过程中存在的信令频繁收发现象。仿真结果表明：与当前常用的WSN安全领域常用的基于多项式和矩阵的无线传感器网络密钥管理安全方案算法(Polynomial and Matrix Based Key Management Security Scheme in Wireless Sensor Networks, P-MB算法)和基于块LU分解的无线传感器网络密钥预分配算法(Key Pre-distribution Approach Using Block LU Decomposition in Wireless Sensor Network, PD-BLU算法)相比,本算法可显著降低节点被俘获的概率,减少网络信令传...