Theoretical studies on the mechanism of acid-promoted hydrolysis of N-formylaziridine in comparison with formamide

[reaction: see text] We present an ab initio study of the acid-promoted hydrolysis reaction mechanism of N-formylaziridine in comparison with formamide. Since the rate of amide hydrolysis reactions depends on the formation of the tetrahedral intermediate, we focused our attention mainly on the reactant complex, the tetrahedral intermediate, and the transition state connecting these two stationary points. Geometries were optimized using the density functional theory, and the energetics were refined using ab initio theory including electron correlation. Solvent effects were investigated by using polarizable continuum method calculations. The proton-transfer reaction between the O-protonated and N-protonated amides was investigated. In acidic media, despite that the N-protonated species is more stable than the O-protonated one, it is predicted that both N-protonated and O-protonated pathways compete in the hydrolysis reaction of N-formylaziridine.     

Theoretical insights into the mechanism of acetylcholinesterase-catalyzed acylation of acetylcholine

Acylation of acetylcholine (ACh) catalyzed by acetylcholinesterase (AChE) has been studied using high-level theoretical calculations on a model system that mimics the reaction center of the enzyme, and compared with uncatalyzed acylation reaction. The geometries of all the intermediates and transition states, activation energies, and solvent effects have been calculated. The calculations predict simultaneous formation of two short-strong hydrogen bonds (SSHB) in the rate-determining transition state structures [the first SSHB involves the hydrogen atom of Ser-200 (H(s)) and another involves the hydrogen atom of His-440 (H(h))]. In the intermediate states, the H-bond corresponding to H(h) involves SSHB, whereas the one corresponding to H(s) does not.     

薄板刚度对点焊接头强度特性影响

本文介绍了三种形状的薄板材料点焊接头试件的拉伸试验及疲劳试验结果,探讨了改变薄板刚度对点焊接头静强度和疲劳寿命的影响。应用断裂力学理论及有限单元法计算焊核周围裂尖各点的应力强度因子K_Ⅰ、K_Ⅱ、K_Ⅲ及有效应力强度因子K_(φθmax),并用这些力学参数分析了不同刚度点焊接头试件的静强度和疲劳寿命。结果表明有效应力强度因子K_(φθmax)是评价拉剪点焊头疲劳寿命的有效力学参数。     

纵向剪切下含共焦刚性核弹性椭圆夹杂中的螺型位错干涉

摘 要 研究了无穷远纵向剪切下无限大基体中含共焦刚性核弹性椭圆夹杂内任意位置螺型位错的干涉问题。运用复变函数保角映射、解析延拓等方法,获得了基体与夹杂区域的应力场的级数形式精确解,并得出了位错像力的解析表达式,导出了纵向剪切下两椭圆界面最大应力及其比值公式。分析结果表明：夹杂内部的刚性核对位错与夹杂的干涉产生明显的扰动效应,排斥硬夹杂内位错,并使之不断趋近弹性夹杂界面。对于软夹杂,夹杂中的位错存在稳定的平衡位置,当位错位于刚性核和平衡位置之间时,位错会趋于弹性夹杂界面;当位错位于平衡位置和弹性夹杂界面之间时,位错会离开界面。结果还显示,夹杂的长轴和短轴之比对位错与夹杂的干涉也有着不可忽视的影响,尤其当位错在刚性核附近时,随着夹杂的长、短轴比值的减小,核对位错的排斥力也明显减弱。本文解答包含了多个以往文献成果。     

Application of fuzzy probability factor superposition algorithm in nuclide identification

Journal of Radioanalytical and Nuclear Chemistry - In this study, a dynamic nuclide identification algorithm based on fuzzy probability factor superposition (FPFS) was proposed for γ spectrum...     

火花直读光谱法对铝合金中各元素含量测量结果的不确定度评定

分析了火花直读光谱法测定铝合金中Si、Fe、Cu、Mg、Mn、Zn、Cr、Ti元素含量测量结果的不确定度来源,对不确定度分量进行了评定与计算,Si、Fe、Cu、Mg、Mn、Zn、Cr、Ti测量结果的相对扩展不确定度分别为2. 9%、2. 5%、2. 6%、2. 7%、2. 6%、2. 6%、2. 5%、2. 7%(包含因子k均为2).     

梯形管内壁等离子体离子注入鞘层扩展MATLAB-PIC数值模拟

基于MATLAB利用Particle-in-cell模型,对梯形管内壁等离子体离子注入过程,进行了二维数值模拟.计算结果表明在中心电极附近出现了"阳极鞘层",该鞘层内部不存在离子,而且在鞘层边缘离子密度最高.在上下管壁上的离子注入剂量呈现"m"形分布.通过对注入过程中等离子体密度分布和不同时间段管壁不同位置离子注入剂量的跟踪,发现"阳极鞘层"扩展行为是导致"m"形分布的原因.由于梯形管形状的不对称性,"阳极鞘层"的边缘向梯形长底方向扩展较快.在注入初始时刻离子注入的能量很低,随着时间延长离子能量逐渐升高,这是由离子初始位置决定的.可见梯形管自身形状决定了鞘层形状和最终的离子注入能量和剂量分布.     

Acupuncture regulates the glucose metabolism in cerebral functional regions in chronic stage ischemic stroke patients----a PET-CT cerebral functional imaging study

ABSTRACT: BACKGROUND: Acupuncture has been applied to aid in the recovery of post-stroke patients, but its mechanism is unclear. This study aims to analyze the relationship between acupuncture and glucose metabolism in cerebral functional regions in post-stroke patients using 18 FDG PETCT techniques. Forty-three ischemic stroke patients were randomly divided into 5 groups: the Waiguan (TE5) needling group, the TE5 sham needling group, the sham point needling group, the sham point sham needling group and the non-needling group. Cerebral functional images of all patients were then acquired using PET-CT scans and processed by SPM2 software. RESULTS: Compared with the non-needling group, sham needling at TE5 and needling/sham needling at the sham point did not activate cerebral areas. However, needling at TE5 resulted in the activation of Brodmann Area (BA) 30. Needling/sham needling at TE5 and needling at the sham point did not deactivate any cerebral areas, whereas sham needling at the sham point led to deactivation in BA6. Compared with sham needling at TE5, needling at TE5 activated BA13, 19 and 47 and did not deactivate any areas. Compared with needling at the sham point, needling at TE5 had no associated activation but a deactivating effect on BA9. CONCLUSION: Needling at TE5 had a regulating effect on cerebral functional areas shown by PET-CT, and this may relate to its impact on the recovery of post-stroke patients.     

煌焦油蓝分光光度法测定微量亚硝酸根

本文研究了在盐酸介质中微量亚硝酸根与煌焦油蓝发生的重氮化反应,建立了测量微量亚硝酸根的新方法。方法的线性范围为０．５￣１２μｇＮＯ２＾－／２５ｍＬ,检出限为０．５μｇ ＮＯ２＾－／２５ｍＬ。方法已用于水中微量亚硝酸根的测定。并对机理进行了初步讨论。     

6,7-二氧代-4-芳胺香豆素的设计、合成及分子对接研究

茶酚-氧位-甲基转移(COMT)酶抑制剂在治疗帕金森病中起到重要作用.通过对现有COMT酶抑制剂托卡朋和恩托卡朋结构与活性关系分析,推断含有儿茶酚结构的香豆素类化合物可能具有潜在的COMT酶抑制活性,因此设计合成了一类新型的6,7-二氧代-4-芳胺香豆素,通过理论计算,研究了此类化合物对COMT酶抑制活性.结果表明,设计的10种6,7-二氧代-4-芳胺香豆素与COMT酶的对接效果均较好,其中具有甲氧基乙基保护的儿茶酚结构化合物6,7-二[2-(甲氧基)乙氧]-4-(苯胺)香豆素(6b4)和6,7-二[2-(甲氧基)乙氧]-4-[(3-乙炔基)苯胺]香豆素(6b5)与COMT酶的对接效果尤为显著.