天然丰度氘核磁共振测定一级和二级动力学氘同位素效应（Ⅲ）——对Grignard

本文报道了用天然丰度^2HNMR测定一级动力学氘同位素效应的方法。这种方法与现有方法不同，它要求在反应时授氢反应物大大过量于受氢底物，在计算时要考虑由^2HNMR测定的反应物和产物的特定部位同位素比率（D／H）i或化合物的平均同位素比率（D／H）。我们用这种方法研究了一些Grignard试剂水解的同位素效应。     

锆-氚反应热力学特性

<正>利用金属氢化物可以方便地对氢同位素氕、氘、氚进行泵输、转移、固态吸附贮存、功能薄膜制造等。目前应用较成熟的有铀[1]、钛[2]、锆钴合金[3]等材料。锆与钛是属于同一族的金属元素,也是一种吸氢密度很高的功能材料,目前国内外已有较多关于氢在锆中固溶[4]、扩散[5-6]等方面的报道,但有关锆吸氚性能     

天然丰度氘核磁共振测定一级和二级动力学氘同位素效应(Ⅱ)——外标的分子内和分子间竞争法

建立了用外标的天然丰度~2 H NMR同时测定一级和不同类型二级动力学同位素效应的方法。用此法测定了苯氯化和溴化,甲苯氯化以及苯甲醇氧化等反应的同位素效应值。     

天然丰度氘核磁共振测定一级和二级动力学氘同位素效应(Ⅲ)——对Grignard试剂水解反应的应用

本文报道了用天然丰度~2HNMR测定一级动力学氘同位素效应的方法。这种方法与现有方法不同,它要求在反应时授氢反应物大大过量于受氢底物,在计算时要考虑由~2HNMR测定的反应物和产物的特定部位同位素比率(D/H):或化合物的平均同位素比率(D/H)。我们用这种方法研究了一些Grignard试剂水解的同位素效应。     

四氯化锆四元催化体系中乙烯齐聚反应的动力学研究

研究了四氧化锆作主催化剂的四元催化体系中，乙烯压力、催化剂浓度和温度对乙烯齐聚反应的影响．测定了稳定态下乙烯齐聚反应的宏观动力学方程和表观活化能．     

锆元素概念的形成和发展

1789年,普鲁士分析化学家克拉普罗特提出黄锆石中含有一种新土质,并将其命名为“锆土”,锆元素假说正式形成。随后,锆的原子重量的测定以及锆元素在元素表中位置的确定,促进了锆元素假说的发展。1914年,荷兰工程师勒利和汉布格首次制得纯度较高的金属锆,这使得锆元素假说得以证实,锆元素概念正式形成。从1924年至2020年,锆同位素的发现使人们对锆元素有了新认识,促使了现代锆元素概念的形成。锆元素概念的形成和发展的过程既是元素的发现史,也是化学思想和化学方法的演进史。     

用于锆稳定同位素测定的化学分离技术

本文采用ＨＤＥＨＰ／环己烷体系萃取锆和钼，并将两 发离以便测定锆的稳定同位素，此外，还研究了作为同 素稀释剂的ＺｒＯ２固体粉末的微波溶样法。     

天然氘核磁共振测定一级和二级动力学氘同位素效应I. 内标的分子内与分子间竞争法

应用氘核磁共振,而不用特别氘代化合物同时测定一级和二级动力学氘同位素效应,其特点是采用外标,并同时考虑分子内和分子间竞争,用建立的方法测定甲苯、乙苯及异丙苯的一级、α-及β-二级效应值。     

疏水催化剂用于水中氚回收的实验研究

本文简要介绍了自制的几种疏水催化剂的主要特性,采用这些催化剂进行了室温下的H—T同位素交换实验,初步考察了氢气流速对催化活性的影响。实验表明,催化剂的催化活性较高,能够用于室温下从氚水中回收氚。     

钌基和铁基催化剂上氨合成催化反应的氘反同位素效应

 氘反同位素效应是合理阐明过渡金属催化剂上氨合成催化反应机理的重要实验依据之一. 在 N2/H2 (或 D2) 体积比 1/3, 0.2 MPa, 633~733 K 和 GHSV = 24 000 或 12 000 h?1 的条件下, 检测到了 Ru 基 (纯 Ru, Ru/?-Al2O3, K-Ru/?-Al2O3, Ru/MgO, K-Ru/MgO 和 Ba-Ru/MgO) 和 Fe 基 (纯 Fe 和 A110-3) 催化剂上强的氘反同位素效应 (rD/rH ? 2), 其数值随催化剂和反应温度的变化而变化. 这可能是动力学同位素效应与热力学同位素效应二者相互强竞争的结果.     

Synthesis of Tritium and Deuterium Labelled Agmatine

Agmatine is a promising anti-opioid dependence and relapse drug1~2 discovered and developed by Beijing Institute of Pharmacology and Toxicology, but the physiological role of agmatine in inhibition of tolerance to and dependence on opioid are not well est…     

催化动力学光度法测定痕量锆（Ⅳ）

研究了在稀盐酸介质中，α，α’－联吡啶存在下，锆催化溴酸钾氧化考马斯亮蓝Ｇ使其褪色这一新的指示反应及其动力学条件，建立了灵敏地测定痕量锆的新方法。该方法检出限为８．９８×１０＾－１１ｇ／ｍＬ，线性范围０－１０．４μｇ／Ｌ，用于合金钢中痕量锆的测定，结果满意．     

Multiple Site Hydrogen Isotope Labelling of Pharmaceuticals

Radiolabelling is fundamental in drug discovery and development as it is mandatory for preclinical ADME studies and late-stage human clinical trials. Herein, a general, effective, and easy to implement method for the multiple site incorporation of deuterium and tritium atoms using the commercially available and air-stable iridium precatalyst [Ir(COD)(OMe)]₂ is described. A large scope of pharmaceutically relevant substructures can be labelled using this method including pyridine, pyrazine, indole, carbazole, aniline, oxa-/thia-zoles, thiophene, but also electron-rich phenyl groups. The high functional group tolerance of the reaction is highlighted by the labelling of a wide range of complex pharmaceuticals, containing notably halogen or sulfur atoms and nitrile groups. The multiple site hydrogen isotope incorporation has been explained by the in situ formation of complementary catalytically active species: monometallic iridium complexes and iridium nanoparticles.     

Theoretical Simulations of Kinetic Isotope Effects on Decarboxylation of 3-Carboxybenzisoxazole

Kinetic isotope effect values on the decarboxylation of 3-carboxybenzisoxazole have been computed using the second-order Kleinert's variational perturbation theory in the framework of Feynman's path integrals along with the potential energy surface obtained at the MP2/6-31+G(d) level. Good agreement with the experimental data was obtained, demonstrating that this novel computational approach for computing KIE values of organic reaction is a viable alternative to the traditional method employing the Bigeleisen equation and harmonic vibrational frequencies. Compared with the experimental measurements, consideration of anharmonicity and tunneling effects can significantly improve the calculated KIE values, reducing the root-mean-square deviation from 1.19 % for traditional method to 0.20 % for path-integral method.     

Kinetic Isotope Effects in Asymmetric Reactions

Kinetic isotope effects are exquisitely sensitive probes of transition structure. As such, kinetic isotope effects offer a uniquely useful probe for the symmetry‐breaking process that is inherent to stereoselective reactions. In this Concept article, we explore the role of steric and electronic effects in stereocontrol, and we relate these concepts to recent studies carried out in our laboratory. We also explore the way in which kinetic isotope effects serve as useful points of contact with computational models of transition structures. Finally, we discuss future opportunities for kinetic isotope effects to play a role in asymmetric catalyst development.     

Deuterium Isotope Effects on Acid-Base Equilibrium of Organic Compounds

Deuterium isotope effects on acid–base equilibrium have been investigated using a combined path integral and free-energy perturbation simulation method. To understand the origin of the linear free-energy relationship of ΔpKa=pKaD2O−pKaH2O versus pKaH2O, we examined two theoretical models for computing the deuterium isotope effects. In Model 1, only the intrinsic isotope exchange effect of the acid itself in water was included by replacing the titratable protons with deuterons. Here, the dominant contribution is due to the difference in zero-point energy between the two isotopologues. In Model 2, the medium isotope effects are considered, in which the free energy change as a result of replacing H₂O by D₂O in solute–solvent hydrogen-bonding complexes is determined. Although the average ΔpKa change from Model 1 was found to be in reasonable agreement with the experimental average result, the pKaH2O dependence of the solvent isotope effects is absent. A linear free-energy relationship is obtained by including the medium effect in Model 2, and the main factor is due to solvent isotope effects in the anion–water complexes. The present study highlights the significant roles of both the intrinsic isotope exchange effect and the medium solvent isotope effect.     

Determination of Iron in Zirconium by Electrolytic Dissolution and Atomic Absorption Spectroscopy

Abstract

A simple method for the determination of iron in the range of 0.01–1.00% in zirconium metal and its alloys is described. The method is based on the electrolytic dissolution of zirconium into an organic solvent and the subsequent measurement of iron by atomic absorption spectroscopy. The method is rapid, requiring 30 minutes for one measurement.     

Mechanistic Insights into RNA Transphosphorylation from Kinetic Isotope Effects and Linear Free Energy Relationships of Model Reactions

Phosphoryl transfer reactions are ubiquitous in biology and the understanding of the mechanisms whereby these reactions are catalyzed by protein and RNA enzymes is central to reveal design principles for new therapeutics. Two of the most powerful experimental probes of chemical mechanism involve the analysis of linear free energy relations (LFERs) and the measurement of kinetic isotope effects (KIEs). These experimental data report directly on differences in bonding between the ground state and the rate‐controlling transition state, which is the most critical point along the reaction free energy pathway. However, interpretation of LFER and KIE data in terms of transition‐state structure and bonding optimally requires the use of theoretical models. In this work, we apply density‐functional calculations to determine KIEs for a series of phosphoryl transfer reactions of direct relevance to the 2′‐O‐transphosphorylation that leads to cleavage of the phosphodiester backbone of RNA. We first examine a well‐studied series of phosphate and phosphorothioate mono‐, di‐ and triesters that are useful as mechanistic probes and for which KIEs have been measured. Close agreement is demonstrated between the calculated and measured KIEs, establishing the reliability of our quantum model calculations. Next, we examine a series of RNA transesterification model reactions with a wide range of leaving groups in order to provide a direct connection between observed Brønsted coefficients and KIEs with the structure and bonding in the transition state. These relations can be used for prediction or to aid in the interpretation of experimental data for similar non‐enzymatic and enzymatic reactions. Finally, we apply these relations to RNA phosphoryl transfer catalyzed by ribonuclease A, and demonstrate the reaction coordinate–KIE correlation is reasonably preserved. A prediction of the secondary deuterium KIE in this reaction is also provided. These results demonstrate the utility of building up knowledge of mechanism through the systematic study of model systems to provide insight into more complex biological systems such as phosphoryl transfer enzymes and ribozymes.     

Hydrogen Isotope Exchange by Homogeneous Iridium Catalysis in Aqueous Buffers with Deuterium or Tritium Gas

We have studied the highly selective homogeneous iridium-catalyzed hydrogen isotope exchange (HIE) with deuterium or tritium gas as an isotope source in water and buffers. With an improved water-soluble Kerr-type catalyst, we have achieved the first insight into applying HIE reactions in aqueous media with varying pH. Density functional theory (DFT) calculations gave consistent insights in the calculated energies of transition states and coordination complexes, further explaining the observed reactivity and guidance on the scope and limitations for HIE reactions in water. Finally, we successfully adapted these findings to tritium chemistry.