Participants in the 4th Sino-French Workshop on Molecular Spectroscopy,Dynamics and Quantum Control

First Row （from left to right）： Yn-xiang Mo, Long-sheng Ma, Hong-mei Su, Dong-hui Zhang Hong-fei Wang, Alain Campargue, Ludovic Daumont, Shui-ming Hu, Patrice Cacciani, Claude Camy-Peyret, Celine Leonard, Xue-ming Yang, Andrea Simoni, Fei Qi, Fu-yi Liu, Ke-li Han     

Halogen Bonding in Haspin-Halogenated Tubercidin Complexes: Molecular Dynamics and Quantum Chemical Calculations

Haspin, an atypical serine/threonine protein kinase, is a potential target for cancer therapy. 5-iodotubercidin (5-iTU), an adenosine derivative, has been identified as a potent Haspin inhibitor in vitro. In this paper, quantum chemical calculations and molecular dynamics (MD) simulations were employed to identify and quantitatively confirm the presence of halogen bonding (XB), specifically halogen∙∙∙π (aromatic) interaction between halogenated tubercidin ligands with Haspin. Consistent with previous theoretical finding, the site specificity of the XB binding over the ortho-carbon is identified in all cases. A systematic increase of the interaction energy down Group 17, based on both quantum chemical and MD results, supports the important role of halogen bonding in this series of inhibitors. The observed trend is consistent with the experimental observation of the trend of activity within the halogenated tubercidin ligands (F < Cl < Br < I). Furthermore, non-covalent interaction (NCI) plots show that cooperative non-covalent interactions, namely, hydrogen and halogen bonds, contribute to the binding of tubercidin ligands toward Haspin. The understanding of the role of halogen bonding interaction in the ligand–protein complexes may shed light on rational design of potent ligands in the future.     

第13届全国分子光谱学学术会议征文通知

中国化学学会物理化学委员会和中国光学会光谱委员联合主办、厦门大学承办的第13届全国分子光谱学术会议,定于2004年11月在厦门召开．会议将邀请国内外著名学者到会作报告,同时进行专题讨论和报告交流．     

特殊缔合体系TFE水溶液分子动力学模拟

三氟乙醇(TFE)水溶液是一类特殊的缔合体系. 采用分子动力学模拟方法结合核磁共振化学位移研究了TFE水溶液体系全浓度范围的氢键网络, 并对动力学模拟结果和核磁共振化学位移进行了比较. 从径向分布函数(RDF)发现, TFE水溶液中存在着强氢键, 而体系中的C—H…O弱相互作用较为明显, 也不能忽略. 氢键网络分析发现TFE 水溶液体系的氢键大致分为以下三个区域: 在水富集区域, 水分子倾向于自身缔合形成稳定的簇结构, 随着TFE 浓度的增加, 水的有序结构受到破坏, 水分子和TFE分子发生交叉缔合作用形成氢键; 在TFE富集区域, 水分子较少, TFE分子自身通过氢键形成多缔体结构. 此外, 分子动力学统计的平均氢键数的变化和文献报导的核磁共振化学位移变化趋势相同, 实验和理论的结果吻合较好.     

离子液体的量化计算及分子动力学模拟研究进展

离子液体是由有机阳离子和无机/有机阴离子构成的盐类,一般在室温或接近于室温下呈液态,因此常被称为室温离子液体(RTIL).依据不同的划分标准,离子液体有多种分类方式:根据年代的不同可将离子液体分为第一代、第二代及第三代离子液体,例如:烷基咪唑和烷基吡啶的金属卤化物盐等[1];根据阳离子的不同可将离子液体分为季鏻     

Quantum Chemical Study of the Preferred Conformations,Molecular Geometries,and Relative Thermodynamic Stabilities of 2-Substituted 4-Methylene-1,3-Dioxolanes and 4-Methyl-1,3-Dioxoles

The preferred conformations, molecular geometries, and relative stabilities of carbon–carbon double-bond exo–endo isomeric 2-substituted 4-methylene-1,3-dioxolanes (a) and 4-methyl-1,3-dioxoles (b) have been studied by DFT calculations at the B3LYP/6-31G* level of theory. The main interest of this work was devoted to the contribution of alkoxy substituents on the relative thermodynamic stabilities of these isomeric unsaturated acetals. Comparison of the computational data with previous experimental findings shows both the enthalpies and entropies of the a b isomerization to be accurately predictable by the DFT calculations. Most importantly, the good agreement between experiment and theory proved also to be applicable to the previously observed unexpectedly large effect of 2-alkoxy substitution on the isomer equilibria.     

纪念唐敖庆先生诞辰100周年特刊序言

<正>今年是唐敖庆老师100周年诞辰。唐老师1915年11月18日出生于江苏宜兴,2008年7月15日11时15分在北京逝世,享年93岁。唐老师以祖国振兴为己任,1949年底在美国哥伦比亚大学获得博士学位后,谢绝导师挽留,冲破重重阻力,于1950年初回到祖国,开始了献身祖国建设的光辉历程。他致力于教育,为祖国培养了以他的"八大弟子"为代表的     

引言

本毛细管电泳(CE)专辑源于“化学生物学之毛细管电动分离分析前瞻研讨会”,会议缘起于庆贺我国CE先锋竺安教授90华诞,意在“荟聚华夏CE豪杰,忆往昔,看今朝,谋未来”。会上,专家学者们共享了毛细管电动分离分析领域的最新成果,就CE创新性研究和发展问题展开了深入讨论。     

Reinterpretation of Dynamic Vibrational Spectroscopy to Determine the Molecular Structure and Dynamics of Ferrocene

Molecular distortion of dynamic molecules gives a clear signature in the vibrational spectra, which can be modeled to give estimates of the energy barrier and the sensitivity of the frequencies of the vibrational modes to the reaction coordinate. The reaction coordinate method (RCM) utilizes ab initio‐calculated spectra of the molecule in its ground and transition states together with their relative energies to predict the temperature dependence of the vibrational spectra. DFT‐calculated spectra of the eclipsed (D_5h) and staggered (D_5d) forms of ferrocene (Fc), and its deuterated analogue, within RCM explain the IR spectra of Fc in gas (350 K), solution (300 K), solid solution (7–300 K), and solid (7–300 K) states. In each case the D_5h rotamer is lowest in energy but with the barrier to interconversion between rotamers higher for solution‐phase samples (ca. 6 kJ mol^?1) than for the gas‐phase species (1–3 kJ mol^?1). The generality of the approach is demonstrated with application to tricarbonyl(η⁴‐norbornadiene)iron(0), Fe(NBD)(CO)₃. The temperature‐dependent coalescence of the ν(CO) bands of Fe(NBD)(CO)₃ is well explained by the RCM without recourse to NMR‐like rapid exchange. The RCM establishes a clear link between the calculated ground and transition states of dynamic molecules and the temperature‐dependence of their vibrational spectra.     

Study on the Structure of a Mixed KCl and K2SO4 Aqueous Solution Using a Modified X-ray Scattering Device,Raman Spectroscopy,and Molecular Dynamics Simulation

The microstructure of a mixed KCl and K₂SO₄ aqueous solution was studied using X-ray scattering (XRS), Raman spectroscopy, and molecular dynamics simulation (MD). Reduced structure functions [F(Q)], reduced pair distribution functions [G(r)], Raman spectrum, and pair distribution functions (PDF) were obtained. The XRS results show that the main peak (r = 2.81 Å) of G(r) shifted to the right of the axis (r = 3.15 Å) with increased KCl and decreased K₂SO₄. The main peak was at r = 3.15 Å when the KCl concentration was 26.00% and the K₂SO₄ concentration was 0.00%. It is speculated that this phenomenon was caused by the main interaction changing, from K-O_W (r = 2.80 Å) and O_W-O_W (r = 2.80 Å), to Cl⁻-O_W (r = 3.14 Å) and K⁺-Cl⁻ (r = 3.15 Å). According to the trend of the hydrogen bond structure in the Raman spectrum, when the concentration of KCl was high and K₂SO₄ was low, the destruction of the tetrahedral hydrogen bond network in the solution was more serious. This shows that the destruction strength of the anion to the hydrogen bond network structure in solution was Cl⁻ > SO₄²⁻. In the MD simulations, the coordination number of O_W-O_W decreased with increasing KCl concentration, indicating that the tetrahedral hydrogen bond network was severely disrupted, which confirmed the results of the Raman spectroscopy. The hydration radius and coordination number of SO₄²⁻ in the mixed solution were larger than Cl⁻, thus revealing the reason why the solubility of KCl in water was greater than that of K₂SO₄ at room temperature.     

Some Mathematical and Algorithmic Challenges in the Control of Quantum Dynamics Phenomena

The theory and practice of control over quantum mechanical phenomena is receiving increasing attention, underscored by striking experimental successes. Nevertheless, many questions of fundamental and practical relevance to the field remain unresolved. With the aim of stimulating further development, this paper formulates a number of theoretical questions, divided into three categories. First, questions related to control law design are discussed, with an emphasis on controllability and optimal control theory. This leads to the second category of open problems relevant to closed loop laboratory implementation of quantum control, including learning and feedback methods. The sensitive dependence of control on basic quantum mechanical interactions motivates the third section, which treats coherent dynamical techniques for identifying the system Hamiltonian. An open issue overarching all of these directions is the need to discover general rules for the control of quantum systems. Although the list of issues raised in this paper is extensive, it should be viewed not as a complete menu for exploration, but rather as a springboard to new challenges as the field evolves.