大环配体五员瓜环的异核配位聚合物的合成及晶体结构（英文）

瓜环是一类由亚甲基桥联苷脲单元形成的新型笼状大环化合物,环绕在其端口极性较强的羰基形成了阳离子键和位点,可以通过离子-偶极相互作用和与脲羰基的氢键作用来键合金属离子,这类化合物在环境、医药及材料等领域具有广阔的应用前景。本文设计并合成了一个五员瓜环(Q[5])桥联K~+和Gd~(3+)形成的新型一维配位聚合物{KGd(H_2O)_3Q[5]}_n-(ClO_4)_(3n)Cl_n·7nH_2O。利用单晶X射线衍射进行结构测定,结果表明:配合物中Q[5]起着一个双五齿配体的作用,每个端口的5个羰基氧原子分别和钾离子和钆离子配位,Q[5]空腔内包结一个氯离子,和钆离子配位水分子同时和K~(+i)(i=x,y-1,z)配位,化合物本身形成沿b轴延伸的一维配位聚合物。     

后过渡金属催化剂的分子模拟研究

应用量子化学计算程序ADF考察含有不同有机配体的过渡金属镍配合物对催化乙烯聚合反应的作用，对由于取代基不同造成催化活性不同的相关机理进行验证计算；应用分子动力学计算程序考察催化剂失活难易程度，应用量子化学计算程序ADF考察聚合分子双键位置及支化度的变化情况，计算结果表明当吡叮环配体中有甲基取代时，反应活性降低。当苯环上1，3，5位出现甲基取代时；反应不易发生。当配体上有较强的给电子基团取代时，反应活性增强。     

互不同随机整数序列的快速选取算法（FSR）研究

研究互不同相的随机整数序列的选取算法是一个非常重要的课题，这里我们给出了一种采用二分技术的互不相同的随机整数快速选取策略（FSR），并证明了采用该算法在某一区间（M，N）内选取R个互不相同的随机整数所需的步长仅O[log2R]，其随机周期达到（N－M－1）！／（N-M-1-R)!，而经典算法所需的步长的R，其随机周期仅为（N－M－1）。     

乳清酸核苷单磷酸盐脱羧动力学同位素效应的理论研究（英文）

采用密度泛函(B3LYP)理论对乳清酸核苷单磷酸盐脱羧酶(ODCase)催化乳清酸核苷单磷酸盐(OMP)脱羧反应的动力学同位素效应进行了理论计算研究,重点讨论分析了水分子对整个催化脱羧反应的影响。本文建立了包含水分子和残基的新分子模型,并对所有分子模型进行结构全优化,获得了反应势垒。计算了N-1的~(15)N动力学同位素效应和C-6的~(13)C动力学同位素效应。计算结果显示:质子化水分子与羧基上的两个羰基氧原子的氢键长度对催化脱羧反应势垒有很大影响,并且计算得到的~(15)N和~(13)C动力学同位素效应与实验结果吻合较好。这些结果都对我们提出的乳清酸核苷单磷酸盐催化脱羧反应机理提供了有利依据。     

Emim-R离子液体气相结构与光谱的密度泛函理论研究

应用B3LYP/6-31G(d)方法研究了气相状态下一系列复杂阴离子BF_4~-、AlCl_4~-、PF_6~-、NO_3~-、CF_3COO~-、CF_3SO_3~-、HSO_4~-及其与阳离子[Emim~ ]形成的离子液体[Emim]BF_4、[Emim]AlCl_4、[Emim]PF_6、[Emim]CF_3COO、[Emim]CF_3SO_3、[Emim] HSO_4、[Emim]NO_3的结构和红外光谱,分析了阴阳离子的结合方式及其相互作用。[Emim]BF_4和[Emim]PF_6的计算结果与前人的计算结果及实验观测值符合得较好。研究发现含有O原子的阴离子与阳离子的相互作用比其它的阴离子都强,其中NO_3最强。     

Mo的亚硝酰基配合物催化的亚胺氢化反应机理的研究

采用密度泛函理论(DFT)的B3LYP方法,对过渡金属Mo的二膦亚硝酰基氢化物[Mo(dimpp)(NO)(CO)_2(H)](MoH,dimpp=1,3-二(二甲基膦基)丙烷)催化的N-苯亚甲基甲胺(BIMA)氢化的反应机理进行了理论研究。Mo原子基于LANL2DZ基组,其它原子基于6-31+G(d,p)基组,对反应势能面上各稳定点和过渡态的进行了几何构型优化和振动频率分析。计算结果表明,该催化反应通过质子-负氢转移的离子氢化机理进行。催化循环由MoH质子化生成酸性η~2-H_2配合物MoHH开始,分3步进行:(1)η~2-H_2配体上的质子转移到亚胺的N原子上生成亚胺正离子;(2)负氢转移到亚胺正离子的碳原子上,生成产物胺;(3)氢分子与金属中心Mo配位生成MoHH。这3个步骤的活化能分别为5.7,8.1和3.6 kcal.mol~(-1)。     

钠离子在分子筛合成中的结构导向作用的分子模拟研究

利用分子力学和分子动力学计算工具,对钠离子的各种水合结构及能量进行了分子力学和动力学的计算,以此研究水合钠离子所起的结构生成剂的作用.用Monte Carlo Docking方法对各种结构的水合钠离子在MFI分子筛微孔结构内的附着行为模拟计算.结果表明,配位数为偶数时水合阳离子的结构较为合理,这种合理性体现在当配位数为偶数时,Na-+nH2O体系中金属离子的位置与氧原子的位置呈现对称结构,Na-+4H2O和Na-+6H2O是相对比较合适的结构;对于钠离子,配位数为4和6,当配位数大于6时,体系将自动转为6配位的情况;钠离子明显具有对周围的水分子结构进行重新排列的作用;钠离子的配位水分子数为4个或6个,而4配位结构是水合钠离子的主要存在方式之一;在MFI结构分子筛的合成中起模板剂作用的应该是Na-+4H2O结构;计算结果对分子筛合成研究中水合离子的结构生成和结构破坏具有重要的意义.     

As~(3+)与DNA4种碱基相互作用的理论研究

砷在进入生物体后,可通过对基因损伤和基因表达等多方面的影响而发挥其毒性。本文运用量子化学计算,研究了As3+与DNA4种碱基的配位作用。从理论上确立了As3+与4种碱基的配合特征和各种配合物的相对稳定性以及As3+对4种碱基配合的选择性。当As3+与碱基结合时,最多能与3个碱基配体形成稳定构型,我们共得到17个稳定的三配体配合物。其中,As3+与O和N所形成配位键As-O和As-N的键长范围分别为(1.76~1.85)?和(1.88~2.01)?。As3+与4种不同碱基作用时,倾向与鸟嘌呤发生配位反应,且易于结合位点羰基O处发生反应。     

膦酰基羧酸调聚物缓蚀性能的量子化学研究

研究中发现膦酰基羧酸调聚物(POCA)对碳钢的缓蚀作用良好,而丙烯酸与2-丙烯酰胺-2-甲基丙基磺酸的共聚物(AA- AMPS共聚物)则几乎无缓蚀作用。量子化学方法计算表明POCA调聚物的前线HOMO分子轨道能量较AA-AMPS共聚物大,所以POCA更容易为铁的空d轨道提供电子;AA-AMPS共聚物中对HOMO轨道电荷密度贡献较大的主要是AMPS分子中酰胺基团的N和O原子,O原子的电子轨道布居数虽然较大,但贡献却比N原子小(10%左右),而N原子贡献虽然较大(75%左右),但电子轨道布居数小,因此很难在酰胺基团处与金属吸附。POCA分子中膦酰基基团的P原子和O原子对HOMO轨道电荷密度贡献分别达到70%和20%,且其轨道电子布居数较大,因此较容易通过膦酰基与金属配位吸附而缓蚀性能良好。POCA的缓蚀功能由引入链分子中的膦酰基基团获得,羧酸基团和磺酸基团基本无作用。     

C3N3(NH2)3、[C(O)NH]3和水双分子间的氢键相互作用

采用密度泛函理论,在B3LYP/6-311+G**水平上对C3N3(NH2)3、[C(O)NH]3、H2O 3种单体在气相中形成的双分了氢键作用体系进行构型优化和频率计算.通过几何优化得到一系列含多个氢键的复合物.频率分析表明,与单体相比,体系形成氢键作用后,参与氢键形成相关的键的红外谱带位置和振动强度都发生明显的变化,其中C3N3(NH2)3-[C(O)NH]3体系中N8-H9键的红移最明显.同时,通过B3LYP/6-311+G**和MP2/6-311+G**水平计算的含基组重叠误差(BSSE)校正的氢键相互作用能分析表明,C3N3(NH2)3-[C(O)NH]3氢键体系的相互作用能最大,其次是([C(O)NH]3)2体系,采用MP2/6-311+G**方法计算的相互作用能分别达到-14.171 kcal·mol-1和-10.217 kcal·mol-1.另外,通过自然键轨道理论揭示氢键相互作用的本质.     

Mutagenicity of heteroaromatic amines: Computational study on the influence of methyl substituents

Quantum mechanical calculations were performed to elucidate the factors determining the variations in mutagenic activity within groups of isomeric heteroaromatic amines that differ in the position of methyl substituents. Formation energies for noncovalent complexes and covalent DNA adducts were evaluated by means of high level quantum chemical methods. According to the computational results in this work, covalent adduct stability is proposed to influence the relative mutagenicities of structurally related heterocyclic amines. The stability of covalent C8-dG DNA adducts was found to be mainly determined by π-stacking interactions between the fused ring system of the heteroaromatic amines and the flanking nucleobases. Relative mutagenicity of amines of very related structure is proposed to be regulated by both nitrenium ion and covalent adduct stabilities.     

Probing the reactivation process of sarin-inhibited acetylcholinesterase with α-nucleophiles: hydroxylamine anion is predicted to be a better antidote with DFT calculations

Inactivation of acetylcholinesterase (AChE) due to inhibition by organophosphorus (OP) compounds is a major threat to human since AChE is a key enzyme in neurotransmission process. Oximes are used as potential reactivators of OP-inhibited AChE due to their α-effect nucleophilic reactivity. In search of more effective reactivating agents, model studies have shown that α-effect is not so important for dephosphylation reactions. We report the importance of α-effect of nucleophilic reactivity towards the reactivation of OP-inhibited AChE with hydroxylamine anion. We have demonstrated with DFT [B3LYP/6-311G(d,p)] calculations that the reactivation process of sarin-serine adduct 2 with hydroxylamine anion is more efficient than the other nucleophiles reported. The superiority of hydroxylamine anion to reactivate the sarin-inhibited AChE with sarin-serine adducts 3 and 4 compared to formoximate anion was observed in the presence and absence of hydrogen bonding interactions of Gly121 and Gly122. The calculated results show that the rates of reactivation process of adduct 4 with hydroxylamine anion are 261 and 223 times faster than the formoximate anion in the absence and presence of such hydrogen bonding interactions. The DFT calculated results shed light on the importance of the adjacent carbonyl group of Glu202 for the reactivation of sarin-serine adduct, in particular with formoximate anion. The reverse reactivation reaction between hydroxylamine anion and sarin-serine adduct was found to be higher in energy compared to the other nucleophiles, which suggests that this α-nucleophile can be a good antidote agent for the reactivation process.     

A modification of the classical Nevanlinna-Pick interpolation algorithm with applications to robust stabilization

A modification is presented of the classical Nevanlinna-Pick interpolation algorithm for bounded-analytic functions which permits interpolation with bounded-real functions. This is an essential modification when the Nevanlinna-Pick theory is applied to problems such as robust stabilization [2], since otherwise compensator transfer functions will in general have complex coefficients when complex interpolation points are present. The theory underlying the modification presented is based on the theory developed by Youla and Saito [4] on interpolation with positive-real functions. The results are applied to a numerical problem in robust stabilization.     

Docking studies of agonists and antagonists suggest an activation pathway of the A3 adenosine receptor

Structural determinants of ligand efficacy in the human A(3) adenosine receptor (AR) were studied using pharmacophore and docking analyses of various categories of A(3) selective ligands: inverse agonist, neutral antagonist (nonnucleoside and nucleoside), and agonist (partial and full). The homology modeling of GPCRs was adapted to provide two templates: the rhodopsin-based resting state for antagonist binding and a putative Meta I state, conformationally altered at a key residue (W6.48), for agonist binding. The preferential binding domains and/or local conformational changes associated with docking of three high affinity A(3)AR ligands were compared: inverse agonist PSB-11 1 ((R)-8-ethyl-4-methyl-2-phenyl-imidazo[2,1-i]purin-5-one); neutral antagonist MRE-3008F20 7 (5-[[(4-methoxyphenyl)amino]carbonyl]amino-8-methyl-2-(2-furyl)pyra-zolo[4,3-e]1,2,4-triazolo[1,5-c]pyrimidine), and full agonist Cl-IB-MECA 21 (2-chloro-N(6)-(3-iodobenzyl)-5'-N-methylcarboxamidoadenosine) to define a distinct recognition mode for each. Ribose-containing agonists were more hydrophilic than nonnucleoside antagonists, and H-bonding ability at the ribose 3'- and 5'-positions was required for agonism. From the receptor perspective, common requirements for activation included the destabilization of H-bond networks at W6.48 and H7.43, the specific interactions of the ribose moiety in its putative hydrophilic pocket at T3.36, S7.42, and H7.43, the stabilization of the complex by inward movement of F5.43, and the characteristic rotation of W6.48. By analogy, outward rotation of the W6.48 side-chain upon activation of an internally-crosslinking mutant M(3) muscarinic receptor was indicated by constrained molecular dynamics (MD). Our results are consistent with an anti-clockwise rotation (from the extracellular view) of transmembrane domains 3, 5, 6, and 7, as proposed for other Family A GPCRs. Thus, the putative conformational changes associated with A(3)AR activation indicate a shared mechanism of GPCR activation similar to rhodopsin.     

Binding of the tautomeric forms of isoniazid-NAD adducts to the active site of the Mycobacterium tuberculosis enoyl-ACP reductase (InhA): a theoretical approach

The front-line antituberculosis drug isoniazid (INH) inhibits InhA, the NADH-dependent fatty acid biosynthesis enoyl ACP-reductase from Mycobacterium tuberculosis, via formation of covalent adducts with NAD (INH-NAD adducts). While ring tautomers were found the main species formed in solution, only the 4S chain INH-NAD tautomer was evidenced in the crystallized InhA:INH-NAD complex. In this study we attempted to explore the modes of interaction and energy binding of the different isomers placed in the active site of InhA with the help of various molecular modelling techniques. Ligand and enzyme models were generated with the help of the Vega ZZ program package. Resulting ligands were then docked into the InhA active site individually using computational automated docking package AUTODOCK 3.0.5. The more relevant docked conformations were then used to compute the interaction energy between the ligands and the InhA cavity. The AM1 Hamiltonian and the QM/MM ONIOM methodologies were used and the results compared. The various tautomers were found docked in almost the same place where INH-NAD was present as predicted by earlier X-ray crystallographic studies. However, some changes of ligand conformation and of the interactions ligand-protein were evidenced. The lower binding energy was observed for the 4S chain adduct that probably represents the effective active form of the INH-NAD adducts, as compared to the 4R epimer. The two 4S,7R and 4R,7S ring tautomers show intermediate and similar binding energies contrasting with their different experimental inhibitory potency on InhA. As a possible explanation based on calculated conformations, we formulated the hypothesis of an initial binding of the two ring tautomers to InhA followed by opening of only the ring hemiamidal 4S,7R tautomer (possibly catalyzed by Tyr158 phenolate basic group) to give the 4S chain INH-NAD tight-binding inhibitor. The predictions of ligand-protein interactions at the molecular level can be of primary importance in elucidating the mechanisms of action of isoniazid and InhA-related resistances, in identifying the effective mycobactericidal entities and, in further step, in the design of a new generation of antitubercular drugs.     

行路由PEA广度贪心调度映射算法

粗粒度可重构单元阵列硬件任务的贪心映射是可重构计算要解决的核心问题。不同的阵列具有不同的硬件约束条件,针对行路由粗粒度可重构单元阵列提出一种广度贪心映射算法BGMA（Breadth Greedy Mapping Algorithm）。该算法首先从第一个节点开始依次扫描,如果节点满足条件则将其映射到PEA上,当遇到不满足映射条件的节点时,该算法将跳过该节点继续寻找满足约束条件的节点进行映射,通过与广度不贪心映射算法BNGMA（Breadth No Greedy Mapping Algorithm）相比较,BGMA的[N1]平均减少了35.1%（PEA6×6）和54.8%（PEA8×8）,[N2]平均减少了35.6%（PEA6×6）和54.6%（PEA8×8）,[CCON]平均减少了15.7%（PEA6×6）和26.2%（PEA8×8）,[TTOTAL]平均减少了20.2%（PEA6×6）和32.1%（PEA8×8）。实验结果表明了贪心策略在映射算法中的重要性。     

基于纳米金颗粒放大的电化学传感器用于三聚氰胺的检测

三聚氰胺与胸腺嘧啶（T）之间能够通过三个氢键结合,以富T的DNA探针为识别元件,结合DNA修饰的纳米金颗粒放大技术,以电活性物质钌胺作为信号分子,发展了一种高灵敏检测三聚氰胺的电化学传感器,该传感器具有良好的特异性和灵敏度,检测下限低至0．5nmol／L。     

金属离子极谱峰电位的精确拟合解析

利用计算机技术对实验测定的铋离子示差脉冲极谱数据进行了如下处理:1)用修正的Gaossian方程拟合实验测定的极谱曲线,得到精确至±0.05mV的极谱峰电位;2)用极谱数据计算机分析系统CFC-Ⅱ计算因Bi(OH)~(2+)络合物的形成而造成的极谱峰电位移动值;3)对校正过的金属离子极谱峰电位值进行多项式曲线拟合,得到整个pH区间铋离子(Bi~(3+))的示差极谱峰电位值。数据处理与分析结果表明:当溶液的pH<2.5时,可以利用关系式E_p(mV)=-0.252[pH]~4+5.8748[pH]~3-37.673[pH]~2+94.303[pH]+19.1计算科离子的极谱峰电位(相对于银/氯化银参比电极);当溶液的pH值在2.5以上时,铋离子的极谱峰电位为101.13mV     

Vibrational control of a class of nonlinear systems by nonlinear multiplicative vibrations

Vibrational control is a nonclassical control principle which proposes a utilization of zero mean parametric excitation of a dynamical system for control purposes. This paper extends nonlinear vibrational control theory developed in [8], [9] to systems controlled by nonlinear multiplicative vibrations. Condition for partial vibrational stabilization with respect to a component of a steady-state vector, the choice of stabilizing vibrations, and the transient motions are discussed for a certain practically important class of nonlinear vibrationally controlled systems. The application of the results is demonstrated on the example of a catalytic reactor, using a combination of numerical and analytical techniques.