金属四重键化合物M2X4（PMe3）4（M=Cr，Mo，W;X=F，CI，Br，I）结构和电子光谱的密度泛函理论研究

采用密度泛函理论方法，在TZ2P-STO基组水平下，对金属四重键化合物M2Cl4（PMe3）4（M=Cr，Mo，W）和Mo2X4（PMe3）4（X=F，Cl，Br，I）的几何结构进行优化，分析了电子结构，并运用TDDFT方法对其低占据激发态进行了计算．考虑相对论效应的ZORA方法能够较好地重现M2X4（PMe3）4的几何结构．M2X4（PMe3）4的电子结构分析表明其d电子的组态为σ^2π^4δ^2，前线轨道能级顺序为πlig〈πd／σd〈δd〈δd^＊．金属原子和卤素配体的改变虽然使轨道能量发生变化，但没有影响轨道的排布顺序．TDDFT方法对M2Xa（PMe3）4δd→δd^＊和π→δd^＊跃迁能量的计算较为准确，对πlig→δd^＊（LMCT）跃迁能量的计算误差较大．金属原子、卤素配体以及相对论效应对激发能的影响可以根据分子轨道能级的变化给予解释．     

Cyanex 923从硫酸体系中萃取钪及其与P507和环烷酸的比较

稀土元素钪(Sc)在相关原料中含量低,伴生杂质元素多,回收困难。针对这一问题,本文系统对比了直链三烷基氧化膦(Cyanex 923)、2-乙基己基磷酸单-2-乙基己基酯(P507)、环烷酸在硫酸体系中对Sc的萃取、分离和反萃。Cyanex 923在高酸度下能完全萃取Sc,而环烷酸和P507则在低酸度下有较高萃取率。Cyanex 923分离Sc与锆(Zr)、钛(Ti)的最佳水相酸度为1 mol/L,分离系数分别为5. 6和10. 6。P507在水相H~+浓度为2 mol/L时对Sc/Zr、Sc/Ti有最大分离系数,分别是21和59. 7。虽然P507有更好的分离效果,但难以反萃。3种萃取剂中仅有Cyanex 923能被有效反萃,在反酸H+浓度为0. 4 mol/L时有最大反萃率。因此,Cyanex 923更适合从含Sc二次资源浸出液中分离回收Sc。     

基于3d元素掺杂的石墨二炔分子传感材料性能调控

二维碳材料因其独特的性质成为凝聚态物理、纳米电子学、生物医药等领域的前沿研究热点。石墨二炔具有天然的半导体特性及独特的大孔网状结构,在纳米电子器件和生物传感方面比石墨烯更具优势。本文使用第一性原理计算研究了单层石墨二炔的纳米带电子输运性质和及石墨二炔对小分子的吸附。我们考虑用掺杂3d金属原子的方法来增强对分子的吸附力。选择在石墨二炔表面吸附能较大的钪(Sc)、钛(Ti)原子,确定石墨二炔表面Sc、Ti单原子在室温下的稳定性,研究了Sc、Ti掺杂石墨二炔用于分子检测的潜在可能。从能带、载流子浓度等方面全面探讨了Sc、Ti掺杂石墨二炔对甲醛分子(HCHO)的响应。又进一步研究了石墨二炔与氨基酸分子间相互作用,发现色散力在相互作用中占主导地位。研究了吸附氨基酸对石墨二炔电子输运的影响,探讨石墨二炔在生物传感方面的潜在应用。     

三重态类硅烯HB＝SiLiF的结构及其与R—H(R=F,OH,NH_2)的插入反应

用密度泛函理论(DFT)和二次组态相互作用(QCISD)方法研究了三重态类硅烯HB=SiLiF的结构及其与RH(R=F,OH,NH2)的插入反应.计算结果表明,类硅烯HB=SiLiF有三种平衡构型,其中四元环构型能量最低,是其存在的主要构型.HB=SiLiF与HF,H2O和NH3发生插入反应的机理相同.QCISD/6-311++G(d,p)//B3LYP/6-311+G(d,p)计算的三个反应的势垒分别为124.85,140.67和148.16kJ·mol-1,反应热分别为-2.22,20.08和23.22kJ·mol-1.相同条件下发生插入反应时,反应活性都是H—FH—OHH—NH2.     

构象对同位乙烯双自由基体系基态自旋多重度及其稳定性影响的理论研究

用DFT,CASSCF和QCISD(T)方法6-31G^*基组计算了构象对同位二取代乙烯双自由基体系基态自旋多重度及其稳定性的影响.结果表明,用DFT或CASSCF方法计算的单、三重态的能量差随自由基与乙烯间的二面角增加成不规则变化;用QCISD(T)方法计算的单、三重态的能量差随二面角的增加而逐渐降低,并呈规律性变化,说明QCISD(T)方法用于计算分子的磁性是可信的.对于同位二取代乙烯双自由基体系,无论双自由基旋转,还是单自由基旋转,高自旋基态稳定性随自由基与乙烯间二面角的增加而降低,只是降低的幅度不同,当二面角接近90°时,同位乙烯由具有平面或近似平面构象时强的铁磁耦合单元变成接近垂直平面构象时弱的反铁磁耦合单元或弱的铁磁耦合单元.     

卤代氰基卡宾自由基XCCN(X=F,Cl,Br)的理论研究

在C_s对称性和ANO-S基组下, 使用全活化空间自洽场方法(CASSCF), 研究了卤代氰基卡宾自由基及其阴离子的低能电子激发态性质. 为了进一步考虑电子的动态相关效应,采用多组态二级微扰理论(CASPT2)获得更加精确的能量值. 计算结果表明, XCCN的基态是三重态. 单重态和三重态的能隙差ΔE_S-T(kJ/mol): 7.4(FCCN)<13.4(ClCCN)<16.6(BrCCN). 计算得到, XCCN(X=F, Cl, Br)最低垂直激发能分别为408.3, 385.4和 345.2 kJ/mol, 这归因于π(a′) →n_xy 的电子跃迁; XCCN的电子亲和势分别为235.7, 233.0和 237.2 kJ/mol, 与HCCN相比, 其电子亲和势变大.     

传统氢键(X—H…Y)还是X—H…π相互作用？ ——无机苯与卤化氢相互作用本质的量子化学研究

在MP2/6-311＋＋G**水平对无机苯(B3N3H6)与卤化氢HX (X＝F, Cl, Br, I)相互作用体系进行了系统研究. 结果表明在B3N3H6-HX (X＝F, Cl, Br, I)体系的平衡几何结构中, HX的H原子倾向于指向B3N3H6环上的N原子, 且从HF到HI相互作用强度依次减弱. 与苯-卤化氢体系比较, 除与HF相互作用B3N3H6较C6H6强外, 其余体系B3N3H6均较C6H6弱(结合能数值相差4 kJ/mol左右). 对称匹配微扰理论(SAPT)能量分解结果说明静电、诱导和色散力对描述B3N3H6-卤化氢体系的相互作用都很重要, 从HF到HI静电能占总吸引作用能的百分比逐渐减少, 色散能占总吸引作用能的百分比逐渐增加, 这种变化趋势与苯-卤化氢体系比较类似, 表明B3N3H6与卤化氢的相互作用随着卤素原子序数的递增, 传统氢键作用趋势减弱, X—H…π相互作用趋势增强.     

F原子与瞬态自由基CH_2SH反应的理论研究

用量子化学从头算和密度泛函理论（DFT）对F原子与自由基CH_2SH在势能面上 的反应进行了研究。在B3LYP/6-311G水平上计算出了各物种的优化构型、振动频率 和零点振动能(ZPVE);各物种的总能量由B3LYP/6-311 + G(2df, pd)//B3LYP/6- 311G计算,另外对反应物和产物还计算了其G3能量。结果表明：首先F通过与C或S 结合的两种途径与CH_2SH相配位,再通过H（4）原子转移形成甲基,然后甲基再旋 转,甲基中H（4）原子最终与F结合,反应产物为HF和CH_2S。反应为放热反应,分 别为ΔH_r = -370.7 kJ/mol (DFT)和-396.94 kJ/mol (G3)。此外依据计算出的反 应热,可得自由基·CH_2SH的生成热Δ_fH°_(298.15) = 146.44 kJ/mol (DFT), 而Δ_fH°_0 = 167.36 kJ/mol (G3)。它们与以前的实验和理论值是一致的。     

类硅烯H2C＝SiLiBr与RH (R＝F, OH, NH2)的插入反应

采用DFT B3LYP和QCISD方法研究了类硅烯H2C＝SiLiBr与RH (R＝F, OH, NH2)的插入反应. 在B3LYP/6- 311＋G(d,p)水平上优化了反应势能面上的驻点构型. 结果表明, H2C＝SiLiBr与HF, H2O或NH3发生插入反应的机理相同. QCISD/6-311＋＋G(d,p)//B3LYP/6-311＋G(d,p)计算的三个反应的势垒分别为148.62, 164.42和165.07 kJ&#8226;mol－1, 反应热分别为－69.63, －43.02和－28.27 kJ&#8226;mol－1. 相同条件下发生插入反应时, 反应活性都是H—F＞H—OH＞H—NH2.     

SiC(X~3Ⅱ)的结构与势能函数的从头计算

应用密度泛函理论B3LYP和B3P86以及组态相互作用方法 CCSD,CCSD(T),QCISD和QCISD(T),采用6-311g,6-311G(df),6-311+G(d,p),6-311++G(3df,3pd),aug-cc-pvdz和D95(d)多种基组,优化计算了SiC分子的平衡结构和能量.通过优化计算结果和实验数据R=0.171 82nm进行对比,选择B3LYP/6-311G(df),CCSD/6-311G(df)和QCISD/6-311G(df)方法对SiC(X3Ⅱ)分子进行单点能扫描,同时计算其光谱参数(Be,αe,ωe,ωexe)和力常数(f2,f3,f4),这些计算结果与实验数值相吻合,为研究SiC/SiC复合材料提供了理论数据参考.     

Scaled quantum chemical studies of the structural and vibrational spectra of acetyl coumarin

The solid phase FT-IR and FR-Raman spectra of acetyl coumarin have been recorded in the regions 4000–50 cm⁻¹. The spectra were interpreted with the aid of normal coordinate analysis following full structure optimization and force field calculations based on density functional theory (DFT) and Hartree-Fock (HF) at 6–31G* and 6–311++G** basis sets. The resulting force fields were transformed to internal coordinates, the calculated vibrational frequencies and normal modes were utilized in the assignment of the observed vibrational fundamentals. The measured spectral data were used to refine the vibrational force constants by means of a small number of scaling factors.     

Synthesis of Pyrimidines,Thienopyrimidines, and Pyrazolopyrimidines

5-Ethoxycarbonyl-4-methyl-2-phenylpyrimidin-6(1H)-thione ( 3 ), which was prepared from the reaction of ethyl g -aminocrotonate 1 with benzoyl isothiocyanate ( 2 ) in refluxing acetone, was reacted with a series of halopgenated reagents to give S-alkyl derivatives 4a-g . Upon treatment of compounds 4a-c with sodium ethoxide were cyclized into thienopyrimidine 10a-c . Pyrimidinethione 3 was reacted with hydrazine hydrate to give hydroxypyrazolopyrimidine derivative 6 . The later compound was obtained by heating compound 4a with hydrazine hydrate under neat conditions, but when the reaction was carried using hydrazine hydrate in ethanol, the corresponding carbohydrazide 5 was produced.     

Synthesis and structure of tris(5-phenyltetrazol-1-yl)methane

The interaction of 5-phenyltetrazolate anion with chloroform in strongly alkaline medium leads to the formation of tris(5-phenyltetrazol-1-yl)methane and 2-dichloromethyl-5-phenyltetrazole. The structures of tris(5-phenyltetrazol-1-yl)-methane and of its isomer tris(5-phenyltetrazol-2-yl)methane have been investigated by X-ray structural analysis and theoretical calculations carried out on the B3LYP/6-31G** basis. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 398–404, March, 2007.     

Cluster Quantum Chemical Study of Triaminotoluene Interaction with a Model Clay Surface

This paper presents the results of an ab initio cluster quantum chemical study at the HF/6-31G level for the triaminotoluene (TAT) molecule interaction with a model clay surface, in particular, a kaolinite-type clay mineral. The latter is characterized by a layer structure that contains three different structure units corresponding to alumina, silica, and an intersection of alumina-silica. According to the obtained results, the physical adsorption of TAT took place both on alumina and silica structure units. In going from silica to alumina-silica units, the two-center adsorption of TAT will result in strong adsorption via formation of a TATH⁺ species stabilized by two strong H bonds. Different channels of interactions of TAT with kaolinite-type clay surfaces (i.e., one-, two-, and three-center adsorption of TAT, an aromatic six-member ring opening of TAT) and its destruction via breaking the methyl-aromatic or amino-aromatic ring bonds are also discussed.     

Natural and artificial light-harvesting systems utilizing the functions of carotenoids

Carotenoids are essential pigments in natural photosynthesis. They absorb in the blue–green region of the solar spectrum and transfer the absorbed energy to (bacterio-)chlorophylls, and so expand the wavelength range of light that is able to drive photosynthesis. This process is an example of singlet–singlet energy transfer and so carotenoids serve to enhance the overall efficiency of photosynthetic light reactions. Carotenoids also act to protect photosynthetic organisms from the harmful effects of excess exposure to light. In this case, triplet–triplet energy transfer from (bacterio-)chlorophyll to carotenoid plays a key role in this photoprotective reaction. In the light-harvesting pigment–protein complexes from purple photosynthetic bacteria and chlorophytes, carotenoids have an additional role, namely the structural stabilization of those complexes. In this article we review what is currently known about how carotenoids discharge these functions. The molecular architecture of photosynthetic systems will be outlined to provide a basis from which to describe the photochemistry of carotenoids, which underlies most of their important functions in photosynthesis. Then, the possibility to utilize the functions of carotenoids in artificial photosynthetic light-harvesting systems will be discussed. Some examples of the model systems are introduced.     

Asymmetric catalysis as a method for the synthesis of chiral organophosphorus compounds

This review discusses methods for the metallo-, organo- and biocatalytic asymmetric synthesis of chiral organophosphorus compounds with many applications in stereoselective synthesis with references to updated literature reports as well as the author’s original research. Asymmetric catalytic hydrogenation and reduction with chiral organometallic complexes, together with actively used asymmetric organocatalytic versions of various reactions enable us to synthesize chiral organophosphonates and phosphinates with high enantioselectivity and purity. Asymmetric catalysis is also an effective tool to realize some classic reactions of phosphorus chemistry in a stereospecific manner.     

Comparative study of kinetics isomerization of substituted polyacetylene (Cl,F and I): Ab initio and DFT calculations

Ab initio and DFT methods were used to investigate the interconversions of substituted polyacetylene conformers C₁₀H₆X₆ (X=F, Cl and I) in the vapour phase. The rates of this geometrical isomerization have been calculated and the Arrhenius parameters evaluated. In the case of unsubstituted polyacetylene as the reference, the B3LYP Arrhenius parameters obtained are A₁=2.99 × 10¹⁷ s^–1 and E_a=17.30 kcal mol^–1. The values of the equilibrium constant for the reaction have also been determined at various temperatures between 300 and 500 K and the value of the energies change calculated. The results also suggest that the straightforward kinetics characterizing the majority of substituted polyacetylene isomerizations above 300 K. The isomerization energies are positive and the barrier heights ΔE_barrier are expected to be sensitive for the magnitude of halogens effects. According to geometries features the Cis → Trans isomerization in the gas phase occurs by a rotational mechanism.     

Identification of potential inhibitor and enzyme-inhibitor complex on trypanothione reductase to control Chagas disease

Chagas is a parasitic disease with major threat to public health due to its resistance against commonly available drugs. Trypanothione reductase (TryR) is the key enzyme to develop this disease. Though this enzyme is well thought-out as potential drug target, the accurate structure of enzyme-inhibitor complex is required to design a potential inhibitor which is less available for TryR. In this research, we aimed to investigate the advanced drug over the available existing drugs by designing inhibitors as well as to identify a new enzyme-inhibitor complex that may act as a template for drug design. A set of analogues were designed from a known inhibitor Quinacrine Mustard (QUM) to identify the effective inhibitor against this enzyme. Further, the pharmacoinformatics elucidation and structural properties of designed inhibitor proposed effective drug candidates against Chagas disease. Molecular docking study suggests that a designed inhibitor has higher binding affinity in both crystal and modeled TryR and also poses similar interacting residues as of crystal TryR-QUM complex structure. The comparative studies based on in silico prediction proposed an enzyme-inhibitor complex which could be effective to control the disease activity. So our in silico analysis based on TryR built model, Pharmacophore and docking analysis might play an important role for the development of novel therapy for Chagas disease. But both animal model experiments and clinical trials must be done to confirm the efficacy of the therapy.     

Molecular structure and spectral properties of thionaphthalimides

The molecular structure and absorption spectra of monothio- and dithio-naphthalimides were compared to their naphthalimide analogues using AM1, PM3 and ZINDO/S semiempirical quantum chemical methods. The substitution of the 4R-naphthalimide oxygen atoms by sulphur atoms resulted in a red-shift of the absorption spectra by Δλ_max60-65 and 100-140 nm, respectively. The thionated naphthalimide derivatives do not show observable fluorescence due to intersystem crossing to the triplet -states localised at the CS groups. The -absorption bands of monothioimides are located at 525-580 nm (ε=60-80) and those for dithioimides at 535-560 nm (ε=140-390) and 628-686 nm (ε=34-68). None of these transitions are solvent sensitive. The -transitions of N-phenylthioimides have also a small contribution from -states due to a partial conjugation between CS group and π-electronic system of the N-phenyl ring. As a result, the bands of aromatic substituted N-phenylthioimides are red-shifted as compared to those of the aliphatic N-methyl-thioimides.     

Interrelationship between total volatile organic compounds emissions,structure and properties of natural rubber/polycaprolactone bio-blends cross-linked with peroxides

Natural rubber/polycaprolactone (NR/PCL) bio-based blends with different organic peroxides were prepared using an internal batch mixer and subsequently cross-linked at 170 °C. Two types of commonly used organic peroxides, dicumyl peroxide and di(tert-butylperoxyisopropyl)benzene peroxide, were applied as free-radical initiator. Cross-linking efficiency of NR/PCL blends were investigated using oscillating disc rheometer measurements, followed by infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis and tensile testing. Total volatile organic compounds (TVOCs) emissions were determined using headspace analysis integrated with gas chromatography with flame ionization detector. Determined TVOCs emissions varying in range 21.6–52.1 μg/g and generally value of this parameter decreased with increasing content of PCL phase in studied blends or with application of more efficient di(tert-butylperoxyisopropyl)benzene peroxide as cross-linking agent. It was found that increasing of TVOCs parameter indicated deterioration of mechanical properties of NR/PCL blends, which corresponded with the changes in chemical structure and thermal properties of cross-linked NR/PCL. This confirms that evaluation of TVOCs parameter is interesting alternative for “conventional methods” to characterization of the studied bio-based blends.