Photocurrent generation by recombinant allophycocyanin trimer multilayer on TiO2 electrode

A recombinant allophycocyanin trimer was successfully immobilized on a mesoporous TiO₂ electrode. The formation of the immobilized surface was confirmed by multilayer adsorption of protein complexes. The key biophotovoltaic parameters were obtained,which showed that the recombinant allophycocyanin trimer could be a candidate for photosensitizer materials.The values of short-circuit current, open-circuit voltage,fill factor,and conversion efficiency were up to 0.73 mA/cm²,0.52 V,0.69,and 0.26%,respectively.     

Fluorinated cotelomers based on vinylidene fluoride (VDF) and hexafluoropropene (HFP): Synthesis, dehydrofluorination and grafting by amine containing an aromatic ring

The synthesis of C₆F₁₃CH₂C(CFCFCF₃)N-C₂H₄-C₆H₅ (11) from the addition of H₂N-C₂H₄-C₆H₅ onto C₆F₁₃CH₂CF₂CF₂CFHCF₃ (3) is presented. C₆F₁₃CH₂CF₂CF₂CFHCF₃ (3) and C₆F₁₃CH₂CF₂CF(CF₃)CF₂H (3′) isomers were obtained from the thermal stepwise cotelomerization of vinylidene fluoride and hexafluoropropene with C₆F₁₃I, followed by the selective reduction of the iodine end atom. At 200 °C, the 3/3′ molar ratio reached 9.0. In contrast to selective reduction, dehydrofluorination led to various derivatives, which were characterized by ¹H NMR and ¹⁹F NMR spectroscopy, and hence a reaction pathway could be suggested. The grafting of an amine containing an aromatic ring onto the cotelomers based on VDF and HFP occurred selectively on VDF/HFP diad and, in some instances a further step involving the formation of an imine was observed. The addition of 2-phenylethylamine onto the dehydrofluorinated intermediates was found to be quantitative.     

Novel discotic liquid crystal oligomers: 1,3,5-triazine-based triphenylene dimer and trimer with wide mesophase

Series of novel 1,3,5-triazine-based triphenylene oligomers 7, 10 and 12 with large bridging polyaromatic core were designed and synthesised by simple procedures in high yields. Their structures were confirmed by FTIR, ¹H NMR, ESI-MS and elemental analyses. Their mesomorphic behaviours were studied by differential scanning calorimetry, polarising optical microscopy and X-ray diffraction. 1,3,5-triazine-based triphenylene monomer 7 has no mesomorphic property, but 1,3,5-triazine-based triphenylene dimer 10 and 1,3,5-triazine-based triphenylene trimer 12 possess excellent mesomorphic properties. The mesomorphic temperature range of compound 12 was as wide as 180°C. These studies indicated that the mesomorphic properties were determined by the numbers of triphenylene units. More units of triphenylene in the oligomers resulted in better mesomorphic properties.     

Li2分子自旋一致激发态a3Σ+u和b3Πu的分析势能函数的从头算

使用对称性匹配簇-组态相互作用方法首次计算了Li₂分子自旋一致激发态a³Σ⁺_u和b³Π_u的离解能、平衡几何及其谐振频率。使用最小二乘法、利用Murrell-Sorbie函数形式拟合出了Li₂分子三重态的第一激发态a³Σ⁺_u 和第二激发态b³Π_u的完整势能函数，并计算了这两个态的光谱常数 (B_e, α_e, ω_e 和 ω_eχ_e) 和力常数 (f₂, f₃和f₄)。得到了Murrell-Sorbie函数形式既适用于基态、又适用于激发态的结论。将计算得到的激发态（a³Σ⁺_u和b³Π_u）的离解能、平衡几何及其谐振频率与实验结果及其它理论计算结果进行了比较。从比较的结果中可以清楚地看出，本文的计算结果在计算精度方面有很大的改进。     

外电场作用下三元环状水分子团簇的特性研究

采用了HartreeFork自洽场方法在321G水平上研究了0～0.01a.u.的外电场对三元环状水分子团(H2O)3基态能量和电偶极距的影响规律,分析了由外电场产生的HellmanFeynman(HF)力(内力和外力)和在这个力的平衡作用下的团簇的稳定结构,结果表明,外电场的大小对三元环状水分子团簇(H2O)3这些性质有明显的影响.通过高斯计算可以得出,在所加的电场范围内,随着外电场的增大总能量下降,电偶极距增大,结构相对更稳定;外电场引起团簇中各个原子的电荷密度改变,导致了各个原子所受的静电力随之变化.     

He-He-Ba三原子体系弱束缚态计算

本文利用含有绝热近似的超球坐标方法计算了碱土金属原子Ba和氦原子组成的弱束缚三原子分子体系He₂Ba的基态性质. 系统地研究了该系统的道函数和超球势曲线特征, 进而得到体系的束缚能. 研究结果显示, ¹³⁸Ba 与⁴He, ³He 的各种组合⁴He-⁴He-¹³⁸Ba, ⁴He-³He-¹³⁸Ba和³He-³He-¹³⁸Ba都分别只有一个束缚态.     

New spectroscopic results on acetylene dimers and trimers

Spectra of acetylene dimers and trimers containing one or more C₂D₂ monomer are studied in the ν₃ fundamental band region of C₂D₂ (≈2440?cm^?1) using a tuneable infrared diode laser to probe a pulsed supersonic slit jet expansion. Four new subbands are observed in the perpendicular band of (C₂D₂)₂, and this enables the first direct determination of the A rotational constant for an acetylene dimer. The value found for A is significantly larger than the previous indirect value based on microwave spectra. The dimer parallel band is observed and found to be highly perturbed, and observations are extended for the mixed dimer C₂D₂ – C₂H₂. The trimers (C₂D₂)₃, (C₂D₂)₂ – C₂H₂, and C₂D₂ – (C₂H₂)₂ are observed spectroscopically for the first time. Establishment of a precise band origin is difficult for (C₂D₂)₃ because of the inherent nature of the spectrum, but this is possible for two out of three of the bands of the mixed trimers.     

Synthesis and characterisation of dialkyltin 2,3-bis(diphenylphosphino)maleic acid adducts

The novel dialkyltin 2,3-bis(diphenylphosphino)maleic acid adducts (R₂Sn)(O,O′-dpmaa) [1a, R = Me; 1b, R = Bu; dpmaa = bis(diphenylphosphino)maleic acid] were synthesised from dpmaa and R₂SnCl₂ or Bu₂SnO. They were fully characterised by elemental analysis, IR- and multinuclear NMR-spectroscopies as well as X-ray crystallography [in the case of 1a as its Ph₂P(O)(CH₂)₂P(O)Ph₂ adduct]. Both were found to be cyclic trimers in the solid state that dissolve in the case of 1b into an equilibrium mixture of oligomers.     

Synthesis of polycyano-anions conjugated with an aromatic ring

The synthesis of polycyano-anions, conjugated with an aryl substituent via an ethylene fragment, by the Knoevenagel condensation reaction of aromatic aldehydes with the malononitrile trimer potassium salt is described.     

Bonding and singlet–triplet gap of silicon trimer: Effects of protonation and attachment of alkali metal cations

We revisit the singlet–triplet energy gap (ΔE_ST) of silicon trimer and evaluate the gaps of its derivatives by attachment of a cation (H⁺, Li⁺, Na⁺, and K⁺) using the wavefunction‐based methods including the composite G4, coupled‐cluster theory CCSD(T)/CBS, CCSDT and CCSDTQ, and CASSCF/CASPT2 (for Si₃) computations. Both ¹A₁ and ³ states of Si₃ are determined to be degenerate. An intersystem crossing between both states appears to be possible at a point having an apex bond angle of around α = 68 ± 2° which is 16 ± 4 kJ/mol above the ground state. The proton, Li⁺ and Na⁺ cations tend to favor the low‐spin state, whereas the K⁺ cation favors the high‐spin state. However, they do not modify significantly the ΔE_ST. The proton affinity of silicon trimer is determined as PA(Si₃) = 830 ± 4 kJ/mol at 298 K. The metal cation affinities are also predicted to be LiCA(Si₃) = 108 ± 8 kJ/mol, NaCA(Si₃) = 79 ± 8 kJ/mol and KCA(Si₃) = 44 ± 8 kJ/mol. The chemical bonding is probed using the electron localization function, and ring current analyses show that the singlet three‐membered ring Si₃ is, at most, nonaromatic. Attachment of the proton and Li⁺ cation renders it anti‐aromatic. © 2015 Wiley Periodicals, Inc.