A novel self-assembly based on double-layer zinc porphyrin sensitizers in supramolecular solar cell

Two new self-assemblies based on zinc porphyrin dyes ZnPx-ZnPA (x?=?1, 2) were synthesized and used for dye-sensitized solar cells. Capping layer dyes consist of zinc porphyrin (ZnP) as core unit and carbazole (P1), phenothiazine (P2) as electron-donating group. The dye ZnPA contains carboxylic group as an anchor porphyrin with upper dyes (denoted as ZnP1 and ZnP2) formed dyads by coordination bonds of Zn-to-ligand self-assembled devices. The assembly modes were also verified by transmission electron microscopy (TEM). The influence of the upper porphyrins on molecular structure as well as photovoltaic performance was investigated via photophysical and electrochemical studies and calculations. With addition of the phenothiazine unit, the ZnP2-ZnPA possesses better light-harvesting capability with a significantly red-shifted Q-band. The photoelectrochemical efficiencies for ZnP2-ZnPA are better than those of ZnP1-ZnPA ascribed to larger J_sc and V_oc.

     

Comparison of the molecular interactions of 7′-carboxyalkyl apigenin derivatives with S. cerevisiae α-glucosidase

As one of the most investigated flavonoids, apigenin, is considered to be a strong α-glucosidase inhibitor. However, the clinical utility of apigenin is limited due to its low solubility. It was reported that the solubility and biological activity can be improved by introducing sole carboxyalkyl group into apigenin, especially the 7′-substitution. With the increase of length of the alkyl chain in carboxyalkyl group, B ring of the apigenin derivative is embedded much more deeply into the binding cavity while the carboxyalkyl stretches to the neighboring cavity. All of the terminal carboxyl groups form hydrogen bonding interactions easily with the surrounding polar amino acids, such as His239, Ser244, Arg312 and Asp349. Thus, the electron density values of the carbonyl in the carboxyl group become higher than the solution status due to the strong molecular interactions. In fact, electron densities of most of the chemical bonds are decreased after molecular docking procedure. On compared with the solution phase, however, dipole moments of most of these molecules are increased, and their vectors are reoriented distinctly in the active sites. It is noticed that all of the Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) are distributed throughout the whole parent apigenin ring in solution phase, whereas the disappeared situation happened on the B rings of some molecules (II–IV) in the active site, leading to higher energy gaps.     

LC-MS/MS法快速测定吡罗昔康制剂中吡罗昔康含量

建立了快速液相色谱-质谱/质谱联用法测定吡罗昔康制剂中吡罗昔康含量的方法。样品以0.1 mol/L盐酸甲醇溶液提取、微孔滤膜过滤、离心后,通过电喷雾离子化(ESI),采用多反应检测(MRM)方式进行正离子检测,用于定量分析的检测离子为m/z 332.2→94.8。采用Shim-pack XR-ODS(3.0 mm×75mm,2.0μm)柱分离,以乙腈-水-甲酸(60:40:0.1,V/V/V)为流动相,流速为0.40 mL/min,在3 min内完成吡罗昔康定量分析。线性范围为2.5～1000.0ng/mL,最低检测限为2.5 ng/mL;日内测定的相对标准偏差小于3.2%,日间测定的相对标准偏差小于3.8%。方法可作为吡罗昔康制剂的质量中吡罗昔康控制方法,并可用于少量血浆样品的测定,也适用于药物代谢动力学研究。     

Exploring the H-abstraction reactions of CHCl·-/CCl2·- with CX3H（X = F,Cl,Br and I） using the density functional theory method

Gas-phase hydrogen abstraction reactions have been compared using the popular density functional theory(DFT) functional BHandHLYP/aug-cc-pVTZ/RECP level of theory,on the basis of the model reaction CHCl·-/CCl2·-+ CX3H(X = F,Cl,Br and I).Our theoretical findings suggest the efficiency of the H-abstraction reactions induced by either CHCl·-or CCl2·-increases as the substrate is changed from CF3H to CI3H,and that CHCl·-has a higher activity in hydrogen abstraction than CCl2·-for a given substrate.The entropy effect at 298 K does not significantly change the trend in reactivity of the various reactions,which is in general controlled by the heights of activation energies △E≠.Therefore,we have explored the origin of the energy barriers △E≠ of the reactions using the activation strain model of chemical reactivity.     

Study of frequency-modulated excitation of Rydberg potassium atoms by using B-spline

With the B-spline expansion technique and a model potential of the alkali atoms, the properties of frequency-modulated excitation of Rydberg potassium atoms in a static electric field and a microwave field are investigated by using the time-dependent two-level approach. We successfully reproduce the square wave oscillations in the low frequency, the stair step population oscillations in the intermediate frequency, and the multiphoton transitions in the high frequency with respect to the unmodulated Rabi frequency, which have been observed experimentally by Noel et al. [Phys. Rev. A 58 2265 (1998)]. Furthermore, we also numerically obtain the discretized Rabi oscillations predicted in the Landau-Zener accumulation model.     

Density functional study of S(N) 2 substitution reactions for CH(3) Cl + CX(1) X(2•-) (X(1) X(2) = HH, HF, HCl, HBr, HI, FF, ClCl, BrBr, and II)

A systematic investigation on the S_N2 displacement reactions of nine carbene radical anions toward the substrate CH₃Cl has been theoretically carried out using the popular density functional theory functional BHandHLYP level with different basis sets 6‐31+G (d, p)/relativistic effective core potential (RECP), 6‐311++G (d, p)/RECP, and aug‐cc‐pVTZ/RECP. The studied models are CX¹X^2?? + CH₃Cl → X²X¹CH₃C^? + Cl^?, with CX¹X^2?? = CH₂^??, CHF^??, CHCl^??, CHBr^??, CHI^??, CF₂^??, CCl₂^??, CBr₂^??, and CI₂^??. The main results are proposed as follows: (a) Based on natural bond orbital (NBO), proton affinity (PA), and ionization energy (IE) analysis, reactant CH₂^?? should be a strongest base among the anion‐containing species (CX¹X^2??) and so more favorable nucleophile. (b) Regardless of frontside attacking pathway or backside one, the S_N2 reaction starts at an identical precomplex whose formation with no barrier. (c) The back‐S_N2 pathway is much more preferred than the front‐S_N2 one in terms of the energy gaps [ΔE(front)?ΔE(back)], steric demand, NBO population analysis. Thus, the back‐S_N2 reaction was discussed in detail. On the one hand, based on the energy barriers (ΔE and ΔE) analysis, we have strongly affirmed that the stabilization of back attacking transition states (b‐TSs) presents increase in the order: b‐TS‐CI₂ < b‐TS‐CBr₂ < b‐TS‐CCl₂ < b‐TS‐CHI < b‐TS‐CHBr < b‐TS‐CHCl < b‐TS‐CF₂ < b‐TS‐CHF < b‐TS‐CH₂. On the other hand, depended on discussions of the correlations of ΔE with influence factors (PA, IE, bond order, and ΔE), we have explored how and to what extent they affect the reactions. Moreover, we have predicted that the less size of substitution (α‐atom) required for the gas‐phase reaction with α‐nucleophile is related to the α‐effect and estimated that the reaction with the stronger PA nucleophile, holding the lighter substituted atom, corresponds to the greater exothermicity given out from reactants to products. © 2012 Wiley Periodicals, Inc. J Comput Chem, 2012     

带阶段结构的扩散的捕食者-食饵模型解的一致有界性和整体存在性

应用能量估计和Gagliardo-Nirenberg型不等式证明了捕食者带阶段结构的具有自扩散和交错扩散的捕食者-食饵模型解的一致有界性和整体存在性.     

Well‐posedness of nonlinear wave equation with combined power‐type nonlinearities

In this paper, we study the initial boundary‐value problem with combined power‐type nonlinearities by utilizing potential well method. We provide an algorithm to compute the depth of the potential well with the help of Mathematica, and derive the invariant subsets, global existence and blowup of solutions. Moreover, we obtain the invariant subsets, global existence and blowup of solutions for the critical case. Copyright © 2011 John Wiley & Sons, Ltd.     

半干旱区菜地土壤与蔬菜中铁、锰含量及健康风险评估——以甘肃省榆中县为例

在甘肃省榆中县蔬菜基地,选择30个点位采集4种蔬菜(120株)及相应的土样,在对重金属Fe、Mn含量分析测试的基础上,开展蔬菜重金属富集能力分析及健康风险评估。结果表明,研究区土壤中Fe、Mn平均质量分数分别为25 424.55和419.83 mg·kg-1,蔬菜中Fe、Mn平均质量分数分别为7.69和2.31 mg·kg-1鲜质量。蔬菜中Fe、Mn平均富集系数分别为3.02×10-4和5.66×10-3,两者相差一个数量级。Fe、Mn在4种蔬菜中的富集系数不同,在芹菜中富集系数最大。Fe、Mn在同一蔬菜中的富集系数亦差别很大,其富集系数的由大到小顺序为Mn,Fe。榆中县居民膳食Fe、Mn每天摄入量分别为11.55 mg和3.47 mg。因此,榆中县居民通过膳食摄入Fe、Mn明显不足,需要通过其他途径补充Fe、Mn。     

基于Lorenz系统的数值天气转折期预报理论探索

以Lorenz系统为研究对象,对数值天气转折期预报中的动力学特征进行了理论研究,通过对Lorenz系统平衡点稳定性的讨论,得到了区分准稳定区域和准不稳定区域的分界曲面,由此标定出准稳定区域和准不稳定区域.在准稳定区域,Lorenz曲线保持相对稳定,能够在该平衡点周围周期运动;在准不稳定区域,Lorenz曲线可能会从这个平衡点周围跃过分界曲面而进入另外一个平衡点周围,即发生突变,这是Lorenz系统的一个重要动力学特征;对数值天气转折期预报与气候突变检测、预测给出一种新理论和新方法.