Evidence for the Chain‐Growth Synthesis of Statistical π‐Conjugated Donor–Acceptor Copolymers

The synthesis of a series of dithienosilole–benzotriazole donor–acceptor statistical copolymers with various donor–acceptor ratios is reported, prepared by Kumada catalyst‐transfer polymerization. Statistical copolymer structure is verified by ¹H NMR and optical absorption spectroscopy, and supported by density functional theory (DFT) calculations. The copolymers exhibit a single optical absorption band that lies between dithienosilole and benzotriazole homopolymers, which shifts with varying donor–acceptor content. A chain extension experiment using a partially consumed benzotriazole solution as a macroinitiator followed by addition of dithienosilole leads to the synthesis of a statistical dithienosilole–benzotriazole block copolymer from a pure benzotriazole block, demonstrating that both chain extension and simultaneous monomer incorporation are possible using this methodology.

     

Monitoring the quality consistency of Weibizhi tablets by micellar electrokinetic chromatography fingerprints combined with multivariate statistical analyses,the simple quantified ratio fingerprint method,and the fingerprint–efficacy relationship

Micellar electrokinetic chromatography fingerprinting combined with quantification was successfully developed and applied to monitor the quality consistency of Weibizhi tablets, which is a classical compound preparation used to treat gastric ulcers. A background electrolyte composed of 57 mmol/L sodium borate, 21 mmol/L sodium dodecylsulfate and 100 mmol/L sodium hydroxide was used to separate compounds. To optimize capillary electrophoresis conditions, multivariate statistical analyses were applied. First, the most important factors influencing sample electrophoretic behavior were identified as background electrolyte concentrations. Then, a Box–Benhnken design response surface strategy using resolution index RF as an integrated response was set up to correlate factors with response. RF reflects the effective signal amount, resolution, and signal homogenization in an electropherogram, thus, it was regarded as an excellent indicator. In fingerprint assessments, simple quantified ratio fingerprint method was established for comprehensive quality discrimination of traditional Chinese medicines/herbal medicines from qualitative and quantitative perspectives, by which the quality of 27 samples from the same manufacturer were well differentiated. In addition, the fingerprint–efficacy relationship between fingerprints and antioxidant activities was established using partial least squares regression, which provided important medicinal efficacy information for quality control. The present study offered an efficient means for monitoring Weibizhi tablet quality consistency.     

中成药质量稳定性的原子吸收光谱鉴别分析

对全国各地用原子吸收光谱仪测定10批次大活络丸中12种无机元素及建立的指纹图谱,尝试用成分数据分析法、向量相似法和模糊聚类法建立全国无机元素的指纹图谱和中药质量控制标准方法,获得较满意的结果。研究表明,建立无机元素指纹图谱控制中成药中无机元素的质量,具有很好的实用性和可操作性,用于全国各地不同厂家生产的大活络丸无机元素的质量控制是切实可行的。     

Benchmark ab initio proton affinity and gas-phase basicity of α-alanine based on coupled-cluster theory and statistical mechanics

We determine the proton affinity (PA) and gas-phase basicity (GB) of amino acid α-alanine at a chemically accurate level by performing explicitly-correlated CCSD(T)-F12b/aug-cc-pVDZ geometry optimizations and normal mode vibrational frequency calculations as well as CCSD(T)-F12b/aug-cc-pVTZ energy computations at the possible neutral and protonated geometries. Temperature effects at 298.15 K considering translational, rotational, and vibrational enthalpy and entropy corrections are obtained via standard statistical mechanics utilizing the molecular geometries and the harmonic vibrational energy levels. Both the amino nitrogen (N) and the carbonyl oxygen (O) atoms are proven to be potential protonation sites and a systematic conformational search reveals 3 N- and 9 O-protonated conformers in the 0.00–7.88 and 25.43–30.43 kcal/mol energy ranges at 0 K, respectively. The final computed PA and GB values at (0)298.15 K in case of N-protonation are (214.47)216.80 and 207.07 kcal/mol, respectively, whereas the corresponding values for O-protonation are (189.04)190.63 and 182.31 kcal/mol. The results of the benchmark high-level coupled-cluster computations are utilized to assess the accuracy of several lower-level cost-effective methods such as MP2 and density functional theory with various functionals (SOGGA11-X, M06-2X, PBE0, B3LYP, M06, TPSS).     

Easy size control of polymer nanoparticles obtained by emulsification–evaporation technique in a microfluidic reactor

The production of polymer nanoparticles with a narrow size distribution on standard T- and X-configuration microfluidic chips with a channel size of 100 μm has been achieved. Introducing ethanol into the aqueous phase in 1:9 ratio (v/v) allowed one to reduce the surface tension of the contacting phases and obtain nanoparticles in the range of 100–150 nm. This makes our approach promising for development of nanoscale drug delivery systems.     

Quantitative Analysis and Differential Evaluation of Radix Bupleuri Cultivated in Different Regions Based on HPLC-MS and GC-MS Combined with Multivariate Statistical Analysis

The quality of Radix Bupleuri is greatly affected by its growing environment. In this study, Radix Bupleuri samples that were harvested from seven different regions across northwest China were examined by high-performance liquid chromatography (HPLC) and gas chromatography (GC) coupled with mass spectrometry (MS) to reveal significant differences in quality contributed by the cultivation region. An HPLC-MS method was firstly established and used in the multiple reaction monitoring mode for the quantitative analysis of five saikosaponins in Radix Bupleuri so as to evaluate the difference in the absolute content of saikosaponins attributable to the cultivation region. The effect on the components of Radix Bupleuri was further investigated based on the profiles of the representative saponins and volatile compounds, which were extracted from the Radix Bupleuri samples and analyzed by HPLC-MS and GC-MS. Multivariate statistical analysis was employed to differentiate the Radix Bupleuri samples cultivated in different regions and to discover the differential compositions. The developed quantitative method was validated to be accurate, stable, sensitive, and repeatable for the determination of five saikosaponins. Further statistical tests revealed that the collected Radix Bupleuri samples were distinctly different from each other in terms of both saponins and volatile compounds, based on the provinces where they were grown. In addition, twenty-eight saponins and fifty-eight volatile compounds were identified as the differentially accumulated compositions that contributed to the discrimination of the Radix Bupleuri samples. The Radix Bupleuri samples grown in Shouyang county showed the highest content of saikosaponins. All of the results indicated that the cultivation region significantly affected the accumulation and diversity of the main chemical components of Radix Bupleuri. The findings of this research provide insights into the effect of the cultivation region on the quality of Radix Bupleuri and the differentiation of Radix Bupleuri cultivated in different regions based on the use of HPLC-MS and GC-MS combined with multivariate statistical analysis.     

A Pressure-Induced Inverse Order–Disorder Transition in Double Perovskites

Given the consensus that pressure improves cation ordering in most of known materials, a discovery of pressure-induced disordering could require recognition of an order–disorder transition in solid-state physics/chemistry and geophysics. Double perovskites Y₂CoIrO₆ and Y₂CoRuO₆ polymorphs synthesized at 0, 6, and 15 GPa show B-site ordering, partial ordering, and disordering, respectively, accompanied by lattice compression and crystal structure alteration from monoclinic to orthorhombic symmetry. Correspondingly, the long-range ferrimagnetic ordering in the B-site ordered samples are gradually overwhelmed by B-site disorder. Theoretical calculations suggest that unusual unit-cell compressions under external pressures unexpectedly stabilize the disordered phases of Y₂CoIrO₆ and Y₂CoRuO₆.     

KiSThelP: A program to predict thermodynamic properties and rate constants from quantum chemistry results†

Kinetic and Statistical Thermodynamical Package (KiSThelP) is a cross‐platform free open‐source program developed to estimate molecular and reaction properties from electronic structure data. To date, three computational chemistry software formats are supported (Gaussian, GAMESS, and NWChem). Some key features are: gas‐phase molecular thermodynamic properties (offering hindered rotor treatment), thermal equilibrium constants, transition state theory rate coefficients (transition state theory (TST), variational transition state theory (VTST)) including one‐dimensional (1D) tunnelling effects (Wigner, and Eckart) and Rice‐Ramsperger‐Kassel‐Marcus (RRKM) rate constants, for elementary reactions with well‐defined barriers. KiSThelP is intended as a working tool both for the general public and also for more expert users. It provides graphical front‐end capabilities designed to facilitate calculations and interpreting results. KiSThelP enables to change input data and simulation parameters directly through the graphical user interface and to visually probe how it affects results. Users can access results in the form of graphs and tables. The graphical tool offers customizing of 2D plots, exporting images and data files. These features make this program also well‐suited to support and enhance students learning and can serve as a very attractive courseware, taking the teaching content directly from results in molecular and kinetic modelling. © 2013 Wiley Periodicals, Inc.     

ZnO Nanobelts and Hollow Microspheres Grown on Cu Foil

ZnO nanobelts, hollow microspheres, and urchins have been prepared on copper foil via a simply low temperature evaporation route. The microstructure, morphologies, and photolu-minescence of the ZnO nanostructures were studied with X-ray diffraction, Raman spectra, scanning electron microscopy and photoluminescence spectra. The width of the nanobelts was about 500 nm and the length was longer than 10μm. The diameter of the hollow microspheres was between 5 and 10μm. A possible growth mechanism of the nanobelts, microspheres and urchins was proposed. The photoluminescence spectrum exhibited strong deep level energy emissions and a weak near band edge emission. These ZnO nanostructures on a copper substrate have the advantages of naturally good adhesion and electrical connection between the ZnO nanostructures and the conductive substrate.     

MgSO4-Na2SO4-H2O三元体系100 ℃沸腾蒸发非平衡态成盐特征

采用140 ℃恒温热源, 对MgSO4-Na2SO4-H2O体系溶液进行100 ℃恒温沸腾蒸发, 蒸发强度为140～160 g/(h•L), 监测初始析盐点和固相析出后固液相组成随蒸发进程的变化, 总结成盐特征, 提出反映非平衡态成盐特征的初级成盐区、扩展成盐区等概念. 研究发现(1)平衡相图上的同成分复盐3Na2SO4• MgSO4和Na2SO4• MgSO4•2.5H2O变为异成分复盐; (2)对Na2SO4和3Na2SO4•MgSO4的平衡共饱和液蒸发, 首先析出的是Na2SO4, 其单固相析出率为60.86%, 3Na2SO4•MgSO4和Na2SO4•MgSO4•2.5H2O的共饱和液也具有相同特征; (3)蒸发过程的初级成盐区与溶解平衡相区有显著区别. 用硫酸钠的耶涅克指数表示相区宽度, Na2SO4初级成盐区宽度从平衡态的21.02扩大到32.76; 而Na2SO4•MgSO4•2.5H2O则从41.40缩减为25.71; (4)在晶种存在的条件下, 各种盐的成盐区比初级成盐区有不同程度的扩展, 如Na2SO4, 3Na2SO4•MgSO4等盐的成盐区分别扩展了7.72和8.81. 扩展成盐区与初级成盐区的交叠形成了非平衡条件下特有的条件成盐区, 析盐种类取决于晶种的种类.