High-performance liquid chromatographic separation of imidazolinone herbicide enantiomers and their methyl derivatives on polysaccharide-coated chiral stationary phases

Many chiral pesticides exhibit enantioselectivity in biotransformation and ecotoxicity in the environment. A significant class of chiral pesticides is imidazolinone herbicides, of which enantioselectivity has not been well studied. Development of efficient chiral separation methods is the first step for allowing characterization of enantioselectivity in environmental processes. In this study, we attempted to resolve enantiomers of imidazolinone herbicides using reversed-phase and normal-phase high-performance liquid chromatography with polysaccharide-type chiral columns. Enantiomers of imazethapyr, imazaquin, and imazamox were separated on a Chiralcel OD-R column using 50mM phosphate buffer-acetonitrile as mobile phase. Enantiomers of imazapyr, imazapic, imazethapyr, imazamox and imazaquin were resolved on a Chiralcel OJ column using n-hexane (0.1% trifluoroacetic acid)-alcohol as mobile phase. The enantiomers of five methyl derivatives of imidazolinone herbicides were also resolved on the Chiralcel OJ column. The Deltak' values revealed a structure-enantioselectivity relationship for the separation behaviors of the enantiomers on the OJ column. The described method was successfully applied for chiral analysis of two imidazolinone herbicides (imazapyr and imazaquin) in spiked soil samples.     

低取代度两亲性β-环糊精及其水相中纳米球的制备

将2-O-(2-羟丙基)-β-环糊精与十二烷基、十四烷基、十六烷基和十八烷基缩水甘油醚在吡啶中反应,合成了4个低取代度的两亲性β-环糊精衍生物(平均取代度分别为1.87、1.95、2.14和1.80)。 将上述4个化合物分散于水中自组装成可稳定2~3周的纳米球,并且均呈现出较好的分散度和均匀性。     

多路段元胞自动机交通流模型

在经典单路段元胞自动机交通流模型的基础上,将多个路段视为一个道路系统,提出并研究了多路段条件下的交通流问题.针对多路段道路的特点,通过引入车辆流入规则、路口随机慢化规则和路口车辆流入规则,控制车辆从上一路段流入下一路段.首先提出了"汽车池"的概念,来控制每一路口车辆的流入;然后通过路口随机慢化,来模拟路口对交通的影响;最后,当车辆离开时,依直行率进入下一路段,实现车流的继续流动.同时,通过数值模拟,仿真了不同条件下的交通情况,对重要参数进行了研究.结果表明,出现了混合流这一新的现象,拥堵地段与非拥堵地段间存在明显的界限.拥堵往往最先从路口开始,然后蔓延到整个路段.多路段道路还存在临界突变的特性.随着车辆流入概率的增大,路口对平均速度和车流密度的影响愈加明显.当流入概率超过一定阈值时,车辆缓慢地增加也会引起整体道路通行能力的迅速下降.     

一种改进的基于信息传播率的复杂网络影响力评估算法

评价网络中节点的信息传播影响力对于理解网络结构与网络功能具有重要意义.目前,许多基于最短路径的指标,如接近中心性、介数中心性以及半局部(SP)指标等相继用于评价节点传播影响力.最短路径表示节点间信息传播途径始终选择最优方式,然而实际上网络间的信息传播过程更类似于随机游走,信息的传播途径可以是节点间的任一可达路径,在集聚系数高的网络中,节点的局部高聚簇性有利于信息的有效扩散,若只考虑信息按最优传播方式即最短路径传播,则会低估节点信息传播的能力,从而降低节点影响力的排序精度.综合考虑节点与三步内邻居间的有效可达路径以及信息传播率,提出了一种SP指标的改进算法,即ASP算法.在多个经典的实际网络和人工网络上利用SIR模型对传播过程进行仿真,结果表明ASP指标与度指标、核数指标、接近中心性指标、介数中心性指标以及SP指标相比,可以更精确地对节点传播影响力进行排序.     

Rapid computation of intermolecular interactions in molecular and ionic clusters: self-consistent polarization plus symmetry-adapted perturbation theory

A method that we have recently introduced for rapid computation of intermolecular interaction energies is reformulated and subjected to further tests. The method employs monomer-based self-consistent field calculations with an electrostatic embedding designed to capture many-body polarization (the "XPol" procedure), augmented by pairwise symmetry-adapted perturbation theory (SAPT) to capture dispersion and exchange interactions along with any remaining induction effects. A rigorous derivation of the XPol+SAPT methodology is presented here, which demonstrates that the method is systematically improvable, and moreover introduces some additional intermolecular interactions as compared to the more heuristic derivation that was presented previously. Applications to various non-covalent complexes and clusters are presented, including geometry optimizations and one-dimensional potential energy scans. The performance of the XPol+SAPT methodology in its present form (based on second-order intermolecular perturbation theory and neglecting intramolecular electron correlation) is qualitatively acceptable across a wide variety of systems-and quantitatively quite good in certain cases-but the quality of the results is rather sensitive to the choice of one-particle basis set. Basis sets that work well for dispersion-bound systems offer less-than-optimal performance for clusters dominated by induction and electrostatic interactions, and vice versa. A compromise basis set is identified that affords good results for both induction and dispersion interactions, although this favorable performance ultimately relies on error cancellation, as in traditional low-order SAPT. Suggestions for future improvements to the methodology are discussed.     

(±)-5,3’-二羟基-7,8-(2,2-二甲基吡喃)-4’-甲氧基黄烷酮的首次全合成

以廉价的异香草醛和2,4,6-三羟基苯乙酮为起始原料,经过C-异戊烯基化、环化、选择性的保护酚羟基、羟醛缩合、催化环化等步骤,脱保护基,以6.7%的总收率首次完成了天然吡喃型黄烷酮(±)-5,3’-二羟基-7,8-(2,2-二甲基吡喃)-4’-甲氧基黄烷酮的全合成.所有新化合物的结构都经过IR,1H NMR,MS,HRMS确认.     

A facile stereoselective synthesis of (E)‐1,2‐disubstituted vinylic selenides via hydromagnesiation of alkylarylacetylenes

Hydromagnesiation of alkylarylacetylenes 1 in diethyl ether gave (E)‐α‐arylvinyl Grignard reagents 2 , which reacted with arylselenenyl bromides 3 in THF to afford stereoselectively (E)‐1,2‐disubstituted vinylic selenides 4 in good yields. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:65–68, 2005; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20066     

新的溶胶-凝胶法制备Ge/SiO2量子点玻璃

以3－三氯锗丙酸和正硅酸乙酯为原料,通过水解、缩聚凝胶热处理及氢气反应,在SiO2凝胶玻璃中析出立方相Ge纳米晶,当x=30时,凝胶玻璃中除了析出立方相Ge纳米晶处,还析出六方相GeO2,利用XRD测试了Ge纳米晶的大小,发现随着掺杂量的增加,纳米颗粒粒径从1nm增大到10nm,电子衍射表明镶嵌在SiO2凝交玻璃中的Ge纳米晶为多晶结构。     

Direct optical resolution of the enantiomers of axially chiral compounds by high-performance liquid chromatography on cellulose tris-(3,5-dimethylphenylcarbamate) stationary phase

Summary The enantiomeric separation of nineteen biphenyl dimethyl dicarboxylate derivatives has been examined by HPLC on a chiral statonary phase prepared by coating aminopropylated silica gel with cellulose tris-(3,5-dimethylphenylcarbamate). It was found that trifluoroacetic acid (TFA) has a dominant effect on chiral separation for acidic compounds. The percentage of 2-propanol in the mobile phase does not have a large effect on the anantioselectivity but the separation was dramatically influenced by the kind of alcohol in the mobile phase. The effect of temperature on the chiral separation is also discussed. Most of the enantiomers investigated could be resolved satisfactorily.     

近红外光谱主成分-所有可能回归法定量分析烤烟、小麦样品中的组分含量

利用主成分-所有可能回归法,建立了烤烟、小麦样品不同组份的近红外光谱定量分析模型。结果表明,烤烟样品的总糖、还原糖以及小麦样品的蛋白质含量的预测模型均有好的定量分析结果,且其预测结果与PLS法预测结果相当。