An ab initio simulation of the UV/Visible spectra of substituted chalcones

The electronic absorption spectra of 29 phenyl-ring substituted chalcones have been investigated with the time-dependent density functional theory (TD-DFT) and polarizable continuum TD-DFT (PCM-TD-DFT). It turns out that the hybrid PBE1PBE functional with the 6-31G basis set provide reliable λ_max when the solvent effects are included in the model. Comparisons with experimental values lead to a mean absolute error of 12 nm (0.136 eV). Moreover, the observed substituent effects are reproduced by calculation qualitatively. The λ_max of substituted chalcone in phenyl ring A is less sensitive to substitution than that in ring B. The linear correlation of Hammett’s substituent constants (σ_P) with LUMO energies is better with respect to HOMO energies. The calculation reveals that the maximum absorption band mainly results from the π→π* transition from HOMO to LUMO. The analysis of the electron density plots of frontier molecular orbitals show that most transitions should be of valence excitation nature.      

Insight into herbicide resistance of W574L mutant Arabidopsis thaliana acetohydroxyacid synthase: molecular dynamics simulations and binding free energy calculations

Acetohydroxyacid synthase (AHAS) is the target enzyme of several classes of herbicides, such as sulfonylureas and imidazolinones. Now many mutant AHASs with herbicide resistance have emerged along with extensive use of herbicides, therefore it is imperative to understand the detailed interaction mechanism and resistance mechanism so as to develop new potent inhibitors for wild-type or resistant AHAS. With the aid of available crystal structures of the Arabidopsis thaliana (At) AHAS-inhibitor complex, molecular dynamics (MD) simulations were used to investigate the interaction and resistance mechanism directly and dynamically at the atomic level. Nanosecond-level MD simulations were performed on six systems consisting of wild-type or W574L mutant AtAHAS in the complex with three sulfonylurea inhibitors, separately, and binding free energy was calculated for each system using the MM-GBSA method. Comprehensive analyses from structural and energetic aspects confirmed the importance of residue W574, and also indicated that W574L mutation might alert the structural charactersistic of the substrate access channel and decrease the binding affinity of inhibitors, which cooperatively weaken the effective channel-blocked effect and finally result in weaker inhibitory effect of inhibitor and corresponding herbicide resistance of W574L mutant. To our knowledge, it is the first report about MD simulations study on the AHAS-related system, which will pave the way to study the interactions between herbicides and wild-type or mutant AHAS dynamically, and decipher the resistance mechanism at the atomic level for better designing new potent anti-resistance herbicides.     

五轴加工中心范成铣磨离轴非球面研究

离轴非球面作为非球面的一部分,是空间光学系统、天文学和高精度测量系统不可或缺的光学器件.针对空间光学对离轴非球面光学元件制造技术的重大需求,开展了离轴非球面反射镜的精密铣磨加工技术研究.分析了五轴联动范成法铣磨离轴非球面的原理,将离轴非球面所在的同轴母镜离散为一系列不同半径的球面环带,将工件坐标系建立在待加工离轴非球面...     

新雌激素衍生物的合成及抗辐射升白生物活性

以17α-炔雌二醇和17β-雌二醇为原料,分别与烯丙基溴、溴代异戊烯反应,通过一步反应合成了4个新雌激素衍生物,分别是17α-炔雌二醇-3-烯丙基醚(ES-1),17β-雌二醇-3-烯丙基醚(ES-2),17α-炔雌二醇-3-异戊烯基醚(ES-3)和17β-雌二醇-3-异戊烯基醚(ES-4),产率分别为92.2%,73.7%,65.9%和67.6%.化合物通过1HNMR,13CNMR,IR,MS及元素分析确证了结构,4个化合物均未见文献报道.初步的抗辐射升白生物活性研究表明,4个化合物对137Csγ-射线引起的小鼠白细胞低下及造血系统功能损伤有一定的保护作用.其中ES-3的升白作用最佳,经统计学处理,3个给药剂量组与对照组比,升白作用均有非常显著性差异(P0.001).     

气相色谱/质谱法检测小鼠肌肉组织和血液中羟基多氯联苯

建立了测定小鼠肌肉和血液中3种羟基多氯联苯的气相色谱/质谱联用(GC-MS)方法.经正己烷-乙酸乙酯(1∶ 1, V/V)提取目标化合物后,结合H2SO4去脂,KOH反萃法对提取液进行净化,以双(三甲基硅烷基)三氟乙酰胺-三甲基氯硅烷(BSTFA-TMCS, 99∶ 1, V/V,)为衍生试剂对羟基多氯联苯进行硅烷化衍生后,在SIM模式下进行GC/MS分析.本方法检出限为2μg/kg.在3种添加水平2.0,5.0和20.0 μg/kg下,小鼠肌肉和血液中3种羟基多氯联苯的回收率范围为73.2%～113.2%;相对标准偏差为1.53%～10.4%.本方法可用于小鼠腹腔注射多氯联苯后,体内多氯联苯羟基代谢物的检测.     

真空蒸馏预富集-电感耦合等离子体发射光谱法测定铂

建立了真空蒸馏预富集-电感耦合等离子体发射光谱法测定铅试样中微量铂的方法.在真空条件下,利用Pb和Pt在较高温度下蒸汽压的差别进行分离,富集后的铂溶解制成溶液后进行电感耦合等离子体发射光谱检测,实现了真空密闭回收铅.针对试样的特点,对真空蒸馏方法理论上的可行性进行研究.结果表明:在蒸馏温度为1250 K,真空度为30 Pa,蒸馏时间为3 h条件下,铂的富集分离效果最好,可富集至99.01%以上.线性范围为0.023～20 mg/L,检出限(3σ)为0.0069 mg/L,对样品测定的相对标准偏差为1.7%(n=6).用本方法对样品中加入的铂标准溶液进行了测定,回收率为99.8%～103.0%.本方法简便快速、无污染,已应用于废电路板贵金属冶余物料中铂的测定.     

An effective sequence characterized amplified region‐PCR method derived from restriction site‐amplified polymorphism for the identification of female Schistosoma japonicum of zoonotic significance

In the present study, restriction site‐amplified polymorphism (RSAP) markers were used to examine the genetic variability of Schistosoma japonicum isolates from different endemic provinces in mainland China. Of the 45 pairs of primers screened, 10 RSAP markers showed a clear banding pattern with good resolution; however, only six exhibited a polymorphism among different isolates. Among six RSAP markers, one pair of primers (R8+R10) was able to differentiate male and female parasites, and amplified one constant specific band for female S. japonicum isolates. The specific band was recovered, re‐amplified and sequenced, and a sequence of 162 bp was obtained. Based on this sequence, a pair of specific primers was designed and used to develop sequence characterized amplified region (SCAR)‐PCR assay for identification and differentiation of female S. japonicum isolates. The SCAR‐PCR assay allowed the specific identification of female S. japonicum, with no amplicons being amplified from male S. japonicum, Fasciola hepatica, Clonorchis sinensis, S. mansoni (male and female parasite). DNA sequencing confirmed the identity of the amplified products. The minimum amount of DNA detectable using SCAR‐PCR assay was 0.3 ng for female S. japonicum. The SCAR‐PCR was able to differentiate effectively the male and female S. japonicum worms collected from 12 geographical origins in eight endemic provinces, the gender of which was known based on the morphological and biological features. These results showed that SCAR‐PCR provides an effective tool for the sex differentiation studies of S. japonicum, identification of female S. japonicum, diagnosis and epidemiological survey of S. japonicum infections in animals and human.     

过冷等规聚丙烯熔体的流变学行为

采用毛细管流变仪研究低于表观熔点的过冷聚丙烯熔体的流变学行为.过冷聚丙烯熔体先经过一段诱导期后,熔体发生凝胶化,剪切黏度在短时间内大幅度升高,最终固化结晶.在诱导期中,过冷聚丙烯熔体的流变行为与高于聚丙烯熔点的常规熔体的流变行为相仿.诱导期的长度与温度有关.在160℃下,诱导期的长度足够长,于是使用过冷聚丙烯熔体进行纺丝加工成为可能.实验结果表明,由过冷熔体制备的初生纤维各项性能与由高温熔体制备的初生纤维亦相似,因此,通过降低喷丝头温度的方法发展一种节能降耗的聚丙烯纤维制造技术有潜在的可能性.     

Simultaneous stacking of cationic and anionic compounds in single run capillary zone electrophoresis by two-end field amplified sample injection

In order to extend the application of field amplified sample injection (FASI) in high throughput analysis, a convenient and simple procedure, namely two-end field amplified sample injection (TE-FASI), was developed for the simultaneous stacking of cationic and anionic compounds in a single run capillary zone electrophoresis (CZE). Following the capillary-filling with a buffer of high conductivity, water plug was loaded into each end of the capillary; and two high-field strength zones were generated at both heads of the column when high voltage was applied. Therefore, under suppressed EOF cations and anions can be selectively FASI stacked at anode and cathode head, respectively. After separation, the stacked anions and cations are detected by a common detector placed in the center of the capillary. Under the optimized conditions, the limits of detection for the model cationic (matrine and oxymatrine) and anionic (5-sulfosalicylic acid) compounds were determined as 0.2, 0.2 and 0.06 ng/mL, respectively. Compared with non-stacking conditions, the sensitivities of these compounds were enhanced 1003-, 1330- and 1380-fold, respectively. The results of reproducibility, linearity and real sample analysis show that the proposed procedure is promising to be applied for the simultaneous quantification detection of trace cationic and anionic analytes.