一种基于遗传算法的肽/蛋白质结合模式虚拟筛选建模技术

“合理”QSAR模型是指在了解配体与受体相互作用模式的前提下建立定量构效关系, 这样避开了传统做法仅仅依靠样本集分子自身信息来构建预测模型的诸多弊端. 本文将此思想应用于肽/蛋白质亲和活性的研究当中, 借助于遗传算法作为虚拟受体结合靶点及相互作用模式的筛选手段得到了一种新的建模技术: 肽/蛋白质结合模式遗传虚拟筛选(genetic virtual screening of combinative mode for peptide/protein, GVSC). 该法成功解决了“合理”QSAR研究中的难题, 即大多数情况下受体结构未知而难以了解配基与之发生的结合方式. 分别使用58个血管紧张素转化酶, 18个Camel抗体蛋白cAb-lys3双位点突变残基对GVSC加以检验, 其结果表明GVSC能够较好地阐明配基与受体之间的作用机理, 并能得到优于传统方法的QSAR模型.     

Sensitive Electrochemical Detection of Thiabendazole in Fruits Using Ag−MoS2 Electrode

Herein, Ag nanoparticles (NPs) modified MoS₂ (Ag−MoS₂) was applied to the surface of glassy carbon (GC) to produce a robust electrochemical sensor for the detection of thiabendazole, a common antifungal in the post-harvesting of fruits. Cyclic voltammetry studies confirmed thiabendazole exhibited an irreversible, diffusion-controlled process on Ag−MoS₂ with a two-fold increase in peak current than the pristine MoS_2. A square wave voltammetry was used for the detection of TBZ. The developed sensor exhibited a linear range between 1–10 μM with LOD down to 0.1 μM (S/N>3). Analysis of TBZ in mango and banana matrices gave a recovery of 91.6–100.4 % indicating the suitability of the sensor for food safety monitoring.     

傅里叶变换近红外光谱法同时定量分析水溶液中乙醇、果糖和葡萄糖

利用乙醇、果糖和葡萄糖在波数为14000-7500cm^-1范围内的吸收值,在近红外谱区用偏最小二乘法（PLS）对体系进行建模,并通过内部和外部样品校验确认最佳数据预处理方法。结果表明,乙醇在0.05-0.25L/L,果糖在0.01-0.05g/mL及葡萄糖在0.005-0.009g/mL的范围内外部校验模型较好的分别是在PLS中所用的一阶偏导（平滑点数是5）、二阶偏导（平滑点数是5）和直线消除法的数据预处理方法所建立的模型,其外部校验预测结果的相对误差在2%左右。此方法具有可同时测定不同样品,简便快速及成本低等优点。     

Hydrido-Carbonyl Rhenium Clusters with a Square Geometry of the Metal Core. Synthesis and X-Ray Characterization of the Novel [Re4(μ-H)3(CO)16]− Anion

Three and tetranuclear ring clusters have been obtained by treatment of [Re₂(CO)₈(THF)₂] with carbonyl-rhenates containing two terminal hydrides. The reaction with [ReH₂(CO)₄]^- provided a selective route to the previously known [Re₃(-H)₂(CO)₁₂]^- triangular cluster anion 1. The reaction with [Re₂H₂(-H)(CO)₈]^- gave the novel [Re₄(-H)₃(CO)₁₆]^- anion 2, containing a rare example of a puckered-square metal cluster. Protonation of 1 is known to afford the neutral [Re₃(-H)₃(CO)₁₂] species 3. Analogously the reaction of 2 with a strong acid afforded the previously known square metal clusters [Re₄(-H)₄(CO)₁₆] 4. The reaction could not be reversed by treatment with bases. Photolysis of 4 gave the unsaturated complex [Re₂(-H)₂(CO)₈] 5: this is the reverse of the dimerization reaction, that in THF at room temperature produces 4 from 5. Thermal treatment (reflux in cyclohexane for 24 h) left 4 almost unchanged. A single crystal X-ray analysis of [NEt₄]2 showed a s/e/s/s (e=eclipsed, s=staggered) conformation of the Re(CO)₄ units, leading to a puckered geometry of the ring, at variance with the square-planar geometry of 4 (all eclipsed). Two of the three hydrides of 2 have been located as bridging the Re–Re edges from inside the metal ring, as previously observed in 4. Density functional computations indicated a puckered conformation as the most stable for both 2 and 4, with very low activation energies for ring inversion (6.6 and 2.2 kcal·mol^-1, respectively), but ruled out solid state fluxionality for 4, whose observed planar geometry must be attributed to packing stabilization.     

Rapid Simultaneous Determination of Andrographolides in Andrographis paniculata by Near-Infrared Spectroscopy

The potential of near-infrared spectroscopy (NIRS) for the quality control of traditional Chinese medicine has been evaluated. Seven quantitative parameters, andrographolide, deoxyandrographolide, dehydroandrographolide, neoandrographolide, moisture, ash content, and alcohol-soluble extract of Andrographis paniculata, were evaluated by NIRS. The reference values of andrographolides were determined by high-performance liquid chromatography, and the others were obtained using the standard methods of the 2015 Chinese Pharmacopoeia. The predicted values were determined by a quantitative model using NIRS based on partial least square regression. Different spectral preprocessing methods, spectral ranges, and optimum number of factors were selected to optimize the models. All models were estimated by the combination of various parameters, including the correlation coefficient of calibration for andrographolide, deoxyandrographolide, dehydroandrographolide, neoandrographolide, moisture, ash content, alcohol-soluble extract (values of 0.980, 0.984, 0.989, 0.983, 0.987, 0.988, 0.979, respectively), root mean square error of calibration (values of 0.156, 0.038, 0.050, 0.029, 0.604, 0.431, 0.135, respectively), root mean square error of prediction (values of 0.169, 0.041, 0.050, 0.033, 0.280, 0.493, 0.140, respectively), root mean square error of cross-validation (values of 0.626, 0.114, 0.158, 0.046, 1.145, 0.774, 0.508, respectively), and ratio of standard deviation to standard error of prediction (values of 4.583, 4.690, 4.796, 4.899, 4.899, 4.690, 5.099, respectively). The results show that the calibration models by NIRS are reliable and can be applied for the quantification for seven parameters from A. paniculata for quality control in traditional Chinese medicine production and processing.     

不可逆电极过程方波伏安法动力学研究 Ⅰ.平行催化体系

本文报道了在不可逆电极过程的强催化体系中，当采用快速方波扫描时，正、逆向电流将出现峰形。依据实验结果，提出了“迁出－进入”的等浓度面理论模型，推导了并讨论了电流方程式。结果表明，文中提出的理论能较好地说明实验结果。     

中药色谱指纹图谱组分保留时间漂移的校准

基于光谱相关色谱方法判断复杂中药色谱指纹图谱的组分相关性,实现同一中药样本在不同实验条件下所得的色谱指纹图谱的相同组分的色谱保留时间漂移的局部最小二乘校正,为合理评价指纹图谱的品质提供较为实用的工具。     

Short Te …︁ Te bonding contacts in a new layered ternary telluride: Synthesis and crystal structure of 2D Nb3GexTe6 (x ≃ 0.9)

The new layered ternary compound Nb₃Ge_xTe₆ (x ? 0.90) was prepared by direct combination of the elements taken in the stoichiometric proportions 3 : 1 : 6, heated at 1 000 °C for 10 days in silica tubes and quenched to room temperature. The phase crystallizes in the orthorhombic symmetry, space group Pnma (#62), with the following single crystal refined parameters: a = 643.18(5) pm, b = 1391.98(11)pm and c = 1 154.07(5) pm, with Z = 4. The structure was refined to an R of 3.4% (R_w = 4.6%), with 1969 independent reflexions and 49 parameters. The structure is based on the close stacking of trigonal prismatic (TP) slabs in the AA/BB mode. The slabs can be seen as built up from face sharing biprisms, which are filled either by one or by two niobium cations situated in the middle of the trigonal prisms. The germanium is located in the middle of the common face of two prisms, leading to a rather unusual anionic square coordination. The refinements showed that this latter cation does not fill completely its square site. No cation was found in the van der Waals gap between the slabs. The mean d_{Ge? Te} distance (276.5 pm) is in agreement with Ge^II cations, while some Te …? Te distances (from 333.84 to 361.65pm) are too short for anions in a simple contact. These bonding distances, already mentionned in some MTe₂ compounds, are to be ascribed to charge transfer in the structure, with a partial oxidation state for the tellurium anions. Short Nb? Nb and Nb? Ge distances (292.0 and 281.3 pm, respectively) imply intercationic bonding within the slabs.     

5 nm Ordered Structures Self-Assembled by C2-Symmetric Hybrids with Polyhedral Oligomeric Silsesquioxane and Hexa-peri-Hexabenzocoronene.

Hybrids consisting of polyhedral oligomeric silsesquioxane (POSS) and hexa-peri-hexabenzocoronene (HBC) with a dumbbell topology and C₂ symmetry were designed and synthesized. They self-assemble into 5 nm ordered structures. In particular, the increased steric effect with increasing POSS units stabilizes a square columnar phase (Col_squ) which is important in nanotemplating. These hybrids containing discotic liquid crystal HBC and POSS units have an excellent etching contrast and present an approach to obtain 5 nm nanopatterns.     

Electrochemical Determination of Lead(II) in Environmental Waters Using a Sulfydryl Modified Covalent Organic Framework by Square Wave Anodic Stripping Voltammetry (SWASV)

A novel sulfhydryl-modified covalent organic framework was designed for the selective determination of lead(II) using square wave anodic stripping voltammetry. The introduction of sulfhydryl groups enhanced the selectivity and sensitivity of the covalent organic framework for analytes. The sulfhydryl-modified covalent organic framework was characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy and X-ray diffraction. Under the optimized conditions, a sulfhydryl-modified covalent organic framework/gold electrode was successfully used for the determination of lead(II) in water samples. The newly developed square wave anodic stripping voltammetry method exhibited wide linearity (0.05 to 20?ng mL^?1, r?=?0.991), a low limit of detection (0.015?ng mL^?1) and good precision, with a relative standard deviation values <5.1%. The limit of detection was lower than 10?ng mL^?1, the level of lead(II) in drinking water permitted by the World Health Organization. The recoveries of three spiked samples ranged from 90.0% to 104.0%, with relative standard deviations <4.9%. Satisfactory reproducibility and good repeatability demonstrated that the newly developed method is very suitable for the detection of lead(II) in real water samples, with significant advantages over existing methods.