中红外、近红外和拉曼光谱法测定商品农药制剂中氰戊菊酯和马拉硫磷的含量

利用近红外、中红外和拉曼光谱法定量分析了商品农药制剂中有效成分氰戊菊酯和马拉硫磷的含量.采用偏最小二乘法(Partial least squares,PLS)建立氰戊菊酯和马拉硫磷的定量模型并进行了优化,用独立检验集对模型适应性进行评价.近红外和中红外法测定氰戊菊酯、马拉硫磷定量模型的相关系数分别是0.9981,0.9994和0.9946,0.9998,外部验证集标准差分别是0.082,0081和0.092,0.075,两种方法的定量效果接近;拉曼法氰戊菊酯和马拉硫磷定量模型的相关系数分别为0.9872和0.9993,外部验证集标准差分别为0.254和0.317,预测精度不及近红外和中红外法高.MIR-ATR,NIR和Raman 3种方法均能满足现场检测农药质量的需要.     

偏最小二乘-导数同步荧光法同时测定生物样品中对羟苯基乳酸、多巴和尿黑酸

在pH=6.00的KH2PO4-NaOH缓冲溶液中,波长差△λ=35nm,采集260～325nm波长范围内的同步荧光光谱数据,并对该数据进行一阶求导后用偏最小二乘法处理,以此建立了偏最小二乘-导数同步荧光光谱法同时测定对羟苯基乳酸(PHPLA)、多巴(Dopa)和尿黑酸(HGA)的新方法。该三种物质的线性范围分别为0.06～3.00、0.06～3.00和0.08～3.00mg/L;检出限分别为0.0307、0.0310和0.0428mg/L。该法用于细胞培养液中PHPLA、Dopa和HGA三组分的同时测定,其测定结果与高效液相色谱法的测定结果相比无显著性差异。     

紫外光谱法结合多元曲线分辨研究黄芩苷的转化规律

采用紫外光谱法采集不同工艺条件下黄芩苷转化过程的光谱数据, 结合多元曲线分辨-交替最小二乘法(MCR-ALS)处理获得的数据, 得到黄芩苷转化反应过程中各组分的光谱图和浓度随时间变化曲线. 结果表明, 黄芩苷转化过程符合两步连续一级反应模型; 根据不同时间点采集的多级质谱和飞行时间质谱信息, 推断了黄芩苷转化产物和可能的转化途径, 转化产物主要包括黄芩苷的同分异构体、 黄芩素和黄芩素二聚体. 对黄芩苷转化规律的研究有助于黄芩制剂的质量控制.     

Dependence of calculated electron effective attenuation lengths on transport mean free paths obtained from two atomic potentials

We report changes in electron effective attenuation lengths (EALs) resulting from use of transport mean free paths (TMFPs) obtained from the Dirac–Hartree–Fock (DHF) potential instead of the Thomas–Fermi–Dirac (TFD) potential in an algorithm used in the National Institute of Standards and Technology (NIST) Electron Effective‐Attenuation‐Length Database (SRD 82). TMFPs from the former potential are believed to be more reliable than those obtained from the latter potential. We investigated changes in the EALs for selected photoelectron and Auger‐electron lines in four elemental solids (Si, Cu, Ag, and W), for Si 2p photoelectrons of varying energy in SiO₂, and for photoelectrons excited by Al Kα X rays in four candidate gate‐dielectric materials (HfO₂, ZrO₂, HfSiO₄, and ZrSiO₄). For each material, we computed the change in the average EAL for a range of overlayer‐film thicknesses from zero to a maximum value corresponding to attenuation of the substrate signal to 10% of its original value. This EAL change was a maximum for electrons emitted normally from the surface and decreased monotonically with increasing emission angle. The maximum EAL change varied between ?4.4% and 2.6% for the three groups of materials. We found that the maximum EAL change correlated mainly with the TMFP change. We found that TMFP changes in other solids could generally lead to maximum EAL changes between ?2.6% and 1.9% for electron energies between 500 and 2000 eV. For lower energies, the maximum EAL changes could be larger for some solids. Our revised EALs for Si 2p photoelectrons in SiO₂ excited by Mg and Al Kα X rays agree within 0.5% with values reported by Seah and Spencer from a detailed analysis of SiO₂ film‐thickness measurements by XPS and other techniques. Copyright © 2006 John Wiley & Sons, Ltd.     

Development of models for prediction of the antioxidant activity of derivatives of natural compounds

Antioxidants are important for maintaining the appropriate balance between oxidizing and reducing species in the body and thus preventing oxidative stress. Many natural compounds are being screened for their possible antioxidant activity. It was found that a mushroom pigment Norbadione A, which is a pulvinic acid derivative, shows an antioxidant activity; the same was found for other pulvinic acid derivatives and structurally related coumarines. Based on the results of in vitro studies performed on these compounds as a part of this study quantitative structure–activity relationship (QSAR) predictive models were constructed using multiple linear regression, counter-propagation artificial neural networks and support vector regression (SVR). The models have been developed in accordance with current QSAR guidelines, including the assessment of the models applicability domains. A new approach for the graphical evaluation of the applicability domain for SVR models is suggested. The developed models show sufficient predictive abilities for the screening of virtual libraries for new potential antioxidants.     

Efficient synthesis of magnetic nanoparticle-Musa acuminata peel composite for the adsorption of anionic dye

The impregnation of magnetite (Mt) nanoparticle (NPs) onto Musa acuminata peel (MApe), to form a novel magnetic combo (MApe-Mt) for the adsorption of anionic bromophenol blue (BPB) was studied. The SEM, EDX, BET, XRD, FTIR and TGA were used to characterize the adsorbents. The FTIR showed that the OH and CO groups were the major sites for BPB uptake onto the adsorbent materials. The average Mt crystalline size on MApe-Mt was 21.13 nm. SEM analysis revealed that Mt NPs were agglomerated on the surface of the MApe biosorbent, with an average Mt diameter of 25.97 nm. After Mt impregnation, a decrease in BET surface area (14.89 to 3.80 m²/g) and an increase in pore diameter (2.25–3.11 nm), pore volume (0.0052–0.01418 cm³/g) and pH point of zero charge (6.4–7.2) was obtained. The presence of Pb(II) ions in solution significantly decreased the uptake of BPB onto both MApe (66.1–43.8%) and MApe-Mt (80.3–59.1%), compared to other competing ions (Zn(II), Cd(II), Ni(II)) in the solution. Isotherm modeling showed that the Freundlich model best fitted the adsorption data (R² > 0.994 and SSE < 0.0013). In addition, maximum monolayer uptake was enhanced from 6.04 to 8.12 mg/g after Mt impregnation. Kinetics were well described by the pseudo-first order and liquid film diffusion models. Thermodynamics revealed a physical, endothermic adsorption of BPB onto the adsorbents, with ΔH^o values of 15.87–16.49 kJ/mol, corroborated by high desorption (over 90%) of BPB from the loaded materials. The viability of the prepared adsorbents was also revealed in its reusability for BPB uptake.     

一个新颖三维配位聚合物Pb(1，4-napdc)(DMF)的合成、结构及热稳定性研究

A novel 3D metal-organic coordination polymer Pb(1,4-napdc)(DMF) (1,4-napdc=naphthalene-1,4-dicarboxylate) was synthesized at room temperature using slow vapor diffusion method to grow single crystal that has been analyzed by X-ray diffraction. The crystal belongs to orthorhombic with space group P2₁2₁2₁. The unit cell parameters are as fellows: a=0.701 3(2) nm, b=1.407 6(3) nm, c=1.521 5(4) nm, V=1.501 8(6) nm³ and Z=4. In the crystal structure of Pb(1,4-napdc)(DMF), the square grids constructed with paddle-wheel units of Pb(Ⅱ) and 1,4-napdc links stack over each other to generate infinite 3D network, which has square apertures (1.158×1.158 nm²) along the crystallographic a-axis. The thermal stability of compound was investigated by differential scanning calorimetry and thermogravimetric analysis. CCDC: 293617.     

一组新氨基酸描述子用于肽定量构效关系研究

用主成分分析从20种天然氨基酸0D～3D结构信息中收集到的共1369个描述子变量得到了一组新氨基酸描述子(SZOTT), 将其用于血管紧张素转化酶抑制剂和苦味二肽结构表征并以偏最小二乘法建立定量构效关系模型, 得复相关系数R_CU²分别为0.894和0.908, 留一法交互检验的复相关系数R_CV²分别为0.828和0.736, 估计均方根误差RMS分别为0.331和0.195. 研究结果表明, SZOTT描述子含信息量大, 操作简便, 结构表达能力强, 有望在多肽定量构效关系研究中得到进一步推广.     

生晒参、全须生晒参中19种有机氯残留农药的毛细管气相色谱测定

建立了生晒参、全须生晒参中19种有机氯农药残留的毛细管气相色谱分析方法。对样品中六六六的4种异构体、滴滴涕的5种异构体、四氯苯胺、六氯苯、五氯硝基苯、七氯、五氯苯胺、艾氏剂、百菌清、环氧七氯、狄氏剂及异狄氏剂共19种有机氯农药的残留量进行了测定。以石油醚-丙酮混合物作为提取剂,样品采用索氏提取,提取液用弗罗里硅土柱层析净化。采用OV-1701石英毛细管气相色谱柱分离样品,ECD检测器进行检测。在3个水平添加时的回收率(n=5)分别为75.7%~96.1%、78.8%~111.6%和81.7%~115·2%;相对标准偏差分别为2.4%~10.6%、2.1%~9.8%和1.4~10.0%。方法用于生晒参和全须生晒参样品中农药残留的测定,结果满意。     

Study of Bimodal Drop Size Distributions of Emulsion

In order to increase the present understanding of bimodal emulsion drop size distributions, systematic series of experiments have been carried out to investigate the effects of formulation variables on bimodal drop size distributions, and probability distribution functions were proposed to analyze the distribution. The results show that, the span of the drop size and Sauter mean diameter become larger when the dispersed phase volume fraction becomes higher and rotor speed becomes lower; the Frechet function represents the experimental data satisfactorily. The prediction model of Sauter mean diameter established by combining the prediction theory of the maximum stable drop diameter and experimental analysis results can fit the experimental data well.