Application of a multivariate approach for analyte focusing by micelle collapse‐micellar electrokinetic chromatography for analyzing sunscreen agents in cosmetics

The operating parameters that affect the performance of the online preconcentration technique “analyte focusing by micelle collapse‐MEKC (AFMC‐MEKC)” were examined using a multivariate approach involving experimental design to determine the sunscreen agents in cosmetics. Compared to the single‐variable approach, the advantage of the multivariate approach was that many factors could be investigated simultaneously to obtain the best separation condition. A fractional factorial design was used to identify the fewest significant factors in the central composite design (cCD). The cCD was adopted for evaluating the location of the minimum or maximum response in this study. The influences of the experimental variables on the response were investigated by applying a chromatographic exponential function. The optimized condition and the relationship between the experimental variables were acquired using the JMP software. The ANOVA analysis indicated that the Tris pH value, SDS concentration, and ethanol percentage influenced the separation quality and significantly contributed to the model. The optimized condition of the running buffer was 10 mM Tris buffer (pH 9.5) containing 60 mM SDS, 7 mM γ‐CD, and 20% v/v ethanol. The sample was prepared in 100 mM Tris buffer (pH 9.0) containing 7.5 mM SDS and 20% v/v ethanol. The SDS concentration in the sample matrix was slightly greater than the CMC value that makes the micelle be easily collapsed and the analytes be accumulated in the capillary. In addition, sunscreen agents in cosmetics after 1000‐fold dilution were successfully determined by AFMC‐MEKC.     

醚化PBS与CMC液体复合材料的相互作用

采用聚乙二醇(PEG)对聚丁二酸丁二醇酯(PBS)进行醚化改性,得到醚化PBS(PEG/PBS),PEG/PBS与羧甲基纤维素(CMC)共混制备了在水相均匀分散的新型(PEG/PBS)-CMC液体复合材料.结合分子模拟技术对PEG/PBS与CMC复合材料的相互作用机理进行了研究.结果表明,PEG/PBS具有预期的化学结构和优异的水润湿性;含醚链段PEG的引入有效提高了PBS分子链的极性和柔顺性,PEG/PBS与CMC之间存在氢键作用、范德华力作用、疏水作用和吸附作用.红外光谱(FTIR)中官能团(如—OH,—OCO—,—COOH,—C—O—C—等)的吸收峰频率发生偏移;光电子能谱(XPS)中C和O元素的结合能分布转移,表明PBS及PEG/PBS与CMC的官能团之间发生了相互作用;偏光显微镜(POM)和X射线衍射(XRD)结果表明,复合材料之间的相互作用为非共价键的结合;扫描电子显微镜(SEM)结果表明醚化改性后(PEG/PBS)-CMC复合材料间的相互作用增强,表面结合更紧密,相容性得到提高.     

High‐performance liquid chromatography separation of unsaturated organic compounds by a monolithic silica column embedded with silver nanoparticles

The optimization of a porous structure to ensure good separation performances is always a significant issue in high‐performance liquid chromatography column design. Recently we reported the homogeneous embedment of Ag nanoparticles in periodic mesoporous silica monolith and the application of such Ag nanoparticles embedded silica monolith for the high‐performance liquid chromatography separation of polyaromatic hydrocarbons. However, the separation performance remains to be improved and the retention mechanism as compared with the Ag ion high‐performance liquid chromatography technique still needs to be clarified. In this research, Ag nanoparticles were introduced into a macro/mesoporous silica monolith with optimized pore parameters for high‐performance liquid chromatography separations. Baseline separation of benzene, naphthalene, anthracene, and pyrene was achieved with the theoretical plate number for analyte naphthalene as 36 000 m^?1. Its separation function was further extended to cis/trans isomers of aromatic compounds where cis/trans stilbenes were chosen as a benchmark. Good separation of cis/trans‐stilbene with separation factor as 7 and theoretical plate number as 76 000 m^?1 for cis‐stilbene was obtained. The trans isomer, however, is retained more strongly, which contradicts the long‐ established retention rule of Ag ion chromatography. Such behavior of Ag nanoparticles embedded in a silica column can be attributed to the differences in the molecular geometric configuration of cis/trans stilbenes.     

Preparation and Characterization of Chitosan Thin Films on Mixed-Matrix Membranes for Complete Removal of Chromium

Herein we present a new approach for the complete removal of Cr^VI species, through reduction of Cr^VI to Cr^III, followed by adsorption of Cr^III. Reduction of chromium from water is an important challenge, as Cr^IV is one of the most toxic substances emitted from industrial processes. Chitosan (CS) thin films were developed on plain polysulfone (PSf) and PSf/TiO₂ membrane substrates by a temperature-induced technique using polyvinyl alcohol as a binder. Structure property elucidation was carried out by X-ray diffraction, microscopy, spectroscopy, contact angle measurement, and water uptake studies. The increase in hydrophilicity followed the order: PSf < PSf/TiO₂ < PSf/TiO₂/CS membranes. Use of this thin-film composite membrane for chromium removal was investigated with regards to the effects of light and pH. The observations reveal 100 % reduction of Cr^VI to Cr^III through electrons and protons donated from OH and NH₂ groups of the CS layer; the reduced Cr^III species are adsorbed onto the CS layer via complexation to give chromium-free water.     

K8[Fe(H2O)W11MnO39]/PANI/V2O5三元复合材料的制备、表征及光催化性能研究

本文运用静电自组装法合成了一种新型三元复合材料K₈[Fe(H₂O)W₁₁MnO₃₉]/PANI/V₂O₅,并采用IR、UV、XRD、XPS、SEM、氮气吸附等方法对其进行表征;然后,以龙胆紫为有机污染物进行光催化实验,对此三元复合催化剂的降解性能进行研究。结果表明:K₈[Fe(H₂O)W₁₁MnO₃₉]/PANI/V₂O₅已被成功复合,且仍然保持Keggin结构,稳定性能良好;在pH=2,龙胆紫C初=5 mg·L^-1,此催化剂用量为5 mg的条件下,其脱色率高达93.09%。可见,此复合催化剂具有优异的研究潜力和实用价值。     

定量的复合金属锂作为三维泡沫锂电极用于锂电池的研究

金属锂作为电池的负极材料具有极高的比容量和极低的氧化还原电位,能够显著提升电池的能量密度。然而,金属锂负极在实际应用中所面临的主要问题是锂枝晶、界面副反应和电极体积变化大的难题。在本文中,我们提出了一种通过将定量的金属锂与三维骨架进行复合形成三维泡沫锂负极的策略,并利用三维泡沫锂来抑制锂枝晶的生长和缓解电极的体积变化。因此,三维泡沫锂电极有利于金属锂负极的高效利用,并能借助其与平面锂箔相比更高的比表面积和更多的反应位点来提升电池的倍率性能。因此,通过采用三维泡沫锂,对称电池的循环寿命和倍率性能都得到了有效的提升。EIS数据结果表明,三维泡沫锂能够减小对称电池的电荷转移阻抗。而且,将三维泡沫锂作为负极组装的LTO全电池,与锂箔作为负极相比,循环1000周平均放电比容量从65 mAh·g^-1提升至121 mAh·g^-1。     

Solvent terminated natural deep eutectic solvent microextraction for concentration of curcuminoids in Curcumae Longae Rhizoma and turmeric tea

A novel solvent terminated microextraction method based on a natural deep eutectic solvent (L-menthol and lactic acid at a molar ratio of 1:2) coupled with high-performance liquid chromatography was proposed, which was utilized for the separation and enrichment of bisdemethoxycurcumin, demethoxycurcumin and curcumin in Curcumae Longae Rhizoma and turmeric tea. The effects of independent parameters on extraction efficiency were optimized by single-factor analysis. Subsequently, four predominated parameters affecting the extraction procedure, including extractant volume, salt concentration, demulsifier consumption, and demulsification time, were further evaluated by a central composite design. Under the optimized conditions, the linear ranges of calibration curves were 0.005–0.5 μg/mL for bisdemethoxycurcumin, 0.004–0.4 μg/mL for demethoxycurcumin, and 0.0045–0.45 μg/mL for curcumin, respectively. In addition, the developed method provided low detection limits (0.1–0.4 ng/mL) and high enrichment factors (279–350). Its intra-day and inter-day precision were carried out by relative standard deviation ranging from 2.2 to 9.2%. Finally, the applicability of this method was assessed by the analysis of Curcumae Longae Rhizoma and turmeric tea samples. The results showed that these samples were detected successfully and the spiked recoveries over the range of 85.3-108.9% with relative standard deviations of 1.6-8.9% were attained, indicating its high relative recoveries with good precision in real sample analysis.     

云南东川区域重金属环境暴露健康风险评价

以云南省昆明市东川主要河流及附近土壤、植物为研究对象,对其进行采样分析,并根据美国环境保护署(U.S.EPA)推荐健康风险评价方法对东川流域多种环境因素进行了重金属的健康风险评价。结果表明,水环境中致癌物质造成的风险最大,风险值在2.35×10^(-4)~8.27×10^(-4),达到U.S.EPA推荐的最大值10^(-4),植物根部的健康风险值为0.40×10^(-1)~7.00×10^(-1),茎叶部分的风险值为2.42×10^(-2)~15.24×10^(-2),根部存在的重金属对人体的健康风险约为茎叶部分的5倍;土壤中非致癌物质的健康风险影响较大,总健康风险值区间为0.64×10^(-1)~3.83×10^(-1)。评价结果可为该区域地表水、土壤和植物资源的污染治理、保护开发提供依据。     

Local Structure Analysis and Modelling of Lignin-Based Carbon Composites through the Hierarchical Decomposition of the Radial Distribution Function

Carbonized lignin has been proposed as a sustainable and domestic source of activated, amorphous, graphitic, and nanostructured carbon for many industrial applications as the structure can be tuned through processing conditions. However, the inherent variability of lignin and its complex physicochemical structure resulting from feedstock and pulping selection make the Process-Structure-Property-Performance (PSPP) relationships hard to define. In this work, radial distribution functions (RDFs) from synchrotron X-ray and neutron scattering of lignin-based carbon composites (LBCCs) are investigated using the Hierarchical Decomposition of the Radial Distribution Function (HDRDF) modelling method to characterize the local atomic environment and develop quantitative PSPP relationships. PSPP relationships for LBCCs defined by this work include crystallite size dependence on lignin feedstock as well as increasing crystalline volume fraction, nanoscale composite density, and crystallite size with increasing reduction temperature.     

同构MOFs复合氧化石墨烯电极材料构筑高性能超级电容器

在水热条件下一步自组装合成系列同构X-MOF （X₆O （TATB）₄（H⁺）₂·（H₂O）₈·（DMF）₂,X=Zn、Co、Ni; H₃TATB=4,4'',4″-s-triazine-2,4,6-triyl-tribenzoic acid; DMF=N,N-二甲基甲酰胺）和氧化石墨烯（GO）的复合材料（X-MOF@GO）,并探究其作为超级电容器电极材料的电化学性能。通过X射线粉末衍射、X射线光电子能谱和扫描电子显微镜测试证明GO和MOFs复合成功。其中,性能最优的Ni-MOFs@1.5GO （GO的添加量为1.5 mL）的比电容高达694.8 F·g^-1（0.5 A·g^-1）,约是Ni-MOF的2倍。电化学测试结果表明：复合材料X-MOF@1.0GO较其原MOF表现出更大的比电容和更好的倍率性能。在3.5 A·g^-1的电流密度下,1 000次循环充放电后,Ni-MOFs@1.0GO仍保持初始比电容量的81.2%。与活性炭（AC）组装的非对称超级电容器Ni-MOF@1.5GO//AC的性能最优,其功率密度为754.3 W·kg^-1时,能量密度为15.4 Wh·kg^-1,且循环3 000次后比电容保持率约为70.0%,显示出较长的循环寿命。