β-Cyclodextrin epichlorohydrin copolymer as a solid-phase extraction adsorbent for aromatic compounds in water samples

A novel solid-phase extraction (SPE) procedure for trace aromatic compounds in water samples has been developed using 12 aromatic compounds as model compounds and GC-MS and UV spectrophotometry for detection. The method is based on the fact that β-cyclodextrin (β-CD) epichlorohydrin (ECH) copolymer (β-CDEP) can extract non-ionized aromatic compounds quantitatively from aqueous samples. The polymer used is a colorless, transparent and insoluble solid with a maximum capacity of 0.82 μmol aromatic compounds per gram. It was synthesized by co-polymerization of β-CD and ECH and characterized by FT-IR and UV. β-CDEP does not contain double bonds, and therefore it does not have appreciable absorbance in the UV region. The optimum pH range for the extraction of aromatic compounds is 2.5-5.0. The method has high extraction efficiency with the recoveries between 90 and 101% for aromatic compounds at 0.02-1.67 ppm levels, and the analytes can be easily eluted by methanol washing after preconcentration.     

Preparation of Titania Monolith Column and Application in Determination of Benzoic Acid by HILIC

The titania monolith column has been synthesized through a template-free sol–gel route, and a simple and reliable method for the determination of benzoic acid by hydrophilic interaction liquid chromatography using the prepared titania monolith has been developed. The influences of acetonitrile, acetate buffer and buffer pH on the retention of benzoic acid were investigated. Benzoic acid in carbonated drinks and fruit beverages samples were determined within 5 min and quantitative analysis was carried out by external standard method with a correlation coefficient (R ²) of 0.9984. The relative standard deviation was 0.91 % and the recovery ranged from 92.5 to 101.3 %. The proposed method is suitable for the analysis of benzoic acid in beverage samples.

     

贵金属掺杂锐钛矿TiO2光催化性能的第一性原理研究

本研究采用基于密度泛函理论的第一性原理方法,对纯锐钛矿TiO2及贵金属（Ru、Pd、Pt、Ag和Au）掺杂锐钛矿TiO2的晶格结构、能带结构、电子态密度及光学性质进行了计算。结果表明：贵金属掺杂后TiO2的晶格体积都出现了不同程度的增大;Pd和Pt掺杂后TiO2体系的禁带宽度减小,Ru、Ag和Au掺杂后体系表现出了一定的金属属性,五种贵金属掺杂TiO2后吸收光谱都有红移的趋势。掺杂形成能计算表明,除Ru金属外,富氧条件下掺杂更容易实现。     

Perturbation solution to heat conduction in melting or solidification with heat generation

The Stefan problem involving a source term is considered in this technical note. As an example, planar solidification with time-dependent heat generation in a semi-infinite plane is solved by use of a perturbation technique. The perturbation solution is validated by reducing the problem to the case without heat generation whose exact solution is available. An application to the case with constant heat generation is presented, for which a closed-form solution is obtained. The effects of heat generation and Stefan number on the evolution of solidification are examined using the perturbation solution.     

Sol–gel synthesis and characterization of titania monolith with bimodal porosity

Monolithic titania materials with macro-mesoporosity bimodal texture have been prepared through a template-free sol–gel approach, based on the reaction of hydrolysis and polycondensation of titanium isopropoxide promoted by the slow released water from esterification between acetic acid and methanol under a strong acidic condition. With the coarsening of the titania oligomers, phase separation and sol–gel transition processes take place so as to form a homogeneous gel system that will change into a monolith after aging, drying and heat treatment. The synthesized titania monolith possesses a specific surface area of 77 m² g⁻¹ (calcined at 350 °C), an anatase with partly rutile crystallite structure and great mechanical strength. The synthesis method applied here is simple and easy to implement as no extra chemical modifier such as poly(ethylene oxide) (PEO) and formamide is needed to control the process. The properties of biomodal porous structure, satisfactory surface area and high mechanical strength will enable the monolith to be served as a chromatography column to separate phosphorus organo-compounds.     

Complexation study of brilliant cresyl blue with beta-cyclodextrin and its derivatives by UV-vis and fluorospectrometry

The complexation reactions of brilliant cresyl blue (BCB) with beta-cyclodextrin (beta-CD), mono[2-O-(2-hydroxypropyl)]-beta-CD (2-HP-beta-CD), mono[2-O-(2-hydroxyethyl)]-beta-CD (2-HE-beta-CD), and heptakis(2,6-di-methyl) -beta-CD (DM-beta-CD) were investigated using UV-vis and fluorospectrometry. The complexation between BCB and CDs could inhibit the aggregation of BCB molecules and could cause its absorbance at 634nm gradually increasing. The fluorescence of BCB was also enhanced with the addition of CDs. The fluorescence enhancement was more notable in neutral and acidic media than in basic media. Hildebrand-Benesi equation was used to calculate the formation constants of beta-CDs with BCB based on the fluorescence differences in the CDs solution. The stoichiometry ratio was found to be 1:1. The complexing capacities of beta-CD and its three derivatives were compared and the results followed the order: 2-HP-beta-CD>2-HE-beta-CD>DM-beta-CD>beta-CD. The effect of temperature on the formation of BCB-beta-CD inclusion complexes has also been examined. The results revealed that the formation constants decreased with the increase of temperature from 1038.9 to 491.6l/mol. Enthalpy and entropy values were calculated and the values were -25.77kJ/mol and 35.04J/kmol, respectively. The thermodynamic measurements suggest that the inclusive process was enthalpic favor. The release of high-energy water molecules and Van der Waals force played an important role in the inclusive process.     

Core-Shell Reactor Partitioning Enzyme and Prodrug by ZIF-8 for NADPH-Sensitive In Situ Prodrug Activation

Enzyme-prodrug therapies have shown unique advantages in efficiency, selectivity, and specificity of in vivo prodrug activation. However, precise spatiotemporal control of both the enzyme and its substrate at the target site, preservation of enzyme activity, and in situ substrate depletion due to low prodrug delivery efficiency continue to be great challenges. Here, we propose a novel core–shell reactor partitioning enzyme and prodrug by ZIF-8, which integrates an enzyme with its substrate and increases the drug loading capacity (DLC) using a prodrug as the building ligand to form a Zn-prodrug shell. Cytochrome P450 (CYP450) is immobilized in ZIF-8, and the antitumor drug dacarbazine (DTIC) is coordinated and deposited in its outer layer with a high DLC of 43.6±0.8 %. With this configuration, a much higher prodrug conversion efficiency of CYP450 (36.5±1.5 %) and lower IC₅₀ value (26.3±2.6 μg/mL) are measured for B16-F10 cells with a higher NADPH concentration than those of L02 cells and HUVECs. With the tumor targeting ability of hyaluronic acid, this core–shell enzyme reactor shows a high tumor suppression rate of 96.6±1.9 % and provides a simple and versatile strategy for enabling in vivo biocatalysis to be more efficient, selective, and safer.     

边界对石墨烯量子点非线性光学性质的影响

石墨烯作为一种新型非线性光学材料,在光子学领域具有重要的应用前景,引起研究人员的极大兴趣.本文运用量子化学计算方法研究了边界引入碳碳双键(C=C)和掺杂环硼氮烷(B₃N₃)环对石墨烯量子点非线性光学性质和紫外-可见吸收光谱的影响.研究发现,扶手椅边界上引入C=C双键后,六角形石墨烯量子点分子结构对称性降低,电荷分布对称性发生破缺,导致分子二阶非线性光学活性增强.石墨烯量子点在从扶手椅型边界向锯齿型边界过渡的过程中,随着边界C=C双键数目的增加,六角形石墨烯量子点和B3N3掺杂六角形石墨烯量子点的极化率和第二超极化率分别呈线性增加.此外,边界对石墨烯量子点的吸收光谱也有重要影响.无论是石墨烯量子点还是B₃N₃掺杂石墨烯量子点,扶手椅型边界上引入C=C双键导致最高占据分子轨道能级升高,最低未占分子轨道能级的降低,前线分子轨道能级差减小,因而最大吸收波长发生了红移.中心掺杂B₃N₃环后会增大石墨烯量子点的分子前线轨道能级差,导致B3N3掺杂后的石墨烯量子点紫外-可见吸收光谱发生蓝移.本文研究为边界修饰调控石墨烯量子点非线性光学响应提供了一定的理论指导.     

Pt-N共掺杂闪锌矿ZnS光催化性质的第一性原理研究

利用基于密度泛函理论的第一性原理计算Pt、N单掺杂及Pt-N不同位置共掺杂闪锌矿ZnS的晶型结构、电荷布局、电子结构以及光学性质.计算结果表明,Pt单掺杂后晶格体积增大,N单掺杂后的晶格体积减小,Pt-N共掺杂时的相对位置不同,晶格参数及电荷布局均存在差异,从而对体系的畸变产生不同影响.形成能计算表明Pt、N非邻位共掺杂相对于邻位共掺杂体系更易实现.电子结构计算结果表明,Pt掺杂ZnS后使材料表现出了一定的金属属性;共掺杂体系中,随着Pt-N距离的增大,N-2p轨道与Zn-3d在价带深能级的局域化作用减弱,价带部分的N-2p轨道逐渐聚集于费米能级附近形成杂质能级,有助于光生电子的跃迁,提高光催化效率.光学性质计算结果表明,共掺杂Pt-N间距离越大,低能区的介电常数虚部ε_2的峰值越大,在可见光区的吸收峰值也越大.     

Preparation of Titania Monolith Column and Application in Determination of Benzoic Acid by HILIC

The titania monolith column has been synthesized through a template-free sol–gel route, and a simple and reliable method for the determination of benzoic acid by hydrophilic interaction liquid chromatography using the prepared titania monolith has been developed. The influences of acetonitrile, acetate buffer and buffer pH on the retention of benzoic acid were investigated. Benzoic acid in carbonated drinks and fruit beverages samples were determined within 5?min and quantitative analysis was carried out by external standard method with a correlation coefficient (R ²) of 0.9984. The relative standard deviation was 0.91?% and the recovery ranged from 92.5 to 101.3?%. The proposed method is suitable for the analysis of benzoic acid in beverage samples.