60Co-γ辐照对食品接触用复合包装袋中挥发性化合物的影响

针对辐照杀菌会使塑料包装产生未知辐解产物的问题,该文采用顶空气相色谱－质谱法（HS/GC－MS）结合MS－DIAL软件对60Co-γ辐照（0 ~ 10 kGy）后的19种商用塑料复合包装袋中的挥发性有机物（VOCs）进行检测。以MS－DIAL软件对谱图的解卷积、峰对齐及物质定性结果,以正交偏最小二乘法判别分析（OPLS－DA）模型对辐照前后材料的VOCs组成进行分析,考察不同辐照剂量下复合包装材料中VOCs组成的变化。结果显示,复合包装中的VOCs以聚合物降解产物烷烃和烯烃为主,60Co-γ辐照前后复合包装中的VOCs组成具有显著差异,且包装产生的VOCs总量随辐照剂量的增加而递增。通过OPLS－DA模型投影变量重要度（VIP）值筛选出17种对差异贡献较大的物质,这些差异物质大多为材料的降解产物,总体呈现检出量随辐照剂量增加而递增的趋势。该研究结果为辐照包装中挥发性非有意添加物质数据库的建立提供了依据。     

液态凝聚态调控的分散质组装及功能

凝聚态化学是研究利用分子间作用力构筑凝聚态物质多层次结构实现物质功能和化学反应的新研究领域。相比于固态凝聚态化学,液态凝聚态化学研究涉及多相态,如液态凝聚态如何影响分散质的存在状态和功能特性等重要课题。从凝聚态化学的角度认识分散质在其中的聚集行为不但有利于获得预期的分子存在结构状态,而且可以探索环境条件对组装结构形成的过程认识。本文在对液态凝聚态的物理化学性质,尤其是与溶质分散和聚集相关方面进行简要概述的基础上,选取典型示例分别阐述了液态凝聚态在分散质组装过程、组装与解组装以及组装体结构转变等方面的作用。在液态凝聚态对物质性质影响方面,从其对染料分子的紫外-可见吸收、电子转移、手性调控以及催化等几个方面进行了讨论。在这些过程中,作为连续相的液态凝聚态的介电常数、极性以及黏度等性质对于分散相的存在状态和性质起到了关键作用。然而,受现有仪器检测范围的限制,液态凝聚态与分散质之间的快速、多变且细微的作用力很难在时间和空间上进行准确测定,而从实验和理论两个方面进行相互拟合来说明液态凝聚态的作用是一个重要且行之有效的策略。     

Enhanced stability designs of cell membrane chromatography for screening drug leads

Cell membrane chromatography is an effective method for screening bioactive components acting on specific receptors in complex systems, which maintains the biological activity of the membrane receptors and improves screening efficiency. However, traditional cell membrane chromatography suffers from poor stability, resulting in a limited life span and low reproducibility, greatly limiting the application of this method. To address this problem, cyanuric chloride-decorated silica gel was used for the covalent immobilization of the cell membranes. Cyanuric chloride reacts with amino groups on the cell membranes and membrane receptors to form covalent bonds. In this way, the cell membranes are not easy to fall off. The column life of the cyanuric chloride-decorated epidermal growth factor receptor/cell membrane chromatography column was extended to more than 8 days, whereas the column life of the normal cell membrane chromatography column dropped sharply in the first 3 days. A cyanuric chloride-decorated epidermal growth factor receptor/cell membrane chromatography online HPLC-IT-TOF-MSn system was applied for screening drug leads from Trifolium pratense L. One potential drug lead, formononetin, which acts on the epidermal growth factor receptor, was screened. Our strategy of covalently immobilizing cell membrane receptors also improved the stability of cell membrane chromatography.     

基于“透过表面接枝”方式制备低分散性和高接枝密度聚合物刷的研究

"透过表面接枝"(grafting-through)是一种聚合物表面改性的新方法,可以显著改善传统grafting-from和grafting-to方法接枝工艺的缺陷,获得兼具高接枝密度和低分散性的聚合物刷产物.本文采用布朗动力学模拟方法,模拟研究了grafting-through方法接枝聚合物刷过程中的主控因素,从微观动力学角度阐明其特有的链增长趋同化效应是保持产物聚合物刷较低分散性的主因.引发效率在grafting-through中可显著提高,且产物聚合物刷的分子量呈现泊松分布.此外,反应中保持高的单体通量,可以同时实现产物聚合物较长的平均链长和较低的分散性,有利于制备性能优异的改性材料.该研究对深入理解grafting-through接枝过程的动力学主控因素,促进grafting-through技术的推广和工艺的改进具有一定的理论指导意义.     

15N/14N Isotopic Exchange in the Dissociative Adsorption of N2 on Tantalum Nitride Cluster Anions Ta3N3-

Adsorption and activation of dinitrogen (N₂) is an indispensable process in nitrogen fixation. Metal nitride species continue to attract attention as a promising catalyst for ammonia synthesis. However, the detailed mechanisms at a molecular level between reactive nitride species and N₂ remain unclear at elevated temperature, which is important to understand the temperature effect and narrow the gap between the gas phase system and condensed phase system. Herein, the ¹⁴N/¹⁵N isotopic exchange in the reaction between tantalum nitride cluster anions Ta₃¹⁴N₃^- and ¹⁵N₂ leading to the regeneration of ¹⁴N₂/¹⁴N¹⁵N was observed at elevated temperature (393-593 K) using mass spectrometry. With the aid of theoretical calculations, the exchange mechanism and the effect of temperature to promote the dissociation of N₂ on Ta3N3? were elucidated. A comparison experiment for Ta₃¹⁴N₄^-/¹⁵N₂ couple indicated that only desorption of ¹⁵N₂ from Ta₃¹⁴N₄¹⁵N₂^- took place at elevated temperature. The different exchange behavior can be well understood by the fact that nitrogen vacancy is a requisite for the dinitrogen activation over metal nitride species. This study may shed light on understanding the role of nitrogen vacancy in nitride species for ammonia synthesis and provide clues in designing effective catalysts for nitrogen fixation.     

Polybenzimidazole dendrimer containing triazine rings-based high-temperature proton exchange membranes with high performances over a wide humidity range

A high-temperature proton exchange membrane with high proton conductivity over a wide humidity range still remains a challenge. PBI dendrimer containing triazine rings (TPBI) was synthesized to approach this aim considering its high content of hygroscopic terminal groups and of larger free volume. A novel proton conductor previously synthesized (zirconium 3-sulfopropyl phosphonate, ZrSP) was doped due to its good proton conductivity over a wide humidity range. TPBI was post-crosslinked with a tetrafunctional epoxy resin (N,N,N′,N′-tetraglycidyl-4,4′-diaminodiphenylmethane, TGDDM) to enhance the mechanical stability at low cross-linking degrees, which allowed high doping levels of ZrSP, and thus, high conductivity. The prepared membranes (TPBI-TGDDM/ZrSP) showed good thermal stability, high proton conductivity over wide humidity range, and good dimensional stability. At suitable degrees of branching, TPBI-TGDDM/ZrSP exhibited superior mechanical property, oxidative stability, methanol barrier property, and membrane selectivity than its linear analog (mPBI-TGDDM/ZrSP). As ZrSP instead of PA was applied as the proton conductor, TPBI-TGDDM/ZrSP showed good durability of proton conductivity, especially in comparison with TPBI-TGDDM/PA, which highly retarded decline in conductivity caused by PA leaking. The proton conductivity at 180 °C of TPBI(20)-TGDDM(10)/ZrSP(50) achieved 142, 84.2 and 23.6 mS cm^?1 at 100%, 50%, and 0 RH, respectively.     

Preparation of superhydrophobic composite paper mulching film

To study the influence of different concentrations of zinc oxide (ZnO)/silicon dioxide (SiO₂) composite coating on hydrophobic property and mechanical stability of paper mulch film, three kinds of ZnO/SiO₂ composite coating paper mulch films (2%, 4%, 6%) with different coating substance contents were prepared by brush coating method. Through particle size analysis, contact angle, rolling angle and mechanical stability test, combined with scanning electron microscope, three-dimensional morphology and roughness measuring instrument, the optimal concentration of ZnO/SiO₂ composite coated paper mulch film was screened out. Through acid-base salt corrosion test, silver mirror reaction and surface self-cleaning, the optimal concentration of composite coated paper mulch film was compared with the original paper mulch film to prove its excellent chemical stability and hydrophobicity. The results show that the paper mulch film with 4% coating material has excellent hydrophobicity and mechanical stability, can effectively reduce the surface roughness of paper mulch film, and has remarkable effects in resisting acid, alkali and salt and self-cleaning.     

Na2EDTA返滴定法测定铜镍合金中的镍含量

采用Na₂EDTA返滴定法测定铜镍合金中的镍含量,用柠檬酸钠、硫代硫酸钠和酒石酸作掩蔽剂,丁二酮肟沉淀分离,以二甲酚橙为指示剂,加入过量的Na2EDTA,用氯化锌标准溶液返滴定,能很好地分离铜及其他杂质的干扰。方法用于测定铜镍合金中的镍含量,测定结果的相对标准偏差(RSD,n=9)为0.046%~0.24%,加标回收率为99.3%~101%。能够满足日常样品的检测要求。     

Activity Guided Isolation of Phenolic Compositions from Anneslea fragrans Wall. and Their Cytoprotective Effect against Hydrogen Peroxide Induced Oxidative Stress in HepG2 Cells

Anneslea fragrans Wall., commonly known as “Pangpo Tea”, is traditionally used as a folk medicine and healthy tea for the treatment of liver and intestine diseases. The aim of this study was to purify the antioxidative and cytoprotective polyphenols from A. fragrans leaves. After fractionation with polar and nonpolar organic solvents, the fractions of aqueous ethanol extract were evaluated for their total phenolic (TPC) and flavonoid contents (TFC) and antioxidant activities (DPPH, ABTS, and FRAP assays). The n-butanol fraction (BF) showed the highest TPC and TFC with the strongest antioxidant activity. The bio-guided chromatography of BF led to the purification of six flavonoids (1–6) and one benzoquinolethanoid (7). The structures of these compounds were determined by NMR and MS techniques. Compound 6 had the strongest antioxidant capacity, which was followed by 5 and 2. The protective effect of the isolated compounds on hydrogen peroxide (H₂O₂)-induced oxidative stress in HepG2 cells revealed that the compounds 5 and 6 exhibited better protective effects by inhibiting ROS productions, having no significant difference with vitamin C (p > 0.05), whereas 6 showed the best anti-apoptosis activity. The results suggest that A. fragrans could serve as a valuable antioxidant phytochemical source for developing functional food and health nutraceutical products.     

Rutin and Quercetin Decrease Cholesterol in HepG2 Cells but Not Plasma Cholesterol in Hamsters by Oral Administration

Rutin (R) and quercetin (Q) are two widespread dietary flavonoids. Previous studies regarding the plasma cholesterol-lowering activity of R and Q generated inconsistent results. The present study was therefore carried out to investigate the effects of R and Q on cholesterol metabolism in both HepG2 cells and hypercholesterolemia hamsters. Results from HepG2 cell experiments demonstrate that both R and Q decreased cholesterol at doses of 5 and 10 µM. R and Q up-regulated both the mRNA and protein expression of sterol regulatory element binding protein 2 (SREBP2), low-density lipoprotein receptor (LDLR), and liver X receptor alpha (LXRα). The immunofluorescence study revealed that R and Q increased the LDLR expression, while only Q improved LDL-C uptake in HepG2 cells. Results from hypercholesterolemia hamsters fed diets containing R (5.5 g/kg diet) and Q (2.5 g/kg diet) for 8 weeks demonstrate that both R and Q had no effect on plasma total cholesterol. In the liver, only Q reduced cholesterol significantly. The discrepancy between the in vitro and in vivo studies was probably due to a poor bioavailability of flavonoids in the intestine. It was therefore concluded that R and Q were effective in reducing cholesterol in HepG2 cells in vitro, whereas in vivo, the oral administration of the two flavonoids had little effect on plasma cholesterol in hamsters.