火花放电原子发射光谱类型标准化校正方式的探讨

在国内,火花放电原子发射光谱分析广泛使用类型标准化进行方法校正。在国外,标准和文献中鲜见使用此方法的相关论述。类型标准化主要采用平移校正和转动校正两种方式,哪种方式更加合理也鲜见报道。国外设备类型标准化的默认设置优先采用转动校正方式,相关国内标准对最优校正方式的规定尚不明确,此默认设置的合理性有待探讨。实验选用低合金钢20CrNi2Mo、R407标准样品和不锈钢317L、0Cr18Ni9标准样品,引用国内相关标准,以正确度临界差为评判依据,模拟类型标准化样品和待测样品“十分接近”和“接近”两种情况下平移校正和转动校正的数据正确度。经数据统计分析,平移校正分析结果均满足要求,转动校正结果在“接近”情况下部分元素不满足要求。结合相关国家标准中元素含量范围和精密度数据进行分析,通过计算允许最大偏倚量并制作曲线图方式展开分析,得出如下结论:在满足文中类型标准化控制要点前提下,分析设置更适合于采用平移校正方式。     

超高效液相色谱⁃四极杆⁃飞行时间质谱对含PET食品接触材料中可迁移非挥发性物质的筛查研究

采用超高效液相色谱⁃四极杆⁃飞行时间高分辨质谱（UPLC⁃Q⁃TOF）对4类不同类型的含聚对苯二甲酸乙二醇酯（PET）材质的食品接触材料在4 %乙酸和50 %乙醇模拟物中的迁移出的非挥发性未知物进行筛查解析。结果表明，产品在4 %乙酸模拟物的迁移风险远小于50 %乙醇模拟物，主要迁移物质为聚合单体形成的寡聚物，抗氧剂、润滑剂、胶黏剂等加工助剂以及生产加工、迁移过程中形成的非有意添加物（NIAS）物质；纯PET材质的产品迁移物质较少，多层复合材料迁移物质较多。复合材质的产品中，PET材质可能在生产时添加了己二酸、癸二酸、新戊二醇等物质，进行了改性处理；此外，部分迁移物质会与模拟物中的乙醇发生反应，生成新的NIAS物质。     

Molecularly imprinted macroporous polymer monolithic layers for L-phenylalanine recognition in complex biological fluids

In present work, the development of macroporous monolithic layers bearing the artificial recognition sites toward L-phenylalanine has been carried out. The set of macroporous poly(2-aminoethyl methacrylate-co-2-hydroxyethyl methacrylate-co-ethylene glycol dimethacrylate) materials with average pore size ranged in 340–1200 nm was synthesized. The applicability of Hildebrand's and Hansen's theories for the prediction of polymer compatibility with porogenic solvents was evaluated. The dependences of average pore size on theoretically calculated parameters were plotted. The linear trend detected for Hansen's theory has indicated the high suitability of this approach to select appropriate porogens. The synthesized monolithic MIP layers were tested toward the ability to rebind phenylalanine-derivative in microarray format. The influence of such factors as average pore size of the material, the concentration of template molecule in polymerization mixture, interaction time of analyte with its imprinted sites on binding efficiency were studied. The developed materials demonstrated good analyte rebinding from buffer solution with recognition factors 2.5–3.4 depending on the MIP sample. The comparable rebinding efficiency was also detected when the analysis was carried using complex biological media. The selectivity of phenylalanine binding from the equimolar mixture of structural analogues was 81.9% for free amino acid and 91.2% for labeled one.     

Adaptation to Endoplasmic Reticulum Stress Enhances Resistance of Oral Cancer Cells to Cisplatin by Up-Regulating Polymerase η and Increasing DNA Repair Efficiency

Endoplasmic reticulum (ER) stress response is an adaptive program to cope with cellular stress that disturbs the function and homeostasis of ER, which commonly occurs during cancer progression to late stage. Late-stage cancers, mostly requiring chemotherapy, often develop treatment resistance. Chemoresistance has been linked to ER stress response; however, most of the evidence has come from studies that correlate the expression of stress markers with poor prognosis or demonstrate proapoptosis by the knockdown of stress-responsive genes. Since ER stress in cancers usually persists and is essentially not induced by genetic manipulations, we used low doses of ER stress inducers at levels that allowed cell adaptation to occur in order to investigate the effect of stress response on chemoresistance. We found that prolonged tolerable ER stress promotes mesenchymal–epithelial transition, slows cell-cycle progression, and delays the S-phase exit. Consequently, cisplatin-induced apoptosis was significantly decreased in stress-adapted cells, implying their acquisition of cisplatin resistance. Molecularly, we found that proliferating cell nuclear antigen (PCNA) ubiquitination and the expression of polymerase η, the main polymerase responsible for translesion synthesis across cisplatin-DNA damage, were up-regulated in ER stress-adaptive cells, and their enhanced cisplatin resistance was abrogated by the knockout of polymerase η. We also found that a fraction of p53 in stress-adapted cells was translocated to the nucleus, and that these cells exhibited a significant decline in the level of cisplatin-DNA damage. Consistently, we showed that the nuclear p53 coincided with strong positivity of glucose-related protein 78 (GRP78) on immunostaining of clinical biopsies, and the cisplatin-based chemotherapy was less effective for patients with high levels of ER stress. Taken together, this study uncovers that adaptation to ER stress enhances DNA repair and damage tolerance, with which stressed cells gain resistance to chemotherapeutics.     

Radiation- and Photo-Induced Oxidation Pathways of Methionine in Model Peptide Backbone under Anoxic Conditions

Within the reactive oxygen species (ROS) generated by cellular metabolisms, hydroxyl radicals (HO^•) play an important role, being the most aggressive towards biomolecules. The reactions of HO^• with methionine residues (Met) in peptides and proteins have been intensively studied, but some fundamental aspects remain unsolved. In the present study we examined the biomimetic model made of Ac-Met-OMe, as the simplest model peptide backbone, and of HO^• generated by ionizing radiation in aqueous solutions under anoxic conditions. We performed the identification and quantification of transient species by pulse radiolysis and of final products by LC-MS and high-resolution MS/MS after γ-radiolysis. By parallel photochemical experiments, using 3-carboxybenzophenone (CB) triplet with the model peptide, we compared the outcomes in terms of short-lived intermediates and stable product identification. The result is a detailed mechanistic scheme of Met oxidation by HO^•, and by CB triplets allowed for assigning transient species to the pathways of products formation.     

Acidification of the electrolyte during the galvanic corrosion of AA7075: A numerical and experimental study

The electrochemical interactions between aluminum alloy 7075 and low-carbon steels under gelled electrolytes were studied. Such electrolytes provided the opportunity to investigate both thick and thin electrolyte systems. The electrolyte was chemically modified to visually track the acidic fronts during the anodic reaction and the subsequent hydrolysis process. Two mathematical models were validated for both thick and ultrathin electrolytes. The acidification of thick electrolytes was extended some millimeters beyond the aluminum alloy surface, whereas the acidic front was localized next to the metallic joint using ultrathin electrolytes. The combination of both numerical and experimental results allows proving (and explaining why) that the acidification process is more aggressive under dilute than under concentrated electrolytes.     

Form selection of concomitant polymorphs: A case study informed by crystallization kinetics modeling

Molecular mechanisms and process kinetics of crystallizing concomitant polymorphs remain poorly understood. Solvent-mediated phase transformation and concomitant crystallization are difficult to be distinguished in practice, as multiple forms can be detected at the same time. Herein, we developed a population balance model to simulate a concomitant crystallization process of two polymorphs of tolfenamic acid. Our kinetic modeling aims to understand concomitant crystallization and help guide form selection of such a molecular system. Crystallization kinetics of ethanolic solutions were uncovered from induction time measurements, as well as seeded and unseeded crystallization experiments. Experimental and simulation results demonstrate that the stable form I crystallizes concomitantly with the metastable form II. The faster growing form II results in an intermediate decline in the composition of form I in crystallized samples, a characteristic feature of the concomitantly crystallized system. A four-quadrant scheme of attainable polymorph outcome was simulated under various crystallization conditions.