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。     

Thermal shock effects on the impact resistance,tolerance and flexural strength of alumina based oxide/oxide ceramic matrix composites

In this study the effects of thermal shock on the impact damage resistance, damage tolerance and flexural strength of Nextel 610/alumina silicate ceramic matrix composites were experimentally evaluated. Composite laminates with balanced and symmetric layup were gradually heated to 1200°C in an air-based furnace and held for at least 30 min before being removed and immersed in water at room temperature. The laminates were then subjected to low velocity impacts via a hemispherical steel impactor. The resultant damage was characterized non-destructively, following which the laminates were subjected to compression tests. Three-point bend tests were also performed to evaluate the effect of thermal shock on the flexural strength and related failure modes of the laminates. Thermally shocked laminates showed smaller internal damage and larger external damage areas in comparison to their pristine counterparts. For the impact energy and resultant damage size considered, the residual compressive strengths for the thermally shocked and pristine laminates were similar.     

Formation of single-crystalline BaTiO3 nanorods from glycolate by tuning the supersaturation conditions

We have studied peculiarities in the formation of single-crystalline barium titanate (BaTiO₃) nanorods from a glycolate-mediated complex via a single-step hydrothermal process under different supersaturation (S_R) conditions. X-ray diffraction (XRD) showed the formation of pure BaTiO₃ with an S_R of above 19. The tetragonality for the BaTiO₃ (c/a) reached 1.013 at S_R = 19–29 and dropped to 1.010 for S_R = 39. According to the transmission electron microscopy (TEM) and XRD analyses, the rod-shaped particles exhibited single crystallinity and crystal growth along the [001] plane. With scanning electron microscopy (SEM), the morphological evolution from a plate-shaped intermediate precursor (S_R = 6–9) to a rod-shaped product with an aspect ratio of 6–9 (S_R = 19–29), and to non-polar material with an irregular structure (S_R = 39), was observed. The negative slope, linear dependence of the particles’ width and length on the supersaturation level in the range S_R = 19–39 was established for the first time. The replacement of the prevailing crystallization mechanism from in-situ topotactic transformation into dissolution-precipitation above S_R = 19 was observed. It was shown that with a simple regulation of the S_R, the structural and morphological characteristics of the obtained BaTiO₃ nanoparticle can be effectively tuned.     

Efficiency improvement of CIGS solar cells using RF sputtered TCO/Ag/TCO thin-film as prospective buffer layer

In this paper, TCO (Transparent Conductive Oxide) incorporating ultrathin Ag intermediate film is proposed as a new buffer layer to enhance the efficiency of CIGS thin-film solar cells (TFSCs). In this regard, versatile multilayer thin-films based on ZnO/Ag/ZnO and ITO/Ag/ITO structures were deposited on glass using RF magnetron sputtering technique to determine the optoelectronic parameters of the multilayer structures. The elaborated samples were then characterized using SEM, EDS, XRD, and UV–Visible absorption spectroscopy techniques to investigate the structure morphological, optical, and electronic properties. The deposited multilayer thin-films showed amorphous-like structure and exhibited a broadband absorbance over the visible and even NIR spectrum ranges, indicating its potential application as alternative buffer layers for thin-film solar cells. In this context, TCO/Ag/TCO/CIGS solar cells have been numerically investigated using the deposited multilayer optoelectronic properties. It was revealed that the estimated efficiency of the ZnO/Ag/ZnO/CIGS-based solar cell could reach 18.5% with an open circuit voltage of 0.7 V and a short-circuit current density of 34.8 mA/cm². The performances exhibited by the investigated solar cell demonstrated that ZnO/Ag/ZnO multilayer can be used as an alternative to the conventional CdS buffer layer for developing high-performance non-toxic CIGS solar cells.     

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.     

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.     

Fine-diameter Si–B–C–N ceramic fibers enabled by polyborosilazanes with N–methyl pendant group

Given the superior thermal stability and electromagnetic features, continuous Si–B–(C)–N ceramic fibers have displayed great potential to fulfill the increasing demand for the high-temperature structural and functional materials. Manufacture of such ceramic fibers depends heavily upon the design of processable polymer precursors. Herein, a class of polyborosilazanes (PBSZs) with high spinnability were created through a facile one-pot synthesis. The trade-off between spinnability and ceramic yield of PBSZs was overcome by using heptamethyldisilazane and hexamethyldisilazane as the co-condensing agents to polymerize silicon and boron chloride monomers. The optimal PBSZs can fabricate continuous Si–B–C–N fibers with homogeneous diameter of 7.9 ± 0.5 μm and high ceramic yield of 80 wt%. Experimental characterization and quantum chemical computation revealed the mechanistic pictures of the impact of pendant groups on the polycondensation, melt spinning, and pyrolyzing process. These insights improve our understanding of spinnable pre-ceramic polymers for exploiting high-performance nitride ceramic fibers.