铌酸锂晶体性能的组成依赖性(英文)

总结了铌酸锂晶体的各项性能指标,显示了其对晶体实际组成的强烈依赖性.利用化学键模型定量地解释了这种依赖性产生的根源,从而说明了制约该晶体性能提高的关键因素是晶体结构中的缺陷控制.     

Adsorption of organic substances on broken clay surfaces: a quantum chemical study

Hydrogen-bonded interactions between local defect structures on broken clay surfaces modeled as molecular clusters and the organic molecules acetic acid, acetate, and N-methylacetamide (NMA) have been investigated. Density functional theory and polarized basis sets have been used for the computation of optimized interaction complexes and formation energies. The activity of the defect structures has been characterized as physical or chemical in terms of the strength of the hydrogen bonds formed. Chemical defects lead to significantly enhanced interactions with stronger hydrogen bonds and larger elongation of OH bonds in comparison to the physical defects. The type of interaction with the defect structure significantly influences the planarity of the model peptide bond in NMA. Both cases, enhancement of the planarity by increase of the CN double bond character and strong deviations from planarity, are observed.     

Defect‐Controlled Electronic Properties in AZn2Sb2 Zintl Phases

Experimentally, AZn₂Sb₂ samples (A=Ca, Sr, Eu, Yb) are found to have large charge carrier concentrations that increase with increasing electronegativity of A. Using density functional theory (DFT) calculations, we show that this trend can be explained by stable cation vacancies and the corresponding finite phase width in A_1?xZn₂Sb₂ compounds.     

Counting of Oxygen Defects versus Metal Surface Sites in Methanol Synthesis Catalysts by Different Probe Molecules

Different surface sites of solid catalysts are usually quantified by dedicated chemisorption techniques from the adsorption capacity of probe molecules, assuming they specifically react with unique sites. In case of methanol synthesis catalysts, the Cu surface area is one of the crucial parameters in catalyst design and was for over 25 years commonly determined using diluted N₂O. To disentangle the influence of the catalyst components, different model catalysts were prepared and characterized using N₂O, temperature programmed desorption of H₂, and kinetic experiments. The presence of ZnO dramatically influences the N₂O measurements. This effect can be explained by the presence of oxygen defect sites that are generated at the Cu‐ZnO interface and can be used to easily quantify the intensity of Cu‐Zn interaction. N₂O in fact probes the Cu surface plus the oxygen vacancies, whereas the exposed Cu surface area can be accurately determined by H₂.     

扶手椅型缺陷硫化钼纳米带电子性质的第一性原理计算

基于密度泛函理论的第一性原理计算,研究了含空位缺陷的扶手椅型二硫化钼纳米带的电子性质.发现缺陷会导致纳米带结构稳定性降低,单空位钼缺陷和三空位缺陷使得纳米带从半导体变成金属性,而单空位硫缺陷和两种双空位缺陷仅减小纳米带的带隙;电子态密度和能带的本征态表明缺陷纳米带费米能级附近的杂质态主要是缺陷态的贡献.研究了四类半导体性质的纳米带带隙与宽度的关系,对于完整的纳米带,带隙随宽度以3为周期振荡变化;而引入空位缺陷后,纳米带的带隙振荡不再具有周期且振荡幅度变小.同时发现,当缺陷的浓度变小后,缺陷仅使纳米带的带隙减小,不会使其变为金属性.这些结果有望打开其在新型纳电子器件中的应用潜能.     

液态丙烯腈低聚物修复聚丙烯腈基碳纤维微孔缺陷

提出一种全新的缺陷修复的方法,即将聚丙烯腈基(PAN)碳纤维T300在液态丙烯腈低聚物(LAN)中浸渍后,再进行预氧化和碳化热处理,可以将T300的拉伸强度提高25%.应用二维小角X射线散射(SAXS)法可以计算出LAN修复缺陷前后T300微孔缺陷的长度(L)、横截面尺寸(lp)、取向角(Beq)、相对体积(Vrel)的变化,结果表明碳纤维的拉伸性能越好,微孔的长度、取向角、相对体积含量越小.T300拉伸性能的提高是由于缺陷修复的结果.应用BET比表面积法、扫描电子显微镜(SEM)表征LAN修复缺陷前后T300的比表面积以及表面形貌的变化,结果表明,T300在LAN中浸渍并经过预氧化和碳化热处理,比表面积变小,表面缺陷明显减少.进一步验证LAN对碳纤维中的微孔缺陷具有修复作用.应用X射线光电子能谱(XPS)法表征LAN修复前后T300表面化学成分的变化,结果表明,LAN修复后含氧官能团(C―OH,C=O,HO―C=O)显著增加,有利于增强碳纤维与树脂基体之间的相互作用,从而提高碳纤维的力学性能.     

Biodegradable thermogel as culture matrix of bone marrow mesenchymal stem cells for potential cartilage tissue engineering

Poly（lactide-co-glycolide）-poly（ethylene glycol）-poly（lactide-co-glycolide）（PLGA-PEG-PLGA） triblock copolymer was synthesized through the ring-opening polymerization of LA and GA with PEG as macroinitiator and stannous octoate as catalyst. The amphiphilic copolymer self-assembled into micelles in aqueous solutions, and formed hydrogels as the increase of temperature at relatively high concentrations（〉 15 wt%）. The favorable degradability of the hydrogel was confirmed by in vitro and in vivo degradation experiments. The good cellular and tissular compatibilities of the thermogel were demonstrated. The excellent adhesion and proliferation of bone marrow mesenchymal stem cells endowed PLGA-PEGPLGA thermogelling hydrogel with fascinating prospect for cartilage tissue engineering.     

Morphology and mechanical behavior of isotactic polypropylene with different stereo‐defect distribution in injection molding

Large amount of work has been published on the isotacticity–properties relationship of isotactic polypropylene (iPP). However, the stereo‐defect distribution dependence of morphology and mechanical properties of iPP injection molding samples is still not clear. In this study, two different isotactic polypropylene (iPP) resins (PP‐A and PP‐B) with similar average isotacticity but different stereo‐defect distribution were selected to investigate the morphology evolution and mechanical properties (tensile and notching) of their injection molding samples using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), 2D wide angle X‐ray diffraction (2D‐WAXD), and scanning electron microscope (SEM). The results of DMA showed that the molecular movement ability of PP‐A (with less uniform distribution of stereo‐defect) was stronger than that of PP‐B, meanwhile the analysis of DSC and SEM suggested that after injection molding, smaller spherullites, and crystals with higher perfection had formed in the specimens of PP‐A. The resulting of tensile properties of PP‐A were found to be better than that of PP‐B. The results of morphology evolution by SEM observation and 2D‐WAXD showed that PP‐A is more likely to occur interspherulite deformation and can disperse the tensile stress more efficiently, and therefore, its crystal structure can withstand a greater force when tensile stress is applied. On the other hand, PP‐B has larger spherulites and boundaries, and low perfection of lamellaes, and the intraspherulte deformation tend to take place. It is easier for the crystal of PP‐B to be broken up and reoriented along the tensile direction. Copyright © 2014 John Wiley & Sons, Ltd.     

The application of high-resolution mass spectrometry-based data-mining tools in tandem to metabolite profiling of a triple drug combination in humans

Patients are usually exposed to multiple drugs, and metabolite profiling of each drug in complex biological matrices is a big challenge. This study presented a new application of an improved high resolution mass spectrometry (HRMS)-based data-mining tools in tandem to fast and comprehensive metabolite identification of combination drugs in human. The model drug combination was metronidazole-pantoprazole-clarithromycin (MET-PAN-CLAR), which is widely used in clinic to treat ulcers caused by Helicobacter pylori. First, mass defect filter (MDF), as a targeted data processing tool, was able to recover all relevant metabolites of MET-PAN-CLAR in human plasma and urine from the full-scan MS dataset when appropriate MDF templates for each drug were defined. Second, the accurate mass-based background subtraction (BS), as an untargeted data-mining tool, worked effectively except for several trace metabolites, which were buried in the remaining background signals. Third, an integrated strategy, i.e., untargeted BS followed by improved MDF, was effective for metabolite identification of MET-PAN-CLAR. Most metabolites except for trace ones were found in the first step of BS-processed datasets, and the results led to the setup of appropriate metabolite MDF template for the subsequent MDF data processing. Trace metabolites were further recovered by MDF, which used both common MDF templates and the novel metabolite-based MDF templates. As a result, a total of 44 metabolites or related components were found for MET-PAN-CLAR in human plasma and urine using the integrated strategy. New metabolic pathways such as N-glucuronidation of PAN and dehydrogenation of CLAR were found. This study demonstrated that the combination of accurate mass-based multiple data-mining techniques in tandem, i.e., untargeted background subtraction followed by targeted mass defect filtering, can be a valuable tool for rapid metabolite profiling of combination drugs in vivo.     

Incorporation of graphene oxide nanosheets into boronate‐functionalized polymeric monolith to enhance the electrochromatographic separation of small molecules

Graphene oxide (GO) nanosheets were incorporated into an organic polymer monolith containing 3‐acrylamidophenylboronic acid (AAPBA) and pentaerythritol triacrylate (PETA) to form a novel monolithic stationary phase for CEC. The effects of the mass ratio of AAPBA/PETA, the amount of GO, and the volume of porogen on the morphology, permeability and pore properties of the prepared poly(AAPBA‐GO‐PETA) monoliths were investigated. A series of test compounds including amides, alkylbenzenes, polycyclic aromatics, phenols, and anilines were used to evaluate and compare the separation performances of the poly(AAPBA‐GO‐PETA) and the parent poly(AAPBA‐co‐PETA) monoliths. The results indicated that incorporation of GO into monolithic column exhibited much higher resolutions (>1.5) and column efficiency (62 000 ～ 110 000 plates/m for toluene, DMF, formamide, and thiourea) than the poly(AAPBA‐co‐PETA). The successful application in isocratic separation of peptides suggests the potential of the GO incorporated monolithic column in complex sample analysis. In addition, the reproducibility and stability of the prepared poly(AAPBA‐GO‐PETA) monolith was assessed. The run‐to‐run, column‐to‐column and batch‐to‐batch reproducibilities of this monolith for alkylbenzenes’ retention were satisfactory with the RSDs less than 1.8% (n = 5), 3.7% and 5.6% (n = 3), respectively, indicating the effectiveness and practicability of the proposed method.