Experimental and theoretical vibrational study of 2,2,2-trifluoroethyl trifluoromethanesulfonate, CF3SO2OCH2CF3

The infrared spectra of 2,2,2-trifluoroethyl trifluoromethanesulfonate (CF3SO2OCH2CF3) were obtained in the gaseous, liquid and solid states as well as the Raman spectrum of the liquid. Quantum chemistry calculations using the density functional theory were used to predict the most stable geometry and conformation of the studied molecule. Subsequently, the harmonic vibrational frequencies and force field were calculated. An assignment of the observed spectral features made after comparison with the related molecules and with the predicted frequencies was used as the basis of a scaling of the original force field in order to reproduce as well as possible the experimental frequencies. With this purpose a set of scale factors was calculated by a least square procedure, leading to a final root mean square deviation (RMSD) of 9.7 cm(-1).     

超临界CO2-丙烷混合物管内传热特性数值研究

采用SST k-w湍流模型对超临界CO₂/丙烷混合工质水平管内的传热特性进行数值模拟研究。管径d=4 mm,加热段L₂=800 mm;混合工质浓度配比为100/0、95/5、90/10、85/15、80/20、75/25;质量流速为150～250 kg·m^?2·s^?1;热流密度为30～40 kW·m^?2,入口温度293 K,入口压力7.5～30 MPa。随着丙烷浓度的增加,CO₂/丙烷二元混合工质的临界压力降低,临界温度升高,丙烷浓度从5%增加到25%,换热系数峰值降低6.19%～31.45%,但增加丙烷浓度可提高拟临界温度后的换热效果。P=7.5～8.5 MPa,换热系数有明显峰值;P=20～30 MPa,换热系数变化规律无明显峰值,并随压力的升高而减小。混合工质的换热系数随质量流速的增大而增大。同一流体温度所对应的换热系数,随着热流密度的增加而减小。     

Al纳米线不同晶向力学行为和变形机制的模拟

采用分子动力学模拟计算方法,考察具有较高层错能的Al纳米线沿不同晶向的力学行为和变形机制。在相同计算条件下与具有较低层错能的Ni、Cu、Au和Ag等FCC金属纳米线进行比较。结果表明：在力学行为方面,Al纳米线的弹性模量呈现明显的结构各向异性,满足E_[111] > E_[110] > E_[100]的关系,这一关系在FCC金属纳米线中普遍成立;Al纳米线的屈服应力随晶向呈现σ_y[100] > σ_y[111] > σ_y[110]的关系,这一关系在具有较低层错能的FCC金属纳米线中不具有普遍性,这与体系中位错形成机制密切相关。根据拉伸变形过程微观结构的演变规律,阐明Al纳米线不同晶向的变形机制,并与具有较低层错能的Ni、Cu、Au和Ag等FCC金属纳米线的变形机制进行比较。结果表明,对于尺度较小的高层错能Al纳米线,Schmid因子和广义层错能均难以准确预测其变形机制。     

亚临界CO2冷库制冷系统性能实验研究

为研究亚临界CO₂冷库制冷系统性能,建立制冷系统压缩机数学模型,分析压缩机吸气温度对输气量、容积效率等性能参数的影响。搭建亚临界CO₂冷库制冷系统试验台,分析储液器出口气、液质量比对系统性能的影响。结果表明,当吸气压力恒定时,吸气温度升高,压缩机实际输气量及容积效率均有小幅度提升。随着储液器出口气、液质量比增大,系统制冷量及压缩机功耗均升高,而系统COP呈先增大后减小的趋势。在气、液质量比为0.16时,COP达到最大值为1.95。     

Photoelectrochemical activity of ZnO:Ag/rGO photo-anodes synthesized by two-steps sol-gel method

This work investigated the influence of silver plasmon and reduced graphene oxide (rGO) on the photoelectrochemical performance (PEC) of ZnO thin films synthesized by the sol-gel method. The physicochemical properties of the obtained photo-anodes were systematically studied by using several characterization techniques. The x-ray diffraction analysis showed that all samples presented hexagonal wurtzite structure with a polycrystalline nature. Raman and energy dispersive x-ray (EDX) studies confirmed the existence of both Ag and rGO in ZnO:Ag/rGO thin films. The estimated grain size obtained from scanning electron microscopy (SEM) analysis decreased with Ag doping, then increased to a maximum value after rGO addition. The UV-vis transmission spectra of the as-prepared ZnO:Ag and ZnO:Ag/rGO thin films have shown a reduction in the visible range with a redshift at the absorption edges. The bandgaps were estimated to be around 3.17 eV, 2.7 eV, and 2.52 eV for ZnO, ZnO:Ag, and ZnO:Ag/rGO, respectively. Moreover, the electrical measurements revealed that the charge exchange processes were enhanced at the ZnO:Ag/rGO/electrolyte interface, accompanied by an increase in the (PEC) performance compared to ZnO and ZnO:Ag photo-anodes. Consequently, the photocurrent density of ZnO:Ag/rGO (0.2 mA·cm^-2) was around 4 and 2.22 times higher than photo-anodes based on undoped ZnO (0.05 mA·cm^-2) and ZnO:Ag (0.09 mA·cm^-2), respectively. Finally, from the flat band potential and donor density, deduced from the Mott-Schottky, it was clear that all the samples were n-type semiconductors with the highest carrier density for the ZnO:Ag/rGO photo-anode.     

Influences of nanoparticles and chain length on thermodynamic and electrical behavior of fluorine liquid crystals

Hydrogen-bonded polar nematic liquid crystal series with the general formula nOBAF (n = 7—12) is studied. The mesomorphic characterization is demonstrated through differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The complexes with short alkyl chains (n=7, 8) present a wide nematic range and monotropic smectic F mesophase, whereas the longer alkyl chain (n=10—12) analogues show high melting and low clearing mesomorphic liquid crystals. The thermal range of the mesophase and the birefringence increase with chain length decreasing. Furthermore, the effect of the nanoparticles (LiNbO₃) on the thermal and the electrical behavior of 8OBAF are investigated. The presence of LiNbO₃ nanoparticles increases the conductivity and reduces the resistivity of the complex.     

陶瓷和金属微波烧结在线实验及微观机理分析

为研究陶瓷和金属微波烧结时的微观演化机理,从而为优化不同材料的烧结过程提供依据,本文采用同步辐射技术对陶瓷(SiC)和金属(Al)的微波烧结微结构演化过程进行实时、无损的观测,并结合有限元模拟分析两者的微结构演化特征及微观机理。通过滤波反投影等数字图像处理技术得到烧结过程中样品内部的二维、三维重建图像,清晰地观察到SiC和Al在颗粒表面和界面演化上存在差异。定量地统计了陶瓷和金属烧结颈相对尺寸与时间的双对数关系,并与陶瓷和金属双球模型的微波烧结模拟结果进行了对比。运用模拟分别对实验中的烧结颈和微观形貌演化进行分析,得出结论:陶瓷和金属微波烧结时的加热机制不同,分别为整体介质损耗加热和表面涡流损耗加热。陶瓷的整体加热将会在材料内部特别是界面产生较高的温度,而金属的表面加热使颗粒表面温度高于界面。由相应的加热机制产生的温度分布差异,将会对材料的物质扩散过程产生不同程度的影响,进而产生不同的微结构。     

Asymmetric allylic alkylation of acyclic allylic ethers with organolithium reagents

A highly efficient, regio- and enantioselective Cu(I) /phosphoramidite-catalyzed asymmetric allylic alkylation of allyl ethers with organolithium reagents is reported. The use of organolithium reagents is essential for this catalytic C?C bond formation due to their compatibility with different Lewis acids. The versatility of allylic ethers under the copper-catalyzed reaction conditions with organolithium reagents is demonstrated in the shortest synthesis of (S)-Arundic acid.     

Quadracyclic adenine: a non-perturbing fluorescent adenine analogue

Fluorescent-base analogues (FBAs) comprise a group of increasingly important molecules for the investigation of nucleic acid structure and dynamics as well as of interactions between nucleic acids and other molecules. Here, we report on the synthesis, detailed spectroscopic characterisation and base-pairing properties of a new environment-sensitive fluorescent adenine analogue, quadracyclic adenine (qA). After developing an efficient route of synthesis for the phosphoramidite of qA it was incorporated into DNA in high yield by using standard solid-phase synthesis procedures. In DNA qA serves as an adenine analogue that preserves the B-form and, in contrast to most currently available FBAs, maintains or even increases the stability of the duplex. We demonstrate that, unlike fluorescent adenine analogues, such as the most commonly used one, 2-aminopurine, and the recently developed triazole adenine, qA shows highly specific base-pairing with thymine. Moreover, qA has an absorption band outside the absorption of the natural nucleobases (>300?nm) and can thus be selectively excited. Upon excitation the qA monomer displays a fluorescence quantum yield of 6.8?% with an emission maximum at 456?nm. More importantly, upon incorporation into DNA the fluorescence of qA is significantly less quenched than most FBAs. This results in quantum yields that in some sequences reach values that are up to fourfold higher than maximum values reported for 2-aminopurine. To facilitate future utilisation of qA in biochemical and biophysical studies we investigated its fluorescence properties in greater detail and resolved its absorption band outside the DNA absorption region into distinct transition dipole moments. In conclusion, the unique combination of properties of qA make it a promising alternative to current fluorescent adenine analogues for future detailed studies of nucleic acid-containing systems.     

Analysis of urinary oligosaccharides in lysosomal storage disorders by capillary high-performance anion-exchange chromatography–mass spectrometry

Many lysosomal storage diseases are characterized by an increased urinary excretion of glycoconjugates and oligosaccharides that are characteristic for the underlying enzymatic defect. Here, we have used capillary high-performance anion-exchange chromatography (HPAEC) hyphenated to mass spectrometry to analyze free oligosaccharides from urine samples of patients suffering from the lysosomal storage disorders fucosidosis, α-mannosidosis, G(M1)-gangliosidosis, G(M2)-gangliosidosis, and sialidosis. Glycan fingerprints were registered, and the patterns of accumulated oligosaccharides were found to reflect the specific blockages of the catabolic pathway. Our analytical approach allowed structural analysis of the excreted oligosaccharides and revealed several previously unpublished oligosaccharides. In conclusion, using online coupling of HPAEC with mass spectrometric detection, our study provides characteristic urinary oligosaccharide fingerprints with diagnostic potential for lysosomal storage disorders.