硅和锗纳米线的原子排布和电荷分布的密度泛函紧束缚方法研究

低维硅锗材料是制备纳米电子器件的重要候选材料，是研发高效率、低能耗和超高速新一代纳米电子器件的基础材料之一，有着潜在的应用价值。采用密度泛函紧束缚方法分别对厚度相同、宽度在0.272 nm~0.554 nm之间的硅纳米线和宽度在0.283 nm~0.567 nm之间的锗纳米线的原子排布和电荷分布进行了计算研究。硅、锗纳米线宽度的改变使原子排布，纳米线的原子间键长和键角发生明显改变。纳米线表层结构的改变对各层内的电荷分布产生重要影响。纳米线中各原子的电荷转移量与该原子在表层内的位置相关。纳米线的尺寸和表层内原子排列结构对体系的稳定性产生重要影响。     

密度泛函理论方法研究填料表面对聚合物摩擦化学的影响

采用超声分散法制备出氧化铝、高岭土、氧化硅/聚四氟乙烯复合材料, 使用线性往复摩擦磨损试验机对比三种复合材料的摩擦学性能. 结果表明 质量分数10%的氧化铝、高岭土能将聚四氟乙烯的磨损率降低约4个数量级, 而氧化硅仅能降低约3个数量级. 对金属对偶表面形成的转移膜的形貌和化学成分进行分析发现 氧化铝、高岭土/聚四氟乙烯在金属对偶面上形成了高度羧酸盐化的转移膜. 用密度泛函理论对三种填料表面上碳氟分子吸附过程进行模拟, 结果显示氧化铝、高岭土表面的路易斯酸性位点促进了碳氟分子的脱氟过程, 产生了更多的羧酸螯合物的中间产物; 氧化硅缺少路易斯酸性位点, 因此不能促进高度羧酸盐化的转移膜形成.     

Controlling thermomechanical behavior of semicrystalline hydrogenated polynorbornene through the cis- to trans-cyclopentylene ratio

Though polynorbornene synthesized by ring-opening metathesis polymerization has an intrinsically all-cis configuration of the cyclopentylene backbone rings, a fraction of these rings can be epimerized to the trans configuration during hydrogenation over suitable catalysts. By varying the method of hydrogenation, semicrystalline hydrogenated polynorbornenes (hPNs) with trans levels between 0 and 36% were obtained. With increasing trans content, the glass transition temperature, melting point, and enthalpy of melting decrease modestly. By contrast, the temperature at which the hPN crystal transitions into a rotationally disordered polymorph varies strongly with trans content, ranging from 126 °C (all-cis) to 71 °C at 27% trans; at trans contents of 34% and above, no rotationally-ordered phase is observed at any temperature. The room-temperature Young's modulus shows no dependence on trans content, while the yield stress drops by 20% at 1% trans content and slowly decreases further with additional epimerization. The temperature dependence of the Young's modulus differs for trans-containing versus all-cis polymers, while the temperature dependence of the yield stress is set by the polymorph type (rotationally ordered vs. disordered).     

High-efficient surface tailoring via reverse atom transfer radical polymerization and reversible addition-fragmentation chain-transfer polymerization in an aqueous system initiated by a monocenter redox pair

The commonly used multi-center initiation methods always lead to the formation of quantities of homopolymer in the surface tailoring based on reverse atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain-transfer (RAFT) polymerization. In this study, a monocenter redox pair constructed of silica bearing tert-butyl hydroperoxide groups and ascorbic acid (SiO₂-TBHP/AsAc) was applied to substitute the commonly used initiation method of R-supported RAFT grafting polymerization. All the propagating radicals were restricted on the surface of solid particles during the whole procedure theoretically, resulting in a higher grafting efficiency of 95.1% combined with the “controllable” feature at 10 h. This redox pair was also used to initiate the reverse ATRP in miniemulsion successfully with a grafting efficiency of 86.3% at 10 h. The grafting efficiency obtained under this monocenter initiation method was significantly higher than that of the frequently reported surface modification by reverse ATRP and RAFT polymerization. In addition, the high-efficient surface tailoring was traced and confirmed by nuclear magnetic resonance, Fourier transform infrared, X-ray photoelectron spectroscopy, thermogravimetric analysis, transmission electron microscopy, and other analysis tests. The advantage of this monocenter redox pair will open a new avenue for the potential “high-efficient” surface tailoring of various materials.     

Design consideration and modelling studies of ultrasound and ultraviolet combined approach for shelf-life enhancement of pine apple juice

Although both ultraviolet (UV) radiation and ultrasound (US) treatment have their capabilities in microbial inactivation, applying any one method alone may require a high dose for complete inactivation, which may affect the sensory and nutritional properties of pineapple juice. Hence, this study was intended to analyse and optimise the effect of combined US and UV treatments on microbial inactivation without affecting the selected quality parameters of pineapple juice. US treatment (33 kHz) was done at three different time intervals, viz. 10 min, 20 min and 30 min., after which, juice samples were subjected to UV treatment for 10 min at three UV dosage levels, viz. 1 J/cm², 1.3 J/cm², and 1.6 J/cm². The samples were evaluated for total colour difference, pH, total soluble solids (TSS), titrable acidity (TA), and ascorbic acid content; total bacterial count and total yeast count; and the standardization of process parameters was done using Response Surface Methodology and Artificial Neural Network. The results showed that the individual, as well as combined treatments, did not significantly impact the physicochemical properties while retaining the quality characteristics. It was observed that combined treatment resulted in 5 log cycle reduction in bacterial and yeast populations while the individual treatment failed. From the optimization studies, it was found that combined US and UV treatments with 22.95 min and1.577 J/cm² ensured a microbiologically safe product while retaining organoleptic quality close to that of fresh juice.     

The impact of insecticides containing deltamethrin and cyfluthrin on the composition of surface compounds in the larvae,females and males of Tenebrio molitor

This paper presents the effect of insecticides on the composition of the surface compounds of one of the most harmful insects, Tenebrio molitor, by analysis using GC–MS. As a result of the use of insecticides, the composition of the chemical compounds on the surface of insects changes, depending on the insecticides used. The most numerous groups of the marked compounds were fatty acids, alkanes, esters and sterols. The content of the identified compounds in the larvae increased at both 24 and 48 h after the application of insecticides, in comparison with the control samples. The content of identified compounds in the samples taken from the females increased 24, 48 and 72 h after the application of insecticides in comparison with the control samples. By contrast, in samples prepared from males, the content of identified compounds decreased 24 h after the application of insecticides, compared with the control samples. The highest content of chemical compounds was for fatty acids and alkanes after the use of insecticides. The content of fatty acids after the application of the insecticide with deltamethrin was 62.1 ± 3.3–466.9 ± 5.9 μg/g, and after the application of the insecticide with cyfluthrin was 49.9 ± 1.9–458.3 ± 4.2 μg/g. However, the content of alkanes after the use of deltamethrin was 115.6 ± 4.2–4672.0 ± 32.1 μg/g, and after the use of cyfluthrin was 189.4 ± 3.8–3975.0 ± 10.2 μg/g.     

Spectroscopic properties and bond dissociation energies of PbX,PbX±, PbX2 and PbX2± (X ​= ​F,Cl, Br,I)

Ab initio calculations have been performed to investigate some of the spectroscopic properties, like geometry, frequency, electron affinity, ionization potential and finally adiabatic bond dissociation energies (BDEs) of lead monohalides, lead dihalides and their ions viz. PbX, PbX^±, PbX₂, $\mathrm{P}\mathrm{b}{\mathrm{X}}_{\mathrm{2}}^{\pm }$ (X ?= ?F, Cl, Br, I) in their ground state at the QCISD(T)//MP2 level of theory using correlation consistent basis sets. For the validation of MP2 optimized geometry and frequency, we further obtained geometry and frequency of all the neutral and ionic systems using QCISD(T) method with the same basis sets. The BDEs of PbX₂ molecules are calculated using the BDEs of $\mathrm{P}\mathrm{b}{\mathrm{X}}_{\mathrm{2}}^{\pm }$ ions and taking ionization potential and electron affinity of various systems. The calculated values are found in good agreement with the available data. Most of the data for ionic systems are reported first time in literature.     

Surface Engineering of Conjugated Polybenzothiadiazoles and Integration with Cobalt Oxides for Photocatalytic Water Oxidation

Conjugated polymers feature promising structure and properties for photocatalytic water splitting. Herein, a hydrolysis strategy was demonstrated to rationally modulate the surface hydrophilicity and band structures of conjugated poly-benzothiadiazoles. High hydrophilicity not only enhances the dispersions of polymeric solids in an aqueous solution but also reduces the absorption energy of water molecules. Besides, both theoretical and experimental results reveal that a more positive valence band potential is generated, which contributes to enhancing the photocatalytic water oxidation performance. Accordingly, the surface-modified conjugated polymers show largely promoted photocatalytic water oxidation activities by deposition of cobalt oxides as cocatalysts.