Conformational effects of 1,5,9-substitution in symmetric bicyclo[3.3.1]nonane analogues

The high-level ab initio calculations on several derivatives of bicyclo[3.3.1]nonane, 1-aza- and 1,5-diazabicyclo[3.3.1]-nonanes show the ‘double chair’ (CC) conformer as optimal for all of them, dominating over the ‘boat–chair’ (BC) form. Conformational effects of several substitution types involving positions 1, 5 and 9 are quantified, and their values are found rather transferable.     

Entire large solutions of semilinear equations involving the fractional Laplacian

We investigate the existence and nonexistence of positive entire large solutions of a class of semilinear equations involving the fractional Laplacian. Sharp lower and upper bounds of the minimal solution, if it exists, are also given.     

塑料薄膜撕扯实验在聚合物教学中的应用及讨论

结合新课标要求,揭示塑料薄膜撕扯实验在聚合物教学中的重要性、必要性。通过教学片段设计,发展学生“宏观辨识与微观探析、证据推理与模型认知”化学学科核心素养,并让学生认识物质的性能不仅取决于结构,也取决于生产工艺。并对人教版初、高中化学教材和教参中相关问题展开讨论和解释,以期更好地服务教学。     

Attraction behaviour of Anagrus nilaparvatae to remote lemongrass (Cymbopogon distans) oil and its volatile compounds

Utilisation of Anagrus nilaparvatae is a promising and effective method for planthoppers manipulation. Twenty-seven components of remote lemongrass (Cymbopogon distans) oil were identified by GC/MS and nine volatiles were selected for behavioural experiments. In this study, we noted that the remote lemongrass oil was attractive to female A. nilaparvatae at concentrations of 0.1 and 1 mg/L. α-Pinene, β-pinene, eucalyptol, carveol and D-carvone attracted female wasps in the dose-dependent bioassays. Blend 1 (a mixture of eucalyptol, D-carvone, carveol, α-pinene, and β-pinene with ratios of remote lemongrass oil volatiles of 625:80:11:5:3) attracted female wasps at 10 mg/L, while blend 2 (a mixture of the same five volatiles at the same loading ratio) attracted them at 0.1 and 1 mg/L. These results suggested that plant essential oils could be attractants for natural enemies to control pests. The ratios of volatiles in the mixtures affect the attractiveness of the synthetic mixtures.     

High-energy x-ray diffraction study on phase transition asymmetry of plastic crystal neopentylglycol

As a prototype material of colossal barocaloric effects, neopentylglycol is investigated by combining high-precision differential scanning calorimetric measurement and high-energy x-ray diffraction measurement. The diffraction data at constant temperatures indicate a first-order phase transition with thermal hysteresis as well as the phase transition asymmetry, specifically, the phase transition is completed faster at cooling than at heating. The analysis of resulting pair distribution function confirms the intermolecular disorder in the high-temperature phase. The phase transition asymmetry is quantitatively characterized by time-resolved x-ray diffraction, which is in agreement with the thermal measurement. Also, such an asymmetry is observed to be suppressed at high pressures.     

Crystallographic and microstructural aspects of the superconductor YBa2Cu3O7-y —an overview

Crystal structures and structural inhomogeneities observed in YBa₂Cu₃O_7-y are reviewed. It is brought out that a proper understanding of the nature of the structural inhomogeneities is essential for exploiting the technological potential of this material. The need for an adequate characterization of specimens used for experiments is emphasized. Practical implications of the ferroelastic nature of the material are discussed.     

Synthesis and investigation of dual pH‐ and temperature‐responsive behaviour of poly[2‐(dimethylamino)ethyl methacrylate]‐grafted gold nanoparticles

Gold nanoparticles (AuNPs) were synthesized by reduction of chloroauric acid (HAuCl₄) aqueous solution with hydrazine monohydrate. The AuNPs were immediately treated with cysteamine to obtain amine‐functionalized nanoparticles (Au‐NH₂). The reaction of Au‐NH₂ with epichlorohydrin and subsequent treatment with sodium hydroxide gave epoxidized AuNPs (Au‐EP). Then, thiol‐capped AuNPs (Au‐SH) were synthesized by reaction of Au‐EP with cysteamine. A ‘grafting to’ approach was utilized to graft bromine‐terminated poly(N ,N ′‐dimethylaminoethyl methacrylate), synthesized via aqueous atom transfer radical polymerization, with various molecular weights (6280, 25 800, 64 200 and 87 600 g mol⁻¹) onto Au‐SH to obtain Au‐P1, Au‐P2, Au‐P3 and Au‐P4 samples, respectively. All samples were exposed to temperature and pH variations, and Z‐average diameter was monitored using dynamic light scattering. According to the results, polymer‐grafted nanoparticles collapsed at lower temperatures with increasing solution pH for all molecular weight ranges due to deprotonation of tertiary amine groups. However, higher molecular weight polymers were more sensitive to pH variation especially in alkaline media. Also, a high degree of agglomeration was observed for Au‐P4 nanoparticles in alkaline media on increasing the temperature to 55 and 65 °C.     

Behaviour of ‘free-standing’ hollow Au nanocages at finite temperatures: a BOMD study

Finite-temperature behaviour of a hollow golden cage (HGC) plays a crucialrole in its potential applications as a catalyst, drug delivery agent, contrasting agent and so on. This physico-chemical property of HGCs is not well understood so far. In that context, Born–Oppenheimer molecular dynamics (BOMD) simulations are performed on a well-known ‘free-standing’ HGC. The cluster considered in this study is the ground state Au₁₈ cluster (a cage with a diameter of about >5.5 Å). The results thus obtained are compared with the BOMD simulation results reported earlier on Au₃₂ icosahedron cage, a conformation with a diameter of nearly. The sphericity of both the clusters is studied using a shape deformation parameter as a function of time and temperature. These results are supplemented by radial distribution function at various temperatures. The observations and analysis of results indicate that, both the clusters retain an HGC conformation from 300 to 400 K, admitting structural fluxionality by the Au₁₈ cluster. Remarkably, the Au₁₈ cluster is able to maintain its hollowness and sphericity up to a high temperature of 1000 K. Underlying structural and electronic properties influencing the individualistic behaviour of cages are highlighted. Composition of the frontier molecular orbitals and the charge distribution play a crucial role in the finite-temperature behaviour of the Au cages. The conclusions are supplemented by supporting calculations on another degenerate ground state Au₁₈ hollow cage and a well-known pyramidal Au₁₈ cage at 300 and 400 K.     

Polymeric Electron Carriers

Polymers containing 1,4-dihydronicotinamide (P-NAH) alloxan (P-A), and viologen (P-V²⁺) moieties were synthesized and characterized. P-NAH reduced various organic substances such as lipoic acid, alloxan, and viologens and also immobilized quinone mediated by alloxan. P-A was reduced to the polymer-bearing alloxan radical and the dialuric acid structure without crosslinks by one- and two-electron reduction, respectively, and P-A also mediated the redox reaction occurring between aqueous and organic (water-immiscible) layers. P-V²⁺ was converted to the stable viologen radical reversibly by one-electron reduction. Electric potentials and currents on photo-reduction of P-V²⁺ and catalytic behavior of P-V²⁺ in the reduction of carbonyl compounds were examined.     

钒液流电池用隔离膜研究进展

钒液流电池是近年来发展最为迅猛的储能电池之一。隔膜作为钒电池的重要组成部分直接关系到钒电池的转化储能效率和使用寿命。本文综述了近年来钒电池用隔离膜的发展现状。全氟磺酸质子交换膜(Nafion膜)作为当前使用最为广泛的隔膜,从传导机理、交换机理和表面涂覆、交联、复合等表面改性技术方面入手做了深入的研究,并对比分析了各种改性方法的优缺点。对磺化的特种工程塑料为主的非氟耐热型质子交换膜和功能化的聚烯烃隔膜在钒电池中的当前进展做了全面总结,并对钒液流电池用电池隔膜的发展方向做了展望。