铵水间质子交换的再研究:不受扩散约束的化学交换

对铵盐水溶液中铵离子与水分子间的质子交换进行了再研究. 以核磁共振(NMR) 波谱学方法测定了不同pH值, 不同温度和含不同共存盐浓度的氯化铵水溶液中质子交换速率, 组分自扩散系数及NMR自旋晶格弛豫时间. 结果显示铵水间的质子交换并不受交换主体分子或离子自扩散的约束. 交换机理包括化学键和氢键的交换. 在溶液中, 水分子以氢键为桥 梁连接铵和其因水解而产生的碱性部分--氨. 在氢交换的过程中, 氨从水分子接受一个氢 成为铵, 同时另外一端的铵提供一个氢给水分子而变成氨, 或者一个氢从水分子转移到氨而同 时另外一个氢从铵转移到水. 在铵水质子交换的过程中没有净的电荷转移. 在低pH条件下, 由水解产生的氨的浓度降低, 亦即铵-水-氨复合物减少, 结果氢交换的可能性降低. 这解释了生物氢交换体系中的一种常见的在低pH值条件下氢交换变慢的现象.     

四元硫化物Cu2Zn(Ti,Zr, Hf)S4:一类新颖光伏材料

采用第一性原理电子结构方法研究了四价过渡金属Ti, Zr和Hf替代Cu₂ZnSnS₄(CZTS)中Sn原子以及Se替代S原子所得到的四元硫族化合物的电子结构、光学性质和晶体结构的稳定性. 实验上用Se替代CZTS中部分S得到的Cu₂ZnSnS_4-xSe_x(CZTSSe)作为光吸收材料, 可以进一步提高光伏效率. 我们计算表明用Se替代S后, CZTSe的价带顶明显下移, 并接近Cu(In, Ga) Se₂ (CIGS)价带顶位置. 与CZTSe的电子结构特征一样, Cu₂Zn(Ti, Zr, Hf)S₄四元硫化物的价带顶与母体材料CZTS相比也向低能移动, 并接近CIGS价带顶位置. 由于高光伏效率要求窗口材料ZnO、缓冲层材料和光吸收材料的价带顶和带隙满足一定的渐进的变化关系, 因此可以预见用Cu₂Zn(Ti, Zr, Hf)S₄作光吸收材料可以有效地提高甚至接近CIGS的光伏效率. 通过计算弹性常数和声子谱, 以及有限温度下第一性原理分子动力学模拟, 发现Cu₂Zn(Ti, Zr, Hf)S₄的结构稳定性与CZTS相近. 进一步计算Cu₂Zn(Ti, Zr, Hf)S₄与不同缓冲层间和窗口材料与缓冲层间的反射系数, 并讨论了ZnSe, In₂S₃, ZnS作为缓冲层材料和TiO₂作为窗口材料对光伏效率可能的影响.     

Nitrosonium complexes of 2,11‐dithia‐5,6,8,9‐tetramethyl[32](1,4)cyclophane: a combined experimental and theoretical study

¹H and ¹³C NMR studies and quantum chemical calculations show the interaction between 2,11‐dithia‐5,6,8,9‐tetramethyl[3₂](1,4)cyclophane and nitrosonium cation to result in the formation of π‐ and n‐complexes. According to DFT/B3LYP/6‐31G(2d,p) calculations, formation of nitrosonium complexes is a strongly exothermic process both in gas phase and in SO₂. Affinity of single‐charged complexes to NO⁺ is usually larger than that of double‐charged and triple‐charged complexes, affinity of all the charged complexes to nitrosonium cation in SO₂ being larger than that in gas phase. The π‐complex with nitrosonium cation coordinated to the methylated aromatic ring is the most stable with structural characteristics being close to those obtained by X‐ray diffraction for nitrosonium π‐complexes of hexamethylbenzene and other arenes. The N―O bond lengths in all the complexes are quite close to each other and larger than that in NO⁺ cation. The S―N bond length increases upon transition from single‐charged to double‐charged and polycharged complexes. Copyright © 2014 John Wiley & Sons, Ltd.     

Calibration method at the N K‐edge using interstitial nitrogen gas in solid‐state nitrogen‐containing inorganic compounds

The standard method of soft X‐ray beamline calibration at the N K‐edge uses the ν = 0 peak transition of gas‐phase N₂. Interstitial N₂ gas trapped or formed within widely available solid‐state ammonium‐ and amine‐containing salts can be used for this purpose, bypassing gas‐phase measurements. Evidence from non‐nitrogen‐containing compounds (KH₂PO₄) and from He‐purged ammonium salts suggest that production of N₂ gas is through beam‐induced decomposition. Compounds with nitrate or nitrite as anions produce coincident features and are not suitable for this calibration method.     

CuO nanoparticles supported on three‐dimensional nitrogen‐doped graphene as a promising catalyst for thermal decomposition of ammonium perchlorate

In the present work, CuO nanoparticles grown on three‐dimensional nitrogen‐doped graphene‐based frameworks (CuO@3D‐(N)GFs) were synthesized using a two‐step method. After the synthesis of three‐dimensional nitrogen‐doped graphene, CuO nanoparticles were deposited on it, by adding cupric acetate followed by thermal treatment. Different analysis methods were used to characterize the products. The as‐prepared nanocomposite was used as a promising catalyst for thermal decomposition of ammonium perchlorate (AP) as one of the most common oxidizer in composite propellants. Differential scanning calorimetry (DSC) and thermogravimetry analysis (TGA) techniques were used to investigate the thermal decomposition of ammonium perchlorate. According to the DSC/TGA, high temperature decomposition of AP decreased to 111 °C in the presence of 4% CuO@3D‐(N)GFs and the total heat release (ΔH) from decomposition of AP increased to 1893 J g^?1 which is much more than 590 J g^?1 for pure AP.     

基于季铵盐改性SiO2空心球的抗菌/减反增透双功能薄膜的制备和研究

兼具减反增透和抗菌性能的双功能薄膜在医疗健康领域具有很重要的应用前景.然而,关于此类薄膜的研究尚且屈指可数.本工作选取最长烷基链为C₁₈的季铵盐为抗菌剂,通过化学键合方式改性酸催化SiO₂溶胶液并与空心球纳米粒子溶胶液复合.然后,采用浸涂法制备出具备抗菌和减反增透双功能的薄膜.通过调节上述两种溶胶液的混合比例,对薄膜的光学性能进行了优化.其中,涂覆最优薄膜的玻璃基底在可见光区域内（400~800 nm）展现出优异的透光性能（T_max=99.2%,T_ave=98.6%）.该方法操作简单,无需经过高温热处理,易于大面积制备,具有潜在的应用前景.     

Antimicrobial modified hydroxyapatite composite dental bite by stereolithography

This study is aimed at the synthesis of antimicrobial hydroxyapatite (HAP)‐based composites for dental application by stereolithography (SLA). A micron‐sized commercial HAP was modified by methacrylate and quaternary ammonium salt, and, then, it was used in different amounts (namely 2.5, 5, and 10 wt%) as filler for a photocurable custom made resin for SLA. Thermal stability, microstructure, and particles size of the pristine (HAP) and modified HAP (mHAP) were evaluated by thermogravimetric analysis (TGA), X‐ray diffraction (XRD), and particle size analyser (CILAS). The suitability of each formulation for stereolithography process was assessed by measuring viscosity, degree of conversion (DC%) by Fourier transform infrared spectroscopy (FTIR), glass transition temperature, and thermal stability. Photo‐cured specimens for physical, mechanical, and antimicrobial testing were built by SLA. The flexural strength of the samples was measured using a 3‐point bending test method, and the fractured surface was analysed by scanning electron microscopy (SEM). The antimicrobial activity of samples was investigated against some standard microorganisms (Staphylococcus aureus, Escherichia coli, and Candida albicans), as representative Gram positive and Gram negative bacteria and fungus, respectively. The flexural strength increased with a filler content up to 5% and slightly decreased for higher content. SEM analysis confirmed the presence of uniformly distributed HAP. The incorporation of mHAP reduced the bacterial and fungal growth in dose‐dependent manner in comparison with the neat samples. Finally, a prototype of dental bite was built by SLA.     

Fullerene-C60 and crown ether doped on C60 sensors for high sensitive detection of alkali and alkaline earth cations

Fullerenes are effective acceptor components with high electron affinity for charge transfer. The significant influences of chemical adsorption of the cations on the electrical sensitivity of pristine C₆₀ and 15-(C₂H₄O)₅/C₆₀ nanocages could be the basis of new generation of electronic sensor design. The density functional theory calculation for alkali and alkaline earth cations detection by pristine C₆₀ and 15-(C₂H₄O)₅/C₆₀ nanocages are considered at B3LYP level of theory with 6–31 G(d) basis set. The quantum theory of atoms in molecules analysis have been performed to understand the nature of intermolecular interactions between the cations and nanocages. Also, the natural bond orbital analysis have been performed to assess the intermolecular interactions in detail. Furthermore, the frontier molecular orbital, energy gap, work function, electronegativity, number of transferred electron (∆N), dipole moment as well as the related chemical hardness and softness are investigated and calculated in this study. The results show that the adsorption of cations (M=Na⁺, K⁺, Mg²⁺ and Ca²⁺) are exothermic and the binding energy in pristine C₆₀ nanocage and 15-(C₂H₄O)₅/C₆₀ increases with respect to the cations charge. The results also denote a decrease in the energy gap and an increase in the electrical conductivity upon the adsorption process. In order to validate the obtained results, the density of state calculations are employed and presented in the end as well.     

N‐Methylimidazolidin‐4‐one organocatalysts: gas‐phase fragmentations of radical cations by experiment and theory

Electron ionisation mass spectra of N‐methylimidazolidin‐4‐one organocatalysts were studied by experimental and theoretical means. The molecular ions mostly undergo alpha cleavages of exocyclic substituents that leave the five‐membered ring intact. The type of substituent strongly dominates the appearance of the spectra. Fragmentation cascades are corroborated by metastable ion mass spectra. Quantum Chemistry Electron Ionisation Mass Spectra calculations correlate reasonably well with the experimental electron ionisation spectra and reveal mechanistic details of fragmentation pathways. The drawbacks and benefits of such calculations are discussed. Copyright © 2017 John Wiley & Sons, Ltd.     

Fast determination of codeine,orphenadrine, promethazine,scopolamine, tramadol,and paracetamol in pharmaceutical formulations by capillary electrophoresis

Paracetamol is an active ingredient commonly found in pharmaceutical formulations in combination with one of the following compounds: codeine, orphenadrine, promethazine, scopolamine, and tramadol. In this work, we propose a unique analytical method for determination of these active ingredients in pharmaceutical samples. The method is based on capillary electrophoresis with capacitively coupled contactless conductivity detection. The separation was achieved on a fused silica capillary (50 cm total length, 40 cm effective length, and 50 μm id) using an optimized background electrolyte composed of 20 mmol/L β‐alanine/4 mmol/L sodium chloride/4 μmol/L sodium hydroxide (pH 9.6). Each sample can be analyzed in a single run (≤2 min) and the limits of detection were 2.5, 0.62, 0.63, 2.5, 15, and 1.6 μmol/L for scopolamine, tramadol, orphenadrine, promethazine, codeine, and paracetamol, respectively. Recovery values for spiked samples were between 94 and 104%.