液相色谱-电喷雾质谱法分析脂肪醇聚氧乙烯醚硫酸钠

采用电喷雾质谱(ESI/MS)技术建立了脂肪醇聚氧乙烯醚硫酸钠(AES)的烷基碳链分布、乙氧基分布及平均EO数、平均相对分子质量的测定方法;采用液相色谱-电喷雾质谱(LC-ESI/MS)测定了AES中的游离十二烷基硫酸钠(SDS)的含量。将本方法应用于实际样品的测定,并与核磁共振法测得的平均EO数进行比较,二者的测定结果相当吻合,从而验证了本法的可靠性。     

Apparent Molar Volume, Heat Capacity, and Conductance of Lithium Bis(trifluoromethylsulfone)imide in Glymes and Other Aprotic Solvents

Lithium bis(trifluoromethylsulfone)imide (LiTFSI) is a promising electrolyte for high-energy lithium batteries due to its high solubility in most solvents and electrochemical stability. To characterize this electrolyte in solution, its conductance and apparent molar volume and heat capacity were measured over a wide range of concentration in glymes, tetraethylsulfamide (TESA), acetonitrile, -butyrolactone, and propylene carbonate at 25°C and were compared with those of LiClO₄ in the same solvents. The glymes or n(ethylene glycol) dimethyl ethers (nEGDME), which have the chemical structure CH₃–O–(CH₂–CH₂–O) _n –CH₃ for n = 1 to 4, are particularly interesting since they are electrochemically stable, have a good redox window, and are analogs of the polyethylene oxides used in polymer-electrolyte batteries. TESA is a good plasticizer for polymer-electrolyte batteries. Whenever required, the following properties of the pure solvents were measured: compressibilities, expansibilities, temperature and pressure dependences of the dielectric constant, acceptor number, and donor number. These data were used in particular to calculate the limiting Debye-Hückel parameters for volumes and heat capacities. The infinite dilution properties of LiTFSI are quite similar to those of other lithium salts. At low concentrations, LiTFSI is strongly associated in the glymes and moderately associated in TESA. At intermediate concentrations, the thermodynamic data suggests that a stable solvate of LiTFSI in EGDME exists in the solution state. At high concentrations, the thermodynamic properties of the two lithium salts approach those of the molten salts. These salts have a reasonably high specific conductivity in most of the solvents. This suggests that the conductance of ions at high concentration in solvents of low dielectric constant is due to a charge transfer process rather than to the migration of free ions.     

A simple line shape technique for electron number density diagnostics of helium and helium-seeded plasmas

The results of an experimental study of the He I 447.1 nm line and its forbidden component at high electron number density are presented and compared with profiles calculated using computer simulation method. Michelson interferometer at 632.8 nm was used to measure plasma electron number density in the range (1–7) × 10²³ m^− 3 while electron temperatures for the same experimental conditions in the range of 25 000 K to 35 000 K were determined using several spectroscopic techniques. The agreement of experimental overall line shape with computer simulation results is within 10% of what is well within theoretical and experimental uncertainty. This favorable comparison enabled the development of a simple approximate formula for the evaluation of electron number density from the measurement of wavelength separation between peaks of allowed and forbidden lines. This technique of plasma diagnostics is not sensitive to the presence of self-absorption of strong He I allowed line. The derivation of approximate formula with estimated accuracy of 15% was followed by detailed comparison with other experimental and theoretical data.     

Light‐Driven Coordination‐Induced Spin‐State Switching: Rational Design of Photodissociable Ligands

The bistability of spin states (e.g., spin crossover) in bulk materials is well investigated and understood. We recently extended spin‐state switching to isolated molecules at room temperature (light‐driven coordination‐induced spin‐state switching, or LD‐CISSS). Whereas bistability and hysteresis in conventional spin‐crossover materials are caused by cooperative effects in the crystal lattice, spin switching in LD‐CISSS is achieved by reversibly changing the coordination number of a metal complex by means of a photochromic ligand that binds in one configuration but dissociates in the other form. We present mathematical proof that the maximum efficiency in property switching by such a photodissociable ligand (PDL) is only dependent on the ratio of the association constants of both configurations. Rational design by using DFT calculations was applied to develop a photoswitchable ligand with a high switching efficiency. The starting point was a nickel–porphyrin as the transition‐metal complex and 3‐phenylazopyridine as the photodissociable ligand. Calculations and experiments were performed in two iterative steps to find a substitution pattern at the phenylazopyridine ligand that provided optimum performance. Following this strategy, we synthesized an improved photodissociable ligand that binds to the Ni–porphyrin with an association constant that is 5.36 times higher in its trans form than in the cis form. The switching efficiency between the diamagnetic and paramagnetic state is efficient as well (72 % paramagnetic Ni–porphyrin after irradiation at 365 nm, 32 % paramagnetic species after irradiation at 440 nm). Potential applications arise from the fact that the LD‐CISSS approach for the first time allows reversible switching of the magnetic susceptibility of a homogeneous solution. Photoswitchable contrast agents for magnetic resonance imaging and light‐controlled magnetic levitation are conceivable applications.     

Effect of dispersion on the diffusion zone in two-phase laminar flows in microchannels

Aim of the present work is to investigate the reaction–diffusion process of a two species system under laminar flow in a T-shaped microchannel. A zone formed at the interface between the aqueous solutions of these two species is affected by advection and diffusion. Through theoretical analyses and experimental results, the effect of dispersion has been shown to influence this diffusion zone. We have defined a parameter called effective diffusivity, to account for the dispersion effects and observed it to be a function of the channel Peclet number. In the limiting case of low Peclet number, this parameter is constant and turns out to be equal to the molecular diffusivity. We have also related effective diffusivity and the dispersion coefficient through scaling estimates.     

Kr对HF(X1Σ+)基频和泛频的影响

运用Monte-Carlo轨迹法研究了Kr(1Sg)+HF(X1Σ+;ν=1,2,3;J=4)→Kr(1Sg)+HF(X1Σ+,ν',J')的碰撞过程,从而分析Kr原子对HF基频和泛频的影响。研究表明：在初始相对平动能Et≤251.0kJ/mol时,Kr原子能够减少产生基频的粒子数反转,增加产生泛频特别是ν'=2能级的粒子数反转,并且,Kr原子有较强的弛豫高转动态（J'≥4）的能力,因此,Kr原子对HF泛频激光在提高光强和增强大气传输能力方面均有 较大的改善。     

Energetics of dioxygen binding into graphene patches with various sizes and shapes

Density functional theory (DFT) calculations were employed to investigate the electronic properties of an H-atom terminated graphene patch (hydrographene) smaller than a rhombic C96H26 structure with zigzag edges. Depending on shapes and sizes of hydrographenes, some hydrographenes have the triplet ground state where unpaired electrons are localized on their zigzag edges. The stability of the triplet spin state is diminished, decreasing the hydrographene sizes. The existence of the localized spin densities allows triplet dioxgen to bind into a hydrographene. According to the DFT calculations, the energetics of the dioxygen bindings is negatively influenced by downsizing hydrographenes, as well as depends on their shapes. The size-and shape-dependences of the dioxygen bindings reflect from the stability of the triplet state of a hydrographene, because its localized unpaired electrons can be utilized to be attached to an unpaired electron of triplet dioxygen.     

锌试剂与赖氨酸相互作用的吸光光度研究

研完了邻{2-[α-(2-羟基-5-磺基苯偶氮)－亚苄基]－肼基}苯甲酸(锌试剂,ZcN)与L-粕氨酸(L-Lys)复合物的吸光光度测定基本条件,在pH1.9的缓冲溶液中,ZCN与Lys结合生成紫红色复合物,最大吸收波长在605nm处,标准工作曲线在5.47×10-6～1.64×l0-4mol·L-1范围内呈线性关系。在最大吸收峰处比锌试剂本身红移145nm,复合物的表观摩尔吸光系数ε为2.5×104。同时,研完了离子强度对反应体系的影响．ZCN作为光谱探针与Lys的结合数。     

L—赖氨酸锌配合物中锌的五配位奇数结构研究

用化学方法合成了Ｌ－赖氨酸锌配合物,并对其晶体结构进行测定,结果发现锌作为中心离子的配位数为５,此配位数不同于已报道的４配位数和６配位数锌的结构形式,属奇数结构。     

纳米材料的结构分析

介绍宏观与微观的纳米粒子具有特殊的结构与性能,采用现代分析测试技术确定纳米材料的结构,并探索其原子或分子组成的规律是目前纳米科学的最微处理的研究内容之一。评述了纳米材料结构分析方法及理论研究的新成果。