苯对N,N-二甲基甲酰胺化合物1H NMR的影响研究

本文研究了N,N-二甲基甲酰胺(DMF)在四氯化碳和苯混合溶剂中的¹H NMR。观察到N,N-二甲基甲酰胺(DMF)分子中两个甲基和混合溶剂中苯的共振吸收峰的化学位移随苯的摩尔分数增加而逐渐移向高场,而且两个甲基共振吸收峰向高场移动的程度不同,α甲基较β甲基为甚。DMF分子中两个甲基和混合溶剂中苯的化学位移可以用线性方程表示(δ=A+Bx),这里x是混合溶剂中苯的摩尔分数。相关系数R接近于-1。     

钙钛矿薄膜的微结构和光电特性优化

分别以纯二甲基甲酰胺、纯二甲基亚砜以及二者不同比例的混合物作为前驱体溶剂,制备钙钛矿薄膜样品.将薄膜样品分为两组,分别将其置于氮气氛围中进行热退火和二甲基亚砜蒸汽氛围中进行溶剂退火,并对薄膜样品的微观结构和光电特性进行系统研究分析.结果表明,与热退火相比,经溶剂退火后样品的平均晶粒尺寸和均匀性显著提升,从而减小了薄膜中晶粒边界或界面的体积分数.采用混合前驱体溶剂和后续溶剂退火增加了薄膜的厚度和可见光的利用率,有效改善了薄膜形貌,优化了结晶质量.同时薄膜光致发光强度的增加,表明薄膜缺陷态密度降低.采用优化后的钙钛矿薄膜作为吸收层制备太阳电池,其光电转换效率达到15.7%.     

磺化乙丙三元胶离聚体溶液的ESR波谱研究

考察了磺化乙丙三元胶锰盐离聚体在二甲苯/正己醇混合溶剂中的ESR谱,结果表明醇对金属离子的溶剂化作用破坏了溶液中Mn²⁺的聚集,出现超精细分裂的ESR谱线,溶剂化程度与醇含量、醇分子体积、温度和Mn²⁺浓度有关,这些结果与离聚体溶液粘性行为得到的结论相一致。     

Probing the Liquid-State Structure and Dynamics of Aqueous Solutions by Fluorescence Spectroscopy

Time-resolved fluorescence spectroscopy of the solvent-sensitive molecule 1,8-anilinonaphthalene sulfonate (ANS) is used to probe the structure and dynamics of an aqueous methanol solution (mole fraction = 0.5). The intensity decay of ANS in the mixed solvent displays single exponential kinetics under ambient conditions. At low temperature, a simple two-state solvent relaxation model describes the fluorescence decay for ANS in both methanol and the mixed solvent. The temperature dependence of ANS fluorescence in the mixed solvent is attributed to the onset of glassy dynamics in the aqueous component at higher temperature, implying a partial demixing of the water and methanol due to self-association. We discuss the absence of more complicated fluorescence decays in such a heterogeneous solvent system.     

1,1-二甲硫基-[1]-烯基丙二酸二甲酯与苯相互作用的1H NMR研究

本文在四氯化碳介质中考察了苯对1,1-二甲硫基-[1]-烯基丙二酸二甲酯的溶剂效应,观察到标题化合物分子内的甲基和溶剂苯的化学位移随着苯的摩尔分数增加而逐渐移向高场,溶剂苯的共振吸收峰是一个尖锐的单峰,同时发现了标题化合物分子中甲基和溶剂苯的化学位移值与混合溶剂苯的摩尔分数呈线性关系.     

2,2-二(甲硫基)乙烯基苯基酮1H NMR溶剂效应的研究

在四氯化碳介质中考察了苯对标题化合物的核磁共振谱的溶剂效应.观察到标题化合物分子中的两个甲硫基和混合溶剂中的苯的共振吸收峰随着苯的摩尔分数增加而逐渐移向高场,而且两个甲硫基向高场移动程度不同,ASIS值也随苯的摩尔分数增加而增加,得到了所有化学位移值和ASIS值与苯的摩尔分数呈线性关系,尝试用溶剂化作用解释了标题化合物的ASIS效应.     

1,1-二甲硫基—[1]—烯基丙二酸二甲酯与苯相互作用的~1H NMR研究

本文在四氯化碳介质中考察了苯对1,1-二甲硫基-[1]-烯基丙二酸二甲酯的溶剂效应,观察到标题化合物分子内的甲基和溶剂苯的化学位移随着苯的摩尔分数增加而逐渐移向高场,溶剂苯的共振吸收峰是一个尖锐的单峰,同时发现了标题化合物分子中甲基和溶剂苯的化学位移值与混合溶剂苯的摩尔分数呈线性关系.     

Influence of Mixed Solvents and Temperature on the Solution Properties of Quaternized Polysulfones

Modification of intrinsic viscosity and the preferential adsorption coefficients of quaternized polysulfones with various contents of ionic chlorine in N,N‐dimethylformamide/water and methanol/water mixed solvents was investigated at different compositions and temperatures. The polyelectrolyte effect induced by an enhanced dissociation of the ionizable groups determines both the modification of the swelling degree of the polymer coil and the difference in composition of the mixed solvent inside and outside the coil. The results obtained were correlated with the interaction parameters of the above‐mentioned polymer/solvent/solvent systems.     

有机溶剂热法合成富勒烯[60]-银核壳结构纳米复合物

把C60、硝酸银、还原剂溶解在混合溶剂中,有机溶剂热法制备了C60-Ag核壳结构纳米复合物。用XRD、TEM/HRTEM、UV-Vis、IR等对产物进行了表征。透射电镜表明产物粒径为80—100nm。紫外-可见光谱分析表明C60的吸收峰出现了红移,而纳米银的吸收峰出现了蓝移,表明纳米银和C60之间发生了电荷从银转移给C60的相互作用。     

β-Phase of poly(vinylidene fluoride) formation in poly(vinylidene fluoride)/poly(methyl methacrylate) blend from solutions

The effect of single and mixed solvent on the crystallization behavior of the PVDF/PMMA blend from solutions was investigated. The films cast from the good solvent N,N-dimethylformamide (DMF) dominantly yielded the β-phase crystal with the highest crystallinity of PVDF. Those deposited from the methyl ethyl ketone (MEK) and tetrahydrofuran (THF) exhibited a mixture of α- and some extra β-phase crystals and presented the low crystallinity of PVDF. The crystallization behavior and morphology of the films cast from the mixed solvent (THF/DMF) revealed an enormous dependence on the DMF content. The increased DMF content in the mixed solvent enhanced the interactions between polymers and solvents, and favored the β-crystal of PVDF formation but hindered the α-phase of PVDF formation. Thus, the total crystallinity of PVDF in the blend film was decreased with the DMF content increasing, because of the decreased α-phase of PVDF. In addition, the morphological feature revealed that the voids between the PVDF spherulites were eliminated remarkably by blending with PMMA. The average size of the connected spherulite on top surface of the film can grow into larger as DMF content increased.     

Influence of the solvent on the segmental dynamics and structure in mixed compositions of polyurethane and styrene-acrylonitrile copolymer

The effect of the tetrahydrofuran (THF), methyl ethyl ketone (MEK), ethyl acetate (EA), and acetone (A) solvents on the structure and segmental dynamics of polyurethane (PU)-(styrene-acrylonitrile) (SAN) mixed compositions are studied by spin-probe EPR spectroscopy, differential scanning calorimetry, and infrared spectroscopy. The molecular mobility τ, the degree of crystallinity χ, the modulus of elasticity E alter only slightly in passing from 100% PU to a 50% PU-50% SAN, but the structural and dynamic properties change abruptly at a high SAN content in the composition, regardless of the type of solvent. The values of τ, χ, and elastic modulus for the mixed compositions increases depending on the type of solvent in the following sequence: THF, MEK, EA, A, which can be explained by the thermodynamic affinity between the solvent and solute. It is also shown that, with growing content of SAN in the composition, the number of intermolecular hydrogen bonds between nitrile and urethane groups (3344-cm^?1 band) increases.     

Solvent effects on chemical processes: new solvents designed on the basis of the molecular–microscopic properties of (molecular solvent + 1,3‐dialkylimidazolium) binary mixtures

The purpose of this work was to analyze the microscopic feature of binary solvent systems formed by a molecular solvent (acetonitrile or dimethylformamide or methanol) and an ionic liquid (IL) cosolvent [1‐(1‐butyl)‐3‐methylimidazolium tetrafluoroborate or 1‐(1‐butyl)‐3‐methylimidazolium hexafluorophosphate]. The empirical solvatochromic solvent parameters E_T(30), π*, α, and β were determined from the solvatochromic shifts of adequate indicators. The behavior of the solvent systems was analyzed according to their deviation from ideality. The study focused on the identification of solvent mixtures with relevant solvating properties in order to select mixed solvents with particular characteristics. The comparison of the molecular–microscopic solvent parameters corresponding to the selected binary mixtures with both ILs considered at similar mixed‐solvent composition revealed that the difference is centered on the basic character of them. A kinetic study of a nucleophilic aromatic substitution reaction between 1‐fluoro‐2,4‐dinitrobenzene (FDNB) and 1‐butylamine (BU) developed in (acetonitrile or dimethylformamide + IL) solvent mixtures is presented in order to investigate and compare the solvent effects on a chemical process. For the explored reactive systems the solvation behavior is dominated by both the dipolarity/polarizability and the basicity of the media, contributing these solvent properties to accelerating the chemical process. Copyright © 2007 John Wiley & Sons, Ltd.     

Meerwein酯与苯相互作用的1H NMR研究

测定了Meerwein酯(1,3,5,7,-四羧甲基二环[3,3,1]壬-2,6-二烯-2,6-二醇)在四氯化碳和苯混合溶剂中随苯的摩尔分数变化的¹H NMR谱.观察到分子中两类不同的甲基的化学位移随苯的摩尔分数增加都逐渐移向高场,分子中不同位置上的甲基的化学位移向高场移动程度不同,原处低场的甲基的δ比原处高场甲基的δ要大,两条吸收峰在苯的摩尔数渐增时先是重合后又渐渐分开,所有化学位移可以用线性方程δ=A+BX表示.     

Competitive adsorption of polymers on metal nanoparticles

We investigate the effect of system properties and adsorption sequence on competitive adsorption of poly(methyl methacrylate) (PMMA) and polystyrene (PS) on narrowly polydispersed cobalt (Co) nanoparticles (D ∼ 27 nm). The adsorbed layer composition is studied using thermo-gravimetric analysis (TGA). We find that adsorbed layers of PS are completely displaced by PMMA when the solvent is a common good solvent. An adsorbed layer of only PMMA is also obtained through competitive adsorption from a common good solvent. However, in a selective solvent that is poor for PS, sequential adsorption leads to the formation of mixed layers.     

N，N－二甲基苯胺~1H核磁共振溶剂效应的研究

本文研究了Ｎ，Ｎ－二甲基苯胺分子在环已烷和苯混合溶剂中的１ＨＮＭＲ谱的溶剂效应，观察到Ｎ，Ｎ－二甲基苯胺分子内的两个甲基和混合溶剂中的苯、环己烷的化学位移随苯的摩尔分数增加而逐渐移向高场，ＡＳＩＳ值随苯的摩尔分数增加而增加。得到了所有化学位移值和ＡＳＩＳ值与苯的摩尔分数呈线性关系；尝试用溶剂化作用解释了苯对Ｎ，Ｎ－二甲基苯胺的ＡＳＩＳ效应。     

离子液体[bmim][PF6]与乙腈混合体系中的激光光解研究

以蒽醌(AQ)作为探针分子,利用激光光解技术研究了咪唑型离子液体1-丁基-3-甲基咪唑六氟化磷([bmim][PF6])与乙腈(MeCN)混合体系中的光化学反应行为.研究结果表明,离子液体[bmim][PF6]自身可与激发三线态的蒽醌分子(3AQ*)进行反应,且表观反应速率常数随着[bmim][PF6]/MeCN比例的不同呈现特殊规律性的变化.在离子液体的摩尔分数(xRTIL)为0.06处观察到一个明显的临界点.当xRTIL＜0.06时,表观速率常数随xRTIL的增大而增大;而当xRTIL＞0.06时,表观速率常数随xRTIL的增大而减小.文章给出了[bmim][PF6]/MeCN混合体系中激光诱导化学反应的动力学常数,并初步推测了其反应机理,进一步揭示了离子液体[bmim][PF6]的一些新的光化学特性.     

Crystalline Phase Formation of Poly(vinylidene fluoride) from Tetrahydrofuran/N,N‐dimethylformamide Mixed Solutions

The present work focused on the effect of the interactions between poly(vinylidene fluoride) (PVDF) chains and solvent molecules on the structure and crystallization behavior of PVDF in films obtained by solution casting. In a single solvent system, the film cast from the good solvent of N,N‐dimethylformamide (DMF), showed dominantly β‐phase crystals with the highest PVDF crystallinity (50.6%) and the largest spherulite size, about 4 μm, at the top surface. The samples deposited from good swelling agents, such as tetrahydrofuran (THF) and methyl ethyl ketone (MEK), exhibited mainly the original α phase with some amount of β‐phase crystals; the crystallization behavior and the morphology of the surface were similar to the original PVDF resin, because of the only partially dissolved PVDF chains in these two solvents. In a mixed solvent system (THF/DMF), the β phase formation linearly increased as the DMF component increased, determined by Fourier transform infrared spectroscopy (FTIR) techniques, owing to increased interactions between PVDF chains and DMF molecules. The film surface consisted of β spherulites with average size of about 3 μm, which were smaller than those grown from pure DMF, because of the increased crystallization rate in the mixed solvent.     

Effect of Non‐Ideal Mixed Solvents on Dimensions of Poly(N‐Vinylpyrrolidone) and Poly(Methyl Methacrylate) Coils

An addition of a small amount of non‐solvent tetrahydrofuran (THF) to good solvent water gave rise to a strong solvent power for poly(N‐vinylpyrrolidone) (PVP). It was found that PVP coils in mixtures of water and THF first swelled as the fraction of THF was increased, and then the coils contracted after a critical composition of the solvent mixture based on the measurement of dilute solution viscosities. It was reached that the power of the mixed solvents was not the simple average of the power of individual components. The influence of the non‐ideal mixing of water and THF on the power of these mixtures for PVP and the dimensions of PVP coils was taken into account. Especially the formation of pseudo‐clathrate hydrate structure with the composition φ _THF ≈ 0.44 was found to be an important factor to change the solvation and dimensions of PVP coils. Some other solvent mixtures for PVP and poly(methyl methacrylate) (PMMA) were also found to be non‐ideal mixtures. The viscosities of these solvent mixtures could show positive or negative deviation from the values obtained from the addition rule. It was shown again that the influence of the non‐ideality of these solvent mixtures on the dimensions of polymer coils was great. The action of mixed solvents changed the dimension of polymer coils, not only because of excluded volume effects but also because of the different molecular interactions present in these mixed solvents.     

The electronic spectra of benzophenone in a mixed hydroxylic solvent

The phosphorescence, phosphorescence excitation, and absorption spectra of benzophenone and several derivatives in a mixed hydroxylic solvent of ethanol and water at 77°K are presented. It is shown that benzophenone exists in this solvent as two hydrogen bonded species, benzophenone hydrogen bonded to ethanol and benzophenone hydrogen bonded to water. The water species shows a blue shifted excitation and emission spectrum relative to the ethanol species. It also has a longer phosphorescence lifetime, although the quantum yields are the same for the two species.