Nonradiative Relaxation of Thiacarbocyanine Dyes in Binary Mixtures

It was found that preferential solvation of cyanine dyes in binary mixtures can strongly affect both their isomerization and aggregation; the comparison of absorption and fluorescence excitation spectra might be a useful tool for studying these nonradiative processes.     

Solvatochromic dipolarity micro‐sensor behaviour in binary solvent systems of the (water + ionic liquid) type: application of preferential solvation model and linear solvation energy relationships

The type of specific intermolecular and interionic interactions that are established when an ionic liquid is dissolved in water was here analysed. The study of the solvatochromic response of dipolarity micro‐sensors based on Reichardt E_T(30) and Kamlet–Abboud–Taft solvent scales and the application of the solvent exchange model confirmed the formation of different intersolvent complexes in binary mixtures of (water + [C₄mim] [BF₄]/[Br]) type. These complexes provide H‐bond or electron pairs to the polar network, respectively. Moreover, for 4‐methoxybenzenesulfonyl chloride hydrolysis reaction in the (water + [C₄mim] [BF₄]) system, a higher inhibition (13 times) on the k_obs values was observed. Multiple linear regression analysis that allows confirming the solvent effect upon the reactive system is due to the hydrogen‐bond donor properties of intersolvent complex formed. Then, the correlation between two different solvent‐dependent processes proved to be successful. Copyright © 2014 John Wiley & Sons, Ltd.     

Solvatochromic behavior of dyes with dimethylamino electron‐donor and nitro electron‐acceptor groups in their molecular structure

Six dyes with N,N‐dimethylaminophenyl and 4‐nitrophenyl or 2,4‐dinitrophenyl groups in their molecular structures were prepared and characterized. These compounds have different conjugated bridges (C?C, C?N, and N?N) connecting the electron‐donor and the electron‐acceptor groups. All compounds are solvatochromic, with reverse solvatochromism occurring. The solvatochromic band observed in each spectrum for the dyes is due to a π ? π* transition, of an intramolecular charge transfer nature, which occurs from the electron‐donor N,N‐dimethylaminophenyl group to the electron‐acceptor group in the molecules, which is reinforced by the structures of the compounds optimized by applying density functional theory, which exhibit high planarity. The reverse solvatochromism was explained considering two resonance structures. The benzenoid form is better stabilized in less polar solvents and characterizes the region displaying positive solvatochromism, while the dipolar form is better stabilized in more polar solvents, in the region of negative solvatochromism. The Catalán multiparametric approach was used to study the contribution of solvent acidity, basicity, dipolarity, and polarizability to the solvatochromism exhibited by the compounds. These compounds are good candidates for the investigation of the polarizability and, to a lesser extent, the dipolarity of the medium, with very little interference from specific interactions of the solvent through hydrogen bonding. Copyright © 2014 John Wiley & Sons, Ltd.     

Spectral properties of 1,3,4-oxadiazole derivatives in binary solvent mixtures

The influence of nonspecific intermolecular interactions on the fluorescence band shift of 1,3,4-oxadiazole derivatives has been investigated in the binary solvents hexane-ethanol, toluene-ethanol, toluene-acetonitrile, and carbontetrachloride-2-propanol. The dependences obtained have been analyzed in terms of preferential solvation. It has been shown that the maximum solvation energy for slightly polar compounds occurs in toluene-ethanol, toluene-acetonitrile, and carbontetrachloride-2-propanol. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 2, pp. 177–181, March–April, 2008.     

Reaction kinetics and solubility in water‐organic binary solutions are governed by similar solvation equilibria

The solvation effects observed in water‐organic solutions were studied by combining data for reaction kinetics and dissolution equilibria by means of a linear free‐energy (similarity) analysis. Kinetic data for the pH‐independent hydrolysis of (4‐methoxyphenyl)‐2,2‐dichloroacetate measured in this work and solubility data for naphthalene, and other substrates of low polarity, in aqueous binary mixtures of methanol, ethanol, acetonitrile, dimethyl sulfoxide (DMSO), and 1,4‐dioxane were used. Linear similarity relationships were discovered for these data over the full range of solvent compositions studied. To gain insight into the similarities observed between these different phenomena, molecular dynamics simulations were carried out for naphthalene and an ester in water–acetonitrile solutions. The results revealed considerable preferential solvation of these substrates by the co‐solvent. Linear relationships between the experimental data and the mole fractions of acetonitrile in the solvation shells of substrates were found. Surprisingly, a linear relationship was found between the mole fractions of acetonitrile in the solvation shells of the ester and naphthalene. This linearity indicated that a similar solvation mechanism governs even such different phenomena as dissolution and reaction kinetics. The relationships between the experimental data and the results of the molecular dynamics calculations found in this work explained the solvent effect observed in water‐organic solutions on the molecular level. Copyright © 2015 John Wiley & Sons, Ltd.     

1,3,4-Oxadiazole Derivatives. Optical Properties in Pure and Mixed Solvents

1,3,4-Oxadiazole derivatives-organic materials are an interesting and continuously developing area of research. This review describes some optical properties and highlights the current applications of these compounds in biomedical and optoelectronic fields. The relationships between polymer structures, environmental factors and optical properties (absorption and fluorescence) of several selected and relevant l,3,4-oxadiazole-containing molecules were presented in this review. These aspects were analyzed in various pure solvents and microheterogeneous media (mixed solvents). Also, the selectivity and sensitivity of some 1,3,4-oxadiazole derivatives-organic materials for different metal ions were discussed and evaluated by using spectral techniques. Finally, some important photophysical characteristics of 34 series of organic materials containing ?1,3,4-oxadiazole rings, were collected in a table.     

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.     

A Spectroscopic Model for the Study of Preferential in the Ground and Excited Electronic States.

The preferential solvation of a solute molecule in mixed solvents is analysed in terms of the spectral solvent shifts. A spectroscopic model is developed in order to know the preferential solvation degree in the ground electronic state as well as in the first excited electronic state by measuring the absorption and fluorescence spectra respec tively.

Triphenylene was found to be a good model probe molecule in n-butanol/carbon tetrachloride mixtures for both electronic states. Furthermore Tryphenylene in its ground electronic state was studied in chloroform/methanol mixtures.     

Selective nonspecific solvation under dielectric saturation and fluorescence spectra of dye solutions in binary solvents

The influence of selective nonspecific solvation on the fluorescence spectra of three substitutedN-methylphthalimides in a binary solvent system consisting of a nonpolar (n-heptane) and a polar (pyridine) component has been studied under conditions close to dielectric saturation. The substantially nonlinearity of the effect is confirmation that the spectral shifts of fluorescence bands depend on the number of polar solvent molecules involved in solvating the dye molecule. The measured fluorescence spectral shifts determined by substituting one nonpolar solvent molecula with a polar one in the proximity of the dye molecule agree quantitatively with the forecasts of the previously proposed semiempirical theory which describes this nonlinear solvation phenomenon.     

Raman Spectra and Solvent-Solute Interaction of Mercury(II)-Thiocyanate Complexes in Some Aprotic Donor Solvents

Raman spectra of the species Hg(SCN)₂, [Hg(SCN)₃], and [Hg(SCN)₄]^2- in solution of ten aprotic donor solvents have been investigated in the region of the Hg-S vibration. Observed frequency values of measured band of Hg(SCN)₂ and [Hg(SCN)₃] in different solutions correlate well with donor strength of the solvents. There is a linearity between Hg-S frequency decreasing and increasing of the interaction of the solvent molecules with the mercury (II) ion in the thiocyanate complexes. No significant frequency changes have be found for [Hg(SCN)₄]^2-. Evidence based on the frequency shifts and depolarization ratios in various solvents supports the view that the Hg(SCN)₂ in solution undergos departure from linearity as a result of increasing solvent coordination to the mercury (II) ion. Almost constant frequencies of Hg-S vibration of [Hg(SCN)₄]^2- in all investigated solvents suggest a regular tetrahedral structure of the ion in solution having much larger radius than corresponding HgX₄ (X=Cl,Br,I) ions.     

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.     

两元混合物反重力流蒸发传热传质数值研究

近年来微槽内的液体流动和传热受到了广泛关注,成为新的研究热点。本文在对热润湿作用下水平螺旋管表面反重力流形成及其流动特性进行探索的基础上,建立了适用于水平螺旋槽管壁面二元混合物反重力流蒸发传热传质耦合的物理模型。模拟结果表明,由于液膜内部存在着传质,径向有明显的浓度梯度,从而降低了蒸发传热的温度推动力。酒精溶液的浓度越...     

外噪声场对二元混合物相分离的驱动作用

采用蒙特卡罗法研究了外高斯噪声场对二元混合物体系相分离的驱动作用.研究发现，高斯噪声场的引入可以加快体系畴的生长，驱动体系形成沿着［1,1］取向的条状畴结构.在噪声强度一定、噪声作用的概率小于0.015时，高斯噪声场消除了深度淬火引起的体系畴的冻结，畴的生长因子随噪声作用概率线性增加.对足够强的高斯噪声场，存在一个最佳的作用概率区域，其间体系能形成取向性好的条状畴结构. 关键词： 高斯噪声 二元混合物 相分离     

On the Statistical Mechanics and Surface Tensions of Binary Mixtures

Within a lattice model describing a binary mixture with fixed concentrations of the species we discuss the relationship between the surface tension of the mixture and the concentrations.     

拉曼光谱方法研究1,1,3,3-四甲基脲的溶剂效应

测量了1,1,3,3-四甲基脲(TMU)在20种不同溶剂中的拉曼光谱,研究了TMU与溶剂之间的相互作用.将TMU羰基的拉曼频移分别与Kirkwood-Bauer-Magat(KBM)参数(ε-1)/(2ε+1)、溶剂受体数(acceptor number,AN)和线性溶剂自由能关系(linear solvation energy relationships,LSER)进行相关分析.结果表明,TMU的C=O键振动频移与KBM参数没有很好的线性关系,和受体数之间存在比较好的相关性,与LSER参数的线性关系最好.按受体数把溶剂分为质子性溶剂和非质子性溶剂,分别和羰基频移有好的相关性.通过对LSER参数的分析,可以很好地解释溶质和溶剂间的相互作用.     

高氯酸锂在有机溶剂中离子溶剂化和离子缔合的红外光谱研究

利用红外光谱技术研究了LiClO4在碳酸丙烯酸,γ－丁内酯和碳酸二乙酯中的离子缔合和离子溶剂化。溶剂分子谱带的变化证明,锂离子与溶剂分子的相互作用主要是通过羰基氧原子进行的,醚氧也可能参与了相互作用,高氯酸锂的v1和v4谱带变化则证明了溶液中离子对的存在,而离子对的种类与溶剂分子的特性有关。     

混合光谱中已知组分光谱的自加强方法研究

通过数学变换手段将混合物光谱中某待测组分（已知纯光谱组分）所包含的信息集中于原点,使得待分析组分光谱在变换结果曲线的原点处贡献最大,称之为纯光谱组分的自加强作用;在杂质光谱所包含谱带中心位置与待分析组分纯光谱差别较大的假设基础之上,通过理论分析可认为杂质光谱在变换结果曲线原点处贡献最小,因而可选择变换结果曲线原点处的小波变换系数作为待测组分定量分析的依据,降低了分析位置选择的人为性,增强了分析手段的可靠性与适应性。模拟对比了理想曲线与含加性高斯白噪声信号的变换结果,证明该方法具有好的抗噪特性。模拟分析结果表明,该方法相比以往文献报道的单纯利用小波系数作为定量分析依据的做法在分析误差方面有很大改善。     

Ground-State Properties and Phase Separation of Binary Mixtures in Mesoscopic Ring Lattices

We investigated the spatial phase separation of the two components forming a bosonic mixture distributed in a four-well lattice with a ring geometry. We studied the ground state of this system, described by means of a binary Bose–Hubbard Hamiltonian, by implementing a well-known coherent-state picture which allowed us to find the semi-classical equations determining the distribution of boson components in the ring lattice. Their fully analytic solutions, in the limit of large boson numbers, provide the boson populations at each well as a function of the interspecies interaction and of other significant model parameters, while allowing to reconstruct the non-trivial architecture of the ground-state four-well phase diagram. The comparison with the L-well (L=2,3) phase diagrams highlights how increasing the number of wells considerably modifies the phase diagram structure and the transition mechanism from the full-mixing to the full-demixing phase controlled by the interspecies interaction. Despite the fact that the phase diagrams for L=2,3,4 share various general properties, we show that, unlike attractive binary mixtures, repulsive mixtures do not feature a transition mechanism which can be extended to an arbitrary lattice of size L.