Solvent Effect on the Fluorescence and Phosphorescence of Morphine and its Model Compounds

In the fluorescence spectra only morphine exhibits large red shifts of the maxima on increasing solvent polarity. In the phosphorescence spectra, phenol, anisole, and 3-methoxyphenol exhibit large red shifts of the maxima on going from nonpolar to polar solvents. For the latter, the results are interpreted in terms of charge-transfer-to-solvent (CTTS) transitions. For morphine, 2- and 4-methoxyphenol, the phosphorescence maxima occur at long wavelengths in both nonpolar and polar solvents, and this is interpreted in terms of CTTS and intramolecular charge transfer processes. The red-shift of the morphine fluorescence band on going to polar solvents is similarly interpreted as a combination of CTTS and intramolecular charge transfer transitions.     

Fluorescence of 3-monomethylamino-N-methylphthalamide in mixtures of polar and nonpolar solvents

Modifications occurring in the fluorescence and excitation spectra of 3-monoethylamino-N-methylphthalimide (3 MANP) dissolved in nonpolar solvents (-hexane and methylcyclohexane) as a function of added n-butanol and n-propanol between -90 and 90°C were measured. The modifications were due to the presence of two types of centres resulting from the interaction of the solvent molecules with the nonpolar solvent on the one hand, and with the polar solvent on the other. The mixed complex character of the fluorescence band was not affected by the concentration of the solution in the range 10^-7?5 x 10^-4 mol/l. An attempt was made to establish a relationship between the emission due to the centres resulting from the interaction with the alcohol molecules and the association degree of the respective molecules.     

The influence of solvent and temperature upon the fluorescence,absorption and excitation spectra of some indole derivatives

We have studied the changes undergone by the fluorescence, absorption and excitation spectra of some indole and carbazole derivatives in various solvents (nonpolar, polar and mixtures of nonpolar with polar solvents), at various temperatures, especially at low temperatures. On the basis of these modifications it has been established that both the solvents through specific interactions and the temperature can lead to the formation of new molecular species. It has been observed that these species may appear both in the excited state and in the ground state of the solute. It has been established that in the case of the achievement of some favourable configurations either under the action of solvent or under the combined action of both the solvent and temperature the investigated compounds (with one exception) form an exciplex with n-propylamine.     

Fluorescence Properties of Donor–Acceptor-Substituted Pyrazoloquinolines

The photophysical properties of three newly synthesized pyrazoloquinolines, composed of N,N-dimethylaniline as donor subunit and various substituted forms of the acceptor pyrazoloquinoline (DPPQ), were investigated by absorption as well as by stationary and time resolved fluorescence spectroscopy. These compounds show generally highly efficient emission in nonpolar and medium polar solvents; the dipole moment of the emitting state increases and the quantum yield decreases with solvent polarity. These results are explained by state reversion in polar solvents: At low polarities emission originates from a state localized on the DPPQ moiety, whereas in the high-polarity regime the next excited state of charge transfer character, in which an electron is promoted from the amino nitrogen lone pair into an excited orbital of the DPPQ moiety, becomes the fluorescent state. This view is corroborated by semiempirical calculations including the solvent reaction field, low-temperature fluorescence measurements, and the observation of effects of protonation on the spectroscopic and photophysical properties.     

Specific effects of a polar solvent in optical absorption spectra of 5,12-tetracenequinone

We have measured the optical absorption spectra of 5,12-tetracenequinone (5,12-naphthacenequinone) in polar protic (methanol) and nonpolar (n-hexane) solvents. It has been shown that shifts of some bands in the polar solvent compared to the nonpolar one are caused by the formation of high hydrogen bonds between methanol molecules and the molecules under study. The occurrence of hydrogen bonds leads to changes in the energy gaps between occupied and unoccupied molecular orbitals of 5,12-tetracenequinone and, as a consequence, to corresponding changes in energies of electronic transitions. Based on analysis of the absorption spectra in different solvents in combination with the data of calculations of electronic spectra and taking into account changes in the orbital pattern under the action of the solvent, we have determined exact electronic configurations of electronically excited singlet states of 5,12-tetracenequinone.     

Study of Polymer-Solvent Interactions of Complex Polysiloxanes Using Dissipative Particle Dynamics

The mesoscopic modeling of three polysiloxanes in solution is reported in this work, with the purpose of predicting their physicochemical properties as functions of the quality of the solvent, so that a judicious choice of polymer/solvent can be made for various applications. The polymers studied were the following polysiloxanes: polydimethylsiloxane (PDMS), polysiloxane with a bulky alkyl side group (PMHS) and a siloxane copolymer with a hydrophilic polar side group (P2DMPAS). The model used and solved through numerical simulations is the one known as dissipative particle dynamics. Density profiles and radial distribution functions were calculated for each system. We analyzed how the polymers behave in the presence of solvents of varying quality and compared their behavior with experimental data. We observed that we could replicate the behavior in good solvents for PDMS and PMHS. We also observed in the simulation box the formation of pseudo-micelles for P2DMPAS.     

分子极性对类胡萝卜素共振拉曼光谱的影响

测量了非极性分子β胡萝卜素和极性分子角黄素, 在非极性溶剂CS₂和极性溶 剂1,2二氯乙烷中243–293 K的温度范围内的共振拉曼光谱. 结果表明, 溶质和溶剂的极性对拉曼光谱影响很大. 非极性分子β胡萝卜素在非极性溶剂CS₂中的拉曼散射截面最大, 线宽最窄, 而极性分子角黄素在极性溶剂1,2二氯乙烷中的拉曼散射截面最小, 线宽最大. 用溶剂效应及线性多烯分子的“相干弱阻尼电子-晶格振动”, “有效共轭长度”模型给予了解释.     

Reorientational motion of acetone in solutions

Dipolar correlation functions of acetone in various solvents are obtained by Fourier transform of infrared spectra. The analysis of the shapes of correlation functions shows that the reorientational process is diffusional in the time scale longer than about 0.3 × 10^?12 sec. In nonpolar solvents the ratios of correlation times τ_A : τ_B : τ_C do not vary in different solvents, and the reorientation around b axis is more restricted than around the other axis. The length of correlation time is dependent on the density of solvent rather than the viscosity. These observations are unexpected if only the electrostatic interaction is considered. In polar solvents correlation times are longer than in nonpolar solvents and the tendency is especially remarkable in τ_B. An electrostatic interaction between polar molecules seems to be responsible for these observations. The solvent effect on the frequency shifts of carbonyl stretching vibration is consistent with the result of correlation times.     

Rheological Behavior of Polyarylsulfone 1‐Butyl‐3‐Methylimidazolium Chloride Solutions

Polyarylsufone polymers are engineering thermoplastics that can only be dissolved in polar solvents. We found that polyarylsufone has good solubility in ionic liquid (IL) with IL being a new kind of green solvent; thus, ILs are potential substitutes for conventional molecular solvents. However, the thermodynamics in ionic liquids are different then those in conventional solvents, so ILs as solvents have attracted enormous attention recently. Rheological behavior is an important factor in polymer material processing. The rheological behavior of polyarylsulfone (PASF) in both N, N,‐dimethylacetamide (DMAc) and ionic liquid 1‐butyl‐3‐methylimidazolium chloride [(Bmim) Cl] were studied in this paper as a function of concentration for concentrated solutions. It is interesting that the rheological behavior of the PASF/(Bmim) Cl solution is very different from that of PASF/DMAc solutions. In DMAc, as concentration increases viscosity increases, while the rheological behavior of the PASF/(Bmim) Cl solution exhibits a maximum in the viscosity‐concentration plots.     

Ultrasound-assisted soil washing processes using organic solvents for the remediation of PCBs-contaminated soils

Ultrasonic soil washing processes using organic solvents were investigated for the development of novel remediation technologies for persistent organic pollutants (POPs)- contaminated soils. Aluminum foil erosion was first tested to understand sonophysical activity in water, methanol (polar) and n-hexane (nonpolar) in a 28 kHz double-bath-type sonoreactor. Significant sonophysical damage on the aluminum foil was observed at the antinodes for all solvents, and the order of degree of sonophysical damage was as follows: water > methanol > n-hexane. Subsequently, conventional (mechanical mixing only) and ultrasonic soil washing (mechanical mixing and ultrasound) techniques were compared for the removal of polychlorinated biphenyls (PCBs) from soil. Two types of contaminated soils, fresh (Soil A, C₀ = 2.5 mg/kg) and weathered (Soil B, C₀ = 0.5 mg/kg), were used and the applied soil-to-liquid (S:L) ratio was 1:5 and 1:10 for methanol and n-hexane, respectively. The polar solvent significantly increased washing efficiencies compared to the nonpolar solvent, despite the nonpolar nature of the PCBs. Washing efficiency was significantly enhanced in ultrasonic soil washing compared to conventional washing, owing to macro- and micro-scale sonophysical actions. The highest washing efficiencies of 90% for Soil A and 70% for Soil B were observed in the ultrasonic washing processes using methanol. Additionally, a single operation of the ultrasonic washing process was superior to two sequential processes with conventional mixing in terms of washing efficiency, consumption of washing agents, treatment of washing leachate, and operation time. Finally, the removal of PCBs in an organic solvent (methanol) was investigated in photolytic and sonolytic processes for the post-treatment of soil washing leachate. A photolysis efficiency of 80% was obtained within 60 min of UV exposure for intensities of 1.0, 2.0, and 4.0 W/cm². The primary mechanism of PCBs degradation is photolytic dechlorination. In contrast, no degradation was detected in the sonolytic process, as the excess organic solvent acted as a strong radical scavenger.     

The Solvent Effect on Spin Exchange in Long-Chain Nitroxide Biradicals

Intramolecular electron spin exchange, as a function of temperature and the solvent viscosity, polarity and relaxation properties of the solvent molecules, has been studied by X-band electron paramagnetic resonance (EPR) spectroscopy in two long-chain flexible nitroxide biradicals existing in fluid solutions in three spectroscopically different spatial conformations. Certain thermodynamic parameters of the conformational rearrangements were calculated from the EPR spectra. Spin exchange in two biradicals dissolved in five different alcohols was compared with that in a nonpolar solvent (toluene), polar protic (water) and aprotic (acetonitrile), and with thermodynamic characteristics of the solvents. Distinct correlations were found between macroscopic (solvent viscosity, polarity) and microscopic (solvent longitudinal relaxation time) characteristics of solvents, and thermodynamic parameters of the intramolecular conformational transitions. Authors' address: Van Anh Tran, Institute of Physical and Theoretical Chemistry, Graz University of Technology, Technikerstrasse 4, 8010 Graz, Austria     

Solvent controlling excited state proton transfer reaction in quinoline/isoquinoline‐pyrazole isomer QP‐I: A theoretical study

In this present work, we theoretically study the excited state intramolecular proton transfer (ESIPT) mechanism about a quinoline/isoquinoline‐pyrazole isomer QP‐I system. Compared with previous experimental results, our calculated results reappear previous data, which further confirm the theoretical level we used is reasonable. We mainly adopt 2 kinds of solvents (nonpolar cyclohexane and polar acetonitrile) to explore solvents effects on this system. Through reduced density gradient (RDG) function, the intramolecular hydrogen bond N1─H2···N3 has been confirmed existing in both S₀ and S₁ states, although the distance between H2 and N3 is not short. In addition, the strengthening N1─H2···N3 in the S₁ state provides possibility for ESIPT. Explorations about charge redistribution reveal the trend of ESIPT, and frontier orbital gap reflects the reactivity in polar and nonpolar solvents. The constructing potential energy curves reveal that potential energy barriers could be controlled and regulated by solvent polarity.     

Transient absorption spectroscopy of a monofullerene C<Subscript>60</Subscript>-bis-(pyropheophorbide <Emphasis Type="Italic">a</Emphasis>) molecular system in polar and nonpolar environments

The population dynamics of the excited and ground states of the monofullerene-bis (pyropheophorbide a) complex (FP1) were studied in polar (DMF) and nonpolar (toluene) solvents using picosecond transient absorption techniques. A strong quenching of the fluorescence signal of FP1 was observed in both solvents, in comparison to the fluorescence of bis (pyropheophorbide a) (P2). This quenching is due to an intramolecular photoinduced electron transfer from the pyropheophorbide a (pyroPheo) moiety to the fullerene C₆₀ monoadduct. In DMF the charge-separated (CS) state of FP1 has a lifetime of 0.32 ns and undergoes a direct transition to the ground state, resulting in a very low value of photosensitised singlet oxygen generation. In toluene, energy transfer from the first excited triplet state of pyroPheo, which has been populated via relaxation of the CS state, generates a considerable amount of singlet oxygen. The lifetime of the CS state in the nonpolar solvent was estimated to be 0.29 ns. It was also shown that in both DMF and toluene the first excited singlet state as well as the triplet state of the fullerene moiety in FP1 are not occupied. PACS 31.70.Dk; 31.70.Hq; 33.50.-j; 34.70.+e     

Interpretation of Viscosity Behavior of a Polyelectrolyte in a Salt‐Free Polar Solvent by Ion‐Association

Abstract

On the basis of three hypothesis: (1) ion association according to the mass action law, (2) no interchain association due to the same sort of charges on the chains, and (3) chain expansion owing to intrachain Coulombic repulsive force, a theoretical equation was derived to describe the viscosity behavior of a polyelectrolyte in a salt‐free polar solvent. The resulting equation fits well with experimental viscosity behavior of a polyelectrolyte solution in polar solvents. With some approximations, the equation leads to the Fuoss empirical equation. The effects of molecular weight, the average distance of two neighboring ionizable groups along the polymer chain, and the nature of the solvent on the polyelectrolyte conformation are discussed.     

Concentration dependent Raman and IR study on salicylaldehyde in binary mixtures

A vibrational spectroscopic study of binary mixtures of salicylaldehyde (SA) in three different solvents (polar and nonpolar) is presented. The vibrational modes ν(CO), hydroxyl stretching mode (C OH) and aldehydic (C H) stretching vibration were analyzed. Changes in wavenumber position and full width half maximum have been explained for neat as well as binary mixtures with different volume fractions of the reference system, SA, in terms of inter‐ and intramolecular hydrogen bonding. The IR spectra of these mixtures have also been taken and compared with the Raman data. The spectral changes have been well explained using the concentration fluctuation model and solute–solvent interaction. Copyright © 2007 John Wiley & Sons, Ltd.     

苏丹Ⅲ在不同溶剂中的紫外-可见光谱研究

研究了苏丹Ⅲ在不同溶剂中的紫外-可见吸收光谱,探讨了极性、非极性及混合溶剂对苏丹Ⅲ的紫外-可见光谱的影响。结果表明,苏丹Ⅲ的主要吸收峰位于200～230 nm,340～360 nm及490～510 nm区间。在200～230 nm的中紫外区,苏丹Ⅲ在极性溶剂中呈双峰吸收,非极性溶剂中随苏丹Ⅲ浓度增加吸收峰由双峰变为单峰,混合溶剂中吸收双峰消失,红移至310 nm处,呈单峰状。苏丹Ⅲ在环己烷、石油醚、甲醇、乙腈和香蕉水这5种溶剂中的摩尔吸光系数(ε)均在104数量级。     

溶剂对石墨烯量子点荧光性质的影响

采用柠檬酸热解法制备了石墨烯量子点(GQDs),研究了非极性溶剂戊烷,极性溶剂乙醇、丙酮、乙二醇对GQDs荧光性质的影响。透射电子显微镜(TEM)和原子力显微镜(AFM)图像表明,制备的GQDs尺寸分布在2~12 nm(平均尺寸为4.9 nm),分散均匀,高度分布在0.5~2 nm。吸收光谱表明,GQDs具有明显的紫外吸收特性,吸收峰位于259 nm和274 nm。光致发光谱表明,GQDs的发光具有明显的溶剂依赖性。GQDs在极性溶剂乙醇、丙酮、乙二醇中,发光峰的位置依赖于激发波长,发射波长在可见光区。而在非极性溶剂戊烷中,GQDs表现出对激发波长不依赖的荧光性能,且发射波长在近紫外。     

One-pot aqueous synthesis of cysteine-capped CdTe/CdS core–shell nanowires

A general hydrothermal method was developed to prepare colloidal gadolinium orthovanadate nanocrystals by using supercritical water as a green solvent. The spectacular properties of supercritical water is advantageous for synthesizing crystalline and surface-modified luminescent nanoparticles capped with long alkyl chains of organic modifiers on the surface of the particles to make them dispersible in nonpolar solvents. The size of the nanoparticles could be controlled within 10–15 nm. Characterization of the hydrothermal product was accomplished using X-ray diffraction, transmission electron microscopy (TEM), high-resolution TEM, Fourier transform infrared spectroscopy, thermo gravimetric analysis, and electron dispersive X-ray scattering. The photoluminescence characterization showed that there is a strong red emission under UV excitation, which broadens the material’s various applications.     

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.     

Combined effect of linear and nonlinear dipole-dipole interactions on the electronic spectra of van der Waals complexes in solutions

A new semiempirical approach previously proposed by the author for describing the regularities of the shift of absorption bands in the IR spectra of ultimately ordered van der Waals complexes is extended to the case of three-component solutions of dyes in binary solvents consisting of neutral (nonpolar) and active (polar) components. This approach is based on the analysis of the specific features of the combined manifestation of nonlinear (complex formation) and linear (solvation) intermolecular forces of dipole-dipole nature in the change in the electrical parameters of interacting molecules. It is shown that the concepts developed enable correct quantitative interpretation of a large amount of available spectral-luminescent data for complexes of 1: 1 composition between molecules of amino-substituted derivatives of phthalimide and molecules of the active component of a binary solvent, with these complexes being solvated by molecules of the nonpolar component of the solvent.