A thermodynamic and photophysical study of the effects of thiourea on the micellar properties of aqueous sodium dodecyl sulphate solution

The micellar properties of sodium dodecyl sulphate (SDS) in aqueous thiourea solutions were investigated with the aim of studying the effect of thiourea on these properties. The critical micelle concentrations (cmc) and the degree of dissociation of the micelle were determined by the conductometric method over the temperature range 298–323 K for different concentrations of thiourea. The cmc values of the surfactant in the presence of thiourea were obtained by following the change in the relative intensities of vibrational fine structure of the pyrene fluorescence spectra. The aggregation numbers were determined by employing the static quenching fluorescence method. The cmc values in the presence of varying electrolyte concentrations (NaCl) were obtained with 8-anilinonaphthalene 1-sulphonate (ANS) as a fluorescence probe, and from these values the degree of dissociation was calculated. The mass action model was applied in the present study to obtain various thermodynamic parameters of micellization. All these properties were compared with the micellar properties of an aqueous urea/SDS system, and it was found that thiourea is a better demicellization agent.     

Interaction of oxovanadium(IV) with carboxylic ligands in aqueous solution: A thermodynamic and visible spectrophotometric study

The hydrolysis of VO²⁺ and the complex with sulfate were studied potentiometrically, spectrophotometrically and calorimetrically, in NaCl aqueous solution (0 < I ≤ 1 mol L^− 1) and at t = 25 °C. The formation of two hydrolytic species VO(OH)⁺ and VO₂(OH)₂²⁺ and one complex with sulfate was found, with log β = − 5.65 for the reaction VO²⁺ + H₂O = VO(OH)⁺ + H⁺, log β = − 7.02 for the reaction 2VO²⁺ + 2H₂O = (VO)₂(OH)₂²⁺ + 2H⁺ and log K = 1.73 for VOSO₄⁰ species (at I = 0.1 mol L^− 1 and t = 25 °C). For these species, using calorimetric data, ΔH and TΔS values were also obtained. By using the above values, interactions of VO²⁺ with acetate (ac), malonate (mal), succinate (suc), 1,2,3-propanetricarboxylate (tca) and 1,2,3,4-butanetetracarboxylate (btc) ligands were studied potentiometrically and spectrophotometrically. The formation of ML⁺, ML₂⁰ and MLOH⁰ for ac; ML⁰, MLH⁺, ML₂²⁻ and ML₂H⁻ for mal; ML⁰, MLH⁺ and MLOH⁻ for suc; ML⁻ and MLH⁰ for tca and ML²⁻, MLH⁻ and MLH₂⁰ for btc were found. Formation constants are reported at I = 0.1 mol L^− 1, together with SIT parameters for the dependence on ionic strength. By visible spectrophotometric measurements, λ_max and ε_max values for the relevant species in solution were determined.     

Detection and characterization of single molecules in aqueous solution

Using a confocal microscope with a single-photon avalanche photodiode as detector, we studied photon bursts of single Rhodamine 6G (R6G) and Rhodamin B-zwitterion (RB) molecules in aqueous solution by excitation of the lowest excited singlet stateS ₁ with a frequency-doubled titanium: sapphire laser. Multichannel scaler traces, the fluorescence autocorrelation function and fluorescence decay times determined by time-correlated single-photon counting have been measured simultaneously. The time-resolved fluorescence signals were analyzed with a maximum likelihood estimator. Fluorescence lifetime patterns in steps of 100 ps were generated by convolution with the excitation pulse. The lifetime of theS ₁ state was derived from the Kullback-Leibler minimum discrimination information. We are able to demonstrate for the first time identification of two different single dye molecules via their characteristic fluorescence lifetimes of 1.79 ± 0.33 ns (RB) and 3.79 ± 0.38 ns (R6G) in aqueous solution.Dedicated to Prof. F. P. Schäfer on the occasion of his 65th birthday.On leave from Department of Physics, Mokwon University, Taejon, 301-729, Korea     

Corrosion behaviour of galvanized steel and electroplating steel in aqueous solution: AC impedance study and XPS

The efficiency of a new triazole derivative, namely, 2-{(2-hydroxyethyl)[(4-methyl-1H-1,2,3-benzotriazol-1-yl)methyl]amino}ethanol (TTA) has been studied for corrosion inhibition of galvanized steel and electroplating steel in aqueous solution. Corrosion inhibition was studied using electrochemical impedance spectroscopy (EIS). These studies have shown that TTA was a very good inhibitor. Data obtained from EIS show a frequency distribution and therefore a modelling element with frequency dispersion behaviour, a constant phase element (CPE) has been used. The corrosion behaviour of galvanized steel and electroplating steel in aqueous solution was also investigated in the presence of 4-methyl-1H-benzotriazole (TTA unsubstituted) by EIS. These studies have shown that the ability of the molecule to adsorb on the steel surface was dependent on the group in triazole ring substituent. X-ray photoelectron spectroscopy surface analysis with TTA shows that it chemisorbed on surface of galvanized steel and electroplating steel.     

Effect of surfactants on the aggregation of pyronin B and pyronin Y in aqueous solution

Molecular dynamics of pyronin B (PyB) and pyronin Y (PyY) in aqueous solution containing different surfactants were investigated by using absorption and fluorescence spectroscopy techniques. First, the interactions of PyB and PyY with the negatively charged surfactant sodium dodecyl sulphate (SDS) were investigated in the below and above critical micelle concentration (cmc). The H-aggregate formation of the dye compounds was observed for below the cmc of SDS surfactant. The absorbance of H-aggregate absorption band of PyB and PyY decreased according to the aggregate-monomer equilibrium by increasing SDS surfactant concentration towards the cmc. Therefore, equilibrium constants of the aggregate formation and oscillator strengths of monomer and aggregate of the dye compounds were calculated from spectral studies. Moreover, aggregate formation dynamics was discussed in terms of thermodynamic functions by using temperature studies. The interactions of PyB and PyY with the positively charged hexadecyltrimethylammonium bromide (CTAB) and neutral Triton X-100 (TX-100) were also studied and it was observed that there was no aggregate formation on the absorption and fluorescence spectra for below and above the cmc.     

A study on the electrical conductivity of multi-walled carbon nanotube aqueous solution

The electrical conductivity was investigated for multi-walled carbon nanotubes (MWNTs) dissolved in chloroform and toluene, respectively. The electrical conductivity remarkably increased with increase in the content of MWNTs, which is in accordance with Archie's equation . Furthermore, a hypothesis of the electronic transport process was proposed to explain the difference between the solution and the solid compound. In addition, the temperature dependence of the electrical conductivity shows that log σ vs. 1/T exist in a good linear relationship. The activation energy of the electrical conductivity decreased with increase in concentration and an inflexion was observed at 60 °C in MWNT/toluene solution.     

黄铜矿在水溶液中的溶解特性和表面性质谱学表征

根据黄铜矿的X射线粉末衍射图谱建立了晶体结构模型,应用ICP-MS,AFM和XPS分析研究了黄铜矿在氩气与氧气环境中不同机械搅拌时间和不同pH值水溶液中的溶解特性和表面性质,建立了黄铜矿在水溶液中的溶解模型。实验结果表明,在纯水中,溶液中的铜和铁的浓度与时间的关系可定义为方程c=ksat+b;低pH值有利于黄铜矿的溶解;表面氧化缓慢,对黄铜矿溶解性影响微弱;纯水中黄铜矿的溶解性对有效比表面积影响不大,酸性条件下黄铜矿的溶解由表面化学反应控制;长时间溶解后黄铜矿表面呈富铜状态;溶解使表面粗糙度和晶格缺陷增加。     

LUMINOL-氢氧化物水溶液的荧光及其声激发

本文提出和初步研究了声致荧光方法,测出了三种luminol-氢氧化物水溶液的声致荧光光谱,并对比了它们的光致荧光光谱。结果表明,这类物质的荧光可以由声波激发获得,而且声激发和光激发的荧光波长都在luminol水溶液的光致荧光的发射波长370—750um之间,属于可见光和近紫外光;相对于光致荧光而言,声激发的这三种溶液的最大荧光峰呈现大致10—20um的红移。     

Dielectric study of aqueous solution of acetonitrile

Time domain reflectometry method has been used in the frequency range of 10 MHz to 10 GHz to determine dielectric properties of aqueous solutions of acetonitrile in temperature range of 0°C to 40°C. The calibration method based on the least squares fit method has been used. The excess permittivity, activation energy, Kirkwood correlation factor and activation energy of acetonitrile-water system have also been determined. The dielectric data show that acetonitrile molecules interact such that the dipoles have a tendency to remain antiparallel.     

乙二醇均相及其TX-100胶束溶液中光敏分子菲醌的激光光解研究

用时间分辨电子自旋共振（TR-ESR）和瞬态吸收光谱技术,研究了菲醌在乙二醇均相及其TX-100含水胶束溶液中的光化学反应机理。化学诱导动态电子极化（CIDEP）谱和瞬态吸收光谱都表明,在乙二醇均相溶液中,菲醌光激发三重态3PAQ* 夺取氢原子形成中性自由基PAQH.,三重态机理是CIDEP形成的主要机理。在TX-100含水胶束溶液中,光解主要得到菲醌负离子基PAQ-．,PAQ-．由PAQH.解离形成,解离过程中伴随着极化转移。     

A study on the electrochemical behaviour of polypyrrole films in concentrated aqueous alkali halide electrolytes

The electrochemical behaviour of polypyrrole films doped with dodecyl benzene sulfonate (PPy/DBS) in LiCl aqueous electrolytes has been investigated in order to find the electrolyte concentration suitable for the operation of PPy/DBS-based soft actuators. For this investigation, PPy/DBS films deposited on gold-coated quartz crystals by electropolymerization and simultaneous cyclic voltammetry and electrochemical quartz crystal microbalance techniques were used. During the first redox cycle, while large water movement is observed along with the counter ions in dilute electrolytes, such water transport in concentrated electrolytes is found to be very low. In dilute electrolytes, water molecules accompany counter ions as solvated molecules and due to osmotic effect. In concentrated electrolytes, water movement is less due to limited availability of free water as well as a smaller osmotic pressure difference. In highly concentrated aqueous electrolytes, the mass of the PPy/DBS film at the end of each redox cycle is found to drift, which can be controlled by changing the concentration of the electrolyte. The PPy/DBS films were also cycled at different scan rates in various alkali halide aqueous electrolytes of concentrations 0.1 and 1 M to determine the effective diffusion coefficients of alkali ions in the films. The effective diffusion coefficients were found to increase with the concentration of the electrolytes and decrease with the increase in size of cations.     

A numerical study of cell behaviour in a ternary solution during the freezing process

Using a continuum model for multi-component phase change system, the freezing of cell suspension in a ternary solution, H2O-NaCl-CPA (cryoprotective agent) inside a flat bag is investigated numerically in this study. The temperature and phase change history, intracellular water loss, and the volume change of the cells at different locations inside cell suspension are calculated. Numerical results reveal that although the sample boundary is cooled at a constant rate, different locations inside the sample experienced different temperature changes and cooling rates. The highest cooling rates occur at internal locations. The cell volume change is location-dependent.     

UV-Raman study and theoretical analogue of picolinic acid in aqueous solution

High quality Raman spectrum of picolinic acid aqueous solution with ultraviolet (UV) excitation of 325 nm was obtained in this article. The state of picolinic acid in aqueous solution has been investigated over a wide range of solution pH values. The distinct changes of UV-Raman spectra accompanied with the pH variations indicate the changes of molecule structure. The calculations based on density functional theory were used to analyze the states of picolinic acid in aqueous solution. By comparing the experimental frequencies with the calculated ones, it can be concluded that when pH value varies from high to low, the picolinic acid tends to change from the anion form to the zwitterion that have the intermolecular hydrogen COOH?N bond.     

Conformation and aggregation of poly-L-proline in solution

Although a large number of physical techniques have been successfully used to investigate many of the properties of poly-L-proline, the work reported here has used a combination of osmometry, light scattering, viscometry, and sedimentation studies to reveal a new aspect of this model biopolymer. Experiments were made both on solutions (propionic acid) of poly-L-proline Form I and Form II and on solutions (propionic acid with a threefold dilution of n-propanol) in which Form II was in the process of converting to Form I. The results indicate that an increase in the measured molecular weight accompanies known optical activity and intrinsic viscosity changes which occur as Form II becomes Form I. It appears that the molecular weight determined at infinite dilution for poly-L-proline I is approximately twice that found for poly-L-proline II, and evidence for concentration-promoted aggregation beyond the level of a dimer has been noted in these Form I solutions. Based on these facts and on the information obtained about the particle shapes, it is proposed that this association occurs by a side-to-side binding of two macro-molecules. Discussion is directed toward how these experimental findings can be incorporated into the established concept of the Form I conformation. Light, scattering experiments were also performed on solutions (propionic acid 3 M in LiBr) in which the high-salt, or collapsed, form of poly-L-proline had been generated from either Form II or Form I material. These results showed that the dissolved particles are composed of single chains and are significantly smaller in size than found in solutions of either form and it appears possible that in the collapsed form poly-L-proline might be represented by rodlike macromolecules possessing trans-peptide bonds and a conformation with a relatively small helical pitch.     

On the influence of dimerisation of lumiflavin in aqueous solution on its optical spectra – a quantum chemical study

The solvent effects on the photophysical and photochemical properties of lumiflavin are studied. By comparing different models for the aqueous environment including gas-phase ab-initio calculations, explicit solvation, continuum solvation model and QM/MM simulations the different aspects of solvation are singled out and analysed in detail. Dimerisation of flavins and its effects on the absorption and emission spectrum of flavins are studied using quantum chemical methods. The absorption and emission spectra of lumiflavin in water are compared to the properties of dimeric lumiflavin and to available experimental data.     

Determination of the effective charge on muonium during its reaction in aqueous solution

The rate of reaction of muonium atoms with solutes of either charge is unaffected by the addition of a high concentration of an inert salt, therefore the effective charge on the muonium at the point of reaction is essentially zero.     

Preparation and characterization of Y-Fe alloy nanowires by template-assisted electrodeposition from aqueous solution

In this study, a method was proposed for the preparation of Y-Fe alloy nanowires by PC membrane template-assisted electrodeposition from aqueous solution. Citric acid  acted as complexing agent was used into the solution to fabricate Y-Fe alloy nanowires. The electrolyte solution consisted of 5 g L^?1 YCl₃, 12.5 g L^?1 FeSO·6H₂O, different concentrations of citric acid , 25 g L^?1 boric acid in deionized water. The energy dispersive spectroscopy (EDS) found that the content of Y in the nanowires can be controlled by citric acid concentration and the current intensity, and the content of Y could reach up to 33.16 wt%. Scanning electron microscopy (SEM), BET specific surface area (BET), and X-ray diffraction (XRD) showed that there was a shift in the structure of nanowires from semicrystalline to amorphous due to the change of Y content, and their shapes were approximately 100 nm in diameter and 6 μm in length; the surface areas of nanowires were about 3.97 m²/g. Fourier transform infrared (FTIR) spectroscopy, UV–Vis diffuse reflectance spectroscopy, and X-ray photoelectron spectroscopy (XPS) indicated the formation of Y-Fe alloy, Y₂O₃ and Fe₂O₃   existed  in the outer layer of nanowires. The magnetic field applied both parallel and perpendicular to the nanowires by alternating gradient magnetometer (AGM) showed small magnetic anisotropy and low coercivity with easy axis of magnetization perpendicular to the nanowires. In addition, the magneto-optic Kerr effect (MOKE) was investigated, and a Kerr rotation angle of 29 mdeg was obtained.     

Kanamycin A: imine formation in aqueous solution

Imine formation in aqueous solution of kanamycin A with pyridoxal 5'‐phosphate and other aldehydes was studied by potentiometry, NMR spectroscopy and computational chemistry. It was found that imines are formed with yields near 100 % at pH 7 in equimolar reactant ratio. In order to identify the kanamycin amino groups involved in the reaction, a NMR spectroscopic study was conducted. The structures of possible imines formed between kanamycin and FURAN or PLP were optimized by molecular mechanics with the OPLS‐2005 force field. The ¹H NMR spectra were calculated at the DFT‐GIAO B3LYP/6‐31G(d) level of theory for all structures and compared with the experimentally observed spectra. From these results a probable structure of the imines was proposed. The results obtained in this work show that kanamycin has the ability to form imine derivatives in high yields due to its anion recognition properties. Copyright © 2012 John Wiley & Sons, Ltd.