Peculiarities of the Perturbation of Water Structure by Ions with Various Hydration in Concentrated Solutions of CaCl2, CsCl,KBr, and KI

The degree of water structuring in solutions of four salts (CsCl, KBr, and KI with a concentration of 1M and CaCl₂ with a concentration of 0.5M) has been analyzed using THz time-domain spectroscopy. It is shown that the degree of water structuring in a solution of salt, prepared based on a highly diluted aqueous solution of the same salt, differs in some cases from the degree of structuring of similar solutions prepared on the basis of highly diluted aqueous solutions of other salts and similarly prepared water. The degree of water structuring increases in salt solutions containing ions with pronounced positive hydration, decreases in salt solutions containing ions with pronounced negative hydration, and does not differs from control in salt solutions containing no ions with pronounced positive or negative hydration.

     

Randomly diluted eg orbital-ordered systems

Dilution effects on the long-range ordered state of the doubly degenerate e(g) orbital are investigated. Quenched impurities without the orbital degree of freedom are introduced in the orbital model where the long-range order is realized by the order-from-disorder mechanism. It is shown by Monte Carlo simulations and the cluster-expansion method that a decrease in the orbital-ordering temperature by dilution is substantially larger than that in the randomly diluted spin models. Tilting of orbital pseudospins around impurities is the essence of this dilution effect. The present theory provides a new viewpoint for the recent resonant x-ray scattering experiments in KCu(1-x)Zn(x)F(3).     

超声波降解溴苯:操作参数与环境因素的影响

本文考察了用超声波降解水中溴苯的动力学与脱卤效应,并研究了重要的操作参数如强度与饱和气体,以及环境干扰因素如悬浮物、地表水其他杂质的影响。结果表明,超声波可以有效地处理溴苯,在20kHz,7.5W／cm2下一级反应常数达0.044／min,脱卤效率达58％。本研究范围内,声强度越高,反应越快。氧气和氩气下降解速率高于空气下。超声降解不受地表水中杂质、纳米级微粒、无机颗粒的影响,但有机悬浮物能在一定程度上干扰溴苯的超声降解。     

Laser Diagnostics of the Mesoscale Heterogeneity of Aqueous Solutions of Polar Organic Compounds

A mesoscale droplet phase, which is spontaneously formed in aqueous solutions of some polar organic compounds, has been experimentally investigated by methods of dynamic light scattering and laser phase microscopy. It is shown that tetrahydrofuran and tert-butanol aqueous solutions demonstrate a strong peak of light scattering intensity in the range of molecular concentrations of about 0.02 to 0.08, which corresponds to inhomogeneities with a characteristic size of about 100 nm. These liquid droplets are enriched with molecules of dissolved substance. A similar light scattering peak for aqueous solutions of glycerol and ethylene glycol is less pronounced. A theoretical model of the phase separation of binary solutions with twinkling (i.e., existing for a finite time) intermolecular hydrogen bonds is developed. The model predicts the existence of an additional low-concentration light scattering peak near the spinodal of the solution free of hydrogen bonds. A characterization of solutions according to the numerical values of twinkling hydrogen bond parameters is outlined.     

Contributions of Exchange and Dipole–Dipole Interactions to the Shape of EPR Spectra of Free Radicals in Diluted Solutions

This report presents a comprehensive analysis of the contributions of the Heisenberg exchange and dipole–dipole interactions in diluted solutions of nitroxide radicals to the shape of their electron paramagnetic resonance (EPR) spectra taking into account all coherence transfer processes. It is shown that these contributions interfere. The approaches to obtain the molecular-kinetic and exchange integral parameters by analyzing the EPR spectrum dependence on the radical concentration and the solvent viscosity are discussed.     

Regularities in the luminescence spectra of solutions with molecular anion impurities

This article deals with the absorption, excitation and luminescence spectra of frozen aqueous solutions of the halide salts and acids with molecular anion impurities CN^-, SCN^-, SeCN^- and CNO^-. It is shown that the spectra at 4.2°K display vibronic structure which is explained by the interaction of electronic transition with intramolecular oscillations of the impurity. Conclusions are also deduced from the results of investigation of temperature dependence of the quantum emission efficiency and the Raman spectra of such systems.     

Investigation of the interaction of dissolved gasses with water in highly diluted aqueous media using the ultraviolet fluorescence and light scattering methods

Light scattering and ultraviolet fluorescence spectra are obtained for highly diluted aqueous solutions with additions of substances that are able to affect the processes with the participation of reactive oxygen species (ROS). A heuristic organization model of the water-gas system with an increased ROS concentration is proposed on the assumption that superoxide anion radical molecules can be adsorbed at interfaces (water-gas, water-solid) and lead to generation of local electric and magnetic fields that contribute to further structuring of water near interfaces. Various exposures (mechanical, acoustic, etc.) to water can result in the separation of the positive and negative charges centers and induce long-time processes of relaxation and further evolution of the system. An increase in the concentration of adsorbed ROS molecules can increase strength of electromagnetic fields near local inhomogeneities and make the system sensitive to low-intensity and low-energy exposures.     

Dielectric Characteristics of Highly Diluted Aqueous Diclofenac Solutions in the Frequency Range of 20 Hz to 10 MHz

Physics of Wave Phenomena - It is found that electrical conduction of highly diluted aqueous diclofenac solutions nonmonotonically depends on their concentration under serial centesimal dilutions...     

Caffeine as non-toxic corrosion inhibitor for copper in aqueous solutions of potassium nitrate

Different electrochemical methods were employed in order to confirm the ability of caffeine (1,3,7-trimethylxanthine) to inhibit the corrosion processes of copper in aqueous potassium nitrate solutions in the absence and in the presence of chloride. Some experiments were repeated in potassium perchlorate in order to compare the influence of the medium. The interaction between the organic compound and the electrode surface occurs independently of the electrode potential. However, maximum interaction was observed at 0.0 V (Ag/AgCl) in aerated solutions, and at −0.25 V (Ag/AgCl) in deaerated solutions.The presence of the organic compound adsorbed on the electrode surface was confirmed by comparing the voltammograms of copper electrode in the absence and presence of 1.5 mmol L⁻¹ of dissolved caffeine. The same results were observed by comparing polarization curves in the absence and in the presence of caffeine.Anodic currents decrease noticeably in the presence of the organic compound. Chronoamperometric experiments were conclusive to prove the inhibitor capability of caffeine to decrease the corrosion dissolution processes of copper under anodic polarization.     

Two‐phase flow electrosynthesis: Comparing N‐octyl‐2‐pyrrolidone–aqueous and acetonitrile–aqueous three‐phase boundary reactions

A microfluidic double channel device is employed to study reactions at flowing liquid–liquid junctions in contact with a boron‐doped diamond (BDD) working electrode. The rectangular flow cell is calibrated for both single‐phase liquid flow and biphasic liquid–liquid flow for the case of (i) the immiscible N‐octyl‐2‐pyrrolidone (NOP)–aqueous electrolyte system and (ii) the immiscible acetonitrile–aqueous electrolyte system. The influence of flow speed and liquid viscosity on the position of the phase boundary and mass transport‐controlled limiting currents are examined. In contrast to the NOP–aqueous electrolyte case, the acetonitrile–aqueous electrolyte system is shown to behave close to ideal without ‘undercutting’ of the organic phase under the aqueous phase. The limiting current for three‐phase boundary reactions is only weakly dependent on flow rate but directly proportional to the concentration and the diffusion coefficient in the organic phase. Acetonitrile as a commonly employed synthetic solvent is shown here to allow effective three‐phase boundary processes to occur due to a lower viscosity enabling faster diffusion. N‐butylferrocene is shown to be oxidised at the acetonitrile–aqueous electrolyte interface about 12 times faster when compared with the same process at the NOP–aqueous electrolyte interface. Conditions suitable for clean two‐phase electrosynthetic processes without intentionally added supporting electrolyte in the organic phase are proposed. Copyright © 2008 John Wiley & Sons, Ltd.     

Femtosecond time-resolved ERE-CARS of PM650

We utilize femtosecond time-resolved electronic resonance-enhanced coherent anti-Stokes Raman scattering (ERE-CARS) to investigate new information for pyrromethene 650 (PM650) dye molecules. For this purpose, the vibrational properties of PM650 are registered in diluted solutions of several organisms. We observe a strong Raman vibrational mode with a wavenumber difference of about 48 cm^? 1 in its organic solutions. This may be linked to the intramolecular electron transfer (ICT) process from the aromatic ring to the cyano group in PM650. The influence of the solvent effects on the vibrational dynamics of PM650 is also investigated. The vibrational properties of PM650 dye molecules diluted in polar organic solutions are light solvent-dependent.     

Study on the Electrospinnability of Polyvinyl Alcohol Solutions by Using Water/N,N-dimethylacetamide or Water/N,N-dimethylformamide as Solvents

The electrospinning of poly(vinyl alcohol) (PVA) (99% hydrolysis degree) aqueous solution with added organic solvents N, N-dimethylacetamide (DMAc) or N, N-Dimethylformamide (DMF) was investigated. After the addition of the organic solvents to the PVA aqueous solutions, the surface tension and conductivity decreased and the viscosity significantly increased, which caused an improved electrospinnability of the PVA solutions. The micro-structures of the three solutions were investigated by dynamic light scattering (DLS), differential scanning calorimetry (DSC) and dynamic viscoelastic measurements. The DLS data revealed that the swelling of the PVA coils was slightly increased but the overlaps of PVA coils decreased greatly after one of the organic solvents was added to the aqueous solution. The DSC data showed both the water-rich phase and PVA-rich phase were destroyed and the solution became more homogenous after the addition due to the interaction between the organic solvent and water. Viscoelastic data showed there was an obvious difference in the storage modulus behavior between the aqueous solutions and the water/solvents solutions. These changes in the micro-structure and properties were the reason for the improved electrospinnability of the PVA solution. According to scanning electron microscopy (SEM), the average diameter of the electrospun PVA nanofibers was about 308 nm for the DMF/water system, and 255 nm for the DMAC/water system, as compared with uneven diameter nanofibers for the water system.     

Absorption properties and stability of certain uranyl compounds at elevated temperatures

The absorption spectra and acidity of several solutions of uranyl salts and complexes in aqueous, inorganic, and organic solvents were investigated at temperatures higher than room temperature (up to 135°C). Conclusions are drawn concerning the stability of some of the compounds studied at these temperatures. Irreversible chemical processes resulting in the formation of new (probably uranium) compounds were noted.     

Application of the method of selective fluorescence excitation to investigation of complexation and solvation processes of polar organic dye molecules in binary solvents

It is proposed to use the method of selective fluorescence excitation to find absorption spectra (fluorescence excitation spectra) of 1 : 1 primary solvated complexes between polar molecules of an organic dye and the active component of a binary solvent, whose neutral component is a nonpolar or low-polarity liquid. The technique was tested with diluted solutions of 4-dimethylaminochalcone (4-DMC) in mixtures of ethylbenzene with dimethyl formamide at extremely low contents of the latter. It is shown that the experimental absolute shift of the long-wavelength vibronic absorption band of three-component DMC solutions is in a good quantitative agreement with the analogous shift obtained independently based on the semi-empirical theory describing the joint effect of nonlinear (complexation) and linear (solvation) dipole-dipole interactions on the shift of spectral bands.     

Activation by nonlinear oscillations and solitonic excitations

Local excitations in molecular systems are studied taking into account the influence of soft impurities. The dynamics of activation processes (high-energy events) due to nonlinear mechanisms is studied. The following examples of classical macroscopic systems with strong nonlinear interaction are investigated: 1D Toda chains, 1D Morse rings, and 3D systems of hard spheres including impurities. It is shown that solitonlike excitations may lead to the concentration of energy at definite sites (weak springs or soft spheres). The accumulation of energy is mainly due to soliton-fusion effects. In thermal equilibrium an optimum temperature exists, where the thermally averaged potential energy is preferably partitioned to the soft springs embedded into a hard-spring solvent. Further, we show that the effect of thermal energy localization and the temperature dependence also persists for solutions of soft spheres in hard-sphere solvents.     

Surfactant-free solution-dispersible Si nanocrystals surface modification by impurity control

Si nanocrystals (Si-NCs) dispersible in polar liquid without surface functionalization by organic molecules have been realized by simultaneously doping n and p type impurities. We show that the codoped Si-NCs are stable in methanol for more than five months, while intrinsic Si-NCs prepared by the same procedure form large agglomerates. The different behavior of the intrinsic and codoped Si-NCs in solutions suggests that doped impurities exist on the surface of Si-NCs and the surface potential is large enough to prevent the agglomeration. The colloidal solution of codoped Si-NCs exhibits broad photoluminescence with the maximum in the near infrared range (1.1-1.3?eV).     

Protonation of norharmane as a sonochemical dosimeter for organic media. The effect of temperature

The sonolysis of different organic and aqueous media in the presence of norharmane produce its protonation. This simple and reversible reaction is particularly suitable as a dosimetric reaction in order to measure the relative amount of cavitation induced by the ultrasonic irradiation in non aqueous solutions. The protonation rate increases when small amounts of chloroform are added to the solution. The frequency (20 and 475 kHz) and temperature effects on the reaction rate are also studied. Our results show that sonication of aqueous solutions at high frequency leads to a strongly oxidant medium.     

Nonequilibrium gas absorption in rotating permeable media

The absorption of ammonia, sulfur dioxide, and carbon dioxide by water and aqueous solutions in rotating permeable media, a cellular porous disk, and a set of spaced-apart thin disks has been considered. The efficiency of cleaning air to remove these impurities is determined, and their anomalously high solubility (higher than equilibrium value) has been discovered. The results demonstrate the feasibility of designing cheap efficient rotor-type absorbers to clean gases of harmful impurities.     

EDXRF determination of impurities in potassium dihydrogenphosphate single crystals and raw materials

A fast and simple preconcentration procedure for recovering various cation impurities from potassium dihydrogenphosphate (KDP) single crystals and raw materials, followed by energy‐dispersive X‐ray fluorescence analysis (EDXRF), is described. The technique is based on the adsorption of metal 8‐hydroxyquinoline complexes from aqueous solutions of KDP on activated carbon, separation of the concentrate on a Nuclepore filter and subsequent determination by EDXRF. To fix activated carbon powder on a filter surface, an amount of 1‐hexadecanol is added to the KDP solution during the preconcentration procedure. The optimum conditions for the best recovery of the impurities were established. It was shown that a preconcentration factor of 100 can be achieved and the detection limit for a number of elements was down to 0.01 µg g^?1. The relative standard deviations were 6–17% for element concentrations of 0.2 µg g^?1. The method was successfully applied to the determination of Fe, Co, Cu, Ni, Zn, Mn, Ti and Bi in KDP single crystals and raw materials. Copyright © 2005 John Wiley & Sons, Ltd.     

Supercritical fluid micronization of risperidone pharmaceutical substance

A comparative study of the supercritical fluid micronization of risperidone pharmaceutical substance with an initial particle size of 50 to 100 μm by the RESS and SAS methods aimed at increasing the bioavailability of risperidone as a drug was performed. Both methods makes it possible to prepare risperidone particle of various forms, 5–20 μm in size. However, the SAS method is preferable, because in contrast to RESS, it does not cause contamination of risperidone with organic solvents used in both processes or any other impurities and also makes it possible to vary the shape and size of particles. It is shown that, during SAS micronization, the polymorphic form of risperidone changes from triclinic to monoclinic.