Solubility of phenobarbital in aqueous cosolvent mixtures revisited: IKBI preferential solvation analysis

The preferential solvation parameters of phenobarbital in aqueous binary mixtures of 1,4-dioxane, t-butanol, n-propanol, ethanol, propylene glycol and glycerol were derived from solution thermodynamic properties by using the IKBI method. This drug is sensitive to preferential solvation effects in all these mixtures. The preferential solvation parameter by the cosolvent (δx_1,3) is negative in almost all the water-rich mixtures but positive in mixtures with similar proportions of solvents and cosolvent-rich mixtures, except in 1-propanol + water mixtures, where negative values are also found in mixtures with x₁ ≥ 0.70. Hydrophobic hydration around the non-polar ethyl and phenyl groups of this drug in water-rich mixtures could play a relevant role in drug solvation. Otherwise, in mixtures of similar solvent compositions and in cosolvent-rich mixtures the preferential solvation by cosolvent could be due to the acidic behaviour of the drug.     

Effect of the Duration of the Mechanical Activation of Granulated Mixtures of 5Ti + 3Si on the Rate of Combustion Wave Propagation and the Elongation of Samples after Synthesis

The effect the duration of the mechanical activation (MA) of preliminarily granulated mixtures of 5Ti + 3Si with titanium powder of different grades has on the dependences of combustion rates and changes in the length of samples after synthesis is studied. The dependences of the average particle size of a mixture on the duration of activation are established. It is shown that initial mixtures containing titanium of different grades have different combustion rates. It is concluded that mechanical activation leads to equalization of the combustion rates for powder mixtures at MA durations of more than 7 min and for preliminarily granulated mixtures at MA durations of 3 min. For powder mixtures, the combustion rate changes nonmonotonically as the duration of MA grows. For preliminarily granulated mixtures, it first slows and then increases monotonically. An explanation of the observed dependences is proposed. It is shown that in contrast to powder mixtures, there is a sudden increase in the relative length of samples during combustion after the MA of granulated mixtures with a duration of 1 min. This is because with granular MA mixtures, the main evolution of gas from the decomposition of bonds occurs behind the combustion front, in contrast to mixtures without MA. It is shown that the dependences of the relative length of the samples after burning on the duration of MA are close to those of mixtures with both grades of titanium.     

Preferential solvation of some antiepileptic drugs in {cosolvent (1) + water (2)} mixtures at 298.15 K

The solubility of lamotrigine (LTG), clonazepam (CZP) and diazepam (DZP) in some {cosolvent (1) + water (2)} mixtures expressed in mole fraction at 298.15 K was calculated from reported solubility values expressed in molarity by using the densities of the saturated solutions. Aqueous binary mixtures of ethanol, propylene glycol and N-methyl-2-pyrrolidone were considered. From mole fraction solubilities and some thermodynamic properties of the solvent mixtures, the preferential solvation of these drugs by both solvents in the mixtures was analysed by using the inverse Kirkwood–Buff integrals. It is observed that LTG, CZP and DZP are preferentially solvated by water in water-rich mixtures in all the three binary systems analysed. In {ethanol (1) + water (2)} mixtures, preferential solvation by water is also observed in ethanol-rich mixtures. Nevertheless, in {propylene glycol (1) + water (2)} and {N-methyl-2-pyrrolidone (1) + water (2)} mixtures preferential solvation by the cosolvent was observed in cosolvent-rich mixtures.     

Reference materials at emission levels of NH3 and HCl

Due to instability in static mixtures, in the past only dynamic preparation techniques for mixtures of NH3 and HCl were maintained; however, recent developments of new passivation techniques for cylinder treatment and commercially available nitrogen with a very low content of impurities have opened up the possibility of preparing stable mixtures in cylinders by gravimetry. Mixtures of NH3 (300 microL/L and 30 microL/L) and HCI (300 microL/L) were prepared in nitrogen in cylinders with different passivation treatments. The mixtures were compared with dynamically prepared mixtures using Photo Acoustic detection (PAS) and FT-IR. The uncertainty is about 3.5% with PAS analysis for NH3 at the 300 microL/L level. For the analysis of HCI with FT-IR the initial uncertainty in the 300 microL/L mixtures is about 7%. Two of the HCI mixtures show significant instability; for the other three mixtures the uncertainty in the measurement is too large to discriminate between stability and instability. The NH3/N2 mixtures are stable within 3.5% for a one-year period. The stability of the 30 microL/L mixtures of NH3 cannot be underpinned by measurement results, but a systematic effect in the measurement procedure seems more likely than instability. Improvement in the measurement procedure should clarify this point.     

Determination of the additive physical properties of the components of complex mixtures

Summary The density, refractive index and absorptivities at chosen wave numbers were determined for all the components of three-component mixtures. The mixtures were treated of three-component mixtures. The mixtures were treated as being of unknown qualitative and quantitative composition. The quantitative gas chromatographic analysis by means of the method of linear relationship was carried out and the values of the physical properties of complex mixtures were measured. The corresponding properties of acetone, benzene and toluene were evaluated from the set of appropriate equations.     

Thermal diffusion as a method for the analysis of hydrocarbon oils

Thermal diffusion and the method by which the single effect can be multiplied and be made applicable to the analysis of hydrocarbon mixtures, are described.The selecting principles for gas mixtures and those for liquid mixtures, according to the “cage-model” are mentioned. Experiments with synthetic mixtures of liquid hydrocarbons generally confirmed these principles. The order of magnitude of the thermal efficiency and the experimental results for a distillate fraction of natural hydrocarbon mixtures are given.     

The single-step approximation

The effect of cryogenic grinding on the indomethacin (IMC) and its mixtures with polyvinylpyrrolidone (PVP) was studied by powder X-ray diffraction and differential scanning calorimetry. Cryoground mixtures were shown to form glass solutions. PVP inhibits the crystallization of IMC from the amorphous state: the crystallization temperature of IMC in the mixtures with PVP increases, and the amorphous state is preserved longer on storage. The mixtures were characterized by Raman spectroscopy. Dissolution of the IMC in the cryoground mixtures is higher as compared to the pure form, also after a prolonged storage.     

Efficient preparation of mesocarbon microbeads by pyrolysis of coal-tar pitch in the presence of rosin

Mesocarbon microbeads (MCMB) were prepared by pyrolysis of coal-tar pitch in the presence of rosin, and characteristics of the pitch-rosin mixtures and the MCMB were studied. Pyrolysis behavior of the pitch-rosin mixtures was investigated by thermogravimetric analysis (TGA), and chemical structures of the pyrolysated pitch-rosin mixtures were studied using Fourier transform infrared spectroscopy (FTIR) technique. Optical textures of the pyrolysated pitch-rosin mixtures were characterized by polarized-light microscopy. In addition, morphologies and microstructures of the MCMB, extracted from the pyrolysated pitch-rosin mixtures, were studied using scanning electron microscopy (SEM) and transmission electron microscopy (TEM), respectively. Results show that the rosin addition contributes to a notable increase of MCMB yield as well as a decrease in the aromaticity index of the pyrolysated pitch-rosin mixtures. Moreover, the pyrolysis conditions have great effect on the morphologies and yields of MCMB. When the pitch-rosin mixtures are pyrolysated at 450 °C for 1.5-2.5 h, the MCMB yields arrive at 33.8-54.6 wt.% of the pyrolysated pitch-rosin mixtures.     

Verfolgung der Verbrennungsreaktionen exothermer Massen auf Basis von Aluminium,Fluoriden und Kaliumnitrat mit Differentialthermoanalyse

DTA was applied to investigate the course of combustion of exothermic mixtures composed of aluminium, fluorides and potassium nitrate, and the results obtained were compared with the simultaneous results of X-ray investigations. The combustion of exothermic mixtures composed of aluminium, fluorides and potassium nitrate is similar to the combustion of mixtures where the potassium nitrate is substituted by sodium nitrate. Two exothermic reactions occur: between 400 and 520?, and between 800 and 1130?, in mixtures with sodium fluoride and between 450? and 650? and 850 and 1130? in mixtures with calcium fluoride. The reaction in the lower temperature range initiates the combustion of the mixture. In sodium fluoride mixtures this reaction takes place at lower temperature and seems to be more intense, since these mixtures inflame earlier than those with calcium fluoride. The reaction in the higher temperature range, which occurs at approximately the same temperature in the two cases, liberates the main part of the useful heat of the exothermic mixtures.     

Theoretical aspects of quantitative mass spectrometry of gas mixtures

The problem of calibration of mass spectrometers with standard gas mixtures is studied theoretically. The results obtained can be used in deciding the number and optimum composition of standard mixtures. An analogy is drawn between this calibration problem and the mathematical theory of experimental design when mixtures are considered. It is shown that calibration based on a number of standard mixtures is more accurate than calibration with pure gases. A procedure for correction of calibration coefficients is described; it can be applied during measurements on the composition of gas mixtures or gas flows. Application to gas mixtures containing CO, N₂ and CO₂ is discussed.     

四苯硼钾由单-到不同混合溶剂的迁移自由能

KBPh4作为一种典型的大阴离子电解质 ,在研究与计算大分子电解质的迁移热力学性质中起着重要的作用 .讨论大分子电解质与不同溶剂间的作用 ,还可以为萃取、色谱及表面活性剂的研究提供理论依据 .一些文献及我们前文曾对四苯硼盐由水到一些纯溶剂 [1,2]及从水到某些水-有机混合溶剂中的标准迁移自由能进行了研究 [3],但对四苯硼盐在有机-有机混合溶剂中的研究报导极少 .本文对 KBPh4由水到水-异丙醇和由甲醇到甲醇-异丙醇混合溶剂的标准迁移自由能进行了研究和探讨 .1实验部分 1.1实验仪器及方法 　　用 CS501型超级恒温槽恒温 ;用 WF…     

Liquid structure of acetic acid-water and trifluoroacetic acid-water mixtures studied by large-angle X-ray scattering and NMR

The structures of acetic acid (AA), trifluoroacetic acid (TFA), and their aqueous mixtures over the entire range of acid mole fraction xA have been investigated by using large-angle X-ray scattering (LAXS) and NMR techniques. The results from the LAXS experiments have shown that acetic acid molecules mainly form a chain structure via hydrogen bonding in the pure liquid. In acetic acid-water mixtures hydrogen bonds of acetic acid-water and water-water gradually increase with decreasing xA, while the chain structure of acetic acid molecules is moderately ruptured. Hydrogen bonds among water molecules are remarkably formed in acetic acid-water mixtures at xA相似文献   

DIHEMATOPORPHYRIN ETHER-PHOSPHOLIPID INTERACTIONS. THE ROLES OF SURFACE CHARGE and LATERAL PHASE SEPARATIONS

Abstract Fluorescence spectroscopy was utilized to investigate the equilibrium interaction of dihem-atoporphyrin ether(s) (DHE) with binary and ternary phospholipid mixtures of defined composition in order to define the roles of net negative surface charge and lateral phase separations in DHE-membrane partitioning. Binary phospholipid mixtures employed were composed of dimyristoyl-phosphatidylcholine (DMPC) mixed with increasing weight percentages of dimyristoylphosphatidylgly-cerol (DMPG) providing controlled variation of net membrane surface charge. Two types of ternary phospholipid mixtures were utilized. Ternary acid mixtures contained various percentages of palmitoyl-lysophosphatidyl choline (LPC) + palmitic acid (PA) dispersed in DMPC. Ternary alcohol mixtures contained various percentages of LPC + hexadecanol (OL) dispersed in DMPC. The ternary phospholipid mixtures are known to be phase separated. At total DHE concentrations of 0.33 μA/ and using 100% DMPC, the DHE partition coefficient (P) is 250 000. This partition coefficient is to some extent dependent on the DHE concentration. The observed partition coefficients show little dependence on surface charge in DMPC-DMPG mixtures. However, P decreases markedly with increasing phase separation in the ternary lipid mixtures. The fluorescence of membrane-bound DHE is dependent on the composition of the ternary mixtures in a manner suggesting micropartitioning of DHE into the phospholipid bulk phase as well as into the disordered regions between laterally phase separated phospholipid domains.     

Alkane/Alcohol mixed monolayers at the solid/liquid interface

In this work, we present the behavior of solid monolayers of binary mixtures of alkanes and alcohols adsorbed on the surface of graphite from their liquid mixtures. We demonstrate that solid monolayers form for all the combinations investigated here. Differential scanning calorimetry (DSC) is used to identify the surface phase behavior of these mixtures, and elastic neutron incoherent scattering has been used to determine the composition of the mixed monolayers inferred by the calorimetry. The mixing behavior of the alcohol/alkane monolayer mixtures is compared quantitatively with alkane/alkane and alcohol/alcohol mixtures using a regular solution approach to model the incomplete mixing in the solid monolayer with preferential adsorption determining the surface composition. This analysis indicates the preferential adsorption of alcohols over alkanes of comparable alkyl chain length and even preferential adsorption of shorter alcohols over longer alkanes, which contrasts strongly with mixtures of alkane/alkane and alcohol/alcohol of different alkyl chain lengths where the longer homologue is always found to preferentially adsorb over the shorter. The alcohol/alkane mixtures are all found to phase separate to a significant extent in the adsorbed layer mixtures even when molecules are of a similar size. Again, this contrasts strongly with alkane/alkane and alcohol/alcohol mixtures where, although phase separation is found for molecules of significantly different size, good mixing is found for similar size species.     

Preferential solvation of nifedipine in some aqueous co-solvent mixtures

Preferential solvation parameters of nifedipine (NIF) in ethanol (EtOH) + water and propylene glycol (PG) + water mixtures were obtained from their thermodynamic properties in solution using the inverse Kirkwood–Buff integrals. Preferential solvation parameter (δx_1,3) by both co-solvents is negative in the water-rich mixtures but positive in almost all the other compositions at 293.2, 303.2 and 313.2 K. Nevertheless, in EtOH-rich mixtures the values of δx_1,3 are also negative. It can be assumed that in water-rich mixtures the hydrophobic hydration around the non-polar groups of NIF plays a relevant role in the solvation. The higher drug solvation by co-solvent in mixtures of similar solvent proportions and in co-solvent-rich mixtures could be due mainly to polarity effects. Moreover, in these mixtures the drug could be acting as a Lewis acid with the co-solvents molecules. Finally, in EtOH-rich mixtures the drug could be acting as a Lewis base with water molecules.     

Structure of 1-Propanol–Water Mixtures Investigated by Large-Angle X-ray Scattering Technique

Large-angle X-ray Scattering (LAXS) experiments at 298 K have been made on 1-propanol–water mixtures over the whole 1-propanol mole fraction range. The radial distribution functions show that the predominant clusters in 1-propanol–water mixtures change at 1-propanol mole fraction x _1pr = 0.1; the tetrahedral-like structure of water is mainly formed in the mixtures with x _1pr≤ 0.1, while hydrogen-bonded chain clusters of 1-propanol molecules predominate in the mixtures at x _1pr > 0.1. From the present results, together with the previous ones on methanol–water, ethanol–water, and 2-propanol–water mixtures, size and shape effects of the hydrophobic groups on the structure of aliphatic alcohol–water mixtures are discussed at the molecular level. The anomalies of the enthalpies of mixing for 1-propanol–water mixtures at 298 K are interpreted on the basis of the proposed change in structure of the mixtures with 1-propanol mole fraction.     

渗透汽化膜分离研究的新进展

渗透汽化膜分离技术是当前分离膜研究领域的前沿课题之一.作为化学分离中的重要组成部分,近年来受到高度重视.本文按渗透汽化膜分离的三大类混合液体系有机液脱水、从水相中分离有机物和有机混合液的分离,综述了近几年渗透汽化膜分离技术研究的新进展.其中,又重点报道了有机混合液分离的最新研究成果,将其分为:极性/非极性化合物、芳香烃/脂肪烃体系、芳香烃/脂环烃体系、同分异构体、多元体系和汽油脱硫等六部分进行了详细叙述.文章最后还对渗透汽化膜分离研究进行了展望.     

X-ray structural studies on microscopic mixing in binary mixtures of dimethyl sulphoxide with acetonitrile and N,N-dimethylformamide

The liquid structures of binary acetonitrile (AN)–dimethyl sulphoxide (DMSO) and N,N-dimethylformamide (DMF)–DMSO mixtures were investigated by the X-ray scattering method. Comparison of the X-ray scattering data of AN–DMSO liquid mixtures with those of neat AN and DMSO revealed that the intermolecular AN–DMSO interactions are practically not detected; that is, the X-ray scattering data of the liquid mixtures are well reproduced by summing up those of neat AN and DMSO weighted by their mole fractions. The same applies for DMF–DMSO mixtures. Thus, each component solvent molecule independently forms self-assembled clusters in the liquid mixtures, the structures of which are the same as those in the neat liquids. The clusters are mixed to form macroscopically homogeneous liquid mixtures. The thermodynamic quantities on mixing process for the AN–DMSO, DMF–DMSO and AN–DMF systems in the literature are well elucidated on the basis of the microscopic structure of the liquid mixtures.     

Spectroscopy of laser-induced dielectric breakdown in gas mixtures

Laser-induced dielectric breakdown has been used to initiate fragmentation in molecular gases and gas mixtures. The emission spectra of the atoms, ions, and molecular fragments has been assigned and used to identify specific components of given mixtures. While this study only reports on mixtures of hydrocarbons and halogenated hydrocarbons, the technique is general and does not rely on laser absorption in any component of the mixtures.