Chemical equilibrium model for the thermodynamic properties of mixed aqueous micellar systems: Application to thermodynamic functions of transfer

Mixed micelles can be formed in water between various pairs of hydrophobic solutes such as surfactants, alcohols and hydrocarbons. These systems can often be studied through the thermodynamic functions of transfer of one of the solutes, usually kept near infinite dilution, from water to an aqueous solution of the other solute. When mixed micelles are formed, these functions change significantly, and often go through extrema, in the region where the binary system micellizes or undergoes some microphase transition.Three main effects are responsible for the observed trends: pair-wise interactions between both solutes in the monomeric form, a distribution of the reference solute between the aqueous and micellar phases and a shift in the monomer-micelle equilibrium in the vicinity of the reference solute. Simple equations can be derived for these three effects which can account for the sign and magnitude of the observed trends using parameters which are derived for the most part from the two binary systems.     

Using molecular dynamics simulations to identify the key factors responsible for chiral recognition by an amino acid-based molecular micelle

Molecular dynamics (MD) simulations were used to investigate the binding of six chiral compounds to the amino acid-based molecular micelle (MM) poly-(sodium undecyl-(L)-leucine-leucine) or poly(SULL). The MM investigated is used as a chiral selector in capillary electrophoresis. The project goal was to characterize the chiral recognition mechanism in these separations and to move toward predictive models to identify the best amino acid-based MM for a given separation. Poly(SULL) was found to contain six binding sites into which chiral compounds could insert. Four sites had similar sizes, shapes, and electrostatic properties. Enantiomers of alprenolol, propranolol, 1,1′-bi-2-naphthyl-2,2′-diyl hydrogen phosphate, 1,1′-bi-2-naphthol, chlorthalidone, or lorazepam were separately docked into each binding pocket and MD simulations with the resulting intermolecular complexes were performed. Solvent-accessible surface area calculations showed the compounds preferentially associated with binding sites where they penetrated into the MM core and shielded their non-polar atoms from solvent. Furthermore, with five of the six compounds the enantiomer with the most favorable free energy of MM association also experienced the most favorable intermolecular hydrogen bonding interactions with the MM. This result suggests that stereoselective intermolecular hydrogen bonds play an important role in chiral discrimination in separations using amino acid-based MMs.GRAPHICAL ABSTRACT     

非水层状液晶的稳定性与相行为

水体系层状液晶已研究较久,非水层状液晶则是近十年来才得到发展。本文以层状液晶的相行为和~2H NMR测量,研究并比较了非水层状液晶十二烷基硫酸钠/正癸醇溶剂以甘油或甲酰胺为溶剂时体系的结构与稳定性。 表面活性剂十二烷基硫酸钠(BDH,简写SDS)经无水乙醇重结晶两次提纯。用铂环法测     

Ionene–surfactant complexes: temperature and humidity sensitive materials

Solid stoichiometric complexes of [3,12]-ionene and dodecyl sulfate form upon reaction of the bromide of the ionene and the silver salt of dodecyl sulfate in methanol. IR, DSC, and TG investigations indicated that the solid complexes are stable between 30 and 120 °C. TG and DSC also showed that the complexes easily take up water at ambient conditions. These samples are optically isotropic. When exposed to an increased humidity they exhibit optical anisotropy, i.e., birefringence, which is caused by the formation of a hexagonal mesogenic phase. Mesogenicity is necessarily accompanied by a further uptake of water (4–5 H₂O molecules per ionic unit), which is dependent on the relative humidity. The phase behavior as a function of temperature and controlled relative humidity was studied using birefringence measurements and polarizing microscopy.     

Influence of 1-decanol on the surface tension and wetting power of a new anionic surfactant derived from sugar

We studied the adsorption behaviour at the liquid/air and liquid/solid interface of a new anionic surfactant derived from sugar, the sodium decyl galacturonate. The surface tension of aqueous solutions, measured in equilibrium and as a function of time, is particularly affected by the presence of decanol, synthesis residue, which amount ranges between about 0 and 13%. The surface tension lowering is accelerated in presence of decanol, owing to its rapid diffusion to the interface or/and because it affects the mobility and adsorption process of the anionic surfactant molecules. The wetting power of surfactant solutions were also investigated in relation with textile treatment applications. We measured the kinetics of absorption of surfactant solutions in a piece of standard cotton and compared it to the absorption of pure decanol, a completely wetting liquid and to the absorption of an alkylpolyglucoside. The time at which the fabric piece is saturated appears to be related to the adsorption of surface-active molecules on the fibers at the advancing liquid front/fabric contact line. Decanol was found to promote absorption and micellar life-time seem to reflect the differences observed at high concentration. This study shows the importance of controlling the amount of surface-active residues which may alter the kinetics of surfactant adsorption, particularly in industrial processes where equilibrium conditions are not reached.     

Interaction of Fluorocarbon Containing Hydrophobically Mdified Polyelectrolyte with Nonionic Surfactants

The interaction of fluorocarbon containing hydrophobically modified polyelectrolyte(FMPAANa) with two kinds of nonionic surfactants(hydrogenated and fluorinated)in a semidilute (0.5wt%) aqueous solution had been studied by rheological measurements,Association behavior was found in both systems.The hydrophobic interaction of FMPAANa with fluorinated surfactant(FC171) is much stronger than that with hydrogenated surfactant(NP7.5) at low surfactoant concentrations.The interaction is strengthened by surfactants being added for the density of active junctions increased.Whereas distinct phenomena for FC171 and NP7.5 start to be found as the surfactants added over their respective certain concentration.The interaction of polyelectrolyte with fluorinated surfactant increases dramatical ly while that with hydrogenated surfactant decreases.     

表面改性对CeO2纳米粉体特性的影响

研究了表面改性对CeO2纳米粉体特性的影响，采用表面活性剂．十二烷基硫酸钠对CeO2粉末颗粒表面进行了改性。未改性和改性的纳米氧化铈用粉体综合性能测试仪、激光粒度仪、比表面积测试仪、X射线仪、扫描电子显微镜进行了表征。结果表明，用十二烷基硫酸钠表面改性能提高纳米氧化铈的流动性和分散性，减小比表面积和团聚，同时也对CeO2粉体颗粒表面改性的机制进行了探讨。     

Mesoscopic simulation of the aggregation behavior of fluorinated surfactant in aqueous solution

The aggregation behavior of fluorinated surfactant in aqueous solution was investigated using dissipative particle dynamics (DPD) simulation method. Simulation results show that fluorinated surfactants behave mainly as their hydrocarbon analogues, having similar sequences of phases and aggregate structures, which are capable of building micelle, hexagonal phase and lamellar phase. But fluorinated surfactants also show interesting differences from hydrocarbon analogues, which can easily form hexagonal and lamellar structures with comparative little curvature. They can also form ellipsoid or rod-like micelles even in very low concentrations instead of spheroid ones. The dynamic aggregation behavior of fluorinated surfactants, as well as the comparison with hydrogenated ones, was also investigated.     

Binary and Ternary Complexes Between Lauryl Hexaoxyethylene, Benzoate and Cyclodextrin. Part II. β-CD

The characterization of binary and ternary complexes of benzoate, lauryl hexaoxyethylene (C₁₂E₆) and -CD is presented. The complexation equilibrium was characterized by UV-Vis spectrophotometry, titration microcalorimetry, capillary electrophoresis, and 2D ROESY ¹H-NMR. Results suggested that -CD forms one complex with C₁₂E₆in the stoichiometric ratio of -CD : C₁₂E₆1.5 : 1, with a stability constant 1.3 × 10⁵ M^-1.5. The 2-D ROESY ¹H-NMR spectrum indicated that C₁₂E₆is included inside the -CD cavity. The primary binding site of C₁₂E₆ is on the lauryl subunit of this molecule. Analogous to a previously reported study of -CD, the combination of -CD and C₁₂E₆precipitated from the solution. Addition of benzoate seemed to dissolve the precipitate and nearly doubled the apparent stability constant of the complex. Results from the various techniques supported formation of ternary complexes between -CD, C₁₂E₆, and benzoate.