Surfactant effect on enhancing (S)-naproxen prodrug production from racemic naproxen by lipase

In the enantioselective esterification of racemic naproxen with 4(2-hydroxyethyl) morpholine by Lipase MY in organic solvents, a productivity improvement of the desired (S)-naproxen ester from 0.42 to 0.72 mM at the reaction time of 130 h was observed, when the surfactantbis (2-ethylhexyl) sodium sulfosuccinate (AOT) was added in the reaction mixture. The presence of a small amount of exogenously added water dramatically activated the enzyme in AOT/cyclohexane-reversed micelles. Desorption of the surfactant molecule from the enzyme mass and solubilization of the enzyme into reversed micelles were used to elucidate an existing maximum of the initial rate of (S)-naproxen synthesis with the water content. Moreover, the effects of alcohol and surfactant concentration on the enzyme activity are reported.     

氧乙烯基对胶团化过程热力学函数的影响

利用表面张力法测定了各种条件下C_8H_(17)(OC_2H_4)_n-SO_4Na(C_8E_nS; n=0,1,3)的cmc, 并计算了胶团的反离子结合度、胶团化过程中的自由能(ΔG°)和熵变(ΔS°)。结果发现: C_8E_nS的cmc随n的增加而下降, 并且下降的幅度逐渐变小; 胶团的反离子结合度也随n的增加而减小; ΔS°随n的增加而增加, 但增加的幅度逐渐变小, 对于离子和非离子表面活性剂都是如此。人们认为这是由于氧乙烯基(EO)具有亲水和疏水二重性, 随着EO数的增加, EO的疏水性相对减弱而亲水能力将相对增加所致。EO的这个特点, 是它在表面活性剂分子中具有特殊表现的根本原因。     

Self aggregation of binary mixtures of sodium dodecyl sulfate and polyoxyethylene alkyl ethers in aqueous solution

The mixed micelles of sodium dodecyl sulphate (SDS) with Brij35 and Brij 97 were studied separately by fluorescence measurement using pyrene as fluorescent probe. In the range of 0–1.0 mole fraction (X) of added SDS to Brij solutions, the cmc value of the mixed micelles varies from 0.085 to 8 mmol with Brij 35 and 0.04 to 8 mmol with Brij 97. The aggregation number also changes. A measure of the stability of mixed micelles is also presented. The interaction parameter ₁₂ and the chain–chain contribution parameter (B₁) are extracted from the analysis of the results. This parameter B₁ is related to the standard free energy change associated with the introduction of one ionic species into a nonionic micelle coupled with the release of one nonionic species from the micelle. The clouding behaviour of Brij 97 in the presence of SDS was investigated and the associated thermodynamic parameters of clouding were generated and discussed.     

阴阳离子型表面活性剂双水相萃取色氨酸衍生物和牛血清白蛋白

溴化十二烷基三乙胺（Ｃ１２ＮＥ）和十二烷基硫酸钠（ＳＤＳ）在一定条件下混合可以形成具有清晰界面的两个水相，称为阴阳离子型表面活性剂双水相。作者研究了利用该双水相萃取３种色氨酸衍生物和牛血清白蛋白的可能性．文中采用工作曲线校正扣除表面活性剂背景的影响，萃取结果准确可信。     

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.     

Determination of low levels of polymer additives migrating from polypropylene to food simulated liquids by capillary SFC and solvent venting injection

Summary Methods for the determination of specific migration of polymer additives from polypropylene to aqueous acetic acid and isooctane have been studied. The migrants were extracted from aqueous acetic acid and characterized by supercritical fluid chromatography (SFC) with flame ionization detection (FID) and mass spectrometry (MS). The isooctane simulant was concentrated and injected directly into the SFC. Injection of extracts after incubation, using the solvent venting injection technique in the SFC, enabled additive concentrations as low as 10 ppb in 150 ml simulant to be determined, corresponding to a specific migration level of approximately 1 g additive/dm² polymer.     

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     

一种新型两性表面活性剂的合成

两性表面活性剂分子既含有阳离子亲水基,又含有阴离子亲水基,因而有其它表面活性剂所不具备的优异性能。本文将月桂酸和N-(2-羟乙基)乙二胺热缩合脱水,得到2-十一烷基-1-(2-羟乙基)-2-咪唑啉(1)。接着在还原剂的作用下,咪唑啉环碳氮双键还原并开环得到一般方法难以合成的N,N-二取代乙二胺(2)。(2)通过甲酰化(3)季铵化,引入两性离子,得到     

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.