Micellization of Sodium Dodecyl Sulfate in Glycerol Aqueous Mixtures

The effect of glycerol on both micellar formation and the structural evolution of the sodium dodecyl sulfate (SDS) aggregates in the context of the action mechanism of the cosolvent has been studied. The critical micelle concentration and the degree of counterion dissociation of the surfactant over a temperature range from 20°C to 40°C were obtained by the conductance method. The thermodynamic parameters of micellization were estimated by using the equilibrium model of micelle formation. The analysis of these parameters indicated that the lower aggregation of the surfactant is mainly due to a minor cohesive energy of the mixed solvent system in relation to the pure water. The effect of glycerol on the mean aggregation number of the micelles of SDS was analyzed by the static quenching method. It was found that the aggregation number decreased with the glycerol content. This reduction in the micellar size seems to be controlled by an increase in the surface area per headgroup, which was ascribed to a participation of glycerol in the micellar solvation layer. Studies on the micropolarity of the aggregates, as sensed by the probe pyrene, indicated that this microenvironmental parameter is almost unaffected by the presence of glycerol in the mixture. However, an increase in the micellar microviscosity at the surface region was observed from the photophysical behavior of two different probes, rhodamine B and auramine O. These results suggest a certain interaction of the cosolvent in the micellar solvation of SDS micelles.     

MULTIPLE EMULSIONS STABILIZED BY COLLOIDAL MICROGRYSTALLINE CELLULOSE

Multiple emulsions stabilized by colloidal microcrystalline cellulose (CMCC, Avicel RC591) at the w/o and o/w interfaces, and by the addition of Span 80 or Span 85 at the w/o interface, were studied by means of brightfield microscopy, freeze-etch electron microscopy, droplet size distribution analysis and rheologic measurements. Stable multiple emulsions were prepared by incorporation of sodium chloride in the innermost aqueous phase, thereby creating an osmotic gradient preventing loss of the inner aqueous phase to the external aqueous phase. Freeze-etch electron microscopy of the multiple emulsions indicated the presence of a network of microcrystalline cellulose at the outer o/w interface. It may be assumed that the surfactant directly stabilized the w/o interface by adsorption at the interface, as well as indirectly by facilitating wetting of the microcrystalline cellulose by the oil. From rheologic measurements, the existence of a three-dimensional network in the external aqueous phase was indicated by the considerable degrees of thlxotropy and significant static yield values of these multiple emulsions.     

Synthetic Approach Toward the Partial Sequences of Betaglycan in the Linkage Region on Solid Support and in Solution Phase

We have synthesized, for the first time, the partial sequence of the betaglycan composed of the tetraosyl hexapeptide, which was directly usable as a probe for enzymatic glycosyl transfer. Stepwise elongation afforded the corresponding tetraosyl trichloroacetimidate. The common glycosyl dipeptide:[β‐d‐GlcA‐(1→3)‐β‐d‐Gal‐(1→3)‐β‐d‐Gal‐(1→4)‐β‐d‐Xyl‐(1→O)‐Ser‐Gly] was synthesized by glycosylation of the corresponding tetraosyl trichloroacetimidate and Ser‐Gly moiety. The glycosyl dipeptide was coupled with other core peptide parts in solution phase and on a solid support. These glycosyl hexapeptides were then transformed into the desired target compounds.     

Micellar Effects on the Oxidation of d‐Glucose by Chromic Acid in Perchloric Acidic Medium

Kinetics of the reaction between d‐glucose and Cr(VI) in the absence and presence of surfactant micelles have been studied by a spectrophotometric method in aqueous‐acidic solutions of perchloric acid. It was observed that the reaction has a nonautocatalytic followed by an autocatalytic pathway. The rate of the initial stage increases with increase in [glucose], [HClO₄] and temperature. Due to precipitation, the effect of cationic micelles of cetyltrimethylammonium bromide (CTAB) could not be studied whereas the oxidation is catalyzed by anionic micelles of sodium dodecyl sulfate (SDS) and nonionic micelles of Triton X‐100 (TX‐100). The results are discussed in terms of the pseudo‐phase kinetic model. Activation parameters are evaluated and a mechanism consistent with the results is proposed. A rate law for the reaction has also been derived. The redox reaction occurs through a Cr(VI)→Cr(IV) path.     

十二烷基硫酸钠水溶液的动态表面吸附性质

利用MPTC型气泡压力张仪研究了十二烷基硫酸钠(SDS)溶液在不同NaCl 浓度下的动态表面吸附性质, 分析了离子型表面活性剂在表面吸附层和胶束中形成双电层结构产生表面电荷对动态表面扩散过程和胶束性质的影响. 结果表明, SDS在表面吸附过程中, 表面电荷的存在会产生5.5 kJ·mol^-1的吸附势垒(E_a), 显著降低十二烷基硫酸根离子(DS^-)的有效扩散系数(D_eff). 十二烷基硫酸根离子的有效扩散系数与自扩散系数(D)的比值(D_eff/D)仅为0.013, 这表明SDS与非离子型表面活性剂不同, 在吸附初期为混合动力控制吸附机制. 加入NaCl可以降低吸附势垒. 当加入不小于80 mmol·L^-1 NaCl后, E_a小于0.3 kJ·mol^-1, D_eff/D在0.8-1.2之间, 表现出与非离子型表面活性剂相同的扩散控制吸附机制. 同时, 通过分析SDS胶束溶液的动态表面张力获得了表征胶束解体速度的常数(k₂). 发现随着NaCl 浓度的增大, k₂减小, 表明SDS胶束表面电荷的存在会增加十二烷基硫酸根离子间的排斥力, 促进胶束解体.     

石墨烯/硫酸铅复合材料的制备及其在铅酸电池中的电化学性能

利用简单的浸渍法制备了石墨烯/硫酸铅复合材料,使得硫酸铅可以直接用作铅酸电池负极材料。该复合材料分别以100 mA·g^-1、200 mA·g^-1和300 mA·g^-1电流密度放电时,平均放电比容量分别可达到110、94和69 mAh·g^-1,而硫酸铅仅为49、5和0.5 mAh·g^-1,显示出复合材料在高倍率充放电下更好的比容量和再接受充电能力。循环伏安测试表明石墨烯的电容效应随扫描速率增大而增强,同时析氢也变得严重,使得复合材料在充放电过程中充电效率比纯硫酸铅低20%。在充放电过程中,石墨烯能够提高硫酸铅1倍以上的放电容量,并将充电电压提高0.1 V。XRD和SEM结果显示硫酸铅均匀分布在石墨烯片层上,没有出现团聚现象。     

Enantioselective Reduction of Prochiral Ketones with NaBH4/Me2SO4/(S)-Me-CBS

The enantioselective reduction of prochiral ketones with NaBH₄/Me₂SO₄/(S)-Me-CBS is described. Borane is generated in situ via the reaction of NaBH₄ with Me₂SO₄ in tetrahydrofuran, which is as efficient as the commercial one. Such in situ–generated borane reagent was applied to reduce prochiral ketones in the presence of chiral oxazaborolidine catalyst directly. The corresponding chiral secondary alcohols were obtained with excellent enantiomeric excesses (93–99% ee) and good to excellent yield (80–99%).     

A rapid way to synthesize Brønsted acidic ionic liquid and its application as an efficient catalyst for esterification

A novel and time-saving method to prepare a Brønsted acidic ionic liquid, 1-carboxymethyl-3-methylimidazolium hydrogen sulfate ([CMI][HSO₄]), in high yield and purity was performed under microwave irradiation. The ionic liquid showed an incomparable catalytic efficiency in the microwave-accelerated esterification of arenecarboxylic acids. Moreover, its ability of being recovered and reused many times without loss of activity has made [CMI][HSO₄] more favorable from the viewpoint of green chemistry.     

In situ single‐crystal to single‐crystal (SCSC) transformation of the one‐dimensional polymer catena‐poly[[diaqua(sulfato)copper(II)]‐μ2‐glycine] into the two‐dimensional polymer poly[μ2‐glycine‐μ4‐sulfato‐copper(II)]

The one‐dimensional coordination polymer catena‐poly[diaqua(sulfato‐κO)copper(II)]‐μ₂‐glycine‐κ²O:O′], [Cu(SO₄)(C₂H₅NO₂)(H₂O)₂]_n, (I), was synthesized by slow evaporation under vacuum of a saturated aqueous equimolar mixture of copper(II) sulfate and glycine. On heating the same blue crystal of this complex to 435 K in an oven, its aspect changed to a very pale blue and crystal structure analysis indicated that it had transformed into the two‐dimensional coordination polymer poly[(μ₂‐glycine‐κ²O:O′)(μ₄‐sulfato‐κ⁴O:O′:O′′:O′′)copper(II)], [Cu(SO₄)(C₂H₅NO₂)]_n, (II). In (I), the Cu^II cation has a pentacoordinate square‐pyramidal coordination environment. It is coordinated by two water molecules and two O atoms of bridging glycine carboxylate groups in the basal plane, and by a sulfate O atom in the apical position. In complex (II), the Cu^II cation has an octahedral coordination environment. It is coordinated by four sulfate O atoms, one of which bridges two Cu^II cations, and two O atoms of bridging glycine carboxylate groups. In the crystal structure of (I), the one‐dimensional polymers, extending along [001], are linked via N—H...O, O—H...O and bifurcated N—H...O,O hydrogen bonds, forming a three‐dimensional framework. In the crystal structure of (II), the two‐dimensional networks are linked via bifurcated N—H...O,O hydrogen bonds involving the sulfate O atoms, forming a three‐dimensional framework. In the crystal structures of both compounds, there are C—H...O hydrogen bonds present, which reinforce the three‐dimensional frameworks.     

Raman spectroscopic characterization of urine of normal and oral cancer subjects

Urine is considered as one of the diagnostically important bio fluids, as it has many metabolites. The distribution and the physiochemical properties of the metabolites may vary during any altered metabolic and pathological conditions. Raman spectroscopy was employed in the characterization of the metabolites of human urine of normal subjects and oral cancer patients in the finger print region (500–1800 cm⁻¹). Principal component analysis‐based linear discriminant analysis was performed to discriminate cancer patients from normal subjects. The discriminant analysis classifies the cancer patients from normal subjects with a sensitivity and specificity of 98.6% and 87.1%, respectively, with an overall accuracy of 93.7%. Copyright © 2014 John Wiley & Sons, Ltd.