鼠李糖脂的合成及pH值对其表面活性和微乳微结构的影响

从铜绿假单胞菌发酵液中提取纯化鼠李糖脂生物表面活性剂. 用高效液相色谱-电喷雾质谱法(HPLC-ESI-MS)对鼠李糖脂提取物的组成进行了测定. 用临界胶束浓度(CMC)分析了pH值对其表面活性的影响, 用微乳液滴粒径和灼电位考察了pH值对鼠李糖脂/正庚烷/硼砂缓冲液微乳体系微结构的影响. 结果表明, 在弱碱性条件下(pH7.5-9.5), pH的变化对鼠李糖脂的表面活性和微乳微结构均有显著影响. pH小于9.0时, CMC随着pH的升高而降低, 在pH 9.0处达到最低. pH大于9.0时, CMC随着pH值的升高而逐渐升高. 这是氢键和极性头基间的静电排斥力共同作用的结果. 微乳液滴的粒径及灼电位绝对值都随pH值的升高呈增大趋势, 只在pH 9.0处例外. 少量十二烷基硫酸钠(SDS)或正丁醇的加入都使微乳粒径明显增大.     

微乳毛细管电动色谱快速分析脂溶性维生素

建立了一种新的微乳体系,成功地应用于微乳毛细管电动色谱(MEEKC)快速分析脂溶性维生素VA、VD3和VE.本微乳液的组成为:1.2%(m/m)十二烷基硫酸钠(SDS)-21%(V/V)正丁醇-18%(V/V )乙腈-0.8%(m/m)正己烷-20 mmol/L H3BO3-Na2B4O7缓冲液( pH 8.4 ).该微乳体系中,助表面活性剂正丁醇和有机溶剂乙腈对脂溶性维生素的分离起到了重要的作用.当分离电压为25 kV,柱温为25 ℃时,VA、VD3和VE在13 min内达到基线分离.3种脂溶性维生素的迁移时间和峰面积的RSD(n= 5)<2.5%和4.5%;VA、VD3和VE分别在20～1000、5～1000和5～1000 mg/L范围内与峰面积呈线性关系;检出限(S/N=3)分别为12、 0.72和0.29 mg/L.本体系应用于市售VE胶囊的测定,结果与标示值相符.     

微乳体系相图及其在液相色谱分离多组分药物应用的研究

采用滴加法和电导率法绘制了十二烷基硫酸钠(SDS)/正丁醇/油相(正辛醇、正辛烷、正庚烷、正己烷)/水四组分微乳体系的拟三元相图。以O/W型微乳区域大小为指标,考察不同油相、表面活性剂与助表面活性剂的质量比对微乳形成的影响,并通过测定电导率、相对粘度以及表面张力等物理化学参数,考察了微乳体系的相行为及特性。根据得到的微乳体系相图,进行色谱条件优化,建立了快速、稳定的测定阿莫西林舒巴坦匹酯片剂中阿莫西林与舒巴坦匹酯二组分含量的方法,结果显示此微乳分离系统有较好的色谱适用性及方法可行性。     

大气中无机盐粒水解过程中的微液滴现象

采用改变相对湿度, 无机盐/金属组合, 测定微液滴体系的pH值和电位分布等方法研究了微液滴形成和生长的特征. 结果表明, 微液滴的形成与大气腐蚀密切相关. 微液滴只在特定的盐粒/金属体系中出现, 微液滴区域具有较高的pH值和较高的电位分布. 此外, 微液滴形成和生长需要两个前提条件：第一, 环境相对湿度应高于盐粒水解液滴液面的饱和蒸汽压；第二, 在水解液滴下的金属能被液滴腐蚀.     

皂化P204微乳体系萃取大豆蛋白的研究

研究了NaOH皂化P204/正辛烷微乳体系萃取大豆蛋白的机理和工艺,考察了大豆加入量、P204的浓度、NaOH的浓度、萃取时间、水相pH值及离子强度等对大豆蛋白萃取率的影响。实验结果表明,该微乳体系萃取大豆蛋白的优化工艺条件为:大豆粉与微乳液的质量体积比1∶10,P204在油相中浓度0.8 mol/L,NaOH的浓度1.25 mol/L,萃取时间15 min,外水相pH值5,萃取率可达88.48%。通过调节水相pH和离子强度可实现大豆蛋白的萃取和反萃取。     

离子液体作为添加剂的反向微乳毛细管电动色谱分析化妆品中的糖皮质激素

建立了以离子液体为添加剂的反向微乳毛细管电泳(IL-MEEKC)法分离测定化妆品中氢化可的松、泼尼松和醋酸氢化可的松3种糖皮质激素的方法.微乳毛细管电泳的最佳缓冲体系组成为:2.4% SDS+6.6%正丁醇+0.5%正辛烷+35 mmol/L BMIM-BF4+20 mmol/L磷酸二氢钠缓冲液(pH 2.2);运行电...     

AOT/H_2O/油微乳液体系的浊度、密度和微观结构

建立了通过精密测量密度、折射率和浊度研究微乳液滴微观性质的方法,获得水与表面活性剂的摩尔比r分别为10.5和12的AOT/H2O/甲苯微乳液体系液滴的微观结构及相互作用参数,得到AOT分子的长度L=1.07nm,用液滴间的相互作用讨论了相变温度与r的关系.用L=1.07nm,通过密度测量得到AOT/H2O/甲苯和AOT/H2O/环己烷两个微乳液体系不同r值下液滴的微观结构参数,与文献报导的数据吻合得很好.发现在微乳液滴中的水的密度明显大于自由水的密度,并随溶剂变化,而AOT分子的构型不变.     

微乳液相色谱法同时分离7种水溶性维生素

采用微乳液相色谱法同时分离7种水溶性维生素(V_(B1)、V_(B2)、V_(B6)、VB_(12)、叶酸、烟酰胺和VC)。考察了微乳流动相体系中表面活性剂、油相、助表面活性剂的种类以及流动相的pH值、柱温等对水溶性维生素分离的影响。优化后微乳体系的组成为:十二烷基硫酸钠(SDS)/聚氧乙烯月桂醇醚(Brij35)/正丁醇/乙酸乙酯/水(质量比为2∶60∶66∶8∶864)。色谱柱为Agilent TC C18(250 mm×4.6 mm,5μm),柱温为30℃,检测波长为254 nm,流速为0.5mL/min。7种水溶性维生素在20 min内达到基线分离。在4~36 mg/L范围内,7种水溶性维生素的质量浓度与峰面积的相关系数均大于0.999 1。不同添加水平下,V_(B1)、V_(B2)、V_(B6)、VC和烟酰胺的平均回收率为93.9%~102.9%。该方法可用于食品和药品中的多种水溶性维生素的分离、鉴别及快速测定。     

AOT/H2O/油微乳液体系的浊度、密度和微观结构

建立了通过精密测量密度、折射率和浊度研究微乳液滴微观性质的方法,获得水与表面活性剂的摩尔比r分别为10.5和12的AOT/H2O/甲苯微乳液体系液滴的微观结构及相互作用参数,得到AOT分子的长度L=1.07 nm,用液滴间的相互作用讨论了相变温度与r的关系.用L=1.07 nm,通过密度测量得到AOT/H2O/甲苯和AOT/H2O/环己烷两个微乳液体系不同r值下液滴的微观结构参数,与文献报导的数据吻合得很好.发现在微乳液滴中的水的密度明显大于自由水的密度,并随溶剂变化,而AOT分子的构型不变.     

磁场对苯胺微乳液聚合体系相行为的影响

通过十二烷基苯磺酸钠(SDBS)/正丁醇(n-butanol)/苯胺/水微乳液体系的拟三元相图,考察了恒定磁场(0.4T)和助表面活性剂与表面活性剂的质量比(Km=mn-butanol/mSDBS)对苯胺微乳液聚合体系的相行为、电导行为以及微乳化作用的影响.结果表明:随着体系醇含量的增加,微乳区面积先增大后减小,当Km值为1.0时,形成的微乳区最大;外加磁场可以增大微乳区面积.通过对外加磁场条件下溶液电导率随水含量变化规律的分析,印证了拟三元相图的表征结果.透射电镜分析结果表明,磁场条件下合成的聚苯胺颗粒比无磁场条件下合成的聚苯胺颗粒小.     

Electric field-induced mobilisation of multiphase solution systems based on the nitration of benzene in a micro reactor

This paper describes the electric field-induced flow characteristics of multiphase solutions in a micro reactor device using the nitration of benzene as a model process. Photolithographic and wet etching techniques were used to fabricate the micro reactor (channels, 200 microns id, 100 microns deep) in a borosilicate glass substrate. The results focus specifically on the flow parameters of reagents/reactants (i.e., voltage, solution concentration and pH ranges and current-voltage relationships) used in this study. The benzene was introduced and mobilised by electroosmotic flow (EOF), as a microemulsion using an appropriate surfactant (sodium dodecyl sulfate), whilst the nitronium ions, produced in situ from mixed H2SO4-HNO3 (the nitrating agent), underwent electrophoretic-induced (electrokinetic) mobility. A co-surfactant, butan-1-ol, was used owing to (a) its relative solubility in the aqueous surfactant solution, (b) its ability to aid the solubilization of benzene, (c) the provision of a water-rich (oil-in-water) rather than oil-rich (water-in-oil) microemulsion system and (d) its lack of significant adverse effects on the EOF. The optimum conditions used for the nitration of benzene within the micro reactor were a run of the microemulsion as main reagent stream, then three 30 s segmented injections of mixed acid, with a 5 s push of the microemulsion into the system after each injection, and then a 60 s stopped-flow reaction time before driving reaction product segments to a collection reservoir.     

Chiral separation of β‐blockers by MEEKC using neutral microemulsion: Analysis of separation mechanism and further elucidation of resolution equation

Based on the investigation of the effect of microemulsion charge on the chiral separation, a new chiral separation method with MEEKC employing neutral microemulsion was established. The method used a microemulsion containing 3.0% (w/v) neutral surfactant Tween 20 and 0.8% (w/v, 30 mM) dibutyl l ‐tartrate in 40 mM sodium tetraborate buffer to separate the enantiomers of β‐blockers. The effect of major parameters on the chiral separation was investigated. The applied voltage had little effect on the resolution, but the chiral separation could be improved by suppressing the EOF. Nine racemic β‐blockers obtained relatively good enantioseparation after appropriate concentrations of tetradecyl trimethyl ammonium bromide were added into the microemulsion to suppress the EOF. These results were explained based on the analysis of the separation mechanism of the method and deduced separation equations. The resolution equation of the method was further elucidated. It was found that the fourth term in the resolution equation, an additional term compared to the conventional resolution equation for column chromatography, represents the ratio of the relative movement distance between the analyte and microemulsion droplets relative to the effective capillary length. It can be regarded as a correction for the effective capillary length. These findings are significant for the development of the theory of MEEKC and the development of new chiral MEEKC method.     

Electrophoretic separations in poly(dimethylsiloxane) microchips using a mixture of ionic and zwitterionic surfactants

The use of mixtures of ionic and zwitterionic surfactants in poly(dimethylsiloxane) (PDMS) microchips is reported. The effect of surfactant concentration on electroosmotic flow (EOF) was studied for a single anionic surfactant (sodium dodecyl sulfate, SDS), a single zwitterionic surfactant (N-tetradecylammonium-N,N-dimethyl-3-ammonio-1-propanesulfonate, TDAPS), and a mixed SDS/TDAPS surfactant system. SDS increased the EOF as reported previously while TDAPS showed an initial increase in EOF followed by a reduction at higher concentrations. When TDAPS was added to a solution containing SDS, the EOF decreased in a concentration-dependent manner. The EOF for all three surfactant systems followed expected pH trends, with increasing EOF at higher pH. The mixed surfactant system allowed tuning of the EOF across a range of pH and concentration conditions. After establishing the EOF behavior, the adsorption/desorption kinetics were measured and showed a slower adsorption/desorption rate for TDAPS than SDS. Finally, the separation and electrochemical detection of model catecholamines in buffer and reduced glutathione in red blood cell lysate using the mixed surfactant system were explored. The mixed surfactant system provided shorter analysis times and/or improved resolution when compared to the single surfactant systems.     

Microemulsion electrokinetic chromatography in suppressed electroosmotic flow environment. Separation of fat-soluble vitamins

Microemulsion electrokinetic chromatography (MEEKC) was carried out in a pH 2.5 phosphate buffer to effectively suppress the electroosmotic flow (EOF). With 66.6% (w/w) 25 mM phosphate buffer pH 2.5, 20.0% (w/w) 2-propanol, 6.6% (w/w) 1-butanol, 6.0% (w/w) sodium lauryl sulphate (SDS), and 0.8% (w/w) n-octane as the separation medium, the fat-soluble vitamins A palmitate, E acetate, and D3 were baseline separated within 11 min. With strongly suppressed EOF, the polarity of the separation voltage was reversed (positive electrode at the outlet); the n-octane micro droplets surrounded by negatively charged SDS molecules migrated towards the detector. The aqueous part of the microemulsion was modified with 20% (w/w) 2-propanol to improve partition between the n-octane phase and the surrounding aqueous medium. The fat-soluble vitamins were separated in order of decreasing hydrophobicity with a high migration time stability (repeatable within 0.1% RSD). Excellent accuracy and precision were obtained when the system was applied for the determination of vitamin E acetate in commercial vitamin tablets; quantitative data corresponded to 97.0% of label claim, intra-day results varied within 1.72% RSD (n=6), and inter-day results varied within 3.22% RSD (n=5).     

PHASE BEHAVIOR OF BRANCHED TAIL ETHOXYLATED CARBOXYLATE SURFACTANT/ELECTROLYTE/ALKANE SYSTEMS.

This paper describes the effect of pH on phase behavior of branched tail EO carboxylate surfactants in electrolyte/ alkane microemulsion system3 which are of possible pertinence to enhanced oil recovery. The pH of the aqueous surfactant solutions was found to have a considerable effect on the salinity requirement for middle phase microemulsion formation. At 70 and 60°C alcohol-free optimal three phase microemulsion systems are formed with all alkanes studied over the entire pH range of 6-12. At lower temperatures and. higher pH values, liquid crystals were found to form in systems which contained lower molecular weight alkanes.     

Preparation and in vitro Release Test of Insulin Loaded W/O Microemulsion

A W/O microemulsion of Tween‐80‐Span‐80/n‐butylalcohol/ethyl‐oleate/H₂O to envelop insulin (INS) was prepared. In order to obtain the maximum solved water, the components of microemulsion to envelop INS were chosen with the pseudo‐ternary phase diagram and the influences of temperature, salinity as well as the pH on microemulsion areas also were investigated. To test the properties of the microemulsion, the conductance was used to divide O/W, W/O and BC regions, the dynamic light scattering to evaluate the particle diameters of microemulsion, the ¹²⁵I isotope tracing method to measure the release rate of INS loaded in W/O microemulsion, and the growth inhibitory effect test to appraise the cytotoxicity on human normal cells. Results show that W/O microemulsion forms when water content below 50% in the microemulsion system. The microemulsion region decreases slightly with the increase of temperature, salinity and the decrease of pH. However, the viscosity measurements along certainly selected dilution lines to the microemulsion indicate that no phase invert occurred. Diameter of microemulsion particle increases with the addition of INS, and the increase is sharp in the first 5 days then very slightly at 68.6 nm within a month. The INS loaded W/O microemulsion possesses eminent sustaining release efficiency and the cytostatic as well as cytotoxic assays illustrate that the microemulsion can be used as drug delivery at small dosage.     

Microemulsion electrokinetic chromatography of corticosteroids. Effect of surfactants and cyclodextrins on the separation selectivity

The separation of neutral hydrophobic corticosteroids (cortisone, cortisone acetate, hydrocortisone, hydrocortisone acetate, prednisolone and prednisolone acetate) by microemulsion electrokinetic chromatography (MEEKC) was studied. In the preparation of microemulsion, heptane was the solvent, n-butanol the co-surfactant and, as anionic surfactants, sodium dodecyl sulfate (SDS) or taurodeoxycholic acid sodium salt (STDC) were employed. Using an acidic running buffer, (phosphate pH 2.5) a strong suppression of the electroosmotic flow (EOF) was observed; this resulted in a fast anodic migration of the analytes partitioned into the negatively charged microemulsion droplets. Under these conditions, STDC showed better separation of corticosteroids than the conventional SDS; however, the use of a single anionic surfactant did not provide the required selectivity. The addition of the neutral surfactant polyoxyethylene glycol octadecyl ether (Brij 76) significantly altered the migration of each analytes allowing a better tuning of separation; however, in order to obtain adequate resolution between couples of adjacent critical peaks, the addition of neutral cyclodextrins (CDs) was found to be essential. This apparently complex system (CD-MEEKC), was optimized by studying the effect of the most important parameters affecting separation: STDC concentration, Brij 76 concentration, nature and concentration of cyclodextrins. Following a rational step-by-step approach, the optimised conditions providing the complete separation of the analytes were found to be: 4.0% STDC, 2.5% Brij 76, 6.6% n-butanol, 1.36% heptane and 85.54% of a solution 5 mM beta-CD in 50 mM phosphate buffer (pH 2.5). The optimized system was preliminary applied to the detection of corticosteroids related substances at impurity level and it could be considered a useful orthogonal alternative to HPLC methods.     

Study on the Activity and Kinetic Characteristics of Glucoamylase in W/O Microemulsion Systems

The activity and kinetic characteristics of glucoamylase has been investigated in W/0 microemulsion systems of AOT/isooctane/buffer, CTAB/isooctane/l-pentanol/buffer and TX-100/ibooctane/I-pentanol/buffer, and compared with that in aquous solution. The effect of various parameters, such as pH optimum, To ptimum and water content, on the activity of the enzyme in microemulsion was determined. The results obtained show that the structure of the microemulsion has strong effect on enzyme activity compared to the k_cat, in aquous solution, the apparent turnover number k'_cat values were decreased in AOT, TX- 100 based system, and in creased in CTAB based system.     

Separation of acidic compounds by strong anion-exchange capillary electrochromatography

Separation of the acidic compounds in the ion-exchange capillary electrochromatography (IE-CEC) with strong anion-exchange packing as the stationary phase was studied. It was observed that the electroosmotic flow (EOF) in strong anion-exchange CEC moderately changed with increase of the eluent ionic strength and decrease of the eluent pH, but the acetonitrile concentration in the eluent had almost no effect on the EOF. The EOF in strong anion-exchange CEC with eluent of low pH value was much larger than that in RP-CEC with Spherisorb-ODS as the stationary phase. The retention of acidic compounds on the strong anion-exchange packing was relatively weak due to only partial ionization of them, and both chromatographic and electrophoretic processes contributed to separation. It was observed that the retention values of acidic compounds decreased with the increase of phosphate buffer and acetonitrile concentration in the eluent as well as the decrease of the applied voltage, and even the acidic compounds could elute before the void time. These factors also made an important contribution to the separation selectivity for tested acidic compounds, which could be separated rapidly with high column efficiency of more than 220000 plates/m under the optimized separation conditions.