β-胡萝卜素微乳液的制备及其稳定性研究

通过绘制拟三元相图选择合适的微乳液组分,制备了β-胡萝卜素的Tween80/乙醇/丁酸乙酯/H2O的O/W型微乳液。考察了温度、盐度和pH对微乳液区域的影响:电导率法区分了微乳液的O/W、W/O和B.C(油-水双连续型)区域;对相同浓度β-胡萝卜素的微乳液和丁酸乙酯溶液进行了光、热稳定性研究,用紫外分光光度法测定样品中β-胡萝卜素的残存率。结果表明,温度升高和pH降低使微乳区稍有减小,盐度对微乳区基本无影响;微乳体系中水的质量分数大于61·5%时形成O/W型微乳液;β-胡萝卜素在微乳液和丁酸乙酯溶液中对光和热都比较敏感,但在微乳液中较稳定。     

不同因素对高效氯氟氰菊酯微乳液相图的影响

通过电导率的测定研究了高效氯氟氰菊酯微乳液的结构及结构转变, 绘制了不同条件下高效氯氟氰菊酯微乳体系的拟三元相图, 讨论了十二烷基苯磺酸钠(SDBS)摩尔分数、电解质浓度、温度等因素对各类型微乳区形成的影响. 结果表明: ①随着SDBS摩尔分数增大, W/O型微乳区面积先减小后增大, BC和O/W型面积先增大后减小; ②随着电解质浓度增大, W/O、BC和O/W型微乳区面积均先增大后减小; ③随着温度升高, W/O型微乳区面积增大, BC和O/W型面积均减小.     

醇对高效氯氟氰菊酯微乳液相图的影响

通过电导率的测定研究了高效氯氟氰菊酯微乳液的结构结构及结构转变。在表面活性剂、高效氯氟氰菊酯环己酮溶液、醇相对含量一定的情况下,当醇为乙醇时,微乳液经历了由W/O到双连续最后到O/W型的变化;当醇为正辛醇时,微乳液经历了由W/O到液晶、双连续最后到O/W型的变化。绘制了不同条件下高效氯氟氰菊酯微乳体系的拟三元相图,讨论了醇种类、醇含量对各类型微乳区形成的影响。结果表明,随着醇碳链的增大,微乳区面积先增大后减小;醇(正辛醇)固定时,随着醇含量增加,微乳区面积先减小后增大。     

SDS/正戊醇-二甲苯-水(盐水)拟三元体系相图和电导研究及纳米ZnO的制备

实验绘制了十二烷基硫酸钠(SDS)/正戊醇(n-C₅H₁₀OH)-二甲苯[C₆H₄(CH₃)₂]-水[或Zn(NO₃)₂溶液]四组分微乳液体系在不同温度时的拟三元相图. 测定了电导率随水(或盐溶液)含量变化的规律, 电导的规律与相图吻合. 依据电解质理论探讨了微乳液的微观结构, 研究表明, 温度对油包水(W/O)反相微乳液区域影响不大, 电解质的加入对油包水(W/O)反相微乳液区域影响较大. 通过SDS/正戊醇-二甲苯-H₂O及SDS/正戊醇-二甲苯-盐水的拟三元体系的相图观察及实验研究, 选择乳化剂(SDS/正戊醇)与二甲苯质量比为4:6的微乳液作为最佳条件, 制备出了ZnO纳米粒子.     

SDS/正戊醇-环己烷-水拟三元体系相图及温度对相图的影响

绘制了35, 45, 55, 65 ℃下, 十二烷基硫酸钠(SDS)/正戊醇-环己烷-水体系的拟三元相图. 分析了温度对相图和微乳液区域的影响. 结果表明, 温度对油包水(W/O)反相微乳液区域大小有影响, 但影响较小, 温度对水包油(O/W)微乳液区域的影响较大, 且随温度的增加, 区域增大. 电导率曲线与相图吻合很好, 并用电解质溶液理论进行了解释.     

碱和盐对十二烷基硫酸钠/正戊醇-环己烷-水拟三元体系相图影响

拟三元相图的研究可为获得制备纳米材料的微乳液提供理论依据。本文首先通过实验绘制了45℃下十二烷基硫酸钠(SDS)/正戊醇-环己烷-水溶液体系的拟三元相图,并用电导法进行了验证,说明电导的测定结果与相图吻合的很好。其次,绘制了45℃及65℃下,SDS/正戊醇-环己烷-水、SDS/正戊醇-环己烷-硝酸锌水溶液和SDS/正戊醇-环己烷-氢氧化钠水溶液体系的拟三元相图并对6个相图进行了比较,研究了碱(NaOH)和盐(Zn(NO_3)_2)对SDS/正戊醇-环己烷-水拟三元体系相图影响。结果表明,硝酸锌及碱的加入使SDS/正戊醇-环己烷-水拟三元相图水包油(O/W)和油包水(W/O)区域明显的缩小。45℃时,SDS/正戊醇-环己烷-氢氧化钠水溶液体系的拟三元相图中的O/W区域甚至消失;65℃时,O/W和W/O区域均存在,且3个相图的W/O和O/W区域有重叠区。在此基础上,确定了制备纳米Zn O的微乳液的条件,即SDS/正戊醇-环己烷-硝酸锌水溶液和SDS/正戊醇-环己烷-氢氧化钠水溶液体系的拟三元相图中W/O区域的重叠区(各相图中的Ⅱ区)。制备的纳米氧化锌为多晶结构,平均粒径为80 nm。     

阴离子型微乳液的电导行为及其溶液结构

根据电导测量,研究了属于W/O→双连续→O/W一类微乳液的十二烷基硫酸钠(SDS)/正丁醇/辛烷/水体系的溶液结构.并探讨了表面活性剂离子对微乳液导电行为的贡献,以及表面活性剂与助表面活性剂含量、油含量对微乳液溶液结构的影响.微乳液的导电行为在W/O子区域中主要是由于SDS阴离子和在O/W子区域中是由于Na离子的影响.在双连续区(IZ)中SDS阴离子和Na阳离子都能影响导电行为增加表面活性剂含量有助于形成O/W微乳液,而助表面活性剂和油含量都增加有助于于形成W/O微乳液.     

双重Pickering乳液模板法制备无机-有机复合空心微球

以疏水性ZnO粒子和亲水性Fe_3O_4粒子稳定的W/O/W型双重Pickering乳液为模板,制备了具有空心结构的无机-有机复合微球.采用X射线衍射(XRD)仪、扫描电子显微镜(SEM)、X射线能谱仪(EDS)、傅里叶变换红外光谱(FTIR)仪及光学显微镜等对制备的无机粒子、乳液和复合材料进行了表征.结果表明,制备了ZnO和Fe_3O_42种无机粒子,油酸能够对Zn O进行有效的疏水改性,改性后的接触角为84.3°.制备的双重Pickering乳液稳定性好、粒径分布较宽(50～200μm),以该双重乳液为模板制备的无机-有机复合材料为空心球形结构,粒径范围为100～200μm.     

油酸-正丙醇-水无表面活性剂反相微乳液电导研究

本文对油酸-正丙醇-水三元体系的相行为进行了研究,表明可形成微乳液.由于体系中无传统表面活性剂,故所形成的微乳液为无表面活性剂微乳液.在反相微乳液区,固定正丙醇/油酸体积比(RP/O)为3∶5、1∶1和2∶1,考察了体系电导率(κ)随分散相体积分数(φd)的变化,结果表明κ随φd的增大先缓慢增加,后急剧增大,符合渗滤特...     

不同阴/阳离子表面活性剂复配体系的缔合结构研究

测定了十二烷基磺酸钠(AS)/十六烷基三甲基溴化铵(CTAB)/正丁醇(n-C4H9OH)/正庚烷(n-C7H16)/水(H2O),十二烷基硫酸钠(SDS)/十六烷基三甲基溴化铵(CTAB)/正丁醇(n-C4H9OH)/正庚烷(n-C7H16)/水(H2O)体系的微乳液正四面体相图,并用电导法划分了AS/CTAB/n-C4H9OH/n-C7H16/H2O体系微乳液的结构(W/O,B.C.和O/W);同时研究AS/CTAB/n-C4H9OH/n-C7H16/H2O/盐类(NaCl,CaCl2或AlCl3)体系和SDS/CTAB/n-C4H9OH/n-C7H16/H2O/盐类(NaCl,CaCl2或AlCl3)体系形成中相微乳的盐宽,从中得出上述两体系中相微乳的盐宽随盐类阳离子价态的增大而的规律。     

Study of nano-emulsion formation by dilution of microemulsions

The influence of different dilution procedures on the properties of oil-in-water (O/W) nano-emulsions obtained by dilution of oil-in-water (O/W) and water-in-oil (W/O) microemulsions has been studied. The system water/SDS/cosurfactant/dodecane with either hexanol or pentanol as cosurfactant was chosen as model system. The dilution procedures consisted of adding water (or microemulsion) stepwise or at once over a microemulsion (or water). Starting emulsification from O/W microemulsions, nano-emulsions with droplet diameters of 20 nm are obtained, independently on the microemulsion composition and the dilution procedure used. In contrast, starting emulsification from W/O microemulsions, nano-emulsions are only obtained if the emulsification conditions allow reaching the equilibrium in an O/W microemulsion domain during the process. These conditions are achieved by stepwise addition of water over W/O microemulsions with O/S ratios at which a direct microemulsion domain is crossed during emulsification. The nature of the alcohol used as cosurfactant has been found to play a key role on the properties of the nano-emulsions obtained: nano-emulsions in the system using hexanol as cosurfactant are smaller in size, lower in polydispersity, and have a higher stability than those with pentanol.     

微乳液结构的研究

测定了十二烷基磺酸钠／正丁醇／２０％苯乙烯／水体系的相平衡，用冷冻刻蚀、ＥＳＲ、ＦＴ－ＩＲ研究了上述体系微乳液的结构，研究表明，苯乙烯含量恒定时，随着体系中水含量增加，电导确定的双连续结构的微乳液经历着从油包水到以连续再到水包油变化，ＦＴ－ＩＲ测定表明，Ｗ／Ｏ微乳兴较Ｏ／Ｗ微乳液的ＯＨ伸缩振动和弯曲振动频率有显著减小，说明Ｗ／Ｏ微乳兴中氢键缔合要比Ｏ／Ｗ强得多。ＥＳＲ测定表明Ｏ／Ｗ微乳液的旋转相关     

Microemulsion of Tween‐80/n‐Butylalcohol/H2O System and Its Entrapment Efficiency of ATRA

Microemulsion of Tween‐80/n‐butylalcohol/H₂O system was prepared, and the microemulsion region as well as the influence of temperature and concentration of NaCl on the region were determined with ternary diagrams. The O/W, W/O, and B.C. regions were divided by the conductance method. The particle diameters of microemulsions with different NaCl concentrations or microemulsion‐enveloping all‐trans retinoic acid (ATRA) were measured with dynamic light scattering in O/W region. The release rate of ATRA was studied with dialysis a bag‐ultraviolet spectrophotometers and the anticancer activity of ATRA in microemulsion was investigated with cancer cells H446. Results showed that O/W microemulsion forms when water content is over 64% in the mixture. The influences of temperature and salinity on microemulsion region were very slight, and even the particle diameter decreased very little with increasing salt and ATRA concentrations. The microemulsion‐enveloping ATRA possessed eminent sustaining release efficiencys and the efficiency was further confirmed with the growth inhibitory effect test on human cancer cells H446.     

丙烯酸酯及苯乙烯微乳体系的相行为及微乳聚合

甲基丙烯酸甲酯;十二烷基磺酸钠;十二烷基磺酸钠;丙烯酸酯及苯乙烯微乳体系的相行为及微乳聚合     

Structural studies of 1-butyl-3-methylimidazolium tetrafluoroborate/TX-100/ p-xylene ionic liquid microemulsions.

The ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4) forms nonaqueous microemulsions with p-xylene, with the aid of the nonionic surfactant TX-100. The phase behavior of the ternary system is investigated, and three microregions of the microemulsions-ionic liquid-in-oil (IL/O), bicontinuous, and oil-in-ionic liquid (O/IL)-are identified by conductivity measurements, according to percolation theory. On the basis of a phase diagram, a series of IL/O microemulsions are chosen and characterized by dynamic light scattering (DLS). The size of aggregates increases on increasing the amount of added polar component (bmimBF(4)), which is a similar phenomenon to that observed for typical water-in-oil (W/O) microemulsions, suggesting the formation of IL/O microemulsions. The microstructural characteristics of the microemulsions are investigated by FTIR and 1H NMR spectroscopy. The results indicate that the interaction between the electronegative oxygen atoms of the oxyethylene (OE) units in TX-100 and the electropositive imidazolium ring may be the driving force for the solubilization of bmimBF4 into the core of the TX-100 aggregates. In addition, the micropolarity of the microemulsions is investigated by using methyl orange (MO) as a UV/Vis spectroscopic probe. A relatively constant polarity of the microemulsion droplets is obtained in the IL microemulsion. Finally, a plausible structure for the IL/O microemulsion is presented.     

Effect of the structures of microemulsions on chemical reactions

Two kinds of chemical reactions were studied in two different microemulsion systems: cetyltrimethylammonium bromide/1-butanol/10 and 25% n-octane/water and sodium dodecyl sulfonate/1-butanol/20% styrene/water. One reaction is a hydrolysis reaction, in which aspirin and 2,4-dinitrochlorobenzene were used as the hydrolysis substrates. The second reaction is the polymerization of styrene, which was initiated by using two initiators, water-soluble K₂S₂O₈ and oil-soluble 2,2′-azobis(isobutyronitrile), and, at the same time, the polymerization of acrylamide, which was initiated by NaHSO₃, was also studied. All the hydrolysis reaction experimental results show that the hydrolysis is greatly affected by the structures and the structural transitions of microemulsions. The hydrolysis rates are higher in water-in-oil (W/O) microemulsion media and decrease with the addition of water. The rates increase in bicontinuous (BC) microemulsions and decrease in oil-in-water (O/W) microemulsions. The transition points of the hydrolysis rates occurred at the two microemulsion structural transition points from W/O to BC and from BC to O/W. The polymerization relationships between the conversions of styrene, the molecular weights of polystyrene and the water contents of the microemulsion system were obtained. The effects of microemulsion structures on the sizes of the polystyrene particles and on the molecular weights of the polymers are discussed. Polystyrene particles with diameters of 10–60 nm were observed by microscopy. Our experimental polymerization results show that microemulsions are suitable as media for the production of polymers, the molecular weights and the particle sizes of which can be controlled and predicted by variations in microemulsion structures. Received: 11 July 1999/Accepted: 26 July 1999     

STATISTICAL MECHANICAL MODEL THEORY OF THE STABILITY OF O/W AND W/O MICROEMULSIONS

A theoretical model to clarify the molecular origin of the mechanical and thermal stabilities of O/W or W/O microemulsion is proposed in which the low concentration of surfactants (emulsifiers) is limited. We assume only a short range interaction between surfactants and a bending stiffness energy which expresses the deformation energy from a preferable monolayer membrane curvature. We have found an interrelation among the interfacial pressure, Δp, of the monolayer due to the adsorption of surfactants in the microemulsion interface, interfacial tensions of oil-water interface and of the microemulsion, and the bending stiffness energy. We conclude that the interfacial tension and the stable form of the microemulsions (O/W type or W/O type) are infuenced largely by the effect of the bending stiffness energy. The interrelationship between the therraodynamical and mechanical stabilities of microemulsions is clarified by the use of our assumption.     

Formation and characterization of self-assembling fish oil microemulsions

The novel fish oil O/W microemulsion system is formed with food-acceptable components, Tween 80, ethyl oleate, fish oil and water. We studied the influence of fish oil proportion in the oil phase on the microemulsion regions. We investigated this system using the dynamic light scattering and transmission electron microscopy; the rheological characteristics and release effect were also explored. The obtained results indicated that the particle sizes of spherical droplets in microemulsions depend significantly on the total oil phase content, varying from 5 to 198 nm. The rheological measurements showed that all studied microemulsions followed shear thinning behavior. Well-controlled release profile of the fish oil microemulsions was found in different dialyzate solutions.     

Microemulsion polymerization of acrylamide and styrene: Effect of the structures of reaction media

Isothermal phase diagrams of the system cetyltrimethylammonium bromide (CTAB)/n‐butanol/n‐octane/water were constructed, and the effect of the oil (n‐octane) contents on the microemulsions was studied at 40 °C. We determined the microemulsion structures of two systems, CTAB/n‐butanol/10% n‐octane/water and sodium dodecyl sulfonate (As)/n‐butanol/20% styrene/water, by conductivity measurements to investigate the polymerization of acrylamide and styrene in the two microemulsion systems. The polymerization kinetics of the water‐soluble monomer acrylamide in CTAB micelles and the different CTAB/n‐butanol/10% n‐octane/water microemulsion media [water‐in‐oil (W/O), bicontinuous (BC), and oil‐in‐water (O/W)] were studied with water‐soluble sodium bisulfite as the initiator. The maximum polymerization rate in CTAB micelles was found at the second critical micelle concentration. A mechanism of polyacrylamide formation and growth was proposed. A connection between the structures of the microemulsions and the polymerization rates was observed; the maximum polymerization rate occurred at two transition points, from W/O to BC and from BC to O/W, and the polyacrylamide molecular weights, which depended on the structures of the microemulsions, were also found. A square‐root dependence of the polymerization rates on the initiator concentrations was obtained in CTAB micelles and O/W microemulsion media. The polymerization of the oil‐soluble monomer styrene in different As/n‐butanol/20% styrene/water microemulsion media (W/O, BC, and O/W) was also investigated with different initiators: water‐soluble potassium persulfate and oil‐soluble azobisisobutyronitrile. A similar connection between the structures of the microemulsions and the conversions of styrene in CTAB/n‐butanol/10% n‐octane/water for the polymerization of acrylamide was observed again. The structures of the microemulsions had an important role in the molecular weights and sizes of polystyrene. The polystyrene particles were 10–20 nm in diameter in BC microemulsion media and 30–60 nm in diameter in O/W microemulsion media according to transmission electron microscopy. We determined the solubilization site of styrene in O/W microemulsion drops by ¹H NMR spectra to analyze the results of the microemulsion polymerization of styrene. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3320–3334, 2001