硅表面活性剂增强的双网络耐高温多孔有机硅弹性体

采用聚醚改性三硅氧烷表面活性剂、 丙烯酸酯改性硅油和水3种组分制备了稳定的油包水(W/O)乳液, 经酸碱催化水解、 紫外引发聚合和干燥除水过程得到了双网络多孔有机硅弹性体. 扫描电子显微镜(SEM)分析结果表明, 所制备的有机硅弹性体具有丰富的孔径结构分布. 压缩强度测试结果表明, 弹性体具备良好的耐压缩性能, 45%压缩应变下循环50次, 仍具备良好的回弹性能. 有机硅弹性体具有优异的耐高温性能, 分解温度为370 ℃, 高于绝大多数多孔有机硅弹性体材料的分解温度. 丙烯酸酯改性硅油的制备工艺成熟、 廉价易得, 显著降低了多孔有机硅弹性体的生产成本, 为规模性开发有机硅材料提供了新的思路和应用前景.     

Fat crystals and water-in-oil emulsion stability

Products such as cosmetics, pharmaceuticals, and crude oil often exist as water-in-oil (W/O) emulsions during their processing or in final form. In many cases, their dispersed aqueous phase is encased in a crystal network and/or by interfacially-adsorbed (‘Pickering’) particles [paraffins, triacylglycerols, polymers, etc.] that promote emulsion kinetic stability by hindering droplet–droplet contact, coalescence and macroscopic phase separation. In processed foods, important questions remain regarding whether a continuous phase fat crystal network or Pickering crystal provides better stabilization. This review explores the following factors related to crystal-stabilized W/O emulsions: i) the key properties dictating fat crystal spatial distribution (at the interface or in the continuous phase); ii) how temperature and freeze–thaw emulsion destabilization are intimately linked with fat crystal spatial distribution, and; iii) why oil-soluble surfactant interactions with the continuous oil phase influence fat crystal wettability and emulsifier efficacy. It is shown that these parameters strongly govern W/O emulsion formation and stability.     

Temperature-controlled change of charge transport mechanisms in nonionic water-in-oil microemulsions

 The temperature-controlled transition from the Stokes charge transport of aqueous nanodroplets to the intrinsic conduction of nanodroplet clusters in nonionic microemulsions was studied. Two different charge transport processes apparent from a minimum value of the conductance have been simulated based on straightforward physical models. Their predictions compare favourably with the observations. Received: 4 September 2001 Accepted: 20 September 2001     

Preparation and characterisation of Na2S and ZnSO4 nanoparticles in water/sodium bis(2-ethylhexyl)sulphosuccinate/n-heptane microemulsions

The preparation procedure for nanoparticles of the water-soluble salts Na₂S and ZnSO₄, two commonly used reagents to synthesise ZnS nanoparticles, by evaporation of volatile components of salt-containing water-in-oil microemulsions is described. In suitable conditions, the evaporation leads to the formation of dry salt–surfactant composites and to the formation of Na₂S or ZnSO₄ nanoparticles. It was found that the salt–surfactant composites can be totally redissolved in a dry apolar organic solvent allowing the formation of virtually water-free solutions containing a considerable amount of the water-soluble salts. The presence of nanoparticles in these solutions and in the composites has been proved by small-angle X-ray scattering and transmission electron microscopy, respectively. By mixing these solutions, the solid–solid reaction between Na₂S and ZnSO₄ nanoparticles leading to the formation of very small-sized ZnS nanoparticles has been ascertained by UV spectrophotometry. Received: 09 February 2001 Accepted: 19 March 2001     

吲哚类菁染料Cy3嵌入的核壳荧光纳米颗粒的制备及其性质研究

以蛋白质或多肽修饰的吲哚类菁染料Cy3为内核, 采用实验条件简单的油包水反相微乳液方法成核, 通过正硅酸乙酯水解形成的网状二氧化硅包壳的方法制备吲哚类菁染料Cy3嵌入的核壳荧光纳米颗粒. 考察了以不同等电点的蛋白质和多肽修饰的Cy3为内核材料对吲哚类菁染料Cy3嵌入的核壳荧光纳米颗粒制备的影响. 结果表明, 分别采用人免疫球蛋白(IgG)或多聚赖氨酸修饰的Cy3为内核材料, 都能制备荧光强度高、荧光稳定性强和染料泄漏极少的Cy3嵌入的核壳荧光纳米颗粒. 进一步对Cy3嵌入的核壳荧光纳米颗粒进行了表征, 并将基于这一新型的荧光纳米颗粒建立起来的生物标记方法初步应用于流感病毒DNA的检测, 其检测线性范围为3.18×10-10～1.27×10-9 mol/L, 检测下限为3.51×10-10 mol/L, 相关系数r为0.986 5.     

A Self-supporting,Surface Carbonized Filter Paper Membrane for Efficient Water-in-Oil Emulsion Separation

Due to the important role of oil source in our life, the separation of water-in-oil emulsion is urgent and necessary. Membrane seperation technology has been an efficient and widely used method in separating oil-water separation. Herein, we report a versatile approach to fabricate surface carbonized membranes with self-standing property from biomass-derived precursor by synergistic charring of phytic acid,arginine and filter paper. The obtained membrane exhibited superhydrophobicity in oil, excellent fouling resistance, and self-supporting ability.The membrane can be cycle-used at least 12 times with high permeation flux(up to 1380 L·m~(-2)·h~(-1)) and separation efficiency(up to 99.4%).     

Aging of an unstable w/o gel emulsion with a nonionic surfactant

We study an unstable highly concentrated emulsion of water droplets in oil with a nonionic surfactant. A technique of light diffusion coupled to a rheometer allows simultaneous measurement of average droplet radius and emulsion shear elastic modulus during time. Over the studied range of volume fraction (from 71 to 95%), we show that Princen and Kiss’ (J Colloid Interface Sci 112:427–437, 1986) model does not apply. A dimensional analysis based on the hypothesis of dominant van der Waals forces is proposed for nonionic surfactants, which is in good agreement with experimental data. We also show that the measured average droplet volume increases linearly with time and that the coalescence rate strongly depends on the volume fraction in relation with different topological conformations of droplets.

Stabilization of water-in-oil emulsions with continuous phase crystals

The role of continuous phase paraffin wax crystals on water-in-mineral oil emulsion ( = 0.2) aggregation, coalescence and sedimentation behavior was studied. Paraffin wax crystal properties were controlled by using two crystallization regimes. In regime 1, pre-crystallized wax was added prior to emulsification. In regime 2 (post-crystallization), molten wax was emulsified and quench-crystallized in situ following emulsification. Based on d_0,0 values, all emulsions containing quench-crystallized wax were more stable than their pre-crystallized equivalents (p < 0.05). Sedimentation analyses indicated that, over a 10-day period, regime 2 emulsions with 0.5% (w/w) or more wax in the continuous phase did not phase separate. Only regime 1 emulsions that contained 2% (w/w) added wax did the same. Brightfield and polarized light microscopy revealed the presence of aggregated wax crystal networks in both post-crystallized and pre-crystallized systems. However, the crystals forming the network were much smaller in the former. Atomic force microscopy and X-ray diffraction indicated that the presence of the emulsifier used to aid in emulsion formation also affected wax morphology and polymorphic behavior. In conclusion, due to the presence of a well-defined network structure, emulsions consisting of wax-crystallized in situ were more stable than emulsions with crystals added prior to emulsification.     

新型有机荧光染料嵌合的核壳荧光纳米材料的研制

采用油包水的反相微乳液方法,首次以羊抗人免疫球蛋白(IgG)标记的异硫氰酸荧光素(FITC)为核材料,成功地制备了FITC的核壳荧光纳米颗粒,克服了采用传统方法制备核壳荧光纳米颗粒中存在的荧光染料泄露的问题.制备的这种核壳荧光纳米颗粒比细胞小很多,且具有生物亲和性,可为纳米生物传感器件提供新型材料.基于该核壳荧光纳米颗粒的标记方法也为生物医学提供了一种新型的非同位素分析方法.     

Fourier transform-IR and 1H NMR studies on the structure of water solubilized by reverse aggregates of calcium bis(2-ethylhexyl) sulfosuccinate in organic solvents

The structure of water solubilized by reverse aggregates of calcium bis(2-ethylhexyl) sulfosuccinate in deuterobenzene and toluene has been probed by Fourier transform-IR and ¹H NMR spectroscopies. The ν_OD band of solubilized HOD (4% D₂O in H₂O) has been recorded as a function of the [water]/[surfactant] molar ratio, W/S. Curve fitting of this band showed the presence of a main peak at 2550 ± 13 cm⁻¹ and a small one at 2405 ± 15 cm⁻¹. As a function of increasing W/S, the frequency of the main peak decreases, its full width at half-height increases, and its area increases linearly. The ¹H NMR chemical shift of solubilized H₂O–D₂O mixtures at W/S = 18.1 has been measured as a function of the deuterium content of the aqueous nanodroplet. These data were used to calculate the so-called “fractionation factor” of the aggregate-solubilized water, the value of which was found to be unity. The results of both techniques show that reverse aggregate-solubilized water, although different from bulk water, does not seem to coexist in “layers” of different degrees of structure, as suggested, for example by the two-state water-solubilization model. Received: 12 July 1999/Accepted: 30 August 1999