CO2响应型Pickering乳液的构筑及应用

互不相溶的油/水两相在固体颗粒的作用下,其中一相以小液滴形式溶于另一相中形成的乳液称为Pickering乳液。由于其制备成本低、稳定性强且环境友好,目前已应用于医药、食品及化妆品等多个领域。在实际的应用中,具有长期稳定性质和可快速乳化/破乳的乳液在石油开采、催化等领域需求广泛,因而制备具有环境刺激响应性质的Pickering乳液迫在眉睫。与pH、磁场、温度、光等刺激手段相比,CO₂响应型乳液具有廉价易得、无污染、响应迅速、生物相容性好等优势,是解决产品循环回收问题的有效策略。目前CO₂刺激响应型Pickering乳液体系仍处于研究的初级阶段,且该乳液的响应机制、构筑策略仍有待明确和拓展。本文总结了Pickering乳液的稳定/响应机制,综述了CO₂响应型Pickering乳化剂的种类及构筑策略,列举了其在乳液聚合、界面催化、生物医药领域的应用进展,并展望了其未来的发展前景。     

Pickering乳液模板法制备Janus粒子

本文以SiO₂粒子稳定的水包油(O/W)型Pickering乳液作为模板, 在乳液连续相进行SI-ATRP, 将聚合物刷接枝到SiO₂粒子外半表面, 破乳得到半修饰的Janus粒子.     

Janus纳米金稳定的Pickering乳液界面催化氧化性能

Janus纳米粒子的结构设计和简易合成是Pickering乳液界面催化的关键. 本文通过在Pickering乳液保护法中操纵共轭亚油酸的自组装、 自交联性和弱还原性, 合成了Janus型自交联吸附胶束修饰的纳米Fe₃O₄ (SCA-Fe₃O₄), 并在其表面原位还原金后, 合成了Janus型催化剂Au-SCA-Fe₃O₄, 考察其同时作为乳化剂和催化剂在乳液界面催化苯甲醇氧化生成苯甲醛的性能. 结果表明, 该Janus纳米粒子的金修饰量(质量分数)仅为0.66%, 兼具乳化性、 催化性和磁响应性. Au-SCA-Fe₃O₄可制备外观稳定(100 μm)和热稳定(90 ℃)的苯甲醇/水型Pickering乳液, 可显著提高互不相溶反应物与催化剂间的接触面积, 使其催化活性达到均匀纳米催化剂的2倍和非乳液催化时的3倍, 其在界面的不可转动性使苯甲醛的选择性高于99.9%, 避免了苯甲醛被过度氧化成苯甲酸.     

Pickering乳液的制备和应用研究进展

Pickering乳液是一种由固体粒子代替传统有机表面活性剂稳定乳液体系的新型乳液。与传统乳液相比,Pickering乳液具有强界面稳定性、减少泡沫出现、可再生、低毒、低成本等优势,在化妆品、食品、制药、石油和废水处理等行业具有广阔的应用前景,受到越来越多研究者们的关注。本文综述了近年来Pickering乳液的研究进展,先介绍Pickering乳液相对于表面活性剂乳液的特色与优势,然后介绍Pickering乳液的制备研究进展,最后介绍Pickering乳液的应用研究进展。     

马来松香酸和纳米氧化铝颗粒协同稳定具有pH响应性的Pickering乳液

使用有机颗粒稳定Pickering乳液受到越来越多的关注, 润湿性可调的有机颗粒且结合纳米无机颗粒协同稳定不同类型的Pickering乳液却鲜有报道. 系统研究了基于具有多羧酸基团的松香基衍生物马来松香(MPA)与纳米Al₂O₃颗粒在不同pH条件下形成的乳液类型及相关机理. 研究发现, 在单一MPA颗粒体系条件下, pH可以诱导乳液的类型由W/O Pickering乳液到O/W Pickering乳液, 到最后O/W乳液的转变, MPA的亲水性随着pH升高而增强是该乳液转变的原因. 当纳米Al₂O₃颗粒加入到MPA中后, 吸附在MPA颗粒上的亲水性Al₂O₃导致MPA颗粒亲水性增加, 从而可以使W/O Pickering乳液转变为O/W Pickering乳液(pH=1). 当pH=6时, MPA分子与纳米Al₂O₃颗粒同时具有较强的亲水性且分别无法形成稳定的乳液, 但两者的混合体系可以形成稳定的W/O Pickering乳液, 这是因为MPA分子与纳米Al₂O₃颗粒可以在水溶液中形成疏水性较强的络合物. 另外, 研究了MPA浓度及油相体积分数对乳液外观及粒径的影响, 发现随着MPA浓度增加Pickering乳液的粒径逐渐减小, 增加油相的体积分数会引起粒径的增大. 最后, 利用Zeta电势、颗粒在油水界面吸附率、接触角及表/界面张力研究了稳定Pickering乳液的稳定机理, 在油水界面上吸附的类似盔甲状颗粒层及颗粒层之间形成的网状结构是乳液液滴保持稳定的原因. 为Pickering乳液的绿色化制备提供了一种新的途径, 将在化妆品、医药及新材料等领域得到重要应用.     

共轭亚油酸修饰Fe3O4纳米颗粒的刺激响应性

采用少量天然不饱和脂肪酸共轭亚油酸(CLA)代替常用油酸对Fe₃O₄纳米颗粒进行表面修饰. 通过引发CLA中共轭双键自交联增强表面修饰牢度, 并利用该修饰层为修饰后的Fe₃O₄纳米颗粒提供第二重pH响应性. 分别通过透射电子显微镜(TEM)表征粒径和形貌、 全反射傅里叶变换红外光谱(ATR-FTIR)表征配位模式、 热重(TG)分析修饰量、 θ角表征表面润湿性、 超景深三维显微技术表征修饰后颗粒稳定的Pickering乳液的粒径及分布等. 结果表明, 修饰后颗粒具有分散性好、 修饰层薄而稳定、 表面疏水性增强及具有明显的pH/磁双重响应性等特征. 修饰后颗粒稳定的Pickering乳液具有乳化剂用量(质量分数0.05%)少、 乳液为高内(油)相(体积分数80%)类型、 pH响应能够开关乳液、 外磁场驱使乳液定向移动等特征, 且模拟实验显示借助该乳液可以有效实现水相有机污染物的萃取与分离.     

两亲性Janus粒子的合成及其在Pickering乳液中的应用

Janus粒子由于在光、电、力、磁及表面亲/疏水性等方面表现出各向异性,因此在稳定乳液、生物医药及功能涂层等方面展现出广阔的应用价值。两亲性Janus粒子是指一侧具有亲水性、另一侧具有疏水性的不对称材料,由于同时具有表面活性剂的性质和固体颗粒的效应,在稳定Pickering乳液方面极具优势。基于此,本文对两亲性Janus粒子的制备方法进行了综述,并对比分析了其优缺点,同时总结了两亲性Janus粒子对Pickering乳液稳定性的影响,最后对其今后的发展进行了展望。     

基于氧化淀粉的新型Pickering苯丙乳液表面施胶剂的合成

以苯乙烯、丙烯酸丁酯为单体,过硫酸铵为引发剂,氧化淀粉作固体粒子乳化剂,采用无皂乳液聚合的方法来制备Pickering苯丙聚合物乳液,考察了不同含量的氧化淀粉对乳液固含量、转化率、卡伯值以及稳定性的影响,并对制备的Pickering苯丙聚合物乳液进行了粒径、红外光谱表征,当氧化淀粉的含量为2%时,制备的Pickering苯丙聚合物乳液转化率为96%,粒径为264.4nm,卡伯值为71.4g/m~2,抗水性和稳定性较好.     

碱式碳酸铜微球的表面改性和组装

报道了通过分散聚合反应在碱式碳酸铜微球表面锚接聚苯乙烯纳米粒子, 以调节其亲水/亲油性的方法. 结果表明, 锚接的聚苯乙烯纳米粒子尺寸愈大, 所得的改性碱式碳酸铜微球疏水性愈强. 用对油和水润湿性适中的改性碱式碳酸铜微球为乳化剂, 能够制备出稳定的油包水型Pickering乳液. 改性碱式碳酸铜微球组装在Pickering乳液的分散相液滴表面, 形成一个固体壳层. 将Pickering 乳液的分散相水核凝胶化, 合成出分级结构琼脂糖凝胶微球.     

基于扩散强化的Pickering界面生物催化系统构建及CO2矿化过程研究

CO₂的有效利用有助于解决环境和生态问题.碳酸酐酶(CA)等酶分子可精准活化CO₂分子以降低反应能垒,为CO₂的高效和高选择性转化提供了一种有前景的途径.然而,酶离开生物体后易失活,且难以重复利用.目前,包埋型固定化酶是常用且有效的提高酶稳定性与回用率的方法之一,但载体的存在会造成反应物CO₂内扩散阻力增加,降低反应活性.此外,CO₂酶促转化是一个气-液-固三相反应过程,反应体系中CO₂的外扩散性能也需要加强.金属有机骨架(MOFs),特别是咪唑酯骨架(ZIFs),常被用作酶固定化的载体.ZIFs的拓扑结构可被设计成不同形貌,进而通过ZIFs的结构工程来加强分子向其中的内扩散.Pickering乳液是指以固体颗粒代替常规表面活性剂而稳定的乳液.当固体颗粒具有催化活性时,催化剂颗粒会扩大液-液-固或气-液-固三相接触面积,从而有效协调反应物在不同相中的扩散时间.如果酶被用作这些颗粒的活性中心,所制备的Pickering乳液也可能具备类似的特性,可加强底物分子向酶的外扩散.本文选择两种具有不同结构的ZIFs(ZIF-L和ZIF-8),原位包埋CA后形成CA@ZIFs颗粒以稳定Pickeirng乳液.ZIF-L和CA@ZIF-L颗粒显示出独特的二维层状堆叠结构.ZIF-8和CA@ZIF-8颗粒呈棱角清晰的十二面体结构.与CA@ZIF-8颗粒相比,CA@ZIF-L颗粒显示出更大的孔径和更宽的孔径分布,这有助于CO₂从CA@ZIF-L颗粒表面扩散至酶活性中心.利用酶活测试来研究内扩散是否通过结构工程得到了加强,发现CA@ZIF-L颗粒的活性比CA@ZIF-8颗粒高22.3%,推测这是由于CA@ZIF-L颗粒特殊的十字花状结构会缩短CO₂从颗粒表面扩散至酶活性中心的距离.同时,十字花状结构可暴露更多的酶活性位点(CA@ZIF-L颗粒的暴露面积是CA@ZIF-8颗粒的~8倍),从而提升了反应物浓度并显示出更高的催化活性.本文还设计了吸附实验来进一步验证上述假设,发现BSA@ZIF-L颗粒对香豆素的吸附率远高于BSA@ZIF-8颗粒,说明与ZIF-8相比,酶包埋于ZIF-L具有更强的捕获小分子的能力,表明CO₂分子向CA@ZIF-L的扩散速度更快,即CA@ZIF-L的十字花状结构可强化系统的内扩散过程.进一步比较了PIBS和游离多酶体系的催化活性,将CO₂通入每个系统,在反应前20 min,PIBS的pH值下降速度比游离体系快得多,说明PIBS通过在气相和液相间构建更大的界面,缩短了CO₂向CA的扩散距离,从而提高了催化效率,促进了CO₂转化.上述假设也通过扩散动力学的计算得到了验证.为进一步研究PIBS的CO₂矿化能力,本文开展了CaCO₃矿化反应,发现PIBS的CaCO₃产量远高于游离多酶体系,表明构建的PIBS在强化内外扩散方面具有显著优势.最后,评估了PIBS在工业应用中的性能,由CA@ZIF-L和CA@ZIF-8颗粒构建的PIBS显示出较好的可回收性,在第8个循环后,PIBS仍可保持8.9 mg/5 min的CaCO₃产量.综上,PIBS可为CO₂的酶促转化和框架提供一个新方法和新平台.     

Fabrication of poly(lactide‐co‐glycolide) scaffold embedded spatially with hydroxyapatite particles on pore walls for bone tissue engineering

Poly(lactide‐co‐glycolide) (PLGA) scaffolds embedded spatially with hydroxyapatite (HA) particles on the pore walls (PLGA/HA‐S) were fabricated by using HA‐coated paraffin spheres as porogens, which were prepared by Pickering emulsion. For comparisons, PLGA scaffolds loaded with same amount of HA particles (2%) in the matrix (PLGA/HA‐M) and pure PLGA scaffolds were prepared by using pure paraffin spheres as porogens. Although the three types of scaffolds had same pore size (450–600 µm) and similar porosity (90%–93%), the PLGA/HA‐S showed the highest compression modulus. The embedment of the HA particles on the pore walls endow the PLGA/HA‐S scaffold with a stronger ability of protein adsorption and mineralization as well as a larger mechanical strength against compression. In vitro culture of rat bone marrow stem cells revealed that cell morphology and proliferation ability were similar on all the scaffolds. However, the alkaline phosphatase activity was significantly improved for the cells cultured on the PLGA/HA‐S scaffolds. Therefore, the method for fabricating scaffolds with spatially embedded nanoparticles provides a new way to obtain the bioactive scaffolds for tissue engineering. Copyright © 2011 John Wiley & Sons, Ltd.     

Growth of lightly crosslinked PHEMA brushes and capsule formation using pickering emulsion interface‐initiated ATRP

In this work, growth of lightly crosslinked poly(2‐hydroxyethyl methacrylate) (PHEMA) brushes and subsequent capsule formation using Pickering emulsion interface‐initiated atom transfer radical polymerization (PEII‐ATRP) were investigated. Initiator‐immobilized silica nanoparticles (2.5 initiators/nm²) assembled at the interface of paraffin oil‐in‐water emulsions and ultimately stable Pickering emulsions were formed. PEII‐ATRP was conducted in the water phase of Pickering emulsions from the part of the surfaces of initiator‐immobilized silica nanoparticles exposed to water by using copper(I) chloride/bipyridine as catalyst at 35 °C. As PHEMA has a character of lightly crosslinking when the polymerization occurs in water, novel hybrid capsules (“colloidosomes”) can be obtained and were observed by confocal laser scanning microscope (CLSM) and optical microscopy (OM). The semipermeability of the resultant hollow capsules was demonstrated by the diffusion of 1‐phenylazo‐2‐naphthol. Meanwhile, the conformation of PHEMA chains can be varied in different solvents, which affects the semipermeability of these hybrid hollow capsules. We expect these hollow capsules can be further utilized to develop microdevices for drugs or cells delivery. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1354–1367, 2009     

Ca2+ Responsive Microgel-Stabilized Pickering Emulsions

As an ionic cross-linker that can change the size of poly(N-isopropylacrylamide-co-acrylic acid) microgel, Ca²⁺ is applied as a trigger to demulsify microgel-stabilized oil/water Pickering emulsions. The influence of Ca²⁺ induced intra-particle ionic cross-linking and inter-particle aggregation on the stability of microgel-stablized “Pickering” emulsion is described. At low and mediate concentration of Ca²⁺, ionic cross-linking can change the internal elasticity of the microgel, and cause the coarsening of the oil droplets. At high concentration of Ca²⁺, microgels flocculate due to the salt out effect and the emulsion is destabilized. This work provide a facile method to control the stability of the Pickering emulsions at ambient condition.     

Pickering‐Emulsion Inversion Strategy for Separating and Recycling Nanoparticle Catalysts

With the recent advances in nanoscience and nanotechnology, more and more nanoparticle catalysts featuring high accessibility of active sites and high surface area have been explored for their use in various chemical transformations, and their rise in popularity among the catalysis community has been unprecedented. The industrial applications of these newly discovered catalysts, however, are hampered because the existing methods for separation and recycling, such as filtration and centrifugation, are generally unsuccessful. These limitations have prompted development of new methods that facilitate separation and recycling of nanoparticle catalysts, so as to meet the burgeoning demands of green and sustainable chemistry. Recently, we have found that Pickering‐emulsion inversion is an appealing strategy with which to realize in situ separation and recycling of nanoparticle catalysts and thereby to establish sustainable catalytic processes. We feel that at such an early stage, this strategy, as an alternative to conventional methods, is conceptually new for readers but that it has potential to become a popular method for green catalysis. This Concept article aims to provide a timely link between previous efforts and both current and future research on nanoparticle catalysts, and is expected to facilitate further investigation into this strategy.     

Particles with tunable wettability for solid-stabilized emulsions

We demonstrate that the wettability of cosmetic grade, silica-coated titanium dioxide nanoparticles may be tuned by simply soaking them in a cyclic silicone oil. This allows for tuning the type of emulsion that they stabilize, from oil-in-water to water-in-oil. By analyzing the sedimentation of water-in-oil emulsions, the effect of the soaking time (wettability) on drop size and drop-drop interactions was investigated. From centrifugation experiments performed up to emulsion breakage, we obtain an effective water-oil interfacial tension for the particle-loaded interfaces, which indicate lateral particle-particle interactions. Finally, we demonstrate that the proposed particle functionalization is terminated upon addition of water followed by emulsification. In addition, it is irreversible and can be accelerated through heating.GRAPHICAL ABSTRACT     

基于Pickering乳液的磁性高强水凝胶的制备及性能表征

合成了一种磁性Fe3O4纳米颗粒稳定的水包油(O/W)Pickering乳液并以其作为交联剂,在适宜条件下引发单体丙烯酰胺聚合来制备了一种新型的磁性高强复合水凝胶.采用X射线衍射(XRD)及场发射扫描电子显微镜(SEM)分别对磁性Fe3O4纳米颗粒和复合水凝胶的结构进行了表征,结果表明Pickering乳胶粒子较均匀地分布在复合凝胶网络中.溶胀性能测试及溶胀动力学分析表明复合水凝胶具有良好的溶胀性能,能够吸收自身干重100倍左右的水,其溶胀过程不遵循Fickian扩散模型;拉伸测试表明该水凝胶具有优异的力学性能,其拉伸强度能够达到150 kPa左右,断裂伸长率能够达到300%左右,并且当其承受的应力释放后能快速地恢复到初始形态.磁性能测试的结果显示该水凝胶具有良好的磁性.     

不同形态双金属氢氧化物颗粒水分散体系及其稳定的Pickering乳液

采用共沉淀法制备了3种形态的MgAl双金属氢氧化物颗粒的水分散体系, 并以其为乳化剂制备了Pickering乳液. 比较了3种颗粒的分散体系及其稳定的Pickering乳液的性质. X射线衍射(XRD)和透射电子显微镜(TEM)表征结果表明, 低结晶度的颗粒以形状不规则、 结构疏松、 表面粗糙的絮状体形式分散于水中, 且颗粒尺寸随高速搅拌分散时间的延长而减小; 而良好结晶的颗粒以形状规则、 结构致密、 表面平滑的六角片存在于水中. Zeta电位测试表明, 3种颗粒在水中均带正电荷, NaCl可降低颗粒的Zeta电位而使其发生絮凝, 但良好结晶颗粒的分散体系在更高NaCl浓度时才出现明显沉淀. 分别采用3种双金属氢氧化物颗粒/NaCl水分散体系制备了水包油(O/W)型Pickering乳液, 并比较了乳液的稳定性. 结果表明, NaCl的引入在一定程度上可提高3类乳液的稳定性; 良好结晶颗粒稳定乳液的能力强于低结晶度的颗粒; 对于低结晶度颗粒, 大颗粒稳定乳液的能力比小颗粒更强.     

Hollow microspheres with covalent‐bonded colloidal and polymeric shell by Pickering emulsion polymerization

Hollow microspheres with SiO₂/polymer binary shell were fabricated from Pickering emulsion stabilized solely by methacryloxypropyltrimethoxysilane‐modified SiO₂ particles, and were characterized by optical microscopy, scanning electron microscopy, Fourier transformation infrared spectrum, thermogravimetric analysis (TGA), and energy dispersive X‐ray spectroscopy. The microspheres were templated by the Pickering droplets and the inner structure was affect by the proportion of crosslinking reagent. TGA result indicated that 60.3% of polymer in the shell was connected with SiO₂ by covalent bond which was formed by copolymerization of styrene and the reactive C?C group on SiO₂ stabilizer. Copyright © 2011 John Wiley & Sons, Ltd.     

Influence of calcium lactate and pH on emulsification of low-methoxylated citrus pectin in a Pickering emulsion

An emulsion was prepared by homogenizing 30% rapeseed oil with 70% (w/w) aqueous solution. The emulsion viscosity increased when the concentrations of calcium lactate and low-methoxylated citrus pectin (LMP) in the emulsion were increased. A stable emulsion was obtained when the concentrations of LMP and calcium lactate were 1% and 9?mM at pH 3, respectively. Optical microscopy and laser scanning confocal microscopy revealed that the stable emulsion was a Pickering emulsion. In the Pickering emulsion, LMP with calcium formed micro gels that can be absorbed on the oil surface. The emulsifying property of LMP could widen the applications of pectin.