Hydrophilic porous polymers based on high internal phase emulsions solely stabilized by poly(urethane urea) nanoparticles

Stable oil-in-water (o/w) Pickering high internal phase emulsions (HIPEs) having an internal phase of up to 95 vol% were prepared with a low-energy emulsification method. A poly(urethane urea) (PUU) aqueous nanodispersion was used as aqueous phase. The PUU nanoparticles of the aqueous nanodispersion acted as a mechanical barrier, and prevented droplet coalescence in the Pickering HIPEs. In addition, open porous hydrophilic polymer foams were obtained by polymerization of the Pickering HIPEs, and the morphology of the foams were tailored by changing the oil:water ratio, PUU nanoparticle and NaCl concentrations. The method used herein provides a simple way to prepare morphology controlled hydrophilic polymer foams using o/w Pickering HIPEs as template.     

非共价改性纳米颗粒稳定Pickering乳液的制备及可逆调控

用具有氧化还原活性分子乙酰基二茂铁吖嗪(Fc⁺A)对磁性纳米颗粒Fe₃O₄@SiO₂进行非共价疏水改性,将改性颗粒作为乳化剂制备Pickering乳液。通过TEM、SEM、FTIR、XRD、接触角测量、光学显微镜等对纳米颗粒及Pickering乳液的结构、形貌和性能进行表征。结果表明：制备的核壳结构纳米颗粒粒径为150 nm左右,分散均匀;Fc⁺A成功修饰到纳米颗粒表面,且随Fc⁺A浓度的增加,改性颗粒的接触角明显增大;Fc⁺A浓度为12.5 mmol/L,乳化剂浓度为0.3%(质量),油水比为4∶6,搅拌速率为10000 r/min,得到的Pickering乳液具有良好的稳定性。而且,所得乳液具双重响应性,通过氧化还原和磁场可实现对乳液稳定性的可逆调控。     

高亲水性纳米二氧化硅颗粒稳定Pickering乳液

用未修饰的高亲水性纳米二氧化硅颗粒(SiO2 NPs)在其等电点附近制备Pickering乳液。结果表明,等电点(pH 2.7)条件下SiO2 NPs借助高能均质与油水界面剧烈混合,并在范德华引力的驱动下以弱吸附的状态在界面处负载,从而稳定得到O/W型Pickering乳液。增加SiO2 NPs的浓度或减小油相体积分数可提高单位油滴界面的颗粒负载率,增大连续相黏度并促进乳液液滴之间形成三维网络结构从而提高乳液稳定性。通过调节连续相的pH以促进SiO2 NPs表面的硅烷醇发生质子化与去质子化的转变,实现乳液多次pH响应循环。     

The construction of pseudo-Janus silica/surfactant assembly and their application to stabilize Pickering emulsions and enhance oil recovery

Nanoparticles with high surface energy and chemical activity have drawn substantial attention in petroleum industry. Recently, Janus nanoparticles exhibited tremendous potential in enhanced oil recovery (EOR) due to their asymmetric structures and properties. In this study, a series of amphiphilic pseudo-Janus@OTAB (PJ@C18) nanoparticles with different concentrations of stearyltrimethylammoium bromide (OTAB) were successfully fabricated. The structures and properties of PJ@C18 were characterized by Fourier transform infrared spectroscopy and ζ-potential measurements. Based on the emulsification experimental results, the interaction models and the self-assembly behavior between hydrophilic nanoparticles (SiO₂@NH₂) and OTAB molecules at the oil/water interface were proposed, which was further confirmed via the measurements of the contact angle and dynamic interfacial tension. Interestingly, it was found that the change of pH value from 7.5 to 4.0 caused the type reversal of the PJ@C18-1000 stabilized Pickering emulsions. Furthermore, the PJ@C18-1000 stabilized Pickering emulsion system with excellent salt and temperature tolerances (10000 mg∙L^–1, 90 °C) significantly improved the oil recovery in the single-tube (more than 17%) and double-tube (more than 25%) sand pack model flooding tests. The findings of this study could help to better understand the construction mechanism of pseudo-Janus silica/surfactant assembly and the potential application of PJ@C18-1000 stabilized Pickering emulsions for EOR.     

Coating of gold nanoparticles by thermosensitive poly(N-isopropylacrylamide) end-capped by biotin

Gold nanoparticles (NPs) were prepared by reduction of HAuCl₄ in aqueous solution and stabilized by poly(N-isopropylacrylamide) (PNIPAM). PNIPAM was prepared by two distinct routes: (i) conventional free-radical polymerization leading to polymer without any reactive end-group, and (ii) Reversible Addition-Fragmentation chain Transfer (RAFT) polymerization with 2-dodecylsulfanylthiocarbonylsulfanyl-2-methyl propionic acid (DMP) as a RAFT agent. PNIPAM with low polydispersity was then end-capped by an α-carboxylic acid and an ω-trithiocarbonate that was converted into an ω-thiol upon hydrolysis. This hetero-telechelic polymer was analyzed by mass spectroscopy, size exclusion chromatography (SEC) and ¹H NMR. Even without thiol end-group, known for chemisorption onto gold, PNIPAM was effective in stabilizing gold NPs (∼1-5 nm). The thermosensitivity of PNIPAM at the surface of gold NPs was, however, dependent on the molecular weight of the chains. Finally, the α-carboxyl end-group of PNIPAM was used to anchor biotin, which is indeed known for complexation with avidin, which is a possible strategy for the coated gold NPs to be involved as building blocks in supramolecular assemblies. TEM and UV-vis spectroscopy were used to characterize the gold nanoparticles.     

Au nanoparticle/graphene oxide hybrids as stabilizers for Pickering emulsions and Au nanoparticle/graphene oxide@polystyrene microspheres

Gold nanoparticle/graphene oxide hybrids (AuNP/GO) were easily fabricated by a redox reaction between GO and chloroauric acid without using any additional reductant and then used to stabilize Pickering emulsions. Factors affecting the properties of the emulsions were studied, including the HAuCl₄/GO mass ratio used to prepare the AuNP/GO, the oil/water ratio, the AuNP/GO concentration, the pH value, and the type and concentration of electrolytes. The emulsions were more stable when stabilized by AuNP/GO made from HAuCl₄/GO mass ratios of 0.375–0.5. High pH values and AuNP/GO concentrations that were too high or too low were unfavorable to the stability of the Pickering emulsions. Adding electrolytes to the systems improved the stability of the Pickering emulsions owing to the reduction of repulsive interactions between AuNP/GO sheets. The AuNP/GO stabilized Pickering emulsions were used to prepare AuNP/GO supported polystyrene (PS) microspheres (AuNP/GO@PS) by polymerizing the Pickering emulsion. The catalytic performance of AuNP/GO@PS for the reduction of 4-nitrophenol was then studied.     

Facile fabrication of nanocomposite microspheres with polymer cores and magnetic shells by Pickering suspension polymerization

Pickering suspension polymerization was used to prepare magnetic polymer microspheres that have polymer cores enveloped by shells of magnetic nanoparticles. Styrene was emulsified in an aqueous dispersion of Fe₃O₄ nanoparticles using a high shear. The resultant Pickering oil-in-water (o/w) emulsion stabilized solely by magnetic nanoparticles was easily polymerized at 70 °C without stirring. Fe₃O₄ nanoparticles act as effective stabilizers during polymerization and as building blocks for creating the organic–inorganic hybrid nanocomposite after polymerization. The fabricated magnetic nanocomposites were characterized by FTIR, XRD, TGA, DSC, GPC, XPS and SEM. The structures of the polymer core and the nanoparticle shell were analyzed. We investigated the effects on the products of the weight of Fe₃O₄ nanoparticles used to stabilize the original Pickering emulsions. Pickering suspension polymerization provides a new route for the synthesis of a variety of hybrid nanocomposite microspheres with supracolloidal structures.     

基于纤维素纳米晶稳定的亚微米Pickering乳液制备

与传统表面活性剂稳定的乳液相比,固体纳米颗粒稳定的Pickering乳液具有较强的界面稳定性、多功能性、低毒性等优势,在生物医药领域具有较大的应用潜力。而相较于尺寸较大的微米级Pickering乳液,亚微米Pickering乳液具有更大的比表面积、更有效的递送效率,有望进一步拓展Pickering乳液在生物医药领域的应用。但由于Pickering乳液的制备影响因素众多,且相互制约,刚性的固体颗粒难以在较小的有限油水界面排布,增加了亚微米Pickering乳液的制备难度。本工作以制备稳定的亚微米Pickering乳液为研究目标,采用具有良好生物相容性的天然多糖–纤维素纳米晶(CNCs)为颗粒乳化剂,角鲨烯作为油相,考察了颗粒浓度、油水比例、水相成分、超声时间及频率对Pickering乳液粒径分布及稳定性的影响,最终得到了具有良好的储存稳定性和抗离心稳定性的粒径为638.7?8.40 nm的亚微米Pickering乳液(CNCs-PE)。通过激光共聚焦显微镜证实了CNCs吸附在油水界面,形成了Pickering乳液结构。利用CCK-8法评价了CNCs和CNCs-PE的细胞毒性,结果表明,两者都具有良好的细胞安全性。此外,将其用于吸附模型抗原OVA,吸附率达到约80%,且肌肉注射部位的切片结果也表明其注射安全性良好。此结果为亚微米Pickering乳液进一步研究提供了参考,并有望拓展CNCs稳定的亚微米Pickering乳液在生物医药领域的应用。     

The tough microcapsules of acrylic acid–styrene–isoprene–styrene quadrablock copolymer shell via Pickering emulsion technique

Pickering emulsion technique has been demonstrated a simple method to fabricate the microcapsules. However, the resulted microcapsules are often fragile. This limits their applications. Here, we report that the microcapsules with the nanostructured shell of poly(acrylic acid‐b‐styrene‐b‐isoprene‐b‐styrene) (ASIS), which is of high toughness and elasticity, could be fabricated via Pickering emulsions using ASIS nanoparticles as stabilizing particles. The surfactant‐free ASIS latex (with theoretical molecular weight for each block: 1.5k–15k–55k–10k) was synthesized by reversible additional fragmentation transfer (RAFT) emulsion polymerization using amphiphilic macro‐RAFT agent [poly(acrylic acid)₂₀‐b‐polystyrene₅ trithiocarbonate] as both reactive surfactant and polymerization mediator. It was found that the ASIS nanoparticles were able to self‐assemble on oil/water interface to stabilize Pickering emulsion of hexadecane in the pH range from 8 to 12. The droplet diameter was finely tuned from 17 to 5 µm by increasing the ASIS particle levels from 0.13 to 12 wt % based on the mass of the ASIS aqueous dispersions. With toluene as a coalescing aid, the capsules with a coherent and nonporous shell were obtained with the dispersed phase volume percentage as high as 50%. The toluene treated capsules were so mechanically strong to survive the utrasonic treatment. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46700.     

阴离子多聚糖修饰Pickering乳液的制备及表征

为了提高淀粉纳米晶(SNC)与季铵盐壳聚糖(QCS)共同稳定的Pickering乳液在p H变化时的稳定性,以阴离子多聚糖海藻酸钠和果胶为原料,通过静电作用对乳液进行表面修饰,制得两种Pickering乳液。通过测定乳液粒径、Zeta电位和体外消化情况,对乳液的稳定性和消化特性进行了表征。结果显示:当水相中海藻酸钠和果胶质量分数均为0.1%(以水相为基准)时,修饰后的两种Pickering乳液在p H=2~7内均能保持粒径不变,且该乳液在25℃下放置90 d,粒径无变化,无乳析现象发生。此外,在体外模拟消化条件下,阴离子多聚糖的加入还能抑制Pickering乳液中油脂和淀粉的消化。     

智能响应型Pickering乳液的制备及在物质分离中的应用进展

Pickering乳液是指由微纳米固体粒子代替传统表面活性剂作为乳化剂而稳定的乳液,具有较强的稳定性和超高油/水界面,能够为多相界面反应和物质传输提供高效稳定的场所。Pickering乳液的乳滴结构和性质与固体颗粒的尺寸形貌及表面性质密不可分,通过调控固体颗粒本身或表面的性质可以赋予Pickering乳液特定的响应性功能,拓宽其应用领域。本文对近年来不同响应型（磁性、CO₂、pH、光、温度等响应型）的Pickering乳液的主要研究成果进行了综述,重点介绍了Pickering乳液的稳定性原理、响应型Pickering乳液的制备方法和结构调控策略,以及近年来Pickering乳液在物质分离提取中的应用研究进展,最后对智能响应型Pickering乳液应用研究的发展趋势进行了展望。     

Submicron mullite hollow spheres synthesized via UV polymerization of Pickering emulsions

We here propose a simple, facile, and effective method to prepare submicron mullite hollow spheres templated from Pickering emulsions. Dual-phase sol consisted of boehmite and silica nanoparticles decorated by pentanoate ion could assemble at water/oil interface irreversibly to form photosensitive Pickering emulsions. The droplets of emulsions could be separated by dilution and formed by photopolymerization to gain hybrid microspheres, which could completely transform to mullite hollow microspheres via binder removal and sintering. It is found that the prepared hollow microspheres possess intact morphology, favorable sphericity, large cavity volume, and bulk density of 0.356 g/cm³. Importantly, the average diameter of mullite hollow spheres obtained via this method could be as low as 0.33–2.31 μm. This steady method is efficient and suitable for various types of inorganic particles, providing an innovative perspective for preparing fine hollow spheres applicable for filtration, drug loading as well as energy storage areas.     

疏水改性核壳结构颗粒对Pickering乳液的稳定作用

为了探究固体颗粒对乳液的稳定作用,采用双亲染料分子罗丹明B对核壳结构的Fe_3O_4@SiO_2纳米颗粒进行疏水改性,并将改性后的纳米颗粒作为稳定剂制备Pickering乳液。通过Zeta电位、FTIR、XRD、SEM、接触角测量、光学显微镜、电导率仪对Fe_3O_4@SiO_2纳米颗粒以及Pickering乳液的结构、形貌和性能进行表征与分析,结果表明:制备的纳米颗粒粒径小,约为150 nm,为单分散球形核壳结构;罗丹明B成功修饰到Fe_3O_4@SiO_2纳米颗粒表面,改性后颗粒接触角由30°增加至120°;随乳化剂颗粒质量浓度的增加,制备的乳液液滴的粒径减小。另外,所得Pickering乳液具有良好的磁场响应性,可通过外加磁场实现对乳液稳定性的可逆调控,且此过程可重复3次以上。     

Reactive Surfactants for Achieving Open-Cell PolyHIPE Foams from Pickering Emulsions

PolyHIPEs, highly porous polymers synthesized within high internal phase emulsions (HIPEs), emulsions with over 74% internal phase, are of interest for applications such as absorbents, reaction supports, and tissue engineering scaffolds. Typically, the surfactant contents for HIPE stabilization are relatively high, ranging from 20 to 30 wt% of the external phase, with the monomers usually being the remainder. One drawback of using surfactants for these applications is the potential for leachables, necessitating intensive purification processes for their removal. Pickering HIPEs, HIPEs stabilized using amphiphilic solid nanoparticles that spontaneously migrate to the oil–water interface, can be used as an alternative HIPE stabilization strategy. Although nanoparticles can add surface functionality advantageous for the application, polyHIPEs from Pickering HIPEs often lack the interconnecting holes needed for the high permeability required for such applications. This work describes a successful approach for designing an HIPE stabilization system that is based on a combination of nanoparticles and reactive surfactants and that generates the desired surface functionality, an interconnected porous structure, and a low leachable content. Such an approach can extend the applicative utility of such polyHIPEs by circumventing the need for extensive purification.     

TiO2纳米颗粒稳定的Pickering乳液用作防晒乳成分研究

采用烷基化改性的TiO_2纳米颗粒为稳定剂,化妆品级白油为油相,黄芪水溶液为水相,制备了一种载药Pickering乳液。利用TEM、接触角测试仪和光学显微镜对TiO_2纳米颗粒及载药Pickering乳液进行了表征。结果表明,该纳米颗粒分散性良好、尺寸均匀,具备良好的稳定乳液能力;通过紫外吸收测试,控制释放药物和清洗对照实验,表明该载药Pickering乳液具有较高的防晒效果和随光照时间控制释放药物以及易于从皮肤表面清洗的特性。     

High pressure emulsification with nano-particles as stabilizing agents

This work presents a technical possibility to produce PSE (particle stabilized emulsions, so called Pickering emulsions) using inorganic nano-particles, which can be highly abrasive. The influence of process parameters (such as inlet flow combination, volume throughput, pressure) and special challenges arising from using nano-particles instead of emulsifier molecules are depicted. Furthermore, the stability and droplet size distributions of oil-in-water (o/w) emulsions stabilized with x～200 and 12 nm Stober silica particles are discussed. Results are compared to those obtained by batch processing using a rotor–stator-system. Process economics as well as efficiency will also be discussed.     

Multihollow nanocomposite microspheres with tunable pore structures by templating Pickering double emulsions

Micrometer-sized dual nanocomposite polymer microspheres with tunable pore structures were fabricated using a simple and straightforward method based on Pickering double emulsions. First, a primary water-in-styrene (oil) emulsion (w₁/o) was prepared using the hydrophobic silica nanoparticles as a particulate emulsifier without any molecular surfactants. Then, a water-in-styrene-in-water (w₁/o/w₂) Pickering emulsion was produced by the emulsification of the primary w₁/o emulsion into water using Fe₃O₄ nanoparticles as external emulsifier. The big styrene droplets containing small water droplets were polymerized after the formation of the double emulsions. Nanocomposite polystyrene microspheres with a multihollow structure were obtained and their morphological structures were studied by scanning electron microscopy (SEM). The pore structure of the microspheres could be tuned by the volume ratio of the internal water phase to the medium oil phase (w₁:o) of the primary emulsions. With increasing w₁:o from 1:8 to 4:1, the amount of the pores in one microsphere increased gradually and the pore structures changed from close to interconnected. The resulting multihollow microspheres had a responsive ability to magnetic stimulus due to the existence of Fe₃O₄ nanoparticles. This kind of multihollow hybrid polymer microspheres is expected to have a wide potential application in materials science and biotechnology.     

刺激响应型Pickering乳液的制备及应用研究进展

固体纳米颗粒代替传统表面活性剂作为乳化剂稳定的Pickering乳液具有高抗聚结性、环境友好性、成本较低等优点,在多种领域具有广阔应用前景。通过适当刺激精确调控乳液稳定性及构建响应型Pickering乳液的研究引起广泛关注。该文详细综述了多种刺激响应型Pickering乳液的构建、调控及其应用。首先阐述了Pickering乳液的稳定性影响因素和备固体颗粒乳化剂表面改性技术;继而介绍了多种刺激响应性Pickering乳液的响应机理和性能;最后综述了Pickering乳液的应用研究;分析展望了Pickering乳液研究应用中存在的问题和发展前景。     

Fabrication of sustained‐release and antibacterial citronella oil‐loaded composite microcapsules based on Pickering emulsion templates

In this work, the citronella oil (CTO)‐loaded composite microcapsules with hydroxyapatite (HAp)/quaternary ammonium salt of chitosan (HACC)/sodium alginate (SA) shells are facilely and effectively fabricated by templating citronella oil‐in‐water Pickering emulsions, which are stabilized with HAp nanoparticles. The microcapsule composite shells are prepared by the electrostatic adsorption of HACC and SA, and then chelation interaction of alginate and Ca²⁺ ions released from HAp nanoparticles. Scanning electronic microscope observation shows that the microcapsules have a spherical shape. Thereafter, Fourier transform infrared spectroscopy and thermal gravimetric analysis results indicate that CTO is successfully loaded into the microcapsules, and the related CTO‐loaded microcapsules possess the thermal stability. Moreover, the in vitro release study of CTO shows that the microcapsules have sustained release activity, and the related CTO release profiles can be well described by Rigter–Peppas model. The antimicrobial assays of microcapsules display the antibacterial effect of CTO‐loaded microcapsules against Staphylococcus aureus and Escherichia coli. Overall, this study opens up new potentiality for unstable active ingredient as an environmental friendly and ingenious microencapsulation in food and agriculture applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46386.     

Synthesis of poly(N‐isopropylacrylamide) by distillation precipitation polymerization and quantitative grafting on mesoporous silica

In this work, syntheses of thermoresponsive poly(N‐isopropylacrylamide) (PNIPAM) with different molecular weights were carried out in ethanol by distillation precipitation polymerization (DPP) technique. The synthesized polymers were fully characterized by attenuated total reflection Fourier‐transform infrared (ATR‐FTIR) spectroscopy, nuclear magnetic resonance spectroscopy, and size exclusion chromatography techniques. The lower critical solution temperatures of the polymers were determined with differential scanning calorimetry. A simple and versatile method for the in situ synthesis and grafting of PNIPAM on mesoporus silica nanoparticles (MSNs) with improved control over quantitative grafting is devised. The PNIPAM grafted MSNs were characterized with ATR‐FTIR, thermogravimetric analysis, transmission electron microscopy, and dynamic light scattering analyses. From the results obtained it is showed that quantitative grafting of PNIPAM on MSNs from 1 to 20% by weight can be tuned by manipulating the in situ DPP reaction conditions. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44181.