Synthesis of raspberry‐like organic–inorganic hybrid nanocapsules via pickering miniemulsion polymerization: Colloidal stability and morphology

Raspberry‐like hybrid nanocapsules with a hydrophobic liquid core were successfully prepared via the copolymerization of styrene, divinylbenzene (DVB), and 4‐vinyl pyridine (4‐VP) in Pickering‐stabilized miniemulsions by using silica particles as the sole emulsifier and hexadecane (HD) as liquid template. When compared with conventional Pickering miniemulsions and Pickering suspensions, the colloidal stability of the current systems is much more sensitive to the variation of reaction parameters such as pH, size, amount of silica particles, and content of 4‐VP. The systems without coagulum were only obtained in a narrow pH range at around 9.5 and by using 12 nm silica particles as emulsifier. The formation of well‐defined raspberry‐like capsules was confirmed by transmission electron microscopy (TEM) and high‐resolution scanning electron microscopy (HRSEM). The stable attachment of silica particles on the surface of hybrid particles was verified by centrifugation and subsequent characterizations, such as Fourier transform infrared spectroscopy, TEM, and HRSEM. The influence of pH and weight content of HD, DVB, and 4‐VP on the particle morphology was extensively investigated. Interestingly, the particle morphology strongly depends on the particle size. When compared with the organic surface‐active surfactant, the formation of capsule morphology could be promoted by the application of silica particles taking advantage of their surface inactivity. The formation mechanisms of capsules/solid particles are discussed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Preparation of mesoporous submicrometer silica capsules via an interfacial sol-gel process in inverse miniemulsion

Mesoporous silica capsules with submicrometer sizes were successfully prepared via the interfacial hydrolysis and condensation reactions of tetraethoxysilane (TEOS) in inverse miniemulsion by using hydrophilic liquid droplets as template. The inverse miniemulsions containing pH-controlled hydrophilic droplets were first prepared via sonication by using poly(ethylene-co-butylene)-b-poly(ethylene oxide) (P(E/B)-PEO) or SPAN 80 as surfactant. TEOS was directly introduced to the continuous phase of an inverse miniemulsion. The silica shell was formed by the deposition of silica on the surface of droplets. The formation of capsule morphology was confirmed by transmission electron microscopy (TEM) and field emission scanning electron microscopy (FESEM). The mesoporous structure was verified by nitrogen sorption measurements. The specific surface area could be tuned by the variation of the amount of cetyltrimethylammonium bromide (CTAB) and TEOS, and the pore size by the amount of CTAB. The influences of synthetic parameters on the particle size and morphology were investigated in terms of the amount of CTAB, pH value in the droplets, TEOS amount, surfactant amount, and type of solvent with low polarity. A formation mechanism of silica capsules was proposed.     

Preparation of dually, pH- and thermo-responsive nanocapsules in inverse miniemulsion

pH- and thermo-sensitive nanocapsules were successfully synthesized via inverse miniemulsion copolymerization of N-isopropyl acrylamide (NIPAM), N,N'-methylene bisacrylamide (MBA), and a functional monomer, 4-vinyl pyridine (4-VP). The size and size distribution of nanocapsules were measured by dynamic light scattering (DLS). The particle morphology was observed by transmission electron microscopy (TEM). The final morphology of particles was strongly influenced by the hydrophobicity of functional monomers. The use of a hydrophilic functional monomer, acrylic acid, led to the formation of solid particles, while the use of the more hydrophobic functional monomer, 4-VP, resulted in the formation of nanocapsules. The particle morphology, size, and size distribution were investigated in terms of the content of 4-VP, MBA, and the type and content of surfactant. The pH- and thermo-sensitivities were characterized by measuring the size variation with the change of temperature and pH. The organic-inorganic nanocapsules were prepared by coating a layer of silica particles on the surface of the sensitive nanocapsules.     

界面聚合法制备聚α-氰基丙烯酸正丁酯毫微囊

采用界面聚合法制备了粒径约 2 0 0nm的聚α 氰基丙烯酸正丁酯毫微囊 ,运用动态激光光散射和透射电镜测定了毫微囊的粒径及其分布 ,系统研究了高分子稳定剂类型、表面活性剂的用量、辅助添加剂的用量、以及后处理条件等因素对毫微囊粒径及其分布的影响 .结果说明 ,在高分子稳定剂中 ,葡聚糖的稳定作用优于Poloxamer 188,而葡聚糖的用量越大 ,毫微囊的粒径越小 ,采用葡聚糖 70比葡聚糖 40更能得到窄分布的毫微囊 .增加表面活性剂吐温 2 0的用量 ,同样减小毫微囊的粒径 .与三油酸甘油酯相比 ,在有机相中加入苯甲醇能够增大毫微囊粒径 ,并改善毫微囊的规整性 .乙醇和丙酮均可作为溶剂添加在有机相中 ,但含乙醇的体系分散较好 ,界面聚合得到聚α 氰基丙烯酸正丁酯毫微囊粒径分布较窄 .此外 ,通过考察浓缩温度发现 ,在2 0℃下真空浓缩时毫微囊粒径基本保持不变 ,而在 30℃下则发生一定程度的毫微囊聚集     

Mechanism of nanocapsules formation by the emulsion-diffusion process

A detailed investigation into the mechanisms of nanocapsule formation by means of the two stages "emulsion-diffusion" process is reported. Such widely used process is still poorly understood. An emulsion of oil, polymer and ethyl acetate is fabricated as a first step; dilution with pure water allows ethyl acetate to diffuse out from the droplets, leaving a suspension of nanocapsules at the end. It has been shown that the size of nanocapsules was related to the chemical composition of the organic phase and the size of primary emulsion through a simple geometrical relationship. As a consequence, most of the properties of the nanocapsules were decided at the emulsification step. The influence of several formulation and processing parameters of the primary emulsion was studied accordingly. The thin polymer membrane of nanocapsules was observed by means of cryo-fracture electron microscopy. Finally two experiments were designed for a mechanistic investigation of the diffusion step. A step-by-step diffusion of the organic solvent takes place by successive partition equilibria of ethyl acetate between the droplets and aqueous phase. A time-resolved experiment shows the fast diffusion (less than 20 ms) related to the small droplet size of the emulsion.     

Preparation of Cu nanoparticles with controlled particle size and distribution via reaction temperature and sonication

This paper presents metallic copper nanoparticles (CuNPs) that differ according to the process parameters used, such as bath temperature and sonication. The effect of different reactions on the size and distribution of CuNPs that had been formed in ethylene glycol solvent were characterized by the X‐ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) analyses after extraction from the solvent. The optimal dimensional properties, including size, distribution, and agglomeration, of CuNPs were determined by controlling the reaction temperature. On the other hand, the mechanically induced sonication process enhances the formation of the selective CuNPs because of the many homogeneous interactions among precursors, reducing agents, and capping agents related to the nucleation and growth of CuNPs. The mechanics of the origin of the diverse CuNPs of different size and distribution are discussed. Copyright © 2016 John Wiley & Sons, Ltd.     

PSt种子与“花瓣”形PSt/PAN复合颗粒的制备

以过硫酸钾为引发剂,在乙醇/水的混合介质中使苯乙烯进行无皂乳液聚合,得到了单分散亚微米级聚苯乙烯(PSt)微球.用扫描电子显微镜研究了引发剂浓度、单体浓度、反应温度和溶剂组成对PSt微球粒径的影响.结果表明,改变上述条件能明显影响其粒径.以所得单分散聚苯乙烯微球为种子,在丙烯酸单封端聚乙二醇大分子单体存在的条件下,使丙烯腈和少量苯乙烯进行新的无皂种子乳液聚合,在合适的条件下制得到了“花瓣”形的聚合物复合颗粒,为深入探讨这类特殊形态聚合物颗粒的形成机理提供了新的佐证.     

Facile fabrication of thermally responsive Pluronic F127-based nanocapsules for controlled release of doxorubicin hydrochloride

Novel core–shell-structured Pluronic-based nanocapsules with thermally responsive properties were successfully prepared using a modified emulsification/solvent evaporation method. The nanocapsules were constructed through the cross-linking reaction between p-nitrophenyl-activated Pluronic F127 and hyaluronic acid (HA) (named Pluronic F127/HA) or poly(ε-lysine) (PL) (named Pluronic F127/PL) at the organic/aqueous interface. The formation, size, and thermal responsiveness of the nanocapsules were characterized by ¹H NMR, transmission electron microscopy (TEM) and dynamic light scattering (DLS). The resultant shell-cross-linked nanocapsules exhibit a larger volume transformation (26 times change in volume for Pluronic F127/HA and 31 times for Pluronic F127/PL) over a temperature range of 4–37 °C because of the temperature-dependent dehydration of cross-linked Pluronic F127 polymer chains. The nanocapsules are about 72?±?4 nm (polydispersity index [PDI]?=?0.08) for Pluronic F127/PL (69?±?5 nm, PDI?=?0.10 for Pluronic F127/HA) at 37 °C with narrow size distribution and expand to about 226?±?23 nm (PDI?=?0.34) for Pluronic F127/PL (206?±?20 nm, PDI?=?0.3) for Pluronic F127/HA at 4 °C with broad size distribution in aqueous solutions. The nanocapsules were used to encapsulate and control the release of doxorubicin hydrochloride (DOX·HCl) in aqueous solution. DOX·HCl was physically encapsulated in the nanocapsules using a soaking–freeze-drying–heating procedure. The release curve and release kinetics disclosed that the thermally responsive hollow nanocapsules are good carries for drug delivery.     

Fabrication, characterization, and supercooling suppression of nanoencapsulated n-octadecane with methyl methacrylate–octadecyl methacrylate copolymer shell

Supercooling of micro- and nanoencapsulated phase change material is widely observed as their diameters depress to a limitation upon cooling. The aim of this study is to suppress the supercooling of nanoencapsulated n-octadecane (NanoC18) using a novel copolymer consisting of long n-alkyl side chains as shell. Nanoencapsulations of n-octadecane with various compositions of poly(methyl methacrylate-co-octadecyl methacrylate) copolymer as shells were carried out by means of miniemulsion polymerization. Fabrication, morphology, diameter distributions, phase change behaviours, and thermal stabilities of nanocapsules were investigated using Fourier transformed infrared spectroscopy, a field-emission scanning electron microscope, a transmission electron microscope, particle size distribution analysis, differential scanning calorimetry, and thermogravimetric analysis. The results indicate that a series of nanocapsules with core/shell structure and spherical shapes are fabricated with average diameters ranging from 373 to 398 nm. The average thickness of the shells is about 60 nm. All the NanoC18 crystallize into a stable triclinic phase via a metastable rotator phase (R_I) from the liquid phase. The crystallization temperature of n-octadecane within poly(methyl methacrylate) nanocapsules is considerably lower than that in bulk phase. Supercooling is effectively suppressed using the comb-like copolymer with crystallizable n-octadecyl side chains as shell. Octadecyl methacrylate is not only employed as a reactive costabilizer to suppress the influence of Ostwald ripening during the formation of nanocapsules but also as a functional monomer in the composition of the copolymer shell in order to suppress the supercooling of NanoC18.     

Polyurea nanocapsules obtained from nano‐emulsions prepared by the phase inversion temperature method

We describe here a new and simple method for preparation of polyurea nanocapsules from nanodroplets that were obtained by the phase inversion temperature (PIT) method. In the first stage, a nano‐emulsion was prepared, by a heating–cooling cycle, in which the oil phase contained an oil soluble monomer (toluene 2 , 4 ‐diisocyanate (TDI)). In the second stage, a water‐soluble monomer and crosslinker (diethylenetriamine (DETA)) was added, leading to formation of a polymeric shell by an interfacial polycondensation reaction. The new method was demonstrated for obtaining nanocapsules of about 100 nm, in which hexadecane, dodecane, or decane were the core materials, without using any special equipment. The morphology and structure of the nanocapsules were evaluated by attenuated total reflection Fourier transform infrared (ATR‐FTIR) measurements and electron microscopy. The thermal behavior of the nanocapsules containing hexadecane was studied by Differential Scanning Calorimetry (DSC) measurements, indicating that such nanocapsules can be utilized in thermal energy storage. Copyright © 2010 John Wiley & Sons, Ltd.     

Thermosensitive Particles with Unusual Morphology Prepared by Dispersion Copolymerization

The monodispersed polymeric particles with an unusual structure were prepared by the dispersion copolymerization of acrylonitrile/styrene（AN/St） in mixed solvents of ethanol/water by using the poly（N-isopropylacrylamide） （PNIPAAm） macromonomer as a reaction stabilizer. It was found that the AN monomer plays a key role in the formation of the particles with special morphology analyzed via scanning electron microscopy （SEM）. The reaction parameters have remarkable influences on the particle size and morphology. The particles possess a thermosensitive property according to the result of laser light scattering（LLS）.     

Silicone nanocapsules templated inside the membranes of catanionic vesicles

A simple and effective way to synthesize hollow silicone resin particles of controlled diameter is presented. The synthesis utilizes catanionic vesicles as templates for the polycondensation/polymerization processes of 1,3,5,7-tetramethylcyclotetrasiloxane (D4H) within their membranes. Two different surfactant systems were used to form the vesicular templates: mixtures of dodecyltrimethylammonium bromide (DTAB) and sodium dodecylbenzenesulfonate (SDBS) in the cationic (the DTAB/SDBS system) or anionic (the SDBS/DTAB system) rich region of the phase diagram. The templates obtained from these surfactant mixtures form spontaneously unilamellar vesicles in aqueous solution. The vesicular templates swell upon addition of D4H, thus increasing their size. The silicone resin was obtained in acid- or base-catalyzed polycondensation and ring-opening polymerization processes of D4H. In the case of the DTAB/SDBS system the formation of a densely cross-linked silicone material with SiO3/2 units allowed the nanocapsules to retain the vesicular shape after removal of the template, whereas in the SDBS/DTAB system, the polymer produces capsules which are too smooth to support surfactant lysis. The morphology of the silicone nanocapsules was analyzed using transmission electron microscopy (TEM) and, in some cases, atomic force microscopy (AFM). TEM and AFM reveal discrete hollow particles with a small amount of linked or aggregated hollow silica shells.     

Controlled fabrication and shape-dependent luminescence properties of hexagonal NaCeF4, NaCeF4:Tb3+ nanorods via polyol-mediated solvothermal route

Hexagonal monodisperse NaCeF(4) and NaCeF(4):Tb(3+) nanorods have been successfully synthesized by a polyol-mediated solvothermal route with ethylene glycol (EG) as solvent. The crystalline phase, size, morphology, and luminescence properties were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and photoluminescence (PL) spectra as well as dynamic decays. The experimental results indicate that the content of NH(4)F and NaNO(3) are crucial in controlling product morphology and size. Nanorods with different aspect ratios could be controllably obtained under settled conditions. Shape-dependent luminescence and energy transfer routes from Ce(3+) to Tb(3+) in NaCeF(4):Tb(3+) nanorods were observed by the modified local crystal field environment around rare earth ions. The 4f-5d transitions of Ce(3+) ions have much higher sensitivity to the anisotropic shape of samples than that of Tb(3+) ions.     

Fabrication of double-walled microspheres for the sustained release of doxorubicin

Double-walled microspheres with poly(L-lactic acid) shells and poly(DL-lactic-co-glycolic acid) cores were fabricated using solvent evaporation technique which involves the phase separation phenomenon of a binary composite of these two polymers. Doxorubicin, a hydrophilic drug, was entrapped within the core of these double-walled microspheres with different core-shell thicknesses and compositions to investigate the in vitro release on this class of microspheres. Microspheres of different size ranging from 50 to 300 microm were also fabricated to investigate whether this method is suitable for fabricating small particles for intramuscular injection applications, and their phase separation and surface morphology were examined by differential scanning calorimetry, scanning electron microscopy, and optical microscopy.     

纳米尺度超声显影微囊的制备及性能表征简

采用双乳液-溶剂挥发法制备了内部包封氟碳液体的聚乳酸-甲氧基聚乙二醇两嵌段共聚物(MePEG-b-PLA)基超声显影纳米微囊;用2种不同嵌段比的MePEG-b-PLA共聚物研究共聚物组成与纳米囊性能的关系;选用聚乙烯醇(PVA)、羧甲基葡聚糖(CMG)和壳聚糖(CS) 3种乳化剂对纳米囊表面进行亲水性修饰. 对所制备纳米囊的粒径、Zeta电位、形貌和水溶液稳定性进行了表征. 结果表明,利用质量分数为1%的PVA和质量分数为1%的CMG组成的复配乳化剂和m(MePEG)：m(PLA)= 1：3的聚合物制得的纳米囊的平均粒径为432.9 nm,水溶液稳定性优良. 利用超声仪对纳米囊体外超声显影性能进行研究,结果表明,所得聚乳酸-甲氧基聚乙二醇纳米囊具有更好的中心成像区域灰度值和更持久的体外超声显影效果. 结合3-(4,5-二甲基噻唑-2)-2,5-二苯基四氮唑溴盐(MTT)比色法研究证实该纳米囊具有低细胞毒性. 在超声影像学领域具有良好的应用前景.     

A Solvothermal Route to Cu2O Nanocubes and Cu Nanoparticles

IntroductionSynthesis of Cu2O and Cu nanostructures has beenactively researched for many decades because bothCu2O and Cu are important industrial materials on ac-count of their novel physical and chemical properties.In particular,Cu2O is a p-type metal ox…     

Preparation and characterisation of polypyrrole colloids in non-aqueous media

We have prepared polypyrrole both as a bulk powder and as a sterically stabilised colloidal dispersion in a noved non-aqueous solvent, 2-merhoxyethanol. The steric stabiliser utilised in the latter system was a poly(vinyl acetate) homopolymer. The electroactivity, morphology, thermal stability and chemical composition of these materials were characterised by d.c. conductivity measurememts, electron microscopy, thermogravimetry, FTIR and visible absorption spectroscopy and clemental microanalyses. The mass ratio of poly(vinyl acetate) to polypyrrole in the colloidal particles was determined indirectly by spectroscopic assay of the post-reaction supernatant solution for non-adsorbed stabiliser.     

纳米尺度超声显影微囊的制备及性能表征

采用双乳液-溶剂挥发法制备了内部包封氟碳液体的聚乳酸-甲氧基聚乙二醇两嵌段共聚物(MePEG-b-PLA)基超声显影纳米微囊; 用2种不同嵌段比的MePEG-b-PLA共聚物研究共聚物组成与纳米囊性能的关系; 选用聚乙烯醇(PVA)、 羧甲基葡聚糖(CMG)和壳聚糖(CS) 3种乳化剂对纳米囊表面进行亲水性修饰. 对所制备纳米囊的粒径、 Zeta电位、 形貌和水溶液稳定性进行了表征. 结果表明, 利用质量分数为1%的PVA和质量分数为1%的CMG组成的复配乳化剂和m(MePEG)∶m(PLA)= 1∶3的聚合物制得的纳米囊的平均粒径为432.9 nm, 水溶液稳定性优良. 利用超声仪对纳米囊体外超声显影性能进行研究, 结果表明, 所得聚乳酸-甲氧基聚乙二醇纳米囊具有更好的中心成像区域灰度值和更持久的体外超声显影效果. 结合3-(4,5-二甲基噻唑-2)-2,5-二苯基四氮唑溴盐(MTT)比色法研究证实该纳米囊具有低细胞毒性. 在超声影像学领域具有良好的应用前景.     

固相合成法制备纳米碳酸锶微球

以六水合氯化锶(SrCl2·6H2 O)和碳酸氢铵(NH4 HCO3)为原料,十二烷基苯磺酸钠(SDBS)为表面活性剂,采用阴离子表面活性剂辅助固相球磨法制备纳米碳酸锶微球.样品采用扫描电镜(SEM)、透射电镜(TEM)、能谱仪(EDX)、X-射线衍射仪、红外光谱FTIR、热重仪和差示扫描仪联用(TG—DSC)等手段表...     

Magnetic polystyrene nanocapsules with core-shell morphology obtained by emulsifier-free miniemulsion polymerization

Nanocapsules containing hexadecane and Fe₃O₄ magnetic nanoparticles as core materials and polystyrene as shell were produced in a new method through emulsifier-free miniemulsion polymerization using 2,2′-azobis(2-amidinopropane) dihydrochloride (V-50) as a water-soluble initiator. The effect of some parameters such as the amounts of Fe₃O₄ and initiator on morphology of resulting nanocapsules was studied. Transmission electron microscopy showed that the products had latex particles having a size range of about 300–1300 nanometer and both magnetic nanocapsules with core-shell morphology and solid particles. The phase transition temperature and phase transition heat of the produced capsules were determined by differential scanning calorimetric analyses. Thermal properties of the latex were compared with those of magneticparticles-free latex and with those of latex free of both magnetic particles and hexadecane. Thermogravimetric analysis was also used to confirm the encapsulation and to determine the amounts of hexadecane and Fe₃O₄ within the capsules.