Study of the preparation of sustained-release microspheres containing zedoary turmeric oil by the emulsion-solvent-diffusion method and evaluation of the self-emulsification and bioavailability of the oil

The purpose of this study was to design a sustained-release formulation of an oily drug. The sustained-release microspheres with self-emulsifying capability containing zedoary turmeric oil (ZTO) were prepared by the quasi-emulsion-solvent-diffusion method. The micromeritic properties, the efficiency of emulsification and the drug-release behavior of the resultant microspheres were investigated. The bioavailability of the microspheres was compared with conventional ZTO self-emulsifying formulations for oral administration using 12 healthy rabbits. An HPLC method was employed to determine the concentration of germacrone in plasma, which was used as an index of ZTO. Spherical and compacted microspheres with average diameters of 100-600 microm have been prepared, and their release behavior in distilled water containing 1.2% (w/v) of polysorbate-80 can be controlled by the ratio of polymer/Areosil200 in the microspheres. The resultant emulsions with mean droplet sizes of 200-500 nm are produced when the microspheres are immersed in phosphate buffer (pH 6.8) under gentle agitation. The stability and the droplet size of the resultant emulsions are also affected by the polymer/Areosil200 ratio in the formulation, while the amount of talc has a marked effect on the self-emulsifying rate. The plasma concentration-time profiles with improved sustained-release characteristics were achieved after oral administration of the microspheres with a bioavailability of 135.6% with respect to the conventional self-emulsifying formulation (a good strategy for improving the bioavailability of an oily drug). In conclusion, the sustained-release microspheres with self-emulsifying capability containing ZTO have an improved oral bioavailability. Our study offers an alternative method for designing sustained-release preparations of oily drugs.     

Preparation of calcium alginate microgel beads in an electrodispersion reactor using an internal source of calcium carbonate nanoparticles

An electrodispersion reactor has been used to prepare calcium alginate (Ca-alginate) microgel beads in this study. In the electrodispersion reactor, pulsed electric fields are utilized to atomize aqueous mixtures of sodium alginate and CaCO3 nanoparticles (dispersed phase) from a nozzle into an immiscible, insulating second liquid (continuous phase) containing a soluble organic acid. This technique combines the features of the electrohydrodynamic force driven emulsion processes and externally triggered gelations in microreactors (the droplets) ultimately to yield soft gel beads. The average particle size of the Ca-alginate gels generated by this method changed from 412 +/- 90 to 10 +/- 3 microm as the applied peak voltage was increased. A diagram depicting structural information for the Ca-alginate was constructed as a function of the concentrations of sodium alginate and CaCO3 nanoparticles. From this diagram, a critical concentration of sodium alginate required for sol-gel transformation was observed. The characteristic highly porous structure of Ca-alginate particles made by this technique appears suitable for microencapsulation applications. Finally, time scale analysis was performed for the electrodispersion processes that include reactions in the microreactor droplets to provide guidelines for the future employment of this technique. This electrodispersion reactor can be used potentially in the formation of many reaction-based microencapsulation systems.     

Fabrication of novel multihollow superparamagnetic magnetite/polystyrene nanocomposite microspheres via water-in-oil-in-water double emulsions

We herein present a novel and simple synthetic strategy for fabricating multihollow superparamagnetic magnetite/polystyrene nanocomposite microspheres via water-in-oil-in-water double emulsions. Amphipathic magnetite nanoparticles surface-modified with oleic acid act as an oil-soluble emulsifier and sodium dodecyl sulfate acts as a water-soluble surfactant in the system. The final products were thoroughly characterized by X-ray powder diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, and field-emission scanning electron microscopy, which showed the formation of multihollow magnetite/polystyrene nanocomposite microspheres. Preliminary results of magnetic properties of multihollow magnetite/polystyrene microspheres were reported. The effect of the content of amphipathic magnetite nanoparticles on the morphology of nanocomposite microspheres was studied. Furthermore, the mechanism of formation of multihollow magnetic nanocomposite microspheres was also discussed.     

Synthesis and plasmonic properties of silver and gold nanoshells on polystyrene cores of different size and of gold–silver core–shell nanostructures

Simple methods of preparing silver and gold nanoshells on the surfaces of monodispersed polystyrene microspheres of different sizes as well as of silver nanoshells on free-standing gold nanoparticles are presented. The plasmon resonance absorption spectra of these materials are presented and compared to predictions of extended Mie scattering theory. Both silver and gold nanoshells were grown on polystyrene microspheres with diameters ranging from 188 to 543 nm. The commercially available, initially carboxylate-terminated polystyrene spheres were reacted with 2-aminoethanethiol hydrochloride (AET) to yield thiol-terminated microspheres to which gold nanoparticles were then attached. Reduction of silver nitrate or gold hydroxide onto these gold-decorated microspheres resulted in increasing coverage of silver or gold on the polystyrene core. The nanoshells were characterized using transmission electron microscopy (TEM), scanning electron microscopy (SEM) and UV–vis spectroscopy. By varying the core size of the polystyrene particles and the amount of metal (silver or gold) reduced onto them, the surface plasmon resonance of the nanoshell could be tuned across the visible and the near-infrared regions of the electromagnetic spectrum. Necklace-like chain aggregate structures of gold core–silver shell nanoparticles were formed by reducing silver nitrate onto free citrate-gold nanoparticles. The plasmon resonance absorption of these nanoparticles could also be systematically tuned across the visible spectrum.     

Novel calcium-alginate capsules with aqueous core and thermo-responsive membrane

Novel calcium-alginate (Ca-alginate) capsules with aqueous core and thermo-responsive membrane are successfully prepared by introducing a co-extrusion minifluidic approach, and the thermo-responsive gating characteristics of Ca-alginate capsule membranes embedded with poly(N-isopropylacrylamide) (PNIPAM) microspheres are investigated systematically. The experimental results show that the prepared Ca-alginate capsules are highly monodisperse, and the average diameter and membrane thickness of Ca-alginate capsules are about 2.96 mm and 0.11 mm respectively. The Ca-alginate capsule membranes exhibit desired thermo-responsive gating property. With increasing the content of PNIPAM microspheres embedded in the Ca-alginate capsule membranes, the thermo-responsive gating coefficient of the capsule membranes increases simply. When solute molecules diffuse through the capsule membrane, the thermo-responsive gating coefficient is significantly affected by the molecular weight of solute molecules.     

Growth mechanism of gold nanoparticles decorated on polystyrene spheres via self-regulated reduction

Uniform polystyrene (PS) microspheres prepared for deposition of metallic nanoparticles were synthesized using the surfactant-free emulsion polymerization based on styrene/potassium persulfate/water (St/KPS/H₂O) system. Owing to the presence of sulfate groups, the PS microspheres can be utilized to reduce gold nanoparticles without adding extra reducing agent into the mixture. The synthesis and characterization of metal-polystyrene nanocomposites are reported, and a possible reduction mechanism is proposed: by heating the aqueous solution in the presence of metal ions and PS, the sulfate chain end groups of the PS hydrolyzed and transformed to hydroxyl groups firstly. The hydroxyl groups function as a reducing agent, and carboxylic groups provide a site to adsorb the gold nuclei. The Au nanoparticles grow in size with the coalescence and dissolving of nuclei through the Ostwald ripening process. The PS microspheres and Au nanoparticles were characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, X-ray power diffraction, and thermal gravimetric analysis.     

SYNTHESIS OF POLY(DIVINYLBENZENE-co-ACRYLIC ACID) HOLLOW MICROSPHERES WITH GOLD NANOPARTICLES ON THE INTERIOR SURFACE

Poly(divinylbenzene-co-acrylic acid) (poly(DVB-co-AA)) hollow microspheres with gold nanoparticles on the interior surfaces were prepared from the gold nanoparticles-coated poly(methacrylic acid) (PMAA@Au@poly(DVB-co-AA)) core-shell microspheres by removal of the PMAA core in water.Au nanoparticles-coated PMAA microspheres were afforded by the in-situ reduction of gold trichloride with PMAA microsphere as stabilizer via the interaction between carboxylic acid groups and Au nanoparticles.Gold nanoparticle...     

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.     

Fluorescence of dyes adsorbed on highly organized,nanostructured gold surfaces

It is shown that fluorescent dyes can be adsorbed selectively on gold nanoparticles which are immobilized on a glass substrate and that the fluorescence originating from the adsorbed dyes exhibits significantly less quenching when compared to dyes adsorbed on bulk gold. Self-assembled monolayers of lissamine sulfide molecules have been studied both on bulk gold and on glass surfaces bearing gold nanoparticles. Gold nanoparticles have been arranged in ordered, two-dimensional patterns, with periodicity in the microm range and used as substrate for the fluorescent dyes. Optical resolution of the fluorescence originating from the pattern has been achieved with laser-scanning confocal microscopy.     

Pickering emulsions stabilized by nanoparticle surfactants

Amphiphilic gold nanoparticles are demonstrated to effectively stabilize emulsions of hexadecane in water. Nanoparticle surfactants are synthesized using a simple and scalable one-pot method that involves the sequential functionalization of particle surfaces with thiol-terminated polyethylene glycol (PEG) chains and short alkane-thiol molecules. The resulting nanoparticles are shown to be highly effective emulsifying agents due to their strong adsorption at oil-water and air-water interfaces. The original nonfunctionalized gold nanoparticles are unable to effectively stabilize oil-water emulsions due to their small size and low adsorption energy. Small-angle X-ray scattering and electron microscopy are used to demonstrate the formation of nanoparticle-stabilized colloidosomes that are stable against coalescence and show significant shifts in plasmon resonance enhancing the near-infrared optical absorption.     

Electrochemical detection of arsenic on a gold nanoparticle array

The detection of As(III) was investigated on a gold nanoparticle array. At the first stage, gold nanoparticles were synthesized on glassy carbon microspheres. The resulting hybrid material was characterized by SEM and the sizes of the nanoparticles were found to be in the range 20–200 nm. At the second stage, glassy carbon microspheres decorated with Au nanoparticles were abrasively attached to the surface of a basal-plane pyrolytic electrode. The resulting gold nanoarray was characterized by the reduction of surface gold oxides. Furthermore, it was found to have good characteristics for the sensing of arsenic via anodic stripping voltammetry with a limit of detection of 0.8 μM and a sensitivity of 0.91 C M⁻¹. The text was submitted by the authors in English.     

Self-organization of bidisperse colloids in water droplets

Most of the colloidal clusters have been produced from oil-in-water emulsions with identical microspheres dispersed in oil droplets. Here, we present new types of binary colloidal clusters from phase-inverted water-in-oil emulsions using various combinations of two different colloids with several size ratios: monodisperse silica or polystyrene microspheres for larger particles and silica or titania nanoparticles for smaller particles. Obviously, a better understanding of how finite groups of different colloids self-organize in a confined geometry may help us control the structure of matter at multiple length scales. In addition, since aqueous dispersions have much better phase stability, we could produce much more diverse colloidal materials from water-in-oil emulsions rather than from oil-in-water emulsions. Interestingly, the configurations of the large microspheres were not changed by the presence of the small particles. However, the arrangement of the smaller particles was strongly dependent on the nature of the interparticle interactions. The experimentally observed structural evolutions were consistent with the numerical simulations calculated using Surface Evolver. These clusters with nonisotropic structures can be used as building blocks for novel colloidal structures with unusual properties or by themselves as light scatterers, diffusers, and complex adaptive matter exhibiting emergent behavior.     

水/正己烷界面上超声波介导组装金纳米粒子薄膜用作SERS基底

本文以高能量的超声波作用于溶胶/疏水溶剂两相体系, 使溶胶相中的纳米颗粒先被加速吸附到乳液油滴的小表面. 随着乳液油滴向上转移, 在界面处破乳, 纳米颗粒就被释放到水/油界面上来, 形成自组装纳米薄膜. 尽管这种组装机制尚不完全清楚(如超声波是否确实如预期那样可以提高纳米粒子的动能), 但这种方法不需要预先对纳米粒子表面疏水修饰, 也不需向体系中添加表面活性有机小分子或电解质等诱导剂, 可快速有效制备表面“洁净”的纳米粒子薄膜, 并可用作高活性SERS基底.     

The preparation of composite microsphere with hollow core/porous shell structure by self-assembling of latex particles at emulsion droplet interface

A submicrometer-scaled polystyrene/melamine-formaldehyde hollow microsphere composite was prepared by self-assembling of sulfonated polystyrene (SPS) latex particles at the interface of emulsion droplets and then being fixed in place using a hard melamine-formaldehyde (MF) composite layer. For control-released purposes, the influential factors that control the size and uniformity of the packed-droplets and the permeability of the composite shell, including the initial particle location, the hydrophilicity and the size of colloidal templates, the oil phase solvent and reserving time of emulsions after the addition of MF prepolymer, were further studied. Relatively uniform sized particle packed-droplets with an average diameter of 10 microm were obtained. The assembled SPS particles kept ordering and minimal conglutination after the preparation of composite microspheres, which allows of controlling the permeability from the interstices between the particles. Porous-mesh-structured MF composite layer was formed to further control the permeability. The morphology of emulsions and composite microspheres were characterized by optical microscopy, scanning and transmission electron microscopy.     

Synthesis and adsorption properties of gold nanoparticles within pores of surface‐functional porous polymer microspheres

Mesoporous polymer microspheres with gold (Au) nanoparticles inside their pores were prepared considering their surface functionality and porosity. The Au/polymer composite microspheres prepared were characterized by transmission electron microscope (TEM), X‐ray diffraction (XRD), and Brunauer–Emmett–Teller (BET) techniques. The results showed that the adsorption of Au nanoparticles could be increased by imparting the pore structure and surface‐functional groups into the supporting polymer microspheres (in this study, poly (ethylene glycol dimethacrylate‐co‐acrylonitrile) and poly (EGDMA‐co‐AN) system). Above all, from this study, it was established that the porosity of the polymer microspheres is the most important factor that determines the distribution and adsorption amount of face‐centered cubic (fcc) Au nanoparticles in the final products. Our study showed that the continuous adsorption of Au nanoparticles with the aid of the large surface area and surface interaction sites formed more favorably the Au/polymer composite microspheres. The BET measurements of Au/poly(EGDMA‐co‐AN) composite microspheres reveals that the adsorption of Au nanoparticles into the pores kept the pore structure intact and made it more porous. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5627–5635, 2004     

微流控法制备的多孔微球对Cr(Ⅵ)的吸附性能

利用玻璃毛细管搭建单级微流控装置制备单分散水包油（O/W）乳液,以乳液为模板,紫外光照射乳液引发自由基聚合,成功制备了单分散甲基丙烯酸甲酯/甲基丙烯酸二甲基氨基乙酯（MMA/DMAEMA）多孔微球。微球粒径偏差系数（CV）值小于5%,单分散性良好。研究了MMA/DMAEMA多孔微球对Cr(Ⅵ)的吸附性能、再生吸附性能、吸附机理。结果表明：pH对微球吸附Cr(Ⅵ)的量有较大影响,当pH=3时,微球对Cr(Ⅵ)吸附率达到52.9%;循环4次后微球吸附率基本不降低,循环性能好;微球吸附符合准二级动力学模型,属于化学吸附;微球等温吸附符合Langmuir模型,属于单分子层吸附。     

Gold nanoparticles/carbon nanotubes composite microspheres for catalytic reduction of 4-nitrophenol

The layer-by-layer assembly of polyethyleneimine and carbon nanotubes is carried out through the electrostatic interactions on colloidal polystyrene templates. The successful spherical growth of polyethyleneimine/carbon nanotube multilayers could be investigated by SEM. The subsequent in situ preparation and deposition of gold nanoparticles on the core–shell composites could yield novel microsphere complexes, which are characterized by SEM, TEM, EDX and XRD. The functional hierarchical microspheres with gold nanoparticles exhibit good catalytic activity in the reaction of reducing 4-nitrophenol to 4-aminophenol.     

Hierarchical Micro/Nanostructures of Natural Polymer for Release Process

In this paper the modeling of drug release process from hierarchical dispersed systems such as nano and microparticles prepared by thermal cross-linking of multiple emulsions is described. The presented model considers the diffusion of a drug through spherical eroding natural polymer matrix and diffusion-convection of the drug in the surrounding medium. Simulated release profiles were compared with experimental data of the drug release from microspheres of various structures. The differences in microspheres structure resulted from changes in mixing intensity of the external surrounding. The simulations of release profiles confirmed the importance of the internal structure of microspheres as well as an intensity of external mixing in the modeling of the controlled release process. The presented model allowed the mass of drug released to be determined with satisfactory agreement with experimental data after optimization of parameters describing internal microspheres structure. The proposed model describing release process of a drug from microspheres can be applied for simulation of release profiles with phasic behavior (primary/lag and continuous release). The model simulations were extended to drug release from nanoparticles with satisfactory results.     

Mesoporous Au/TiO2 nanocomposite microspheres for visible-light photocatalysis

Mesoporous Au/TiO(2) nanocomposite microspheres have been synthesized by using a microemulsion-based bottom-up self-assembly (EBS) process starting from monodisperse gold and titania nanocrystals as building blocks. The microspheres had large surface areas (above 270 m(2) g(-1)) and open mesopores (about 5 nm), which led to the adsorption-driven concentration of organic molecules in the vicinity of the microspheres. Au nanoparticles, which were stably confined within the microspheres, enhanced the absorption over the broad UV/Vis/NIR spectroscopic range, owing to their strong surface plasmon resonance (SPR); as a result, the Au nanoparticles promoted the visible-light photo-induced degradation of organic compounds.     

Calcium-Alginate Nanoparticles Formed by Reverse Microemulsion as Gene Carriers

Natural biopolymers are widely used in the field of drug and gene delivery. In this study, alginate nanoparticles were prepared using water-in-oil microemulsion as a template followed by calcium crosslinking of guluronic acid units of alginate polymer. After collected by ultracentrifugation, alginate nanoparticles were analyzed by electron microscopy to obtain the size and morphology which were varied with the ratio of water, oil, and surfactant used. To examine the potency of Ca-alginate nanoparticles as carriers for gene delivery, GFP-encoding plasmids were encapsulated in these nanoparticles to investigate the degree of endocytosis by NIH 3T3 cells and ensuing transfection rate. Our results showed that Ca-alginate nanoparticles with an average size around 80 nm in diameter are very efficient gene carriers, in comparison with plasmid DNA condensed by polyethyleneimine (PEI).