A novel method of fabrication of latex-stabilized water-core colloidosomes at room temperature

Colloidosomes have attracted great interest in recent years because of the capability of storage and delivery of useful materials in various fields. In this article, a novel technique for formation of colloidosomes at room temperature suitable for encapsulation of biomaterials was examined. We demonstrate the formation of colloidosomes of 18.0 μm in size at room temperature by adding a small amount of ethanol into the continuous phase of sunflower oil. Poly(methyl methacrylate-co-butyl acrylate) latex particles of 185 nm in size, used in this study, were found to aggregate when ethanol was added to their suspension. We suggest that the shell of the water-core emulsions was locked by the aggregation of latex particles due to the diffusion of ethanol into the aqueous latex suspension.     

Temperature-responsive semipermeable capsules composed of colloidal microgel spheres

We present semipermeable, hollow capsules (colloidosomes) that expand and contract upon heating and cooling. The capsules are composed of micrometer-sized poly(N-isopropylacrylamide)-co-acrylic acid microgel particles, which exhibit a reversible size transition near 34 degrees C. The microgel particles assemble on the surfaces of water droplets in oil. Addition of the diblock copolymer poly(butadiene-b-N-methyl 4-vinyl pyridinium iodide) to the oil results in soft, elastic membranes of microgel particles that remain intact after the droplet interfaces are dissolved. Under heating, the capsules contract reversibly by 13% or irreversibly by 40% in radius. These stimulus-responsive colloidosomes might be useful for controlled release or as microscopic actuators.     

The effect of double-chain surfactants on armored bubbles: a surfactant-controlled route to colloidosomes

We find that the gas phases of air bubbles covered with anionic or cationic polystyrene latex particles dissolve on exposure to cationic and catanionic surfactants. The particles on the bubble interface are released as singlets or aggregates when the surfactant has a single hydrophobic chain, while porous colloidal capsules (colloidosomes) with the same aqueous phase inside as out are obtained when the surfactant has two hydrophobic chains. The formation of colloidosomes from the particle-covered bubbles does not appear to depend significantly on the charge of the particles, which makes it unlikely that bilayers of surfactant are stabilizing the colloidosome. While the exact mechanism of formation remains an open question, our method is a simple one-step process for obtaining colloidosomes from particle-covered bubbles.     

Encapsulation of yeast cells in colloidosomes

Polymeric colloidosomes encapsulating viable Baker's yeast cells were prepared. To make the capsules, an aqueous suspension of 153 nm poly(methyl methacrylate-co-butyl acrylate) latex particles plus yeast cells is emulsified in a continuous phase of sunflower oil. By adding a small amount of ethanol to the oil phase, the latex particles at the surface of the emulsion droplets aggregate, forming the colloidosome shells. The microcapsules have been examined using optical, confocal, and scanning electron microscopies. The viability of the yeast cells was tested using fluorescent molecular probes. The encapsulated Baker's yeast cells were able to metabolize glucose from solution, although at a slower rate compared to nonencapsulated yeast. This demonstrates diffusion limitation through the colloidosome shell. The diffusive resistance could be increased by manufacturing colloidosomes with a double latex shell.     

Black Gold: Plasmonic Colloidosomes with Broadband Absorption Self‐Assembled from Monodispersed Gold Nanospheres by Using a Reverse Emulsion System

A facile approach for the fabrication of novel black plasmonic colloidosomes assembled from Au nanospheres is developed by an emulsion‐templating strategy. This self‐assembly process is based on a new reverse water‐in‐1‐butanol emulsion system, in which the water emulsion droplets can dissolve into 1‐butanol (oil) phase at an appropriate rate. These Au colloidosomes possess hexagonal close‐packed multilayer shells and show a low reflectivity and intense broadband absorption owing to the strong interparticle plasmonic coupling, which is further investigated by a finite‐difference time‐domain method. This method is universal and is suitable for self‐assembly of different noble‐metal nanoparticles into different colloidosomes. These colloidosomes have important applications in photothermal therapy, biosensors, and drug delivery.     

Clay-based colloidosomes

Poly(ethylene imine) (PEI) has been adsorbed onto the surface of Laponite clay nanoparticles from aqueous solution at pH 9 in order to produce an efficient hybrid Pickering emulsifier. This facile protocol allows formation of stable sunflower oil-in-water Pickering emulsions via homogenization at 12,000 rpm for 2 min at 20 °C. The effect of varying the extent of PEI adsorption on the Pickering emulsifier performance of the surface-modified Laponite is investigated for five oils of varying polarity using aqueous electrophoresis, thermogravimetric analysis, and laser diffraction studies. A minimum volume-average emulsion droplet diameter of around 60 μm was achieved at a Laponite concentration of 0.50% by mass when utilizing a PEI/Laponite mass ratio of 0.50. Such emulsions proved to be very stable toward droplet coalescence over time scales of months, although creaming is observed on standing within days due to the relatively large droplet size. These conditions correspond to submonolayer coverage of the Laponite particles by the PEI, which ensures that there is little or no excess PEI remaining in the aqueous continuous phase. This situation is confirmed by visual inspection of the underlying aqueous phase of the creamed emulsion when using fluorescently labeled PEI. These Pickering emulsions are readily converted into novel clay-based colloidosomes via reaction of the primary and/or secondary amine groups on the PEI chains adsorbed at the Laponite surface with either oil-soluble poly(propylene glycol) diglycidyl ether or water-soluble poly(ethylene glycol) diglycidyl ether cross-linkers. These colloidosomes were sufficiently robust to survive the removal of the internal oil phase after washing with excess alcohol, as judged by both optical and fluorescence microscopy. However, dye release studies conducted with clay-based colloidosomes suggest that these microcapsules are highly permeable and hence do not provide an effective barrier for retarding the release of small molecules.     

Polyamine-functional sterically stabilized latexes for covalently cross-linkable colloidosomes

Sterically stabilized polystyrene latexes were prepared by aqueous emulsion polymerization using a poly(ethylene imine) (PEI) stabilizer in the presence of 4-vinylbenzyl chloride (4-VBC; 1.0 wt % based on styrene). Partial quaternization of the amine groups on the PEI chains by 4-VBC occurs in situ, hence producing a chemically grafted steric stabilizer. Such 4-VBC-modified PEI chains were grafted more efficiently onto the polystyrene particles than unmodified PEI, as judged by aqueous electrophoresis, XPS, and nitrogen microanalysis. Moreover, partially quaternized PEI gave significantly smaller polystyrene particles than those synthesized in the absence of any PEI stabilizer or those synthesized using unmodified PEI. The partially quaternized PEI-stabilized polystyrene latex proved to be an effective emulsifier at pH 9, forming stable oil-in-water Pickering emulsions when homogenized (12,000 rpm, 2 min, 20 °C) with four model oils, namely, n-dodecane, methyl myristate, isononyl isononanoate, and sunflower oil. The primary and/or secondary amine groups on the PEI stabilizer chains were successfully cross-linked using three commercially available polymeric reagents, namely, tolylene 2,4-diisocyanate-terminated poly(propylene glycol) (PPG-TDI), poly(propylene glycol) diglycidyl ether (PPG-DGE), or poly(ethylene glycol) diglycidyl ether (PEG-DGE). Cross-linking with the former reagent led to robust colloidosomes that survived the removal of the internal oil phase on washing with excess alcohol, as judged by optical microscopy and SEM. PPG-TDI reacted very rapidly with the PEI stabilizer chains, with cross-linking being achieved during homogenization. Well-defined colloidosomes could be formed only by using sunflower oil and isononyl isononanoate with this cross-linker at 20 °C. However, cooling to 0 °C allowed colloidosomes to be formed using n-dodecane, presumably because of the slower rate of cross-linking at this reduced temperature. PPG-DGE proved to be a more generic cross-linker because it formed robust colloidosomes with all four model oils. However, cross-linking was much slower than that achieved using PPG-TDI, with intact colloidosomes being formed only after ～12 h at 20 °C. The PEG-DGE cross-linker allowed cross-linking to be conducted at 20 °C from the aqueous phase (rather from within the oil droplets for the oil-soluble PPG-TDI or PPG-DGE cross-linkers). In this case, well-defined colloidosomes were obtained at 50 vol % with surprisingly little intercolloidosome aggregation, as judged by laser diffraction studies.     

Effects of Dissipation on Contact Angle Measurements Using a Dynamic Method

We report studies of the effect of hydrothermal treatment on physical properties such as crystalline phase, size, and morphology of nanosized cadmium sulfide (CdS) particles. CdS precipitates have been synthesized by the reaction of Cd(NO(3))(2) with Na(2)S at room temperature. These CdS precipitates have been hydrothermally treated in the range 120-240 degrees C with variation of the treatment time. The effects of acid catalysts and other additives were also investigated. The particles prepared were characterized by XRD, TEM, and BET methods. With increased hydrothermal treatment temperature and time, crystallization from amorphous to crystalline form, cubic or hexagonal, and an increase of particle size occurred. CdS particles of well-developed hexagonal form were obtained at a hydrothermal treatment temperature of 240 degrees C; the primary hexagonal grain size was on the order of 20-30 nm. The addition of an acid catalyst, HCl, or of Cd(NO(3))(2) into the precipitate sol promoted crystal growth and phase transformation during the hydrothermal treatment, but another additive, Na(2)S, showed the opposite trend. It appears that hydrothermal treatment combined with proper additives could be an effective method for preparation of nanosize crystalline CdS particles. Copyright 2001 Academic Press.     

Preparation of nanometer-sized In2O3 particles by a reverse microemulsion method

Nanometer-sized indium oxide (In(2)O(3)) particles have been prepared by chemical reaction of inorganic indium compounds and ammonia gas in a reverse microemulsion system consisting of water, Triton X-100 (surfactant), n-heptanol (co-surfactant), and n-octane (oil). Precursor hydroxides precipitated in the droplets of water-in-oil (W/O) microemulsion were calcined at different temperatures to form indium oxide powder. The factors affecting the particle size have been discussed; the calcination temperature is considered to be the important factor for controlling the size. In(2)O(3) calcined at 400 degrees C had a spherical form and a narrow size distribution. Calcination at 800 degrees C led to the formation of particles not only of irregular shape, but also of a wide size distribution. With the increase in calcination temperature from 400 to 800 degrees C, the average size of the particles grew from 7 to about 40 nm. The species of reactants used in the aqueous phase had a significant effect on the size of the particles. The average diameter of In(2)O(3) particles derived from reactant InCl(3) was 7 nm; that of particles derived from In(NO(3))(3) was 15 nm. The In(2)O(3) nanoparticles were characterized by transmission electron microscopy and X-ray diffraction. The phase behavior of the microemulsions is discussed.     

Preparation of hydroxyapatite via microemulsion route

Hydroxyapatite (HAp) was prepared using a microemulsion route in combination with the pH-shock wave method. The samples as received consisted of amorphous aggregated particles, which had remarkable mesoporosity with a narrow pore size distribution. After being heated at 650 degrees C, the A-type carbonate hydroxyapatite was crystallized at 635 degrees C in particles of similar size (40--120 nm) with no internal porosity. At a higher temperature (900 degrees C) a sintering process took place, resulting in network of a larger particles, consisting of HAp and beta-tricalcium phosphate (beta-TCP). The crystallization of HAp occurs at 635 degrees C with an activation energy of 62.7--72.2 kcalmol(-1).     

Systematic control of size,shape, structure,and magnetic properties of uniform magnetite and maghemite particles

As an application of the gel-sol method especially developed for the synthesis of general monodisperse particles in large quantities, uniform hematite (alpha-Fe2O3), magnetite (Fe3O4), and maghemite (gamma-Fe2O3) particles, precisely controlled in size, aspect ratio, and internal structure, have been prepared. For the synthesis of uniform ellipsoidal single-crystal particles of alpha-Fe2O3, a highly condensed suspension of fine beta-FeOOH particles doped with a prescribed amount of PO4(3-) ion in their interiors was aged at 140 degrees C for 24 h with seed particles of alpha-Fe2O3 in an acidic medium containing optimum concentrations of HCl and NaNO3. Systematic control of the aspect ratio and mean size was achieved by regulating the concentration of PO4(3-) ion incorporated into the beta-FeOOH particles and the number of seeds added. The resulting hematite particles were converted into magnetite by reduction in a H2 stream at 330 degrees C for 6 h; the magnetite was then oxidized to maghemite in an air stream at 240 degrees C for 2 h. Magnetite and maghemite thus prepared retained the original shape of the hematite. On the other hand, polycrystalline hematite particles of different sizes and aspect ratios were also prepared by aging a condensed Fe(OH)3 gel in the presence of different concentrations of SO4(2-) ion and seeds. The polycrystalline hematite particles were similarly converted into magnetite and then maghemite. The magnetic properties of these magnetite and maghemite particles were analyzed as a function of their mean particle volume, aspect ratio, and internal structure.     

Effect of colloidal particle size on adsorbed monodisperse and bidisperse monolayers

Coating hydrogel films or microspheres by an adsorbed colloidal shell is one synthesis method for forming colloidosomes. The colloidal shell allows control of the release rate of encapsulated materials, as well as selective transport. Previous studies found that the packing density of self-assembled, adsorbed colloidal monolayers is independent of the colloidal particle size. In this paper we develop an equilibrium model that correlates the packing density of charged colloidal particles in an adsorbed shell to the particle dimensions in monodisperse and bidisperse systems. In systems where the molar concentration in solution is fixed, the increase in adsorption energy with increasing particle size leads to a monotonic increase in the monolayer packing density with particle radius. However, in systems where the mass fraction of the particles in the adsorbing solutions is fixed, increasing particle size also reduces the molar concentration of particles in solution, thereby reducing the probability of adsorption. The result is a nonmonotonic dependence of the packing density in the adsorbed layer on the particle radius. In bidisperse monolayers composed of two particle sizes, the packing density in the layer increases significantly with size asymmetry. These results may be utilized to design the properties of colloidal shells and coatings to achieve specific properties such as transport rate and selectivity.     

Plasmonic Colloidosomes as Three‐Dimensional SERS Platforms with Enhanced Surface Area for Multiphase Sub‐Microliter Toxin Sensing

Colloidosomes are robust microcapsules attractive for molecular sensing because of their characteristic micron size, large specific surface area, and dual‐phase stability. However, current colloidosome sensors are limited to qualitative fluorogenic receptor‐based detection, which restrict their applicability to a narrow range of molecules. Here, we introduce plasmonic colloidosome constructed from Ag nanocubes as an emulsion‐based 3D SERS platform. The colloidosomes exhibit excellent mechanical robustness, flexible size tunability, versatility to merge, and ultrasensitivity in SERS quantitation of food/industrial toxins down to sub‐femtomole levels. Using just 0.5 μL of sample volumes, our plasmonic colloidosomes exhibit >3000‐fold higher SERS sensitivity over conventional suspension platform. Notably, we demonstrate the first high‐throughput multiplex molecular sensing across multiple liquid phases.     

Shape-controllable synthesis of crystalline Ni complex particles via AOT-based microemulsions

This article presents a simple method for the fabrication of shape-controllable Ni complex particles via an AOT-based single microemulsion. In this approach, Ni(2+)/N2H4/EG solution is used as the dispersed phase, and cyclohexane is used as the continuous phase to obtain a microemulsion by the aid of the anionic surfactant AOT. The primary Ni complex particles with diameters of 20-30 nm were first formed in the reverse micelles and then self-organized into spindle-like, ellipse-like, cuboid, and cubic morphologies, depending on the reaction conditions. When aged at 100 degrees C for 24 h, these Ni complex particles changed into crystalline Ni. A possible evolution mechanism of the Ni complex particles with different morphologies is also discussed.     

A novel preparation method for microspheres of water soluble polymers using polypropyleneglycol as the dispersion medium

Polypropyleneglycol (PPG) was used as a dispersion medium for the preparation of microspheres (MS) consisting of starch, gelatin, whey protein or dextran. Aqueous solutions of the polymers were dispersed in PPG at various initial temperatures and then the systems were cooled to 0.5 degrees C to allow water in the dispersed phase to dissolve in PPG. The particle size of the starch-MS was dependent on the initial temperature of PPG in the preparation process. There were two different processes for particle generation in the procedure. One of them was via the formation of a temporary emulsion during the early phase of dispersion of the aqueous polymer solution into PPG. The other was via the stable emulsion in which the aqueous polymer solution was dispersed in water-saturated PPG. The particle size generated in the former process was dependent on the initial temperature: a high temperature gave large particles but a low temperature gave small particles, while that in the latter process was temperature-independent. This preparation method for MS will be useful for the formulation of heat-sensitive material, such as protein-containing drugs.     

All‐Silica Submicrometer Colloidosomes for Cargo Protection and Tunable Release

Colloidosomes have received considerable attention for the controlled delivery of active ingredients in medicine, agrochemicals, and cosmetics. However, most reported colloidosomes are highly permeable and size is larger than 1 μm. All silica colloidosomes have now been prepared with adjustable size, compact shell and low permeability. Our approach is based on the formation of inverse water‐in‐oil (w/o) emulsions stabilized solely by hydrophobic silica nanoparticles and subsequent locking of the particle at the oil–water interface by a simple sol–gel reaction of silica precursor at room temperature. The colloidosomes obtained display a robust and closed shell, ensuring a long‐term retention of small hydrophilic molecules such as Methylene Blue. Remarkably, unlike all other reported silica colloidosomes, a timely and stepwise release of the encapsulated cargo can be triggered by adding ethanol or surfactant without destroying the capsule shell.     

Thermal oxidation of 6 nm aerosolized silicon nanoparticles: size and surface chemistry changes

The earliest stages of thermal oxidation of 6 nm diameter silicon nanoparticles by molecular oxygen are examined using a tandem differential mobility analysis (TDMA) apparatus, Fourier-transform infrared (FTIR) spectroscopy, time-of-flight secondary ion mass spectroscopy (ToF-SIMS), and X-ray photoelectron spectroscopy (XPS). Particles are synthesized in and then extracted from a nonthermal RF plasma operating at approximately 20 Torr into the atmospheric pressure TDMA apparatus. The TDMA apparatus was used to measure oxidation-induced size changes over a broad range of temperature settings and N2-O2 carrier gas composition. Surface chemistry changes are evaluated in situ with an FTIR spectrometer and a hybrid flow-through cell, and ex situ with ToF-SIMS and XPS. Particle size measurements show that, at temperatures less than approximately 500 degrees C, particles shrink regardless of the carrier gas oxygen concentration, while FTIR and ToF-SIMS spectra demonstrate a loss of hydrogen from the particles and minimal oxide formation. At higher temperatures, FTIR and XPS spectra indicate that an oxide forms which tends toward, but does not fully reach, stoichiometric SiO2 with increasing temperature. Between 500 and 800 degrees C, size measurements show a small increase in particle diameter with increasing carrier gas oxygen content and temperature. Above 800 degrees C, particle growth rapidly reaches a plateau while FTIR and XPS spectra change little. ToF-SIMS signals associated with O-Si species also show an increase in intensity at 800 degrees C.     

Synthesis of core/shell nanoparticles of Au/CdSe via Au-Cd bialloy precursor

We present a novel method for the preparation of ultrasmall Au/CdSe core/shell particles. Au-Cd bialloy particles of 4.7 nm diameter were prepared as the precursor. The Cd component in the precursor reacted with the Se source at a temperature of 205 degrees C and was heated to 250 degrees C, leading to formation of a Au/CdSe core/shell structure. The sizes of Au/CdSe nanoparticles have a narrow distribution with an average size of 6.0 nm and Au core of 2.2 nm diameter. The X-ray diffraction pattern and the images of the high-resolution electron transmission microscopy show that the Au cores and the CdSe shells of Au/CdSe core/shell nanoparticles are both well crystallized, and the CdSe shells are in a cubic phase. The absorption spectrum of the Au/CdSe nanoparticles combines the absorption behaviors of the Au cores and the CdSe shells.     

Colloidosomes from the controlled interaction of submicrometer triglyceride droplets and hydrophilic silica nanoparticles

The self-assembly of hydrophilic silica nanoparticles at the surface of charged submicrometer triglyceride droplets has been investigated with the aim to optimize the preparation of stable colloidosomes. The droplet charge, oil phase volume fraction, droplet/nanoparticle ratio, and salt concentration play important roles in controlling nanoparticle interactions and are reflected in the colloidosome zeta potential, size, stability, and interfacial structure (visualized by freeze-fracture SEM). Silica nanoparticle interactions with negatively charged droplets are weak, and partially covered droplets are identified. Positively charged droplets are strongly coated by silica nanoparticles and undergo charge reversal at specific droplet to nanoparticle ratios and electrolyte concentrations. Droplets at volume fractions (varphi) <10 (-4) undergo time-dependent limited coalescence until nanoparticle coverage is complete. For varphi in the range 10 (-4) to 2.5 x 10 (-4) and at certain critical droplet to nanoparticle ratios, droplets undergo neutralization or charge reversal coupled with aggregation and precipitation; this occurs in a time-independent manner. Specific conditions have been identified where stable 1-3 mum colloidosomes can be phase separated from heterocoagulates of droplets and nanoparticles.     

颗粒乳化剂的研究及应用

近年来,颗粒乳化剂因其在食品、采油、化妆品、医药、催化以及功能纳米材料制备等领域具有潜在应用前景而备受关注。本文综述了近来颗粒乳化剂的研究进展,归纳了颗粒乳化剂的种类,包括:无机纳米粒子、表面改性或杂化的无机粒子、有机纳米粒子以及特殊的颗粒乳化剂Janus粒子;并对颗粒乳化剂能够在油水界面稳定吸附的热力学机理和动力学行为进行了阐述,颗粒乳化剂在油水界面接触角以及粒径大小是其在界面稳定吸附的关键参数,而颗粒在油水界面的排布方式则主要受粒子之间相互作用的影响。重点介绍了颗粒乳化剂的热点应用,包括:(1)利用颗粒乳化剂制备Pickering乳液,以及通过对颗粒乳化剂的功能化,使得Pickering乳液具备环境响应性(即pH、盐浓度、温度、紫外光、磁场敏感响应性);(2)以颗粒乳化剂为构筑基元、以Pickering乳液为模板制备Janus颗粒、Colloidosome、具有多级结构的粒子或膜,以及多孔结构材料;(3) Janus粒子在催化领域的应用。