Structure-defined c60/polymer colloids supramolecular nanocomposites in water

We report a new supramolecular method for the synthesis of well-defined pristine C 60/polymer colloid nanocomposites in water. The colloids include polymer micelles and emulsion particles. To a polymer colloid solution in water or alcohol, we introduced C 60 solution in a solvent that is miscible with water or alcohol. After the two solutions mixed, polymer colloids and C 60 spontaneously assembled into stable colloidal nanocomposites. After a dialysis process, a nanocomposite dispersion in pure water was obtained. As characterized by DLS and (Cryo-)TEM, the nanocomposites have a core-shell structure with C 60 aggregated on the surface of emulsion particles or micellar cores. The resulting nanocomposites have many potential applications such as biomedicals and photovoltaics.     

Swelling-based method for preparing stable, functionalized polymer colloids

We describe a swelling-based method to prepare sterically stabilized polymer colloids with different functional groups or biomolecules attached to their surface. It should be applicable to a variety of polymeric colloids, including magnetic particles, fluorescent particles, polystyrene particles, PMMA particles, and so forth. The resulting particles are more stable in the presence of monovalent and divalent salt than existing functionalized colloids, even in the absence of any surfactant or protein blocker. While we use a PEG polymer brush here, the method should enable the use of a variety of polymer chemistries and molecular weights.     

Polystyrene‐Core–Silica‐Shell Hybrid Particles Containing Gold and Magnetic Nanoparticles

Polystyrene‐core–silica‐shell hybrid particles were synthesized by combining the self‐assembly of nanoparticles and the polymer with a silica coating strategy. The core–shell hybrid particles are composed of gold‐nanoparticle‐decorated polystyrene (PS‐AuNP) colloids as the core and silica particles as the shell. PS‐AuNP colloids were generated by the self‐assembly of the PS‐grafted AuNPs. The silica coating improved the thermal stability and dispersibility of the AuNPs. By removing the “free” PS of the core, hollow particles with a hydrophobic cage having a AuNP corona and an inert silica shell were obtained. Also, Fe₃O₄ nanoparticles were encapsulated in the core, which resulted in magnetic core–shell hybrid particles by the same strategy. These particles have potential applications in biomolecular separation and high‐temperature catalysis and as nanoreactors.     

Anomalous dependence of particle size on supersaturation in the preparation of iron nanoparticles from iron pentacarbonyl

Anisotropic colloidal particles consisting of different compositions and geometry are useful for various applications. These include optical biosensing, antireflective coatings and electronic displays. In this work we demonstrate a simple and cost-effective method for fabricating anisotropic colloidal particles bearing a snowman-like shape. This is achieved by first settling the positively-charged polystyrene latex (PSL) colloids and negatively-charged silica colloids in deionized water onto a glass substrate, forming heterodoublets. The temperature is then raised above the glass transition temperature of the polymer. As a result, the silica particle spontaneously rises to the top of the PSL particle forming a snowman like structure. We have extended this method to different sizes and shown that the structure of the hybrid particles can be tuned by adjusting the size ratio between the silica and the PSL colloids. The surface coverage of the PSL, and hence of the snowman particles, on the glass substrate can also be varied by changing the ionic strength of the solution during the adhesion of PSL to the glass.     

Enzymatic synthesis of pH-responsive polyaniline colloids by using chitosan as steric stabilizer

Polyaniline colloidal particles were prepared by enzymatic polymerization of aniline using chitosan as steric stabilizer and toluenesulfonic or camphorsulfonic acids as doping agents. Fourier transform infrared and UV-vis spectroscopic studies indicate that enzymatic polymerization of aniline in dispersed media results in the emeraldine salt form of polyaniline. The morphology of the colloids was studied by transmission electron microscopy. Toluenesulfonic acid produced mainly oblong particles whereas rod-like shaped particles were obtained using camphorsulfonic acid. Polyaniline particles with good colloidal stability and size below 200 nm were obtained using 1.0 wt% of chitosan in the reaction media, indicating that this polymer was highly efficient as a steric stabilizer. The content of chitosan attached to the polyaniline colloids was approximately 20 wt% as indicated by elemental analysis. The colloids synthesized either with toluenesulfonic or camphorsulfonic acid showed a strong pH-dependent colloidal stability and underwent rapid flocculation in near neutral or alkaline media. This interesting behavior could be exploited in separation technology applications.     

Colloidal particles coated and stabilized by DNA-wrapped carbon nanotubes

Single-walled carbon nanotubes (SWNTs) are dispersed in water via wrapping with short segments of single-stranded DNA (ssDNA). Small angle neutron scattering suggests a power-law exponent that is consistent with clustered nanotubes and hence marginal stability. The SWNT-ssDNA complex is used to stabilize dispersions of hydrophilic colloidal particles with the nanotubes adhered to the surface of the colloids. Near-infrared fluorescence microscopy demonstrates the interfacial band-gap fluorescence of these SWNT-coated particles, suggesting potential routes to novel platforms and applications.     

Iron oxyhydroxide colloids stabilized with polysaccharides

 Neutralization of iron salts in aqueous solutions of κ-carrageenan and cellulose sulfate results in iron oxyhydroxide–polysaccharide hybrid colloids with unusual pH stability up to pH 13. It is shown that both polysaccharides form a tight polymer layer surrounding the inorganic particles, which in the case of κ-carrageenan is cross-linked by helical domains forming a self-assembled nanoreactor. The stabilized iron oxyhydroxide particles can undergo further reactions, for example, it is possible by a chemical reaction to produce stabilized magnetite particles. Repetition of the loading/neutralization steps in the reaction results in hybrids with iron contents much higher than the stoichiometric balance of iron and functional groups of the polymer (greater than 100% Fe/SO₄ ⁻). This combination of high iron content with a natural polysaccharide stabilizer makes these colloids interesting for a number of applications, for example, for nutritional purposes or as contrasting agents for tomography. Received: 7 September 1999 Accepted in revised form: 6 December 1999     

A general method for the controlled embedding of nanoparticles in silica colloids

A novel method for the controlled embedding of multiple nanoparticles of various materials, such as gold nanoparticles, quantum dots, and magnetic nanoparticles, in silica colloids is presented. After adsorption of the amphiphilic polymer poly(vinylpyrrolidone) on hydrophobic or hydrophilic stabilized nanoparticles, these are adsorbed on silica spheres and covered by variable-thickness silica shells. This silica coating protects the embedded nanoparticles against chemical transformations, which is of crucial importance for the biocompatibility of particles containing toxic elements. Moreover, it is found that the optical properties of the nanoparticles are retained. Possible applications of multicore particles are briefly discussed.     

Colloids of pure proteins by hard templating

Colloidal particles from pure proteins are favorable over composite colloids (usually polymer-based) for applications in drug delivery and biocatalysis. This is due to degradation issue and protein unfolding. Hard templating based on porous CaCO₃ cores has been recently adopted for fabrication of pure protein colloids. In comparison to conventional techniques, the templating offers (i) a control over particles size and (ii) mild preparation conditions without any additives, shear forces, and exposure to high temperature or gas-water interface. In this review, the current achievements in CaCO₃-based templating of protein colloids are given. The focus is on physicochemical and material properties of the colloids such as stability, mechanical properties, and internal structure. These properties are considered as a function of pH, ionic strength, and protein denaturation degree. Understanding of these basic aspects gives an option to formulate the protein colloids by hard templating achieving desired particle properties that is crucially important for future applications.     

Complex aggregates of silica microspheres by the use of a polymer template

Evaporation of a droplet of silica microsphere suspension on a polystyrene and poly(methyl methacrylate) blend film with isolated holes in its surface has been exploited as a means of particles self-assembly. During the retraction of the contact line of the droplet, spontaneous dewetting combined with the strong capillary force pack the silica microspheres into the holes in the polymer surface. Complex aggregates of colloids are formed after being exposed to acetone vapor. The morphology evolution of the underlying polymer film by exposure to acetone solvent vapor is responsible for the complex aggregates of colloids formation.     

Microstructure and depletion forces in polymer-colloid mixtures from an interfacial statistical associating fluid theory

By using a classical density functional theory (interfacial statistical associating fluid theory), we investigate the structure and effective forces in nonadsorbing polymer-colloid mixtures. The theory is tested under a wide range of conditions and performs very well in comparison to simulation data. A comprehensive study is conducted characterizing the role of polymer concentration, particle/polymer-segment size ratio, and polymer chain length on the structure, polymer induced depletion forces, and the colloid-colloid osmotic second virial coefficient. The theory correctly captures a depletion layer on two different length scales, one on the order of the segment diameter (semidilute regime) and the other on the order of the polymer radius of gyration (dilute regime). The particle/polymer-segment size ratio is demonstrated to play a significant role on the polymer structure near the particle surface at low polymer concentrations, but this effect diminishes at higher polymer concentrations. Results for the polymer-mediated mean force between colloidal particles show that increasing the concentration of the polymer solution encourages particle-particle attraction, while decreasing the range of depletion attraction. At intermediate to high concentrations, depletion attraction can be coupled to a midrange repulsion, especially for colloids in solutions of short chains. Colloid-colloid second virial coefficient calculations indicate that the net repulsion between colloids at low polymer densities gives way to net attraction at higher densities, in agreement with available simulation data. Furthermore, the results indicate a higher tendency toward colloidal aggregation for larger colloids in solutions of longer chains.     

Aggregation of amphiphilic polymers in the presence of adhesive small colloidal particles

The interaction of amphiphilic polymers with small colloids, capable to reversibly stick onto the chains, is studied. Adhesive small colloids in solution are able to dynamically bind two polymer segments. This association leads to topological changes in the polymer network configurations, such as looping and cross-linking, although the reversible adhesion permits the colloid to slide along the chain backbone. Previous analyses only consider static topologies in the chain network. We show that the sliding degree of freedom ensures the dominance of small loops, over other structures, giving rise to a new perspective in the analysis of the problem. The results are applied to the analysis of the equilibrium between colloidal particles and star polymers, as well as to block copolymer micelles. The results are relevant for the reversible adsorption of silica particles onto hydrophilic polymers, used in the process of formation of mesoporous materials of the type SBA or MCM, cross-linked cyclodextrin molecules threading on the polymers and forming the structures known as polyrotaxanes. Adhesion of colloids on the corona of the latter induce micellization and growth of larger micelles as the number of colloids increase, in agreement with experimental data.     

Colloidal aggregation in polymer blends

We consider here a low-density assembly of colloidal particles immersed in a critical polymer mixture of two chemically incompatible polymers. We assume that, close to the critical point of the free mixture, the colloids prefer to be surrounded by one polymer (critical adsorption). As result, one is assisted to a reversible colloidal aggregation in the nonpreferred phase, due the existence of a long-range attractive Casimir force between particles. This aggregation is a phase transition driving the colloidal system from dilute to dense phases, as the usual gas-liquid transition. We are interested in a quantitative investigation of the phase diagram of the immersed colloids. We suppose that the positions of particles are disordered, and the disorder is quenched and follows a Gaussian distribution. To apprehend the problem, use is made of the standard phi(4) theory, where the field phi represents the composition fluctuation (order parameter), combined with the standard cumulant method. First, we derive the expression of the effective free energy of colloids and show that this is of Flory-Huggins type. Second, we find that the interaction parameter u between colloids is simply a linear combination of the isotherm compressibility and specific heat of the free mixture. Third, with the help of the derived effective free energy, we determine the complete shape of the phase diagram (binodal and spinodal) in the (Psi,u) plane, with Psi as the volume fraction of immersed colloids. The continuous "gas-liquid" transition occurs at some critical point K of coordinates (Psi(c) = 0.5,u(c) = 2). Finally, we emphasize that the present work is a natural extension of that, relative to simple liquid mixtures incorporating colloids.     

pH- and thermosensitive polyaniline colloidal particles prepared by enzymatic polymerization

Polyaniline colloids were prepared by enzymatic polymerization using chitosan and poly(N-isopropylacrylamide) as steric stabilizers. The resulting nanoparticles undergo flocculation by changing the pH or temperature of the aqueous dispersions. The environmentally responsive behavior of these colloids contrasts with that of polyaniline colloids synthesized using poly(vinyl alcohol) as the steric stabilizer. The colloid size was a function of the steric stabilizers and ranged from approximately 50 nm for polyaniline particles prepared in the presence of chitosan and partially hydrolyzed poly(vinyl alcohol) up to 350 nm for the particles synthesized using poly(N-isopropylacrylamide). UV-visible and Fourier transform infrared spectroscopic studies indicate that polyaniline colloids are spectroscopically similar to those obtained by traditional dispersion polymerization of aniline by chemical oxidation. These polyaniline colloids have potential applications in thermochromic windows and smart fluids.     

Micellization of amphiphilic block copolymers and use of their micelles as nanosized reaction vessels

Amphiphilic block copolymers made by a variety of techniques form in selective solvents micelles of well defined size and shape. We report on the underlying principles of micelle formation, as revealed by light scattering experiments. In addition, we will delineate some applications of these block-copolymer micelles where we focus on two technological relevant cases, namely the stabilization of polymer particles in low cohesion energy environments as well as the stabilization of metal and semiconductor colloids inside specially functionalized block copolymer micelles. In the latter case, stable hybride materials are obtained where the properties both of the polymer and the inorganic are added in a synergistic way. First data on special catalytic properties, the generation of superparamagnetic materials, and special colloids with optical functionality are presented.     

Static and dynamic light scattering study of fluorinated polymer colloids with a crystalline internal structure

The light scattering properties of polymer colloids made of polytetrafluoroethylene with added copolymers are described in some detail. The particles possess a partially crystalline internal structure which makes them optically anisotropic, and consequently gives rise to a strong depolarized component in the scattered light intensity. We present a complete theory of static and dynamic light scattering which includes the effects of polycrystallinity, of optical polydispersity, and of interparticle interactions. We also discuss applications to surfactant adsorption studies, to sedimentation experiments and to fractal aggregation processes     

Effect of polymer size and chain length on depletion interactions between two colloids

A density functional theory based on the weighted density has been developed to investigate the depletion interactions between two colloids immersed in a bath of the binary polymer mixtures, where the colloids are modeled as hard spheres and the polymers as freely jointed tangent hard-sphere chain mixtures. The theoretical calculations for the depletion forces between two colloids induced by the polymer are in good agreement with the computer simulations. The effects of polymer packing fraction, degree of polymerization, polymer/polymer size ratio, colloid/polymer size ratio on the depletion interactions, and colloid-colloid second virial coefficient B2 due to polymer-mediated interactions have been studied. With increasing the polymer packing fraction, the depletion interaction becomes more long ranged and the attractive interaction near the colloid becomes deeper. The effect of degree polymerization shows that the long chain gives a more stable dispersion for colloids rather than the short chain. The strong effective colloid-colloid attraction appears for the large colloid/polymer and polymer/polymer size ratio. The location of maximum repulsion Rmax is found to appear Rmax approximately sigmac+Rg2 for the low polymer packing fraction and this is shifted to smaller separation Rmax approximately sigmac+sigmap2 with increasing the polymer packing fraction, where sigmap2 and Rg2 are the small-particle diameter and the radius of gyration of the polymer with the small-particle diameter, respectively.     

Responsive hydrogel colloids: Structure,interactions, phase behavior,and equilibrium and nonequilibrium transitions of microgel dispersions

Soft and responsive colloids based on polymer hydrogels have moved into the focus of the colloid community. This review gives a brief overview of the recent literature on the structure and phase behavior of neutral and ionic poly(N-isopropylacrylamide) microgel dispersions from dilute to over-packed conditions, focusing in particular on the ability of these particles to adapt their size and shape in response to external stimuli. The review is hierarchical; it first covers the aspects of an individual microgel particle viz., the internal structure of inhomogeneous and homogeneously cross-linked particles, followed by studies of ensembles of particles covering in particular structural ordering, phase behavior, and liquid–solid and solid–solid transitions. Insights on the ability of the microgel particles to deform, compress, and interpenetrate beyond the close-packed volume fractions are discussed. Building complex architectures using microgel particles for fundamental studies as well as future applications is reviewed towards the end of the article.     

核-壳结构微球的制备进展

综述了近年来核-壳结构微球制备方面的研究进展,介绍了高分子胶束交联、模板逐层组装、模板微球表面原位引发聚合、动态溶胀法、种子聚合法以及溶胶-凝胶法等主要制备方法,并对各种方法所涉及的核-壳微球形成机理进行了必要阐述.     

Polymer dispersions as intermediate state during the synthesis of specialty polymers

Heterophase polymerization in combination with ceric ion redox initiation offers some unique features with respect to the preparation of block copolymers and block copolymer particles. Various kinds of amphiphilic multi-block copolymers as well as electrosterically or sterically stabilized particles are easy accessible. A special feature of these particles is that they may consists of two different hydrophilic blocks and thus, leading to particles with a structured hydrophilic shell. The amphiphilic multiblock copolymers are used to form a new class of polymer dispersions by self-organization so-called polymeric colloidal complexes. In general, the particles of these complexes are structured and exhibit very often multiple morphologies. This principle of formation of polymer colloids is an easy way to prepare particles with an unusual morphology such as Janus-type particles.