One-Step Synthesis of Biphasic, Cavity-forming Polymer Particles via Dispersion Copolymerization of Styrene and Sulfobetaine Methacrylate.

A one-step dispersion copolymerization technique is demonstrated to fabricate biphasic particles as an approach to streamline the production of particles with complex morphology. The model system studies a monomer feed of hydrophobic styrene and hydrophilic, zwitterionic sulfobetaine methacrylate (SBMA) in a water/isopropanol cosolvent mixture. The resulting particles have a core-shell morphology that can be transformed, simply by washing the particles with water, into particles with a single surface opening connected to an interior cavity. Results indicate that particle morphology is dependent on the presence of nanoscopic SBMA-rich aggregates in the initial reaction mixture to act as nucleation sites, forming an SBMA-rich core encased in a styrene-rich shell. Systematic study of the morphology evolution reveals that the difference in monomer solubility profile can be exploited to control compositional drift of the particle composition during copolymerization yielding copolymer with sufficiently different composition to form phase-separated particle morphology. When SBMA is replaced with various ionic comonomers, the cavity-forming morphology is observed when reaction conditions result in low solubility of the comonomer in the cosolvent mixture. Based on these results, design guidelines are developed that may be applied to a variety of systems requiring complex and responsive particles made from chemically distinct comonomer pairings.

Polymer Colloids: Moving beyond Spherical Particles.

When thinking about colloidal particles, the fist image that comes into mind is that of tiny little polystyrene spheres with a narrow size distribution. While spherical polymer colloids are one of the workhorses of colloid science, scientists have been working on the development of progressively advanced strategies to move beyond particles with spherical shapes, and prepared polymer colloids with more complex morphologies. This short review aims at providing a summary of these developments, focusing primarily on methods applicable to submicron particles, with an eye towards their applications and some discussion about advantages and drawbacks of the various approaches.

Composite Polymer Colloids for SERS-Based Applications.

Polymers and nanoparticles can be combined into different materials with applications in various fields like catalysis, biotechnology, or drug delivery, to cite just a few. Colloidal composites may vary significantly, ranging from a single nanoparticle stabilized by a polymer shell through a polymeric carrier decorated with hundreds of particles. We review here composite colloids comprising gold nanoparticles, with an emphasis in systems with potential application in surface enhanced Raman scattering (SERS). The focus is on selected strategies for synthesis and functionalization, such as: encapsulation of gold nanoparticles by amphiphilic polymers, polymeric matrices as nanoparticle carriers and smart polymer based composites. We stress the benefits derived from the combination of polymers and metal particles toward SERS, such as chemical and colloidal stabilization in complex environments, and collective optical effects through hot spot generation for optimized SERS enhancement or improved imaging tags.

Development of a Biorelevant, Material-Sparing Membrane Flux Test for Rapid Screening of Bioavailability-Enhancing Drug Product Formulations.

Bioavailability-enhancing formulations are often used to overcome challenges of poor gastrointestinal solubility for drug substances developed for oral administration. Conventional in vitro dissolution tests often do not properly compare such formulations due to the many different drug species that may exist in solution. To overcome these limitations, we have designed a practical in vitro membrane flux test, that requires minimal active pharmaceutical ingredient (API) and is capable of rapidly screening many drug product intermediates. This test can be used to quickly compare performance of bioavailability-enhancing formulations with fundamental knowledge of the rate-limiting step(s) to membrane flux. Using this system, we demonstrate that the flux of amorphous itraconazole (logD = 5.7) is limited by aqueous boundary layer (ABL) diffusion and can be increased by adding drug-solubilizing micelles or drug-rich colloids. Conversely, the flux of crystalline ketoconazole at pH 5 (logD = 2.2) is membrane-limited, and adding solubilizing micelles does not increase flux. Under certain circumstances, the flux of ketoconazole may also be limited by dissolution rate. These cases highlight how a well-designed in vitro assay can provide critical insight for oral formulation development. Knowing whether flux is limited by membrane diffusion, ABL diffusion, or dissolution rate can help drive formulation development decisions. It may also be useful in predicting in vivo performance, dose linearity, food effects, and regional-dependent flux along the length of the gastrointestinal tract.

Uniform, convex structuring of polymeric colloids via site-selected swelling.

Non-spherical, polymeric colloids serve as building blocks for advanced functional materials. We propose a novel method to produce morphologically controlled, non-spherical particles by generating site-selected, convex structures on polystyrene (PS) particles. It consists of two simple procedures: a monolayer of PS particles is illuminated with UV light and is subsequently immersed in a fluorinated solvent (HFIP). UV irradiation generates site-selected, oxidized domains on PS particles with a different solvent affinity than unoxidized PS, and HFIP immersion preferentially swells the oxidized domains. Such swelling gives rise to site-selected, convex structures on PS particles. By adjusting UV irradiation conditions, including incident and azimuth angles, the oxidized sites, i.e., the swelled portions, can be accurately situated, allowing us to produce various convex shapes, including chiral shapes at desired positions on PS particles.

The Paradoxical Behavior of Rough Colloids at Fluid Interfaces.

Colloidal particles adsorb and remain trapped at immiscible fluid interfaces due to strong interfacial adsorption energy with a contact angle defined by the chemistry of the particle and fluid phases. An undulated contact line may appear due to either particle surface roughness or shape anisotropy, which results in a quadrupolar interfacial deformation and strong long-range capillary interaction between neighboring particles. While each effect has been observed separately, here we report the paradoxical impact of surface roughness on spherical and anisotropic ellipsoidal polymer colloids. Using a seeded emulsion polymerization technique, we synthesize spherical and ellipsoidal particles with controlled roughness magnitudes and topography (convex/concave). Via in situ measurement of the interfacial deformation around colloids at an air-water interface, we find that while surface roughness strengthens the quadrupolar deformation in spheres as expected by theory, in stark contrast, it weakens the same in ellipsoids. As roughness increases, particles of both shapes become more hydrophilic, and their apparent contact angle decreases. Using numerical predictions, we show that this partially explains the decreased interfacial deformation and capillary interactions between the ellipsoids. Therefore, particle surface engineering has the potential to decrease the capillary deformation by asymmetric particles via changing their capillary pinning, as well as wetting behavior at fluid interfaces.

Fluid Flow Templating of Polymeric Soft Matter with Diverse Morphologies.

It is challenging to find a conventional nanofabrication technique that can consistently produce soft polymeric matter of high surface area and nanoscale morphology in a way that is scalable, versatile, and easily tunable. Here, the capabilities of a universal method for fabricating diverse nano- and micro-scale morphologies based on polymer precipitation templated by the fluid streamlines in multiphasic flow are explored. It is shown that while the procedure is operationally simple, various combinations of its intertwined mechanisms can controllably and reproducibly lead to the formation of an extraordinary wide range of colloidal morphologies. By systematically investigating the process conditions, 12 distinct classes of polymer micro- and nano-structures including particles, rods, ribbons, nanosheets, and soft dendritic colloids (dendricolloids) are identified. The outcomes are interpreted by delineating the physical processes into three stages: hydrodynamic shear, capillary and mechanical breakup, and polymer precipitation rate. The insights into the underlying fundamental mechanisms provide guidance toward developing a versatile and scalable nanofabrication platform. It is verified that the liquid shear-based technique is versatile and works well with many chemically diverse polymers and biopolymers, showing potential as a universal tool for simple and scalable nanofabrication of many morphologically distinct soft matter classes.

Synthesis of dimpled polymer particles and polymer particles with protrusions - Past, present, and future.

Since the development of emulsion polymerization techniques, polymer particles have become the epitome of standard colloids due to the exceptional control over size, size distribution, and composition the synthesis methods allow reaching. The exploration of different variations of the synthesis methods has led to the discovery of more advanced techniques, enabling control over their composition and shape. Many early investigations focused on forming particles with protrusions (with one protrusion, called dumbbell particles) and particles with concavities, also called dimpled particles. This paper reviews the literature covering the synthesis, functionalization, and applications of both types of particles. The focus has been on the rationalization of the various approaches used to prepare such particles and on the discussion of the mechanisms of formation not just from the experimental viewpoint but also from the standpoint of thermodynamics. The primary motivation to combine in a single review the preparation of both types of particles has been the observation of similarities among some of the methods developed to prepare dimpled particles, which sometimes include the formation of particles with protrusions and vice versa. The most common applications of these particles have been discussed as well. By looking at the different approaches developed in the literature under one general perspective, we hope to stimulate a more ample use of these particles and promote the development of even more effective synthetic protocols.

Advances in Polymeric Colloids for Cancer Treatment.

Polymer colloids have remarkable features and are gaining importance in many areas of research including medicinal science. Presently, the innovation of cancer drugs is at the top in the world. Polymer colloids have been used as drug delivery and diagnosis agents in cancer treatment. The polymer colloids may be of different types such as micelles, liposomes, emulsions, cationic carriers, and hydrogels. The current article describes the state-of-the-art polymer colloids for the treatment of cancer. The contents of this article are about the role of polymeric nanomaterials with special emphasis on the different types of colloidal materials and their applications in targeted cancer therapy including cancer diagnoses. In addition, attempts are made to discuss future perspectives. This article will be useful for academics, researchers, and regulatory authorities.

Synthesis of non-spherical polymer particles using the activated swelling method.

The preparation of particles with non-spherical shapes is a challenging endeavor, often requiring a significant ingenuity, complex experimental procedures and difficulties to obtain reproducible results. In this work we prove that monodisperse non-spherical polymer particles possessing asymmetric Janus structure can be easily produced by using an activated swelling method in combination with a control of the rate of free radical polymerization through the addition of the inhibitors 4-methoxyphenol (MEHQ) and O2. Monodisperse non cross-linked polystyrene particles, used as seeds, are activated by the addition of an initiator, which promotes their swelling ability, and then swollen with a monomers mixture (methyl methacrylate, glycidyl methacrylate and ethylene glycol dimethacrylate), before being polymerized in presence of both MEHQ and O2. Our results show that only when both MEHQ and O2 are present during the course of the polymerization, the particles shape can be controlled, from spherical to asymmetrical. A variety of particles shapes can be obtained, ranging from dimpled spheres, flattened spheres and Janus particles by varying the swelling ratio, always with excellent monodispersity and reproducibility. Finally, to provide even more complex functionalities to these non-spherical polymer particles, iron oxide nanocrystals were grown within the polymer matrix resulting in superparamagnetic particles.

Miniemulsion polymerization as a versatile tool for the synthesis of functionalized polymers.

The miniemulsion technique is a particular case in the family of heterophase polymerizations, which allows the formation of functionalized polymers by polymerization or modification of polymers in stable nanodroplets. We present here an overview of the different polymer syntheses within the miniemulsion droplets as reported in the literature, and of the current trends in the field.

Tuning CO2-induced reversible redispersion or irreversible destabilisation for latex separation.

HYPOTHESIS: The CO2-sensitive dispersion/precipitation transition of polymer latexes fabricated based on a responsive emulsifier is a promising way to conveniently acquire bulk polymer materials. Nevertheless, the tedious synthesis procedures for switchable surfactants and the harsh operating requirements for the sensitive latexes constrain the applicability of the approach for latex preparation. Therefore, a new strategy for generating latexes with tunable CO2 responsiveness in a maneuverable way is urgently needed. EXPERIMENTS: In this work, a CO2-switchable electrostatic interaction is introduced to construct responsive latexes. A series of lightly crosslinked poly(diethylaminoethyl methacrylate-styrene) [P(DEA-St)] latexes with different PDEA contents were fabricated via one-pot emulsion copolymerization, with divinylbenzene and sodium dodecylsulfate (SDS) used as the crosslinker and anionic emulsifier, respectively. The influence of the DEA feeding ratio on the resulting P(DEA-St) colloids was characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. Then, a cyclic CO2/N2 input was introduced to verify the response transitions of polymer latexes. FINDINGS: Accompanied by the stepwise decrease of DEA feeding ratio, the morphology of the resulting copolymerized nanoparticles changed from an ambiguous bulge to the typical spherical pattern. In addition, the P(DEA-St) latexes treated by cyclic CO2/N2 exhibit four different types of response modes, namely (i) CO2-switchable swelling/deswelling transition, (ii) CO2-reversible dispersion/coagulation transition, (iii) CO2-induced irreversible destabilisation and (iv) CO2-insensitive latexes. The CO2-responsive destabilisation is highly applicable in the separation and transportation fields of commercial latex products, such as poly(methyl methacrylate), poly(n-butyl acrylate) and poly(butyl methacrylate) colloids.

pH Tunable Thin Film Gradients of Magnetic Polymer Colloids for MRI Diagnostics.

Magnetic polymer colloids comprising of magnetite (Fe3O4) nanoparticles and Eudragit E100 were employed to fabricate thin film gradients and were investigated for in-vitro magnetic resonance imaging. Magnetic polymer colloids (MPC) and polyacrylic acid (PAA) with stimuli-responsive cationic and anionic functional groups respectively facilitate the formation of thin film gradients via layer by layer technique. The characteristics of films were controlled by changing the pH and level of the adsorbing solutions that lead to the development of gradient films having 5.5, 10.5 and 15.5 bilayers. Optical microscopy, scanning electron microscopy and magnetic force microscopy was carried out to determine the surface coverage of films. Surface wettability demonstrated the hydrophilicity of adsorbed colloids. The developed thin-film gradients were explored for in vitro magnetic resonance imaging that offers a point of care lab-on-chip as a dip-stick approach for ultrasensitive in-vitro molecular diagnosis of biological fluids.

Linear and Nonlinear Dynamic Behavior of Polymer Micellar Assemblies Connected by Metallo-Supramolecular Interactions.

The linear and nonlinear rheology of associative colloidal polymer assemblies with metallo-supramolecular interactions is herein studied. Polystyrene-b-poly(tert-butylacrylate) with a terpyridine ligand at the end of the acrylate block is self-assembled into micelles in ethanol, a selective solvent for the latter block, and supramolecularly connected by complexation to divalent metal ions. The dependence of the system elasticity on polymer concentration can be semi-quantitatively understood by a geometrical packing model. For strongly associated (Ni2+, Fe2+) and sufficiently concentrated systems (15 w/v%), any given ligand end-group has a virtually 100% probability of being located in an overlapping hairy region between two micelles. By assuming a 50% probability of intermicellar crosslinks being formed, an excellent prediction of the plateau modulus was achieved and compared with the experimental results. For strongly associated but somewhat more dilute systems (12 w/v%) that still have significant overlap between hairy regions, the experimental modulus was lower than the predicted value, as the effective number of crosslinkers was further reduced along with possible density heterogeneities. The reversible destruction of the network by shear forces can be observed from the strain dependence of the storage and loss moduli. The storage moduli of the Ni2+ and Zn2+ systems at a lower concentration (12 w/v%) showed a rarely observed feature (i.e., a peak at the transition from linear to nonlinear regime). This peak disappeared at a higher concentration (15 w/v%). This behavior can be rationalized based on concentration-dependent network stretchability.

Synthesis of Janus and Patchy Particles Using Nanogels as Stabilizers in Emulsion Polymerization.

Polymer nanogels are used as colloidal stabilizers in emulsion polymerization. The nanogels were made by the covalent cross-linking of block copolymer micelles, the macromolecular building blocks of which were synthesized using a combination of catalytic chain transfer emulsion polymerization and reversible addition-fragmentation chain transfer (RAFT) of methacrylate monomers. The use of the nanogels in an emulsion polymerization led to anisotropic Janus and patchy colloids, where a latex particle was decorated by a number of patches on its surface. Control of the particle size and patch density was achieved by tailoring of the reaction conditions, such as varying the amount of nanogels, pH, and salt concentration. Overall, the emulsion polymerization process in the presence of nanogels as stabilizers is shown to be a versatile and easily scalable route toward the fabrication of Janus and patchy polymer colloids.

Polymeric nanostructures with pH-labile core for controlled drug release.

Efficient and stimuli-triggered controlled delivery of therapeutics is one of the important issues in modern advanced therapy. In the present work, a versatile route for the synthesis of core cross-linked polymeric nanostructures (CLPN) through thiol-acrylate Michael addition reaction via the formation of ß-thiopropionate has been described. The acid groups of the poly(acrylic acid) block of poly(ethylene glycol)-b-poly(N-isopropylacrylamide)-b-poly(acrylic acid) triblock copolymer were reacted with 2-hydroxyethyl acrylate (HEA) to yield the corresponding acrylate-functionalized copolymer (P1). Following this, P1 was reacted with a thiol functionalized cross-linker (CL) resulting in the formation of core cross-linked polymeric nanoparticles through acrylate-thiol Michael reaction. The ability of these nanoparticles to encapsulate drug molecules inside their core and their effective release following a pH-triggered controlled degradation of the core were demonstrated. The temperature sensitive release behaviour of the system was also studied. The non-toxic nature of the precursor polymers and the core cross-linked polymeric nanoparticles was also established, that further substantiated their potential as carriers for controlled release of drugs.

High Charge-Carrier Mobility of 2.5 cm(2) V(-1) s(-1) from a Water-Borne Colloid of a Polymeric Semiconductor via Smart Surfactant Engineering.

Semiconducting polymer nanoparticles dispersed in water are synthesized by a novel method utilizing non-ionic surfactants. By developing a smart surfactant engineering technique involving a selective post-removal process of surfactants, an unprecedentedly high mobility of 2.51 cm(2) V(-1) s(-1) from a water-borne colloid is demonstrated for the first time.

Design of antimicrobial membrane based on polymer colloids/multiwall carbon nanotubes hybrid material with silver nanoparticles.

The aim of this study was to obtain membranes with antimicrobial activity presenting a complex sandwich-type structure. The outer layers are comprised of poly(methyl methacrylate) membranes, whereas the inner active layer consists of a modified commercial membrane to achieve antimicrobial properties. This activity arises due to the presence of silver nanoparticles in a material with a hybrid composition deposited on a commercial membrane. This hybrid material consists of polymer colloids and multiwall carbon nanotubes used for both the stabilization of the active layer by the interconnections of the polymer particles and as active component. The filtration tests revealed a good stability of the materials and an increased hydrophilicity of the hybrid membranes. The antimicrobial properties have been evaluated using Staphylococcus aureus and Escherichia coli, and have been correlated with the content and migration rate of silver ions.