This article reports on the preparation of environmentally responsive "hairy" nanoparticles by growth of mixed poly(tert-butyl acrylate) (PtBA)/polystyrene (PS) brushes from silica particles using living radical polymerization techniques and subsequent hydrolysis of PtBA to produce amphiphilic mixed poly(acrylic acid) (PAA)/PS brushes. Silica particles were synthesized by the Stober process and were functionalized with an asymmetric difunctional initiator-terminated monolayer. Surface-initiated atom transfer radical polymerization of tBA was carried out in the presence of a free initiator. Kinetics study showed that the polymerization was well controlled. By cleaving PtBA off the particles, the molecular weights of the grafted and free polymers were found to be essentially identical. Mixed PtBA/PS brushes were obtained by the nitroxide-mediated radical polymerization of styrene from PtBA particles. The M(n) of the grafted PS was found to be the same as that of the free PS formed in the solution from the free initiator. Amphiphilic mixed PAA/PS brush-coated nanoparticles were synthesized from mixed PtBA/PS particles by hydrolysis of PtBA with iodotrimethylsilane. Tyndall scattering experiments and (1)H NMR study showed that the mixed PAA/PS particles can be dispersed and form a stable suspension in CHCl(3), a selective solvent for PS, and also in CH(3)OH, a selective solvent for PAA, demonstrating the capability of these hairy nanoparticles to undergo chain reorganization in response to environmental changes.

The modification of silicon oxide with poly(ethylene glycol) to effectively eliminate protein adsorption has proven to be technically challenging. In this paper, we demonstrate that surface-initiated atom transfer radical polymerization (SI-ATRP) of oligo(ethylene glycol) methyl methacrylate (OEGMA) successfully produces polymer coatings on silicon oxide that have excellent protein resistance in a biological milieu. The level of serum adsorption on these coatings is below the detection limit of ellipsometry. We also demonstrate a new soft lithography method via which SI-ATRP is integrated with microcontact printing to create micropatterns of poly(OEGMA) on glass that can spatially direct the adsorption of proteins on the bare regions of the substrate. This ensemble of methods will be useful in screening biological interactions where nonspecific binding must be suppressed to discern low probability binding events from a complex mixture and to pattern anchorage-dependent cells on glass and silicon oxide.

This article reports on the synthesis of thermosensitive polymer brushes on silica nanoparticles by atom transfer radical polymerization (ATRP) and the study of thermo-induced phase transitions in water. Silica nanoparticles were prepared by the Stöber process and the surface was functionalized by an ATRP initiator. Surface-initiated ATRPs of methoxydi(ethylene glycol) methacrylate (DEGMMA) and methoxytri(ethylene glycol) methacrylate (TEGMMA) were carried out in THF at 40 degrees C in the presence of a free initiator, benzyl 2-bromoisobutyrate. The polymerizations were monitored by 1H NMR spectroscopy and gel permeation chromatography. The hairy hybrid nanoparticles were characterized by thermogravimetric analysis and scanning electron microscopy, and the thermoresponsive properties were investigated by variable temperature 1H NMR spectroscopy and dynamic light scattering. The cloud points of free poly(DEGMMA) and poly(TEGMMA) in water were around 25 and 48 degrees C, respectively. The thermo-induced phase transitions of polymer brushes on silica nanoparticles began at a lower temperature and continued over a broader range (4-10 degrees C) than those of free polymers in water (< 2 degrees C).

We report the synthesis and thermosensitive properties of well‐defined water‐soluble polyacrylates and polystyrenics with short pendant oligo(ethylene glycol) groups. Four monomers, methoxydi(ethylene glycol) acrylate (DEGMA), methoxytri(ethylene glycol) acrylate (TEGMA), α‐hydro‐ω‐(4‐vinylbenzyl)tris(oxyethylene) (HTEGSt), and α‐hydro‐ω‐(4‐vinylbenzyl)tetrakis(oxyethylene) (HTrEGSt), were prepared and polymerized by nitroxide‐mediated radical polymerization with 2,2,5‐trimethyl‐3‐(1‐phenylethoxy)‐4‐phenyl‐3‐azahexane as an initiator. Kinetics and gel permeation chromatography analysis showed that the polymerizations were controlled processes yielding polymers with controlled molecular weights and narrow polydispersities. All polymers could be dissolved in water, forming transparent solutions, and undergo phase transitions when the temperature was above a critical point. The thermosensitive properties were studied by turbidimetry and variable‐temperature 1H NMR spectroscopy. The cloud points of the polymers of DEGMA, TEGMA, HTEGSt, and HTrEGSt were around 38, 58, 13, and 64 °C, respectively. For all four polymers, the cloud point increased with decreasing concentration and increasing molecular weight in the studied molecular weight range of 5000–30,000 g/mol. The removal of the nitroxide group from the polymer chain end resulted in a higher cloud point. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2454–2467, 2006