Novel nanoscale theragnostic devices were successfully prepared through attachment of well defined, multifunctional polymer chains to gadolinium (Gd) metal-organic framework (MOF) nanoparticles. Copolymers of poly(N-isopropylacrylamide)-co-poly(N-acryloxysuccinimide)-co-poly(fluorescein O-methacrylate) were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. The succinimide functionality was utilized as a scaffold for attachment of both a therapeutic agent, such as methotrexate, and a targeting ligand, such as H-glycine-arginine-glycine-aspartate-serine-NH(2) peptide. Employment of a trithiocarbonate RAFT agent allowed for reduction of the polymer end groups to thiolates providing a means of copolymer attachment through vacant orbitals on the Gd(3+) ions at the surface of the Gd MOF nanoparticles. These versatile, nanoscale scaffolds were shown to be biocompatible and have cancer cell targeting, bimodal imaging, and disease treatment capabilities. This unique method provided a simple yet versatile route of producing polymer-nanoparticle theragnostic materials with an unprecedented degree of flexibility in the construct, potentially allowing for tunable loading capacities and spatial loading of targeting/treatment agents, while incorporating bimodal imaging capabilities through both magnetic resonance and fluorescence microscopy.

A tethered triblock copolymer has been synthesized by sequential monomer addition to a self-assembled monolayer of (11-(2-bromo-2-methyl)propionyloxy)undecyltrichlorosilane. Si/SiO2//polystyrene-b-poly(methyl acrylate)-b-polystyrene (PS-b-PMA-b-PS) and Si/SiO2//PMA-b-PS-b-PMA were prepared by the “grafting from” method using atom transfer radical polymerization. The resulting triblock brushes were characterized by ATR−FTIR, water contact angles, ellipsometry, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). Free polymer formed during the brush formation was characterized by gel permeation chromatography. Treatment of the triblock brushes with block-selective solvents caused reversible changes in the water contact angles and AFM. AFM analysis revealed a patterned nanomorphology when the brush was treated with a good solvent for the mid-block. We have interpreted this nanomorphology in terms of a folded brush structure where the two end blocks aggregate and force the mid-block to the air interface. XPS and water contact angle observations are consistent with this interpretation.

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Grafting from" surface-initiated atom transfer radical polymerization (ATRP) techniques were used to synthesize semifluorinated diblock copolymer brushes from silica substrates. Synthesis of either a polystyrene or poly(methyl acrylate) homopolymer brush was performed first (inner block) followed by polymerization of a semifluorinated monomer (outer block). The semifluorinated outer block consisted either of poly(pentafluorostyrene), poly(heptadecafluorodecyl acrylate), poly(pentafluoropropyl acrylate), or poly(trifluoroethyl acrylate). Analysis of the homopolymer and diblock copolymer brush layers was conducted using ellipsometry, ATR-FTIR, tensiometry, XPS, and AFM. Solvent-induced diblock rearrangement experiments were performed using a selective solvent for the hydrocarbon polymer block to generate a fluorine-deficient surface. With the exception of the systems containing PHFA, all the diblock systems were shown to exhibit water contact angles typical for the hydrocarbon polymer block after solvent treatment. Poor rearrangement for diblock copolymer brushes containing PHFA was observed when compared to all other semifluorinated diblock copolymer systems. The extent of diblock rearrangement was correlated to the calculated values for the solubility parameters of each block.

Diblock copolymer polyelectrolyte brushes of either polystyrene (PS) or poly(methyl acrylate) (PMA) and poly(acrylic acid) (PAA) were synthesized using sequential monomer addition from a tethered 2-bromoisobutyrate initiator. Si/SiO2//PS-b-poly(tert-butyl acrylate) (P(t-BA)) and Si/SiO2//PMA-b-P(t-BA) were prepared by the “grafting from” method using atom transfer radical polymerization. The PAA block was prepared by hydrolysis of poly(tert-butyl acrylate) (P(t-BA)) and the polyelectrolyte was formed by subsequent treatment with either aqueous silver acetate or sodium tetrapalladate. Conversion of P(t-BA) to PAA and attachment of either silver or palladium ions to the PAA block was confirmed using ATR-FTIR spectroscopy, water contact angle measurements, and X-ray photoelectron spectroscopy. Solvent switching of the diblock copolymer brush using DMF and anisole was incomplete both before and after treatment with silver acetate, although the degree of switching was larger before treatment. The polyelectrolyte diblock copolymer brushes were used for the synthesis of inorganic nanoparticles by reduction of the treated PAA. These samples were characterized using AFM, XPS, and ATR−FTIR.

The synthesis of a variety of well-defined diblock copolymer brushes, including poly(methyl methacrylate) (PMMA)-b-poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA), PMMA-b-poly(styrene) (PSty), and PSty-b-poly(methyl acrylate), was achieved via surface immobilized reversible addition−fragmentation chain transfer (RAFT) polymerization. Initially, silicon surfaces were modified with RAFT chain transfer agents (CTAs) by utilizing a modified atom transfer addition reaction involving a silicon wafer modified with (11-(2-bromo-2-methyl)propionyloxy)undecyltrichlorosilane and dithiobenzoyl disulfide. Diblock copolymer brushes were then prepared via sequential surface initiated RAFT polymerization from the immobilized CTA. Various characterization techniques including ellipsometry, contact angle measurements, grazing angle attenuated total reflectance−Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy were used to characterize the immobilization of CTAs on the silicon wafer and the subsequent polymer formation. The addition of free CTA was required for the formation of well-defined diblock copolymer brushes, which subsequently resulted in the presence of free polymer chains in solution. The free polymer chains were isolated and used to estimate the molecular weights and polydispersity index of chains attached to the surface.

We present an account of our research into polyelectrolyte polymer brushes that are capable of acting as stimuli-responsive films. We first detail the synthesis of poly(acrylic acid) polymer brushes using ATRP in a "grafting from" strategy. Significantly, we employed a chemical-free deprotection step that should leave the anchoring ester groups intact. We have demonstrated how these polymer assemblies respond to stimuli such as pH and electrolyte concentration. We have used poly(acrylic acid) polymer brushes for the synthesis of metallic nanoparticles and review this work. We have used XPS, ATR-FTIR, and AFM spectroscopy to show the presence of silver and palladium nanoparticles within polymer brushes. Finally, we report the synthesis of AB diblock polyampholyte polymer brushes that represent an extension of polyelectrolyte polymer brushes.

A novel surface modification technique was employed to produce a polymer modified positive contrast agent nanoparticle through attachment of well-defined homopolymers synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. A range of RAFT homopolymers including poly[N-(2-hydroxypropyl)methacrylamide], poly(N-isopropylacrylamide), polystyrene, poly(2-(dimethylamino)ethyl acrylate), poly(((poly)ethylene glycol) methyl ether acrylate), and poly(acrylic acid) were synthesized and subsequently used to modify the surface of gadolinium (Gd) metal-organic framework (MOF) nanoparticles. Employment of a trithiocarbonate RAFT agent allowed for reduction of the polymer end groups under basic conditions to thiolates, providing a means of homopolymer attachment through vacant orbitals on the Gd3+ ions at the surface of the Gd MOF nanoparticles. Magnetic resonance imaging (MRI) confirmed the relaxivity rates of these novel polymer modified structures were easily tuned by changes in the molecular weight and chemical structures of the polymers. When a hydrophilic polymer was used for modification of the Gd MOF nanoparticles, an increase in molecular weight of the polymer provided a respective increase in the longitudinal relaxivity. These relaxivity values were significantly higher than both the unmodified Gd MOF nanoparticles and the clinically employed contrast agents, Magnevist and Multihance, which confirmed the construct's ability to be utilized as a positive contrast nanoparticle agent in MRI. Further characterization confirmed that increased hydrophobicity of the polymer coating on the Gd MOF nanoparticles yielded minimal changes in the longitudinal relaxivity properties but large increases in the transverse relaxivity properties in the MRI.