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The radiolytic degradation of di-2-ethylhexyl-isobutyramide (DEHiBA) was examined by subjecting the compound to gamma irradiation, measuring the remaining concentration of the intact compound, identifying the degradation products, and measuring uranium distribution ratios. The combined effects of radiation dose, contact with aqueous solutions of HNO3, and aeration were also examined. The DEHiBA displayed significant stability at doses up to 1000 kGy, undergoing a slow exponential concentration decrease that was accompanied by the appearance of multiple degradation products. The most abundant compounds that were formed by radiolysis resulted from cleavage of the Ccarbonyl–N and Cethylhexyl–N bonds, generating di-ethylhexylamine and mono-ethylhexyl-isobutyramide. Acid contact did alter the radiolytic pathways, with acid favoring cleavage of the Ccarbonyl-N bond, while a more diverse array of compounds was formed in the absence of acid. Pulsed radiolysis experiments were also conducted, in which pico...

Non-vinyl-based ‘grafted from’ polymer brushes have generated much interest and growth in the past decade due to the potential for stiffer backbones, long-range order, and new backbone functional groups, compared to the traditional vinyl-based polymer brushes. This area of polymer brushes has been spurred on by recent advancements of new polymerization techniques, such as chain-growth condensation polymerization, that allow for the conversion of traditional step-growth polymers into the required chain-growth polymers to form polymer brushes via the ‘grafting from’ technique [1] . This exciting new category of polymer brushes forms semi-flexible or rigid-rod structures that have potential in a variety of applications including organic photovoltaics, organic light emitting diodes, tribological coatings, membranes for water purification and desalination, membranes for fuel cells, high performance coatings, and biosensing due to aromatic groups in the backbone, secondary bonding forces connecting chains, or conjugated backbones [2] , [3] . This review will focus on the synthesis and characterization of non-vinyl-based polymer brushes, primarily prepared via the ‘grafting from’ technique, while also including an overview of potential applications of these systems and highlighting prospective areas for future developments.

The potential of monoamide-based extraction chromatographic materials for actinide recovery was assessed by monitoring uranium partitioning into six different materials. These materials were comprised of two solid supports (Amberlite XAD 4 and XAD 7) coated with one of three extractants: di-2-ethylhexyl butyramide (DEHBA), di-2-ethyhexyl isobutryamide (DEHiBA), or di-2-ethyhexyl acetylamide (DEHAA). This report considers differences in uranium partitioning depending on the solid support, extractant, aqueous phase conditions and amount of extractant coating on a given support. Studies indicate the acetyl amide extractant coated onto XAD 7 is a top candidate for further investigation. This is an interesting finding as the acetyl amide is not generally considered a particularly useful extractant for solvent extraction separations due to its tendency to form a third phase. This information contrasts the general paradigm that a given extractant can be equally useful for extraction chromatographic or solvent extraction separations and indicates that the development of future classes of extraction chromatographic materials should carefully consider the role of alkyl groups in their optimization. Additionally, the efficacy of the developed monoamide materials are compared with more classically utilized organophosphorous materials to consider opportunities for advancement in f-element separations.

Despite recent advances in the understanding of fundamental cancer biology, cancer remains the second most common cause of death in the United States. One of the primary factors indicative of high cancer morbidity and mortality and aggressive cancer phenotypes is tumors with a low extracellular pH (pHe). Thus, the ability to measure tumor pHe in vivo using noninvasive and accurate techniques that also provide high spatiotemporal resolution has become increasingly important and is of great interest to researchers and clinicians. In an effort to develop a pH-responsive magnetic resonance imaging (MRI) contrast agent (CA) that has the potential to be used to measure tumor pHe, well-defined pH-responsive polymers, synthesized via reversible addition-fragmentation chain transfer polymerization, were attached to the surface of gadolinium-based nanoparticles (GdNPs) via a "grafting to" method after reduction of the thiocarbonylthio end groups. The successful modification of the GdNPs was verified by transmission electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis and dynamic light scattering. The performance of the pH-responsive polymer modified GdNPs was then evaluated for potential use as smart MRI CAs via monitoring the relaxivity changes with changing environmental pH. The results suggested that the pH-responsive polymers can be used to effectively modify the GdNPs surface to prepare a smart contrast agent for MRI.

Synthesis of well-defined, surface-initiated poly(N-octyl-p-benzamide) brushes was demonstrated using a new “grafting from” chain growth technique. A solution-based chain growth polycondensation technique was adopted from literature and modified to form a polyaramid brush by taking advantage of the differences in substituent effects between the activated surface-grafted initiator (methyl 4-(methyl(3-(trimethoxysilyl)propyl)carbamoyl)benzoate) and the deactivated deprotonated monomer (methyl 4-(octylamino)benzoate). The surface-immobilized polymer brushes on silicon wafers were characterized using ellipsometry, goniometry, grazing-angle attenuated total reflectance–Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. In addition, polyaramid brushes were grown from high surface area Stober silica and studied using thermogravimetric analysis, and the degrafted polymers were characterized using gel permeation chromatography and nuclear magnetic resonance spectroscopy. This is believe...

Well‐defined tertiary amine‐based pH‐responsive homopolymers and block copolymers were synthesized via reversible addition‐fragmentation chain transfer (RAFT) polymerization using 4‐cyanopentanoic acid dithiobenzoate (CPAD) as the RAFT agent for homopolymers and a poly(ethylene glycol) (PEG) macro‐RAFT agent for the block copolymers.¹H NMR and gel permeation chromatography results confirmed the successful synthesis of these homopolymers and block copolymers. Kinetics studies indicated that the formation of both the homopolymers and the block copolymers were well defined. The pKa titration experiments suggested that the homopolymers and the related block copolymers have a similar pKa. The dynamic light scattering investigation showed that all of the block copolymers underwent a sharp transition from unimers to micelles around their pKa and the hydrodynamic diameter (Dₕ) was not only dependent on the molecular weight but also on the composition of the block copolymers. The polymer solution of PEG‐b‐PPPDEMA formed the largest micelle compare to the PEG‐b‐PDPAEMA and PEG‐b‐PDBAEMA with a similar molecular weight. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 1010–1022

Functional imaging is a novel area in radiological sciences and allows for the non-invasive assessment and visualization of specific targets such as gene and protein expression, metabolic rates, and drug delivery in intact living subjects. As such, the field of molecular imaging has been defined as the non-invasive, quantitative, and repetitive imaging of biomolecules and biological processes in living organisms. For example, cancer cells may be genetically altered to attract molecules that alter the magnetic susceptibility, thereby permitting their identification by magnetic resonance imaging. These contrast agents and/or molecular reporters are seen as essential to the task of molecular medicine to increase both sensitivity and specificity of imaging. Therefore, there are five general principles which need to be fulfilled in order to conduct a successful in vivo molecular imaging study: (1) selection of appropriate cellular and subcellular targets; (2) development of suitable in vivo affinity ligands (molecular probes); (3) delivery of these probes to the target organ; (4) amplification strategies able to detect minimal target concentrations; and (5) development of imaging systems with high resolution. Although there has been a wide range of routes taken to incorporate both imaging agents and a disease-targeting moiety into diagnostic devices, arguably the most interesting of these routes employs the use of nanoparticles. Nanoscale diagnostic systems that incorporate molecular targeting agents and diagnostic imaging capabilities are emerging as the next-generation imaging agents and have the potential to dramatically improve the outcome of the imaging, diagnosis, and treatment of a wide range of diseases. The present review addresses chemical aspects in development of molecular probes based upon gadolinium nanoparticles and their potential role in translational clinical imaging and therapy.

Poly(acrylic acid) (PAA) surface-modified gold nanorods, contained in deionized ultra filtered (DIUF) water, served as templates for the formation of gold (Au), palladium (Pd), and platinum (Pt) nanoparticles upon reduction with NaBH4. This provided nanoparticles with respective diameters of 7.0 ± 0.7, 4.1 ± 0.4, and 5.1 ± 0.5 nm. Varying amounts of Pt metal salt were used in EG, which acts as both a solvent and a reducing agent, ranging from 0.1, 0.2, and 1.0 mg/mL, to provide control over nanoparticle diameters of 2.0 ± 0.5 nm, to 4.0 ± 0.5 nm, and 6.2 ± 1.9 nm, respectively. Nanoparticle diameter was also controlled in DIUF water by varying the amount of Pt metal salt from 0.1, 0.2, and 1.0 mg/mL, producing Pt particle diameters, respectively, increasing from 2.7 ± 0.3 nm to 4.1 ± 0.5 nm, and 6.0 ± 0.6 nm.

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.

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.

The synthesis of diblock copolymer brushes, including poly(styrene) (PSty)-b-PSty, PSty-b-poly(acrylic acid), PSty-b-poly(N-isopropylacrylamide), and poly(methyl acrylate)-b-poly(N,N-(dimethylamino)ethyl acrylate), was achieved utilizing a combination of surface-mediated atom transfer radical polymerization (ATRP) and reversible addition−fragmentation chain transfer (RAFT) polymerization techniques. Conversion of bromine end groups of homopolymer brushes formed by ATRP via a modified atom transfer addition reaction to a RAFT agent and diblock extension via RAFT polymerization allowed the direct formation of well-defined stimuli-responsive diblock copolymer brushes. The addition of sacrificial initiator and/or chain transfer agent permitted formation of well-defined diblock copolymer brushes and 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. Ellipsometry, contact angle measurements...

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 s...

Imaging contrast agents for magnetic resonance imaging (MRI) and computed tomography (CT) have received significant attention in the development of techniques for early-stage cancer diagnosis. Gadolinium (Gd) (III), which has seven unpaired electrons and a large magnetic moment, can dramatically influence the water proton relaxation and hence exhibits excellent MRI contrast. On the other hand, gold (Au), which has a high atomic number and high x-ray attenuation coefficient, is an ideal contrast agent candidate for x-ray based CT imaging. Gd metal organic framework (MOF) nanoparticles with tunable size, high Gd (III) loading and multivalency can potentially overcome the limitations of clinically utilized Gd chelate contrast agents. In this work, we report for the first time the integration of GdMOF nanoparticles with gold nanoparticles (AuNPs) for the preparation of a MRI/CT bimodal imaging agent. Highly stable hybrid GdMOF/AuNPs composites have been prepared by using poly(acrylic acid) as a bridge between the GdMOF nanoparticles and AuNPs. The hybrid nanocomposites were then evaluated in MRI and CT imaging. The results revealed high longitudinal relaxivity in MRI and excellent CT imaging performance. Therefore, these GdMOF/AuNPs hybrid nanocomposites potentially provide a new platform for the development of multi-modal imaging probes.

Two distinct oligomeric species of similar mass and chemical functionality (M w≈2,000 g/mol), one a linear methyl methacrylate oligomer (radius of gyration R g≈1.1 nm) and the other a hybrid organic–inorganic polyhedral silsesquioxane nanocage (methacryl-POSS, r≈1.0 nm), were subjected to thermal and rheological tests to compare the behaviors of these geometrically dissimilar molecules over the entire composition range. The glass transition temperatures of the blends varied monotonically between the glass transition temperatures of the pure oligomer (T g=−47.3°C) and the pure POSS (T g=−61.0°C). Blends containing high POSS contents (with volume fraction φ POSS≥0.90) exhibited enhanced enthalpy relaxation in differential scanning calorimetry (DSC) measurements, and the degree of enthalpy relaxation was used to calculate the kinetic fragility indices m of the oligomeric MMA (m=59) and the POSS (m=74). The temperature dependences of the viscosities were fitted by the free-volume based Williams–Landel–Ferry (WLF) and Vogel–Fulcher–Tammann (VFT) framework and a dynamic scaling relation. The calculated values of the fragility from the WLF–VFT fits were similar for the POSS (m=82) and for the oligomer (m=76), and the dynamic scaling exponent was similar for the oligomeric MMA and the POSS. Within the range of known fragilities for glass-forming liquids, the temperature dependence of the viscosity was found to be similarly fragile for the two species. The difference in shape of the nanocages and oligomer chains is unimportant in controlling the glass-forming properties of the blends at low volume fractions (φ POSS

We report the preparation of a poly(acrylic acid) polymer brush from a flat silica substrate using a surface-initiated atom transfer radical polymerization of tert-butyl acrylate. Significantly, we use a chemical free deprotection strategy through pyrolysis of the tert-butyl esters to the corresponding carboxylic acids. This eliminates the possibility of loss of the polymer brush from the surface via acidolysis of the ester group in the surface bound initiator. We have verified the formation of the poly(acrylic acid) brush through ATR-FTIR, ellipsometry, water contact angle analysis, and XPS. We also demonstrate the stimuli-responsive nature of these brushes with respect to pH and added electrolyte concentration.

The synthesis of tethered block copolymer brushes via the use of controlled/living free radical polymerization techniques presents many significant advantages over traditional free radical polymerization techniques. In our group, we have found that the most versatile controlled/living free radical polymerization techniques are atom transfer radical polymerization (ATRP) and reversible addition fragmentation transfer (RAFT) polymerization. Both diblock and ABA type triblock copolymer brushes have been synthesized using either ATRP or RAFT. Of particular interest with block copolymer brushes, are their ability to reversibly rearrange upon treatment with selective solvents. This rearrangement of block copolymer brushes can result in the formation of unusual surface morphologies that have been attributed to the formation of either pinned micelles or folded structures. We have demonstrated that other external stimuli besides block-selective solvents can be used to induce brush reorganization, namely temperature and treatment with supercritical CO2. � 2004 Elsevier B.V. All rights reserved.

“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 t...

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...

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 t...

Here an in-depth analysis of reversible addition–fragmentation chain transfer (RAFT) polymerization kinetics is reported in order to provide better definition of poly(3-hexylthiophene) (P3HT) rod–coil block copolymers thru a more thorough understanding of the RAFT polymerization of the coil block. To this end, a new P3HT macroRAFT agent is synthesized and utilized to prepare rod–coil block copolymers with P3HT and poly(styrene), poly(tert-butylacrylate), and poly(4-vinylpyridine), and the RAFT polymerization kinetics of each system are fully detailed. This is achieved by a comprehensive analysis of characterization data from 1H nuclear magnetic resonance spectroscopy, gel permeation chromatography, and matrix-assisted laser desorption ionization time of flight spectroscopy, which are used as complementary techniques in order to address difficulties in accurately characterizing the synthesized polymer systems. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 3575–3585

Direct esterification of a hydroxyl functional polyester resin with p-hydroxybenzoic acid (PHBA) was carried out at 200-230 degreesC in the presence of p-toluene sulphonic acid and xylene. Acid value, molecular weight distribution, differential scanning calorimetry and both H-1 and C-13 NMR analysis were used to monitor the reaction. The optical texture of the final products were examined using a polarising optical microscope. The products from the reaction were the polyester with approximately 1 PHBA molecule per polymer chain end and unreacted PHBA. The dominant reaction in the system appears to be transesterification, resulting in a decrease of the molecular weight during the reaction. A liquid crystalline phase was not formed as multiple grafts of PHBA were not formed. (C) 2000 Elsevier Science S.A. All rights reserved.

A novel surface modification technique was employed to produce a polymer-modified, positive contrast agent nanoparticle for targeted magnetic resonance imaging (MRI). A range of both hydrophilic and hydrophobic homopolymers, along with novel multifunctional copolymers of poly(N-(2-hydroxypropyl) methacrylamide)-co-poly(N-methacryloxysuccinimide)-co-poly(fluorescein O-methacrylate), were synthesized using reversible addition-fragmentation chain transfer (RAFT) polymerization. These polymers were subsequently used to modify the surface of gadolinium (Gd) metal-organic framework (MOF) nanoparticles. The succinimide functionality of the copolymer was utilized as a scaffold for attachment of the targeting ligands, H-glycine-arginine-glycine-aspartate-serine-NH2 peptide or the antibody for epidermal growth factor. Reduction of the trithiocarbonate RAFT polymer end groups to thiolates provided a means of polymer attachment through vacant orbitals on the Gd3+ ions at the surface of the Gd MOF nanoparticles. MRI confirmed that the relaxivity rates of these novel polymer-modified structures were easily tuned by changes in size and shape of the nanoparticles or by modifying the molecular weight and chemical structure of the polymers attached to the surface of the nanoparticles. In most cases, the relaxivity values were significantly higher than both the unmodified Gd MOF nanoparticles and the clinically employed contrast agents, Magnevist® and MultiHance®. These versatile, polymer-modified nanoscale scaffolds were shown to provide biocompatibility, cancer cell targeting, and diagnostic imaging through positive contrast in MRI and fluorescence microscopy. This unique method provided a simple yet versatile route of producing polymer-modified nanoparticles for targeted MRI of cancer with an unprecedented degree of flexibility in the construct, potentially allowing for tunable loading capacities and spatial loading of targeting agents while incorporating bimodal imaging capabilities.

Gadolinium metal-organic framework (Gd MOF) nanoparticles are an interesting and novel class of nanomaterials that are being studied as a potential replacement for small molecule positive contrast agents in magnetic resonance imaging (MRI). Despite the tremendous interest in these nanoscale imaging constructs, there are limitations, particularly with respect to controlling the particle size, which need to be overcome before these nanoparticles can be integrated into in vivo applications. In an effort to control the size, shape, and size distribution of Gd MOF nanoparticles, hydrotropes were incorporated into the reverse microemulsion synthesis used to produce these nanoparticles. A study of how hydrotropes influenced the mechanism of formation of reverse micelles offered a great deal of information with respect to the physical properties of the Gd MOF nanoparticles formed. Specifically, this study incorporated the hydrotropes, sodium salicylate (NaSal), 5-methyl salicylic acid, and salicylic acid into the reverse microemulsion. Results demonstrated that addition of each of the hydrotropes into the synthesis of Gd MOFs provided a simple route to control the nanoparticle size as a function of hydrotrope concentration. Specifically, Gd MOF nanoparticles synthesized with NaSal showed the best reduction in size distributions in both length and width with percent relative standard deviations being nearly 50% less than nanoparticles produced via the standard route from the literature. Finally, the effect of the size of the Gd MOF nanoparticles with respect to their MRI relaxation properties was evaluated. Initial results indicated a positive correlation between the surface areas of the Gd MOF nanoparticles with the longitudinal relaxivity in MRI. In particular, Gd MOF nanoparticles with an average size of 82 nm with the addition of NaSal, yielded a longitudinal relaxivity value of 83.9 mM⁻¹ [Gd³⁺] sec⁻¹, one of the highest reported values compared to other Gd-based nanoparticles in the literature to date.

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.