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Charles L McCormick

Publications and source records attributed to Charles L McCormick.

10 recordsLinked to original sources
PubMed2007

Effect of sequential layer-by-layer surface modifications on the surface energy of plasma-modified poly(dimethylsiloxane).

Surface-initiated grafting of N,N-dimethylacrylamide, styrenesulfonate (SS), and (ar-vinylbenzyl)trimethylammonium chloride (VBTAC) from microwave plasma carboxylated, initiator-functionalized poly(dimethylsiloxane) (PDMS) surfaces was accomplished utilizing reversible addition-fragmentation chain transfer (RAFT) polymerization. Surface spectroscopic attenuated total reflectance (ATR) FT-IR analysis and atomic force microscopy (AFM) measurements were utilized to determine surface grafting and morphological surface features. The VBTAC-grafted PDMS provided a smooth, hydrophilic cationic surface for creating layer-by-layer (LBL) surfaces via alternating deposition of well-defined poly(SS) and poly(VBTAC), also prepared via aqueous RAFT. Comparisons of the ATR FT-IR spectra of the LBL assemblies and those of respective anionic poly(SS) and cationic poly(VBTAC) components confirmed strong electrostatic complexation of a fraction of the sulfonate and quarternary ammonium species in the layers as well as the existence of noncomplexed species. AFM images of surface topology indicated the presence of domains, likely phase-separated segments of the respective homopolymers, as well as interlayer mixing. The employed LBL methodology results in formation of stable, highly hydrophilic surfaces on a PDMS substrate. To our knowledge, this is the first study that illustrates surface functionalization of PDMS using microwave plasma and RAFT polymerization, followed by LBL deposition of polyelectrolytes.

Journal Article↗
PubMed2007

Layer-by-layer assembly of pH-responsive, compositionally controlled (co)polyelectrolytes synthesized via RAFT.

Homo- and block copolyelectrolytes that have well-defined structures and are responsive to pH were synthesized via reversible addition-fragmentation chain-transfer (RAFT) polymerization and employed to produce layer-by-layer (LBL) films. Acrylamido monomers with carboxylate, sulfonate, and amine functionality were utilized to provide both strong and weak homopolyelectrolytes and mixed strong/weak copolyelectrolyte systems. Multilayer films were prepared under specified conditions of pH and ionic strength and analyzed via atomic force microscopy and ellipsometry to study the effects of changes in the local molecular environment on film morphologies. The pH responsiveness and integrity of the multilayer assemblies were investigated by exposing films to solutions of varying pH in a fluid cell and performing in situ AFM analysis. The multilayer dimensions, morphology, and integrity were found to depend on the molecular architecture of the polyelectrolytes, with changes in segmental type and repeating unit distribution producing dramatic differences in film characteristics. These results suggest the possibility of producing LBL assemblies of precisely controlled dimensions and properties by specifically tailoring copolymer structure. To our knowledge, this is the first report of LBL assembly of RAFT-synthesized homo- and copolyelectrolyte multilayer complexes.

Journal Article↗
PubMed2006

Fluorescent labeling of RAFT-generated poly(N-isopropylacrylamide) via a facile maleimide-thiol coupling reaction.

We report a facile labeling technique in which the telechelic thiocarbonylthio functionality of well-defined poly(N-isopropylacrylamide) (PNIPAM) prepared by room temperature RAFT polymerization is first converted to the thiol and subsequently reacted with a maleimido-functional fluorescent dye, N-(1-pyrene)maleimide (PM). Nearly monodisperse PNIPAM (M(n) = 39 500 g/mol, M(w)/M(n) = 1.07) was synthesized using a trithiocarbonate-based CTA, 2-dodecylsulfanylthiocarbonylsulfanyl-2-methyl propionic acid (DMP), and a conventional azo-initiator, namely, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70), as the primary source of radicals. The key to successful conjugation of PM to PNIPAM is the implementation of a two-step reduction process involving (1) the cleavage of the trithiocarbonate with a strong reducing agent, in this case, NaBH4, to form a mixture of polymeric thiols and disulfides and (2) the conjugation of PM to the pure polymeric thiol in the presence of tris(2-carboxyethyl)phosphine.HCl (TCEP). We show that TCEP efficiently eliminates the formation of polymeric disulfides and thus allows for the desired addition of the free polymeric thiol across the maleimide double bond. This concept is demonstrated using SEC-MALLS and UV-vis spectroscopy measurements.

Acrylamides↗
PubMed2004

Aqueous RAFT polymerization: recent developments in synthesis of functional water-soluble (co)polymers with controlled structures.

Reversible addition-fragmentation chain transfer (RAFT) polymerization has been the focus of intensive research over the past few years since this methodology allows the synthetic tailoring of macromolecules with complex architectures including block, graft, comb, and star structures with predetermined molecular weight, terminal functionality, and narrow molecular weight distribution. In this paper we recount significant milestones in achieving controlled free radical homopolymerization and block copolymerization of water-soluble and amphiphilic monomers including nonionic, cationic, anionic, and zwitterionic species. It is shown that under aqueous conditions, control of homopolymerization and further blocking to extend the molecular weight or to produce precisely structured block copolymers require not only careful selection of reagents (initiator, chain transfer agent, and monomer) but also regulation or elimination of hydrolysis of the omega-terminal thiocarbonylthio functionality. The technological potential of such systems is illustrated for the stimuli (pH) reversible micellization of amphiphilic block copolymers and for stabilization and stimuli responsive aggregation of gold nanoparticles bearing covalently tethered co(polymers). Given the advantages of RAFT over other controlled free radical techniques for preparation of water-soluble architectures, it may be anticipated that this technology will be at the forefront of nano- and microscale self-assembly in electronics and biotechnology.

Journal Article↗
PubMed2002

Facile preparation of transition metal nanoparticles stabilized by well-defined (co)polymers synthesized via aqueous reversible addition-fragmentation chain transfer polymerization.

Herein we disclose a facile method for the preparation of (co)polymer-stabilized transition metal colloids, via the "grafting-to" approach. The method takes advantage of the fact that (co)polymers synthesized in aqueous media, in a controlled fashion, via reversible addition-fragmentation chain transfer bear thiocarbonylthio end groups. These are readily reduced to yield (co)polymers with thiol end groups. When the reduction is performed, with NaBH(4), for example, in aqueous media in the presence of an appropriate transition metal species, (co)polymer-stabilized metal nanoparticles are formed in which the size and size distribution are dependent upon the individual transition metals. Colloid formation is confirmed by transmission electron microscopy and UV-vis spectroscopy.

Journal Article↗
PubMedDate not supplied

Experimental evidence for multiple assembled states of Sc3 from Schizophyllum commune.

The hydrophobin Sc3 from the fungus Schizophyllum commune assembles from the aqueous phase into ordered structures with substantially different characteristics depending upon experimental conditions. Under the first condition, a vortexing procedure widely reported in the literature, interfacial assembly yields highly ordered, stacked beta-sheets. We have also observed a previously unreported assembly of Sc3 under a second condition, which occurs in a time-dependent manner from quiescent solution. The resulting types of assembled states have been compared utilizing fluorescence techniques, sodium dodecyl sulfate polyacrylamide gel electrophoresis, immunoblotting, density gradient centrifugation, and phase contrast and atomic force microscopy. A model based on this study and previous literature is proposed that suggests three distinct states of Sc3: (1) soluble Sc3 consisting of unimers or multimers in micelle-like association, (2) interfacially assembled I-Sc3 with highly ordered, stacked beta-sheets, presumably formed in a templated manner at the air/water interface of microscopic bubbles generated by vortexing, and (3) solution-assembled S-Sc3, a less-ordered structure formed in a time-dependent manner in the absence of an interface.

Benzothiazoles↗
PubMedDate not supplied

Facile, controlled, room-temperature RAFT polymerization of N-isopropylacrylamide.

Poly(N-isopropyl acrylamide) is a thermoresponsive polymer that has been widely investigated for drug delivery. Herein, we report conditions facilitating the controlled, room-temperature RAFT polymerization of N-isopropylacrylamide (NIPAM). The key to success is the appropriate choice of both a suitable RAFT chain transfer agent (CTA) and initiating species. We show that the use of 2-dodecylsulfanylthiocarbonylsulfanyl-2-methyl propionic acid, a trithiocarbonate RAFT CTA, in conjunction with the room-temperature azo initiator 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), in DMF, at 25 degrees C, yields conditions leading to NIPAM homopolymerizations which bear all of the characteristics of a controlled/"living" polymerization. We also demonstrate facile size exclusion chromatographic analysis of PNIPAM samples in DMF at 60 degrees C, directly on aliquots withdrawn during the polymerizations, which avoids the problems previously reported in the literature.

Acrylamides↗
PubMedDate not supplied

Direct, controlled synthesis of the nonimmunogenic, hydrophilic polymer, poly(N-(2-hydroxypropyl)methacrylamide) via RAFT in aqueous media.

Poly(N-(2-hydroxypropyl)methacrylamide) (PHPMA) is a nonimmunogenic, neutral-hydrophilic polymer currently employed in the delivery of anticancer drugs. Herein, we report conditions that facilitate the direct, controlled RAFT polymerization of HPMA in aqueous media. We demonstrate that the use of 4-cyanopentanoic acid dithiobenzoate and 4,4'-azobis(4-cyanopentanoic acid) as the chain transfer agent (CTA) and initiating species, respectively, in the presence of an acetic acid buffer solution at 70 degrees C is a suitable condition leading to controlled polymerization. The "living" nature of these polymerizations is demonstrated via chain-extension of an HPMA macroCTA to yield the corresponding poly(HPMA-b-HPMA) "homopolymer".

Magnetic Resonance Spectroscopy↗