@article {2473, title = {Poly(oligo(ethylene glycol)acrylamide) Brushes by Surface Initiated Polymerization: Effect of Macromonomer Chain Length on Brush Growth and Protein Adsorption from Blood Plasma}, journal = {Langmuir}, volume = {25}, number = {6}, year = {2009}, note = {ISI Document Delivery No.: 418JRTimes Cited: 12Cited Reference Count: 45Kizhakkedathu, Jayachandran N. Janzen, Johan Le, Yevgeniya Kainthan, Rajesh K. Brooks, Donald E.}, month = {Mar}, pages = {3794-3801}, type = {Article}, abstract = {Three hydrolytically stable polyethyleneglycol (PEG)-based N-substituted acrylamide macromonomers, methoxypolyethyleneglycol (350) acrylamide (MPEG(350)Am) methoxypolyethyleneglycol (750) acrylamide(MPEG(750)Am) and methoxypolyethyleneglycol (2000)acrylamide (MPEG(2000)Am) with increasing PEG chain length were synthesized. Surface-initiated aqueous atom transfer radical polymerization (ATRP) using CuCl/1,1,4,7,10,10-hexamethyl triethylene tetramine (HMTETA) catalyst was utilized to generate dense polymer brushes from these monomers via an ester linker group on the surface of model polystyrene (PS) particles. The molecular weight, hydrodynamic thickness, and graft densities of the grafted polymer layers were controlled by changing the reaction parameters of monomer concentration, addition of Cu(II)Cl-2, and sodium chloride. The graft densities of surface-grafted brushes decreased with increasing PEG macromonomer chain length, 350 > 750 >> 2000, under similar experimental conditions. The molecular weight of grafts increased with increase in monomer concentration, and only selected conditions produced narrow distributed polymer chains. The molecular weight of grafted polymer chains differs significantly to those formed in solution. The hydrodynamic thicknesses of the grafted polymer layers were fitted to the Daoud and Cotton model (DCM) for brush height on spherical surfaces. The results show that the size of the pendent groups on the polymer chains has a profound effect on the hydrodynamic thickness of the brush for a given degree of polymerization. The new PEG-based surfaces show good protection against nonspecific protein adsorption from blood plasma compared to the bare surface. Protein adsorption decreased with increasing surface density of grafted polymer chains. Poly(MPEG(750)Am) brushes were more effective in preventing protein adsorption than poly(MPEG(350)Am) even at low graft densities, presumably due to the increase in PEG content in the grafted layer.}, keywords = {AQUEOUS ATRP, COPOLYMER BRUSHES, density, METHYL-METHACRYLATE, MODEL, N-DIMETHYLACRYLAMIDE), OLIGO(ETHYLENE GLYCOL) METHACRYLATE, PHOSPHORYLCHOLINE, POLY(N, POLYMERS, TRANSFER RADICAL POLYMERIZATION}, isbn = {0743-7463}, url = {://000264145000068}, author = {Kizhakkedathu, J. N. and Janzen, J. and Le, Y. and Kainthan, R. K. and Brooks, D. E.} } @article {2697, title = {Surface Modification of Polyvinyl Chloride Sheets via Growth of Hydrophilic Polymer Brushes}, journal = {Macromolecules}, volume = {42}, number = {9}, year = {2009}, note = {ISI Document Delivery No.: 441PNTimes Cited: 7Cited Reference Count: 65Zou, Yuquan Kizhakkedathu, Jayachandran N. Brooks, Donald E.}, month = {May}, pages = {3258-3268}, type = {Article}, abstract = {Poly(N,N-dimethylacrylamide) (PDMA) brushes were successfully grown from polyvinyl chloride (uPVC) sheets via well-controlled surface-initiated atom transfer radical polymerization (SI-ATRP). An ATRP initiator containing a chloropropionate moiety was chemically tethered onto the surface of PVC via it novel wet chemical modification. Negatively charged sulfate groups were introduced to facilitate polymerization. By incorporating a chemically cleavable group into the initiator, molecular weight, polydispersity and graft density of a series of PDMA brushes synthesized on the flat surface were unambiguously characterized for the first time by gel permeation chromatography. ATR-FTIR, contact angle, SEM and AFM were used to characterize the PDMA grafted surfaces. Reaction conditions Such as monomer concentration, reaction time, copper(II) concentration and salt additives were varied to systematically investigate their effects on molecular weight and graft density of the PDMA grafted from PVC. Molecular weights of grafted PDMA brushes varied from ca. 20 000 to 2 170 000 Da, while craft density ranged from 0.08 to 1.13 chains/nm(2). Polydispersity of grafted PDMA brushes was controlled between 1.20 and 1.60 by Cu(II) complex addition. Kinetic studies revealed that the surface initiation was a slow process and graft density increased during the reaction. The brush uniformity increased with increasing reaction time. Reinitiation of the obtained PDMA brushes was demonstrated, suggesting that the polymerization is "living". The successful growth of a PDMA-b-poly(N-isopropylacrylamide) (PNIPAM) copolymer brush was verified by GPC and AFM.}, keywords = {AQUEOUS ATRP, ATOMIC-FORCE MICROSCOPY, CARBON NANOTUBES, COPOLYMER BRUSHES, density, GLYCOL), GRAFT, PLASMA-PROTEIN ADSORPTION, POLY(ETHYLENE, SELF-ASSEMBLED MONOLAYERS, SERUM-ALBUMIN, TRANSFER RADICAL POLYMERIZATION}, isbn = {0024-9297}, url = {://000265781300007}, author = {Zou, Y. Q. and Kizhakkedathu, J. N. and Brooks, D. E.} } @article {1040, title = {Laser-light-scattering study of internal motions of polymer chains grafted on spherical latex particles}, journal = {Journal of Physical Chemistry B}, volume = {108}, number = {48}, year = {2004}, note = {ISI Document Delivery No.: 875JUTimes Cited: 6Cited Reference Count: 35}, month = {Dec}, pages = {18479-18484}, type = {Article}, abstract = {Using atom-transfer radical polymerization, we have prepared core-shell particles by grafting thermally sensitive poly(N-isopropylacrylamide) (PNIPAM) chains on a spherical polystyrene latex core (with a radius of similar to287 nm) via the "grafting-from" approach. As the temperature increases from 25 degreesC to 35 degreesC, the PNIPAM shell shrinks from a thickness of 625 nm to 110 nm and the chain density near the core increases from 7.3 x 10(-3) g/cm(3) to 7.2 x 10(-2) g/cm(3). Using such core-shell particles, we have, for the first time, been able to study dynamics of long chains anchored on a particle in dilute dispersion by laser-light scattering. Our results showed that, besides the translational diffusion of the particle as a whole, there also exists an additional slow relaxation mode that is only observable at larger scattering vectors (q),which are presumably related to internal motions of the shell. In the fully swollen state, the relaxation rate of the slow motion ((slow)) is insensitive to the observation length (1/q); however, its contribution to the scattering intensity (A(slow)) increases as q increases. In the shrunken state, (slow) slightly decreases as q increases. (slow) can be scaled to the shell thickness ((brush)) as (slow) proportional to (alpha)(brush), with alpha = -2.5 +/- 0.2, which is smaller than the predicated value of 3.}, keywords = {AQUEOUS ATRP, BRUSHES, CONFORMATION, DYNAMICS, GLOBULE TYPE TRANSITIONS, INTERFACE, LAYERS, MODEL, POLY(N-ISOPROPYLACRYLAMIDE), SIMULATION}, isbn = {1520-6106}, url = {://000225417200015}, author = {Yang, C. and Kizhakkedathu, J. N. and Brooks, D. E. and Jin, F. and Wu, C.} }