Relating side chain organization of PNIPAm with its conformation in aqueous methanol

被引:74
作者
Mukherji, Debashish [1 ]
Wagner, Manfred [1 ]
Watson, Mark D. [1 ,2 ]
Winzen, Svenja [1 ]
de Oliveira, Tiago E. [3 ]
Marques, Carlos M. [4 ]
Kremer, Kurt [1 ]
机构
[1] Max Planck Inst Polymer Res, Ackermannweg 10, D-55128 Mainz, Germany
[2] Univ Kentucky, Lexington, KY 40506 USA
[3] Univ Fed Rio Grande do Sul, Porto Alegre, RS, Brazil
[4] Univ Strasbourg, CNRS, Inst Charles Sadron, Strasbourg, France
关键词
POLY(2-METHACRYLOYLOXYETHYL PHOSPHORYLCHOLINE) GEL; TO-COIL TRANSITION; MOLECULAR-DYNAMICS; PREFERENTIAL ADSORPTION; PHASE-TRANSITION; GOOD SOLVENTS; DIFFUSION; POLY(N-ISOPROPYLACRYLAMIDE); WATER; CONONSOLVENCY;
D O I
10.1039/c6sm01789d
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Combining nuclear magnetic resonance (NMR), dynamic light scattering (DLS), and ms long all-atom simulations with two million particles, we establish a delicate correlation between increased side chain organization of PNIPAm and its collapse in aqueous methanol mixtures. We find that the preferential binding of methanol with PNIPAm side chains, bridging distal monomers along the polymer backbone, results in increased organization. Furthermore, methanol-PNIPAm preferential binding is dominated by hydrogen bonding. Our findings reveal that the collapse of PNIPAm is dominated by enthalpic interactions and that the standard poor solvent (entropic) effects play no major role.
引用
收藏
页码:7995 / 8003
页数:9
相关论文
共 49 条
[1]  
[Anonymous], 1990, Polymers in Solution: Their Modelling and Structure
[2]   THE MISSING TERM IN EFFECTIVE PAIR POTENTIALS [J].
BERENDSEN, HJC ;
GRIGERA, JR ;
STRAATSMA, TP .
JOURNAL OF PHYSICAL CHEMISTRY, 1987, 91 (24) :6269-6271
[3]   MOLECULAR-DYNAMICS WITH COUPLING TO AN EXTERNAL BATH [J].
BERENDSEN, HJC ;
POSTMA, JPM ;
VANGUNSTEREN, WF ;
DINOLA, A ;
HAAK, JR .
JOURNAL OF CHEMICAL PHYSICS, 1984, 81 (08) :3684-3690
[4]   A statistical theory of coil-to-globule-to-coil transition of a polymer chain in a mixture of good solvents [J].
Budkov, Yu A. ;
Kolesnikov, A. L. ;
Kalikin, N. N. ;
Kiselev, M. G. .
EPL, 2016, 114 (04)
[5]   Canonical sampling through velocity rescaling [J].
Bussi, Giovanni ;
Donadio, Davide ;
Parrinello, Michele .
JOURNAL OF CHEMICAL PHYSICS, 2007, 126 (01)
[6]   EFFECTS OF DIFFUSION ON FREE PRECESSION IN NUCLEAR MAGNETIC RESONANCE EXPERIMENTS [J].
CARR, HY ;
PURCELL, EM .
PHYSICAL REVIEW, 1954, 94 (03) :630-638
[7]   Phase behavior of poly(N-isopropylacrylamide) in binary aqueous solutions [J].
Costa, ROR ;
Freitas, RFS .
POLYMER, 2002, 43 (22) :5879-5885
[8]   Solvent-induced immiscibility of polymer brushes eliminates dissipation channels [J].
de Beer, Sissi ;
Kutnyanszky, Edit ;
Schoen, Peter M. ;
Vancso, G. Julius ;
Mueser, Martin H. .
NATURE COMMUNICATIONS, 2014, 5
[9]  
de Gennes P, 1979, Scaling concepts in polymer physics
[10]   Why does high pressure destroy co-non-solvency of PNIPAm in aqueous methanol? [J].
de Oliveira, Tiago E. ;
Netz, Paulo A. ;
Mukherji, Debashish ;
Kremer, Kurt .
SOFT MATTER, 2015, 11 (44) :8599-8604