Conformation-specific self-assembly of thermo-responsive poly(ethylene glycol)-b-polypeptide diblock copolymer. 2013

Junyang Shen, and Chongyi Chen, and Wenxin Fu, and Linqi Shi, and Zhibo Li
Key Laboratory of Functional Polymer Materials, Ministry of Education, and Institute of Polymer Chemistry, Nankai University, Tianjin 300071, China.

Poly(ethylene glycol)-block-poly(γ-(2-methoxyethoxy)esteryl-L-glutamate) (PEG-b-poly-L-EG2Glu) was synthesized via ring-opening polymerization (ROP) of L-EG2Glu N-carboxyanhydride (NCA) using PEG-NH2 as macroinitiator. This diblock contained a thermo-responsive poly-L-EG2Glu block, which adopted primarily helical conformation in pristine aqueous solution. We found that PEG-b-poly-L-EG2Glu diblock can display two levels of self-assembly behaviors associated with hydrophobic interactions and conformation-specific reassembly, respectively. Upon temperature increase, the PEG-b-poly-L-EG2Glu diblock formed wormlike micelles, in which the poly-L-EG2Glu formed the micelle core and maintained helical conformation. However, extension of thermal annealing time drove the secondary structure transformation of the poly-L-EG2Glu block from helical conformation to β-sheet, which accounted for an assembly structure transition from wormlike micelles to nanoribbons. The critical factor was that poly-L-EG2Glu block can undergo thermo-induced hydrophobicity and conformation transformation, which offered an additional parameter to tune the nature of molecular interactions, i.e., intermolecular versus intramolecular hydrogen bonding interactions. The corresponding conformation and assembly structure changes were characterized using FTIR and electron microscopy, respectively.

UI MeSH Term Description Entries
D008968 Molecular Conformation The characteristic three-dimensional shape of a molecule. Molecular Configuration,3D Molecular Structure,Configuration, Molecular,Molecular Structure, Three Dimensional,Three Dimensional Molecular Structure,3D Molecular Structures,Configurations, Molecular,Conformation, Molecular,Conformations, Molecular,Molecular Configurations,Molecular Conformations,Molecular Structure, 3D,Molecular Structures, 3D,Structure, 3D Molecular,Structures, 3D Molecular
D010316 Particle Size Relating to the size of solids. Particle Sizes,Size, Particle,Sizes, Particle
D010455 Peptides Members of the class of compounds composed of AMINO ACIDS joined together by peptide bonds between adjacent amino acids into linear, branched or cyclical structures. OLIGOPEPTIDES are composed of approximately 2-12 amino acids. Polypeptides are composed of approximately 13 or more amino acids. PROTEINS are considered to be larger versions of peptides that can form into complex structures such as ENZYMES and RECEPTORS. Peptide,Polypeptide,Polypeptides
D011092 Polyethylene Glycols Polymers of ETHYLENE OXIDE and water, and their ethers. They vary in consistency from liquid to solid depending on the molecular weight indicated by a number following the name. They are used as SURFACTANTS, dispersing agents, solvents, ointment and suppository bases, vehicles, and tablet excipients. Some specific groups are NONOXYNOLS, OCTOXYNOLS, and POLOXAMERS. Macrogols,Polyoxyethylenes,Carbowax,Macrogol,Polyethylene Glycol,Polyethylene Oxide,Polyethyleneoxide,Polyglycol,Glycol, Polyethylene,Glycols, Polyethylene,Oxide, Polyethylene,Oxides, Polyethylene,Polyethylene Oxides,Polyethyleneoxides,Polyglycols,Polyoxyethylene
D013499 Surface Properties Characteristics or attributes of the outer boundaries of objects, including molecules. Properties, Surface,Property, Surface,Surface Property
D013696 Temperature The property of objects that determines the direction of heat flow when they are placed in direct thermal contact. The temperature is the energy of microscopic motions (vibrational and translational) of the particles of atoms. Temperatures
D058105 Polymerization Chemical reaction in which monomeric components are combined to form POLYMERS (e.g., POLYMETHYLMETHACRYLATE). Polymerizations

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