Coil–globule transition

Polymer science
Properties Architecture Tacticity Morphology Degradation Phase behavior Mark–Houwink theory UCST LCST Flory–Huggins solution theory Coil–globule transition
Synthesis Chain-growth polymerization Free-radical polymerization Controlled radical polymerization ATRP RAFT Nitroxide-mediated radical polymerization Step-growth polymerization Condensation polymerization Addition polymerization
Classification Functional type Polyolefin Polyethylene Polypropylene Polyisobutylene Polyurethane Polyester Polycarbonate Vinyl polymers PVC PVA PVAc Polystyrene Structure Homopolymer Copolymer Gels Hydrogels Self-healing hydrogels
Characterization GPC FTIR X-ray crystallography DSC NMR TGA DMA Rheology Rheometry Viscometry
Scientists Flory Heeger MacDiarmid Shirakawa Natta Edwards de Gennes Ziegler Staudinger Goodyear Baekeland Hayward Braconnot
Applications Industrial production Extrusion Blow molding Applied coatings Protective Coatings 3D printing Consumer products Tires Whitewalls Cookware and bakeware Bakelite Food Container Vinyl record Kevlar Plastic bottle Plastic bag
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In polymer physics, the coil–globule transition is the collapse of a macromolecule from an expanded coil state through an ideal coil state to a collapsed globule state, or vice versa. The coil–globule transition is of importance in biology due to the presence of coil-globule transitions in biological macromolecules such as proteins^[1] and DNA.^[2] It is also analogous with the swelling behavior of a crosslinked polymer gel and is thus of interest in biomedical engineering for controlled drug delivery. A particularly prominent example of a polymer possessing a coil-globule transition of interest in this area is that of Poly(N-isopropylacrylamide) (PNIPAAm).^[3]

In its coil state, the radius of gyration of the macromolecule scales as its chain length to the three-fifths power. As it passes through the coil–globule transition, it shifts to scaling as chain length to the half power (at the transition) and finally to the one third power in the collapsed state.^[4] The direction of the transition is often specified by the constructions 'coil-to-globule' or 'globule-to-coil' transition.

This transition is associated with the transition of a polymer chain from good solvent behavior through ideal or theta solvent behavior to poor solvent behavior. The canonical coil–globule transition is associated with the Upper critical solution temperature and the associated Flory theta point. In this case, collapse occurs with cooling and results from favorable attractive energy of the polymer to itself. A second type of coil–globule transition is instead associated with the lower critical solution temperature and its corresponding theta point. This collapse occurs with increasing temperature and is driven by an unfavorable entropy of mixing.^[5] An example of this type is embodied by the polymer PNIPAAM, mentioned above. Coil globule transitions may also be driven by charge effects, in the case of polyelectrolytes. In this case pH and ionic strength changes within the solution may trigger collapse, with increasing counterion concentration generally leading to collapse in a uniformly charged polyelectrolyte.^[6] In polyampholytes containing both positive and negative charges, the opposite may hold true.

• Upper critical solution temperature
• Lower critical solution temperature
• Critical point
• Ideal solution