All-In-One "Schizophrenic" Self-Assembly of Orthogonally Tuned Thermoresponsive Diblock Copolymers.

Smart, fully orthogonal switching was realized in a highly biocompatible diblock copolymer system with variable trigger-induced aqueous self-assembly. The polymers are composed of nonionic and zwitterionic blocks featuring lower and upper critical solution temperatures (LCSTs and UCSTs). In the system investigated, diblock copolymers from poly( N-isopropyl methacrylamide) (PNIPMAM) and a poly(sulfobetaine methacrylamide), systematic variation of the molar mass of the latter block allowed for shifting the UCST of the latter above the LCST of the PNIPMAM block in a salt-free condition.

Block and Gradient Copoly(2-oxazoline) Micelles: Strikingly Different on the Inside.

Herein, we provide a direct proof for differences in the micellar structure of amphiphilic diblock and gradient copolymers, thereby unambiguously demonstrating the influence of monomer distribution along the polymer chains on the micellization behavior. The internal structure of amphiphilic block and gradient co poly(2-oxazolines) based on the hydrophilic poly(2-methyl-2-oxazoline) (PMeOx) and the hydrophobic poly(2-phenyl-2-oxazoline) (PPhOx) was studied in water and water-ethanol mixtures by small-angle X-ray scattering (SAXS), small-angle neutron scattering (SANS), static and dynamic light scattering (SLS/DLS), and H NMR spectroscopy. Contrast matching SANS experiments revealed that block copolymers form micelles with a uniform density profile of the core.

pH Responsiveness of hydrogels formed by telechelic polyampholytes.

We investigate the influence of pH on the rheological and structural properties of hydrogels formed by hydrophobic association of the sticky ends of the triblock terpolymer poly(methyl methacrylate)-b-poly(2-(diethylamino)ethyl methacrylate-co-methacrylic acid)-b-poly(methyl methacrylate) (PMMA-b-P(DEA-co-MAA)-b-PMMA). The middle block is a weak polyampholyte having a pH dependent charge density and sign, which enables tuning of the rheological and structural properties by pH variation. Small-angle neutron scattering (SANS) studies of solutions in DO at 0.

Quantifying the Interactions in the Aggregation of Thermoresponsive Polymers: The Effect of Cononsolvency.

The aggregation kinetics of thermoresponsive core-shell micelles with a poly(N-isopropyl acrylamide) shell in pure water or in mixtures of water with the cosolvents methanol or ethanol at mole fractions of 5% is investigated during a temperature jump across the respective cloud point. Characteristically, these mixtures give rise to cononsolvency behavior. At the cloud point, aggregates are formed, and their growth is followed with time-resolved small-angle neutron scattering.