Part of the solution: A PEG with a discrete triangular structure exhibits hydrophilicity/hydrophobicity switching upon increasing temperatures, and suppresses the thermal aggregation of lysozyme to retain nearly 80 % of the enzymatic activity. CD and NMR spectroscopic studies revealed that, with the structured PEG, the higher-order structures of lysozyme persist at high temperature, and the native conformation is recovered after cooling.

Teil der Lösung: Ein Polyethylenglycol (PEG) mit diskreter Dreieckstruktur wechselt bei Temperaturerhöhung von hydrophil nach hydrophob und verhindert die thermische Aggregation von Lysozym, das so nahezu 80 % seiner enzymatischen Aktivität behält. CD‐ und NMR‐spektroskopischen Studien zufolge bleiben in Gegenwart des strukturierten PEG die Lysozymstrukturen höherer Ordnung auch bei hohen Temperaturen erhalten, und nach dem Abkühlen liegt wieder die native Konformation vor.

Thermoresponsive materials with a lower critical solution temperature (LCST) are receiving growing attention, of which examples of non-polymeric small molecules are limited. Monodisperse oligoethylene glycol amphiphiles that contain aromatic units with a LCST in water have been developed and applied to peptide extraction. Concentration-dependent hysteretic transmittance changes were observed in response to temperature elevation and reduction. Dynamic light scattering measurements and phase contrast microscopy revealed the formation of micrometer-sized aggregates upon heating at a concentration above 5.0 mM; these aggregates self-assembled to form larger aggregates upon cooling before dissolution. The "interaggregate" interactions are likely to cause the hysteretic behavior. As an application of this thermodriven phase separation, selective extraction of peptide fragments containing high percentages of hydrophobic and aromatic amino acid residues was successfully demonstrated.

No abstract

As a new type of topological poly(ethylene glycol) (PEG) analogue, a series of polygonal PEGs with digonal to hexagonal structures were developed. Polygonal PEGs with structures between the digonal and tetragonal types showed molecular-level dispersion in water at 20 °C, whereas the pentagonal and hexagonal PEGs aggregated, which is suggestive of enhanced hydrophobicity by ring expansion. Heating induced conformational changes in the polygonal PEGs and increased their hydrophobicity. Among the polygonal PEGs, only the trigonal and hexagonal PEGs showed a distinct thermal response to form and increase the size of the aggregates, respectively. Given that tetragonal and pentagonal PEGs only marginally responded to heat treatment, the thermal responses are likely due to a topological effect. At low temperatures, the larger polygonal PEGs are more restricted despite the expanded rings. The trigonal PEG showed the largest change in mobility, whereas the tetragonal PEG exhibited the smallest change. Hence, the topology of the polygonal PEGs influences the intramolecular packing and the local dynamics.