Distinct thermoresponsive behaviour of oligo- and poly-ethylene glycol protected gold nanoparticles in concentrated...

In this work, the methoxy terminated oligo- and polyethylene glycol of different chain lengths (EGn, n = 7, 18, 45 and 136) is grafted on AuNP surfaces under conditions where they attain maximum grafting densities. These EGn-AuNPs gain stability relative to the pristine c-AuNPs in aqueous solutions and in a wide temperature interval and they form stable suspensions in solutions of high NaCl concentrations. To show the thermoresponsive properties of these EGn-AuNPs, temperature titration experiments are carried out in the presence of increasing amounts of salts. The concentrations of NaCl are chosen by checking the stability of EGn-AuNPs at room temperature and choosing the highest concentrations that allow them to form stable suspensions. The analysis of the temperature titration experiments monitored by UV-visible spectroscopy and dynamic light scattering allows us to establish the existence of transitions from individual to assembled nanoparticles, the reversibility of the temperature transitions and hysteretic behaviour in these systems. While EG7-AuNPs only show reversible temperature transitions in the presence of 5 mM NaCl, EG18-AuNPs do up to 1 M NaCl, becoming only partially reversible in 2 M NaCl. The titrations of EG45-AuNPs in 3 and 5 M NaCl show irreversible temperature transitions. Finally, EG136-AuNPs present a complex and interesting behaviour with two temperature transitions, the first one showing hysteresis and the second being reversible.