@misc{10481/90290, year = {2024}, month = {4}, url = {https://hdl.handle.net/10481/90290}, abstract = {Finding new ways to tune the behavior of thermoresponsive microgels in bulk and confined at 2D liquid interfaces is key to achieve a deeper understanding and control of these smart materials. We studied the interaction of positively and negatively charged pNIPAM microgels with the Keggin-type polyoxometalates Na3PW12O40 (POM3−) and H4SiW12O40 (POM4−). In bulk, we observed charge inversions of the positively charged microgels below and above the volume phase transition temperature (VPTT) at significantly low POM concentrations as 5 ⋅ 10−5 M. In the presence of POM, both microgels exhibited a deswelling-swelling-deswelling behavior below the VPTT, and a two-step further deswelling above the VPTT for the positively charged microgels. When the later were confined at 2D water/air interfaces, adding 10−5 M of POM3− below the VPTT was equivalent to heating above the VPTT and compressing the monolayer from 5 to 20 mN m−1. Above the VPTT, the diameter at the interface did not change while the portion immersed in the subphase further deswelled, in agreement with the behavior in bulk. Adding more POM3− did not change the diameter at the interface nor the height of the microgels, showing a saturation effect in 2D. The restructuring of the pNIPAM polymeric network by the POM3− was characterized by EDS mapping and XPS. The microgel monolayers with POM3− improved their resistance to plasma etching, which could be useful for soft colloidal lithography.}, organization = {Universidad de Granada / CBUA}, organization = {University of Granada}, organization = {University of Málaga}, organization = {MCIN/AEI/ 10.13039/501100011033 PID2020-116615RA-I00}, organization = {EMERGIA EMC21_00008}, organization = {Junta de Andalucía PY20-00241, A-FQM-90-UGR20}, organization = {FEDER “ERDF A way of making Europe”}, publisher = {Elsevier}, keywords = {Microgels}, keywords = {Keggin-type polyoxometalates}, keywords = {Interface}, keywords = {Ion specificity}, keywords = {Self-assembly}, keywords = {Soft colloidal lithography}, title = {Tuning the bulk behavior and 2D interfacial self-assembly of microgels by keggin-type polyoxometalate ionic specificity}, author = {Rubio Andrés, Antonio and Bastos González, Delfina María and Fernández Rodríguez, Miguel Ángel}, }