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Polish Academy of Sciences

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Katsuhiko Ariga

National Institute for Materials Science (JP)

Recent publications
1.  Sciortino F., Mir S.H., Pakdel A., Oruganti A., Abe H., Witecka A., Awang Shri D.N., Rydzek G., Ariga K., Saloplastics as multiresponsive ion exchange reservoirs and catalyst supports, Journal of Materials Chemistry A, ISSN: 2050-7488, DOI: 10.1039/d0ta05901c, Vol.8, No.34, pp.17713-17724, 2020

Abstract:
Developing saloplastics composed of Compacted Polyelectrolyte Complexes (COPECs) represents a promising strategy for assembling multifunctional and processable polymer matrices in a simple manner. Here, a comprehensive investigation of the potential application of saloplastics as ion reactors for designing catalysts has been performed. First the propensity of saloplastics to exchange and concentrate ions has been elucidated through investigating the influence of Na+ to Cu2+ cation exchange within COPECs assembled from poly(methacrylic acid) (PMAA) and poly(allylamine hydrochloride) (PAH). The multi-scale responses of PMAA/PAH COPECs upon incubation with CuCl2 solutions at pH 3 and 4.5 were investigated chemically by ATR-FTIR, ICP, XPS, DSC and TGA, morphologically by SEM, and mechanically by strain-to-break measurements. Both the amplitude and the kinetics of the COPEC response were driven by the deprotonation rate of PMAA chains, enabling the formation of bridge complexes with Cu2+ and impacting the saloplastic's composition (water content and polyelectrolytes), structure (emergence of macropores) and mechanical properties. Kinetic-based tuning of the molality of copper ions trapped in PMAA/PAH COPECs was demonstrated, enabling the usage of saloplastics as reactors. This ability allowed controlling the growth of Cu(0) nanoparticles in saloplastics by thermal annealing, ultimately adjusting their catalytic activity toward carbon monoxide (CO) oxidation. This work highlights how the ionic reservoir properties of saloplastics must be accounted for when designing the applications of COPEC-based materials.

Affiliations:
Sciortino F. - other affiliation
Mir S.H. - other affiliation
Pakdel A. - World Premier International Center for Materials Nanoarchitectonics (MANA) (JP)
Oruganti A. - other affiliation
Abe H. - other affiliation
Witecka A. - IPPT PAN
Awang Shri D.N. - Universiti Malaysia Pahang (MY)
Rydzek G. - National Institute for Materials Science (JP)
Ariga K. - National Institute for Materials Science (JP)
2.  Rydzek G., Pakdel A., Witecka A., Shri D.N.A., Gaudière F., Nicolosi V., Mokarian-Tabari P., Schaaf P., Boulmedais F., Ariga K., pH-Responsive Saloplastics Based on Weak Polyelectrolytes: From Molecular Processes to Material Scale Properties, Macromolecules, ISSN: 0024-9297, DOI: 10.1021/acs.macromol.8b00609, Vol.51, No.12, pp.4424-4434, 2018

Abstract:
Compact polyelectrolyte complexes (COPECs), also named saloplastics, represent a new class of material with high fracture strain and self-healing properties. Here, COPECs based on poly(methacrylic acid) (PMAA) and poly(allylamine hydrochloride) (PAH) were prepared by centrifugation at pH 7. The influence of postassembly pH changes was monitored chemically by ATR-FTIR, ICP, DSC, and TGA, morphologically by SEM, and mechanically by strain to break measurements. Postassembly pH stimuli misbalanced the charge ratio in COPECs, impacting their concentration in counterions, cross-link density, and polymer chain mobility. At the material level, changes were observed in the porosity, composition, water content, and mechanical properties of COPECs. The cross-link density was a prominent factor governing the saloplastic's composition and water content. However, the porosity and mechanical properties were driven by several factors including salt-induced plasticization and conformational changes of polyelectrolytes. This work illustrates how multiple-scale consequences arise from a single change in the environment of COPECs, providing insights for future design of stimuli-responsive materials.

Affiliations:
Rydzek G. - National Institute for Materials Science (JP)
Pakdel A. - World Premier International Center for Materials Nanoarchitectonics (MANA) (JP)
Witecka A. - IPPT PAN
Shri D.N.A. - Universiti Malaysia Pahang (MY)
Gaudière F. - Université de Strasbourg (FR)
Nicolosi V. - Trinity College (IE)
Mokarian-Tabari P. - Trinity College (IE)
Schaaf P. - Institut National de la Santé et de la Recherche Médicale (FR)
Boulmedais F. - Université de Strasbourg (FR)
Ariga K. - National Institute for Materials Science (JP)

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