Thermoresponsivity of poly(N-isopropylacrylamide) microgels in water-trehalose solution and its relation to protein behavior

JOURNAL OF COLLOID AND INTERFACE SCIENCE

卷:604

Article

Rosi, Benedetta Petra¹  Tavagnacco, Letizia^2,3  Comez, Lucia⁴  Sassi, Paola⁵  Ricci, Maria⁵  Buratti, Elena^2,3  Bertoldo, Monica^6,7  Petrillo, Caterina¹  Zaccarelli, Emanuela^2,3  Chiessi, Ester⁸  Corezzi, Silvia¹ 

[1] Univ Perugia, Dipartimento Fis & Geol, I-06123 Perugia, Italy

[2] Sapienza Univ Roma, CNR, ISC, I-00185 Rome, Italy

[3] Sapienza Univ Roma, Dipartimento Fis, I-00185 Rome, Italy

[4] Univ Perugia, CNR, IOM, Dipartimento Fis & Geol, I-06123 Perugia, Italy

[5] Univ Perugia, Dipartimento Chim Biol & Biotecnol, I-06123 Perugia, Italy

[6] Univ Ferrara, Dipartimento Sci Chim Farmaceut & Agr, I-44121 Ferrara, Italy

[7] CNR, ISOF, Area Ric, I-40129 Bologna, Italy

[8] Univ Roma Tor Vergata, Dipartimento Sci & Tecnol Chim, I-00133 Rome, Italy

关键词: Poly(N-isopropylacrylamide) (PNIPAM);    Microgels;    Trehalose;    Cosolvents and cosolutes;    Lower critical solution temperature (LCST);    Volume phase transition;    Biomimetic material;    Bioprotection;    Hydration water;   

DOI  :  10.1016/j.jcis.2021.07.006

来源: Elsevier

【 摘 要 】

Hypotheses: Additives are commonly used to tune macromolecular conformational transitions. Among additives, trehalose is an excellent bioprotectant and among responsive polymers, PNIPAM is the most studied material. Nevertheless, their interaction mechanism so far has only been hinted without direct investigation, and, crucially, never elucidated in comparison to proteins. Detailed insights would help understand to what extent PNIPAM microgels can effectively be used as synthetic biomimetic materials, to reproduce and study, at the colloidal scale, isolated protein behavior and its sensitivity to interactions with specific cosolvents or cosolutes. Experiments: The effect of trehalose on the swelling behavior of PNIPAM microgels was monitored by dynamic light scattering; Raman spectroscopy and molecular dynamics simulations were used to explore changes of solvation and dynamics across the swelling-deswelling transition at the molecular scale. Findings: Strongly hydrated trehalose molecules develop water-mediated interactions with PNIPAM microgels, thereby preserving polymer hydration below and above the transition while drastically inhibiting local motions of the polymer and of its hydration shell. Our study, for the first time, demonstrates that slowdown of dynamics and preferential exclusion are the principal mechanisms governing trehalose effect on PNIPAM microgels, at odds with preferential adsorption of alcohols, but in full analogy with the behavior observed in trehalose-protein systems. (c) 2021 Elsevier Inc. All rights reserved.

【 授权许可】

Free