PMID- 35969637 OWN - NLM STAT- MEDLINE DCOM- 20220826 LR - 20220826 IS - 1944-8252 (Electronic) IS - 1944-8244 (Linking) VI - 14 IP - 33 DP - 2022 Aug 24 TI - Carbonic Anhydrase-Mimicking Supramolecular Nanoassemblies for Developing Carbon Capture Membranes. PG - 37595-37607 LID - 10.1021/acsami.2c06270 [doi] AB - As a ubiquitous family of enzymes with high performance in converting carbon dioxide (CO(2)) into bicarbonate, carbonic anhydrases (CAs) sparked enormous attention for carbon capture. Nevertheless, the high cost and operational instability of CAs hamper their practical relevance, and the utility of CAs is mainly limited to aqueous applications where CO(2)-to-bicarbonate conversion is possible. Taking advantage of the chemical motif that endows CA-like active sites (metal-coordinated histidine), here we introduce a new line of high-performance gas separation membranes with CO(2)-philic behavior. We first self-assembled a histidine-based bolaamphiphile (His-Bola) molecule in the aqueous phase and coordinated the resulting entities with divalent zinc. Optimizing the supramolecular synthesis conditions ensured that the resultant nanoparticles (His-NPs) exhibit high CO(2) affinity and catalytic activity. We then exploited the His-NPs as nanofillers to enhance the separation performance of Pebax MH 1657. The hydrogen-bonding interactions allowed the dispersion of His-NPs within the polymer matrix uniformly, as confirmed by microscopic, spectroscopic, and thermal analyses. The imidazole and amine functionalities of His-NPs enhanced the solubility of CO(2) molecules in the polymer matrix. The CA-mimic active sites of His-NPs nanozymes, on the other hand, catalyzed the reversible hydration of CO(2) molecules in humid conditions, facilitating their transport across the membranes. The resulting nanocomposite membranes displayed excellent CO(2) separation performance, with a high level of stability. At a filling ratio as low as 3 wt %, we achieved a CO(2) permeability of >145 Barrer and a CO(2)/N(2) selectivity of >95 with retained performance under humid continuous gas feeds. The bio-inspired approach presented in this work offers a promising platform for designing durable and highly selective CO(2) capture membranes. FAU - Nilouyal, Somaye AU - Nilouyal S AD - Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University, 606-8501 Kyoto, Japan. AD - Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-Ku, 615-8510 Kyoto, Japan. FAU - Karahan, H Enis AU - Karahan HE AUID- ORCID: 0000-0002-7753-1024 AD - Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University, 606-8501 Kyoto, Japan. AD - Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-Ku, 615-8510 Kyoto, Japan. AD - Synthetic Fuels & Chemicals Technology Center (ITU-SENTEK), Istanbul Technical University, Maslak, 34469 Istanbul, Turkey. FAU - Isfahani, Ali Pournaghshband AU - Isfahani AP AUID- ORCID: 0000-0001-5188-385X AD - Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University, 606-8501 Kyoto, Japan. AD - Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-Ku, 615-8510 Kyoto, Japan. FAU - Yamaguchi, Daisuke AU - Yamaguchi D AUID- ORCID: 0000-0001-9643-4513 AD - Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University, 606-8501 Kyoto, Japan. AD - Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-Ku, 615-8510 Kyoto, Japan. FAU - Gibbons, Andrew H AU - Gibbons AH AD - Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University, 606-8501 Kyoto, Japan. AD - Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-Ku, 615-8510 Kyoto, Japan. FAU - Ito, Masateru M M AU - Ito MMM AD - Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University, 606-8501 Kyoto, Japan. AD - Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-Ku, 615-8510 Kyoto, Japan. FAU - Sivaniah, Easan AU - Sivaniah E AD - Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University, 606-8501 Kyoto, Japan. AD - Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-Ku, 615-8510 Kyoto, Japan. FAU - Ghalei, Behnam AU - Ghalei B AUID- ORCID: 0000-0003-2848-9138 AD - Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University, 606-8501 Kyoto, Japan. AD - Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-Ku, 615-8510 Kyoto, Japan. LA - eng PT - Journal Article DEP - 20220815 PL - United States TA - ACS Appl Mater Interfaces JT - ACS applied materials & interfaces JID - 101504991 RN - 0 (Bicarbonates) RN - 0 (Polymers) RN - 142M471B3J (Carbon Dioxide) RN - 4QD397987E (Histidine) RN - EC 4.2.1.1 (Carbonic Anhydrases) SB - IM MH - Bicarbonates MH - Carbon Dioxide/chemistry MH - *Carbonic Anhydrases/chemistry MH - Histidine MH - Polymers OTO - NOTNLM OT - bolaamphiphiles OT - carbon dioxide OT - membrane technology OT - nanozyme OT - self-assembly EDAT- 2022/08/16 06:00 MHDA- 2022/08/27 06:00 CRDT- 2022/08/15 13:52 PHST- 2022/08/16 06:00 [pubmed] PHST- 2022/08/27 06:00 [medline] PHST- 2022/08/15 13:52 [entrez] AID - 10.1021/acsami.2c06270 [doi] PST - ppublish SO - ACS Appl Mater Interfaces. 2022 Aug 24;14(33):37595-37607. doi: 10.1021/acsami.2c06270. Epub 2022 Aug 15.