PMID- 29675246 OWN - NLM STAT- PubMed-not-MEDLINE LR - 20220216 IS - 2041-6520 (Print) IS - 2041-6539 (Electronic) IS - 2041-6520 (Linking) VI - 9 IP - 7 DP - 2018 Feb 21 TI - A water-soluble supramolecular complex that mimics the heme/copper hetero-binuclear site of cytochrome c oxidase. PG - 1989-1995 LID - 10.1039/c7sc04732k [doi] AB - In mitochondria, cytochrome c oxidase (CcO) catalyses the reduction of oxygen (O(2)) to water by using a heme/copper hetero-binuclear active site. Here we report a highly efficient supramolecular approach for the construction of a water-soluble biomimetic model for the active site of CcO. A tridentate copper(ii) complex was fixed onto 5,10,15,20-tetrakis(4-sulfonatophenyl)porphinatoiron(iii) (Fe(III)TPPS) through supramolecular complexation between Fe(III)TPPS and a per-O-methylated beta-cyclodextrin dimer linked by a (2,2':6',2''-terpyridyl)copper(ii) complex (Cu(II)TerpyCD(2)). The reduced Fe(II)TPPS/Cu(I)TerpyCD(2) complex reacted with O(2) in an aqueous solution at pH 7 and 25 degrees C to form a superoxo-type Fe(III)-O(2)(-)/Cu(I) complex in a manner similar to CcO. The pH-dependent autoxidation of the O(2) complex suggests that water molecules gathered at the distal Cu site are possibly involved in the Fe(III)-O(2)(-)/Cu(I) superoxo complex in an aqueous solution. Electrochemical analysis using a rotating disk electrode demonstrated the role of the FeTPPS/CuTerpyCD(2) hetero-binuclear structure in the catalytic O(2) reduction reaction. FAU - Kitagishi, Hiroaki AU - Kitagishi H AUID- ORCID: 0000-0003-4682-7217 AD - Department of Molecular Chemistry and Biochemistry , Faculty of Science and Engineering , Doshisha University , Kyotanabe , Kyoto 610-0321 , Japan . Email: hkitagis@mail.doshisha.ac.jp. FAU - Shimoji, Daiki AU - Shimoji D AD - Department of Molecular Chemistry and Biochemistry , Faculty of Science and Engineering , Doshisha University , Kyotanabe , Kyoto 610-0321 , Japan . Email: hkitagis@mail.doshisha.ac.jp. FAU - Ohta, Takehiro AU - Ohta T AUID- ORCID: 0000-0003-4140-5293 AD - Picobiology Institute , Graduate School of Life Science , University of Hyogo , RSC-UH LP Center , Hyogo 679-5148 , Japan. FAU - Kamiya, Ryo AU - Kamiya R AD - Department of Molecular Chemistry and Biochemistry , Faculty of Science and Engineering , Doshisha University , Kyotanabe , Kyoto 610-0321 , Japan . Email: hkitagis@mail.doshisha.ac.jp. FAU - Kudo, Yasuhiro AU - Kudo Y AD - Department of Molecular Chemistry and Biochemistry , Faculty of Science and Engineering , Doshisha University , Kyotanabe , Kyoto 610-0321 , Japan . Email: hkitagis@mail.doshisha.ac.jp. FAU - Onoda, Akira AU - Onoda A AUID- ORCID: 0000-0002-5791-4386 AD - Department of Applied Chemistry , Graduate School of Engineering , Osaka University , 2-1 Yamadaoka , Suita 565-0871 , Japan. FAU - Hayashi, Takashi AU - Hayashi T AUID- ORCID: 0000-0002-2215-935X AD - Department of Applied Chemistry , Graduate School of Engineering , Osaka University , 2-1 Yamadaoka , Suita 565-0871 , Japan. FAU - Weiss, Jean AU - Weiss J AUID- ORCID: 0000-0001-7753-8958 AD - Institut de Chimie de Strasbourg , UMR 7177 , CNRS , Universite de Strasbourg , 4 Rue Blaise Pascal , 67000 Strasbourg , France. FAU - Wytko, Jennifer A AU - Wytko JA AD - Institut de Chimie de Strasbourg , UMR 7177 , CNRS , Universite de Strasbourg , 4 Rue Blaise Pascal , 67000 Strasbourg , France. FAU - Kano, Koji AU - Kano K AD - Department of Molecular Chemistry and Biochemistry , Faculty of Science and Engineering , Doshisha University , Kyotanabe , Kyoto 610-0321 , Japan . Email: hkitagis@mail.doshisha.ac.jp. LA - eng PT - Journal Article DEP - 20180115 PL - England TA - Chem Sci JT - Chemical science JID - 101545951 PMC - PMC5892347 EDAT- 2018/04/21 06:00 MHDA- 2018/04/21 06:01 PMCR- 2018/01/15 CRDT- 2018/04/21 06:00 PHST- 2017/11/02 00:00 [received] PHST- 2018/01/12 00:00 [accepted] PHST- 2018/04/21 06:00 [entrez] PHST- 2018/04/21 06:00 [pubmed] PHST- 2018/04/21 06:01 [medline] PHST- 2018/01/15 00:00 [pmc-release] AID - c7sc04732k [pii] AID - 10.1039/c7sc04732k [doi] PST - epublish SO - Chem Sci. 2018 Jan 15;9(7):1989-1995. doi: 10.1039/c7sc04732k. eCollection 2018 Feb 21.