ba8aa529fc386516340d1d59afbf9ac9 IntChiMol_a2022v23n23p14640.pdf 26b746abea26c7531e67a7647e60355dcd164802 IntChiMol_a2022v23n23p14640.pdf 315d1453abb3e71a4e5df56f5c5fcf05adbf9e305012b55ac9ecf2e8ea304926 IntChiMol_a2022v23n23p14640.pdf Title: Photocatalytic Hydrogen Production and Carbon Dioxide Reduction Catalyzed by an Artificial Cobalt Hemoprotein Subject: The covalent insertion of a cobalt heme into the cavity of an artificial protein named alpha Rep (Rep) leads to an artificial cobalt hemoprotein that is active as a catalyst not only for the photo-induced production of H2, but also for the reduction of CO2 in a neutral aqueous solution. This new artificial metalloenzyme has been purified and characterized by Matrix Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry (MALDI-TOF MS), circular dichroism, and UltraViolet–Visible spectroscopy. Using theoretical experiments, the structure of this biohybrid and the positioning of the residues near the metal complex were examined, which made it possible to complete the coordination of the cobalt ion by an axial glutamine Gln283 ligand. While the Co(III)–porphyrin catalyst alone showed weak catalytic activity for both reactions, 10 times more H2 and four times more CO2 were produced when the Co(III)–porphyrin complex was buried in the hydrophobic cavity of the protein. This study thus provides a solid basis for further improvement of these biohybrids using well-designed modifications of the second and outer coordination sphere by site-directed mutagenesis of the host protein. Keywords: artificial metalloenzymes; cobalt porphyrin; proton reduction; CO2 reduction; catalysis Author: Guillermo A. Oliveira Udry, Laura Tiessler-Sala, Eva Pugliese, Agathe Urvoas, Zakaria Halime, Jean-Didier Maréchal, Jean-Pierre Mahy and Rémy Ricoux Creator: LaTeX with hyperref Producer: pdfTeX-1.40.21 CreationDate: Thu Nov 24 08:10:50 2022 CET ModDate: Thu Nov 24 08:24:57 2022 CET Tagged: no UserProperties: no Suspects: no Form: none JavaScript: no Pages: 15 Encrypted: no Page size: 595.276 x 841.89 pts (A4) Page rot: 0 File size: 3544608 bytes Optimized: no PDF version: 1.7 name type encoding emb sub uni object ID ------------------------------------ ----------------- ---------------- --- --- --- --------- EROCFA+VnURWPalladioL Type 1 Custom yes yes no 10 0 OVPTGN+EURM10 Type 1 Builtin yes yes no 15 0 PVJDFL+URWPalladioL-Bold Type 1 Custom yes yes no 19 0 BELHPM+URWPalladioL-Roma Type 1 Custom yes yes no 24 0 UOVBLT+URWPalladioL-Ital Type 1 Custom yes yes no 28 0 BTFGED+VnURWPalladioL-Bold Type 1 Custom yes yes no 32 0 IRWHZX+TimesNewRomanPSMT Type 1C WinAnsi yes yes no 50 0 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no 332 0 FIAFHI+PalatinoLinotype,Italic TrueType WinAnsi yes yes no 335 0 IOLAWT+PazoMath-Italic Type 1 Builtin yes yes no 345 0 Jhove (Rel. 1.22.1, 2019-04-17) Date: 2023-09-22 02:34:09 CEST RepresentationInformation: IntChiMol_a2022v23n23p14640.pdf ReportingModule: PDF-hul, Rel. 1.12.1 (2019-04-17) LastModified: 2023-09-21 19:54:14 CEST Size: 3544608 Format: PDF Version: 1.7 Status: Well-Formed and valid SignatureMatches: PDF-hul MIMEtype: application/pdf PDFMetadata: Objects: 563 FreeObjects: 1 IncrementalUpdates: 0 DocumentCatalog: PageLayout: SinglePage PageMode: UseNone Outlines: Item: Title: Introduction Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@262b2c86 Item: Title: Results and Discussion Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@371a67ec Children: Item: Title: Synthesis of Co(III)Mal-PPIXMME 4 Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@5ed828d Item: Title: Biohybrid Preparation Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@50d0686 Item: Title: UV Visible Characteristics of the (A3A3')Y26C-4 Biohybrid Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@7a3d45bd Item: Title: Computational Modeling Studies Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@1e7c7811 Item: Title: Photocatalytic Activity of the (A3A3')Y26C-4 Biohybrid Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@77ec78b9 Children: Item: Title: Light-Driven H+ Reduction Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@1a3869f4 Item: Title: Light-Driven CO2 Reduction Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@a38d7a3 Item: Title: Materials and Methods Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@77f99a05 Children: Item: Title: Synthesis of Co(III)Mal-PPIX 4 Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@63440df3 Children: Item: Title: Protoporphyrin IX Dimethyl Ester (PPIX DME) Hydrolysis B23-ijms-2045580 Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@3aeaafa6 Item: Title: Synthesis of Maleimido-Ethylamido-Protoporphyrin IX Monomethyl Ester Mal-PPIX MME 3 Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@76a3e297 Item: Title: Insertion of Cobalt into Maleimido-Ethylamido-Protoporphyrin IX Monomethyl Ester Mal-PPIX MME Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@4d3167f4 Item: Title: Production and Purification of Rep Proteins Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@ed9d034 Children: Item: Title: Protein Production Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@6121c9d6 Item: Title: Protein Purification Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@87f383f Item: Title: Covalent Anchoring of Compound 4 into (A3A3')Y26C Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@4eb7f003 Item: Title: Photocatalysis Experiments Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@eafc191 Item: Title: Spectroscopic Characterization of the (A3A3')Y26C-4 Biohybrid Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@612fc6eb Item: Title: Spectroscopic Characterization of the (A3A3')Y26C-4 Biohybrid Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@1060b431 Item: Title: Computational Methods Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@612679d6 Item: Title: Conclusions Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@11758f2a Item: Title: References Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@e720b71 Info: Title: Photocatalytic Hydrogen Production and Carbon Dioxide Reduction Catalyzed by an Artificial Cobalt Hemoprotein Author: Guillermo A. Oliveira Udry, Laura Tiessler-Sala, Eva Pugliese, Agathe Urvoas, Zakaria Halime, Jean-Didier Maréchal, Jean-Pierre Mahy and Rémy Ricoux Subject: The covalent insertion of a cobalt heme into the cavity of an artificial protein named alpha Rep (Rep) leads to an artificial cobalt hemoprotein that is active as a catalyst not only for the photo-induced production of H2, but also for the reduction of CO2 in a neutral aqueous solution. This new artificial metalloenzyme has been purified and characterized by Matrix Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry (MALDI-TOF MS), circular dichroism, and UltraViolet Visible spectroscopy. Using theoretical experiments, the structure of this biohybrid and the positioning of the residues near the metal complex were examined, which made it possible to complete the coordination of the cobalt ion by an axial glutamine Gln283 ligand. While the Co(III) porphyrin catalyst alone showed weak catalytic activity for both reactions, 10 times more H2 and four times more CO2 were produced when the Co(III) porphyrin complex was buried in the hydrophobic cavity of the protein. This study thus provides a solid basis for further improvement of these biohybrids using well-designed modifications of the second and outer coordination sphere by site-directed mutagenesis of the host protein. 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