title: Hemoglobin and red blood cells catalyze atom transfer radical polymerization.
abstract: Hemoglobin (Hb) is a promiscuous protein that not only transports oxygen, but also catalyzes several biotransformations. A novel in vitro catalytic activity of Hb is described. Bovine Hb and human erythrocytes were found to display ATRPase activity, i.e., they catalyzed the polymerization of vinyl monomers under conditions typical for atom transfer radical polymerization (ATRP). N-isopropylacrylamide (NIPAAm), poly(ethylene glycol) methyl ether acrylate (PEGA), and poly(ethylene glycol) methyl ether methacrylate (PEGMA) were polymerized using organobromine initiators and the reducing agent ascorbic acid in acidic aqueous solution. In order to avoid chain transfer from polymer radicals to Hb's cysteine residues, the accessible cysteines were blocked by a reaction with a maleimide. The formation of polymers with bromine chain ends, relatively low polydispersity indices (PDI), first order kinetics and an increase in the molecular weight of poly(PEGA) and poly(PEGMA) upon conversion indicate that control of the polymerization by Hb occurred via reversible atom transfer between the protein and the growing polymer chain. For poly(PEGA) and poly(PEGMA), the reactions proceeded with a good to moderate degree of control. Sodium dodecyl sulfate (SDS) gel electrophoresis, circular dichroism spectroscopy, and time-resolved ultraviolet-visible (UV-vis) spectroscopy revealed that the protein was stable during polymerization, and only underwent minor conformational changes. As Hb and erythrocytes are readily available, environmentally friendly, and nontoxic, their ATRPase activity is a useful tool for synthetic polymer chemistry. Moreover, this novel activity enhances the understanding of Hb's redox chemistry in the presence of organobromine compounds.
authors.affiliation: Department of Chemistry, University of Basel, Switzerland.
authors.forename: Tilana B
authors.initials: TB
authors.lastname: Silva
authors.forename: Mariana
authors.initials: M
authors.lastname: Spulber
authors.forename: Marzena K
authors.initials: MK
authors.lastname: Kocik
authors.forename: Farzad
authors.initials: F
authors.lastname: Seidi
authors.forename: Himanshu
authors.initials: H
authors.lastname: Charan
authors.forename: Martin
authors.initials: M
authors.lastname: Rother
authors.forename: Severin J
authors.initials: SJ
authors.lastname: Sigg
authors.forename: Kasper
authors.initials: K
authors.lastname: Renggli
authors.forename: Gergely
authors.initials: G
authors.lastname: Kali
authors.forename: Nico
authors.initials: N
authors.lastname: Bruns
mesh_terms: D000180:Acrylic Resins / Q000737:chemistry; D000818:Animals; D001205:Ascorbic Acid / Q000737:chemistry*; D055162:Biocatalysis; D002417:Cattle; D004912:Erythrocytes / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry*; D006454:Hemoglobins / Q000737:chemistry*; D006801:Humans; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D010084:Oxidation-Reduction; D011092:Polyethylene Glycols / Q000737:chemistry; D058105:Polymerization; D011109:Polymethacrylic Acids / Q000737:chemistry; D011145:Polyvinyls / Q000737:chemistry; D055550:Protein Stability; D019163:Reducing Agents / Q000737:chemistry; D000099166:Polyacrylamides
chemical_list: D000180:Acrylic Resins; D001205:Ascorbic Acid; D005609:Free Radicals; D006454:Hemoglobins; D011092:Polyethylene Glycols; D011109:Polymethacrylic Acids; D011145:Polyvinyls; D019163:Reducing Agents; D000099166:Polyacrylamides