title: CORM-EDE1: A Highly Water-Soluble and Nontoxic Manganese-Based photoCORM with a Biogenic Ligand Sphere.
abstract: [Mn(CO)5Br] reacts with cysteamine and 4-amino-thiophenyl with a ratio of 2:3 in refluxing tetrahydrofuran to the complexes of the type [{(OC)3Mn}2(μ-SCH2CH2NH3)3]Br2 (1, CORM-EDE1) and [{(OC)3Mn}2(μ-SC6H4-4-NH3)3]Br2 (2, CORM-EDE2). Compound 2 precipitates during refluxing of the tetrahydrofuran solution as a yellow solid whereas 1 forms a red oil that slowly solidifies. Recrystallization of 2 from water yields the HBr-free complex [{(OC)3Mn}2(μ-S-C6H4-4-NH2)2(μ-SC6H4-4-NH3)] (3). The n-propylthiolate ligand (which is isoelectronic to the bridging thiolate of 1) leads to the formation of the di- and tetranuclear complexes [(OC)4Mn(μ-S-nPr)2]2 and [(OC)3Mn(μ-S-nPr)]4. CORM-EDE1 possesses ideal properties to administer carbon monoxide to biological and medicinal tissues upon irradiation (photoCORM). Isolated crystalline CORM-EDE1 can be handled at ambient and aerobic conditions. This complex is nontoxic, highly soluble in water, and indefinitely stable therein in the absence of air and phosphate buffer. CORM-EDE1 is stable as frozen stock in aqueous solution without any limitations, and these stock solutions maintain their CO release properties. The reducing dithionite does not interact with CORM-EDE1, and therefore, the myoglobin assay represents a valuable tool to study the release kinetics of this photoCORM. After CO liberation, the formation of MnHPO4 in aqueous buffer solution can be verified.
authors.affiliation: Institute of Inorganic and Analytical Chemistry, Friedrich Schiller University Jena , Humboldtstraße, 8, D-07743 Jena, Germany.
authors.forename: Ralf
authors.initials: R
authors.lastname: Mede
authors.affiliation: Leibniz Institute of Photonic Technology (IPHT) , Albert-Einstein-Straße 9, D-07745 Jena, Germany.
authors.forename: Moritz
authors.initials: M
authors.lastname: Klein
authors.affiliation: Center for Sepsis Control and Care (CSCC), Friedrich Schiller University Jena and Jena University Hospital , Erlanger Allee 101, D-07747 Jena, Germany.
authors.forename: Ralf A
authors.initials: RA
authors.lastname: Claus
authors.affiliation: Institute of Inorganic and Analytical Chemistry, Friedrich Schiller University Jena , Humboldtstraße, 8, D-07743 Jena, Germany.
authors.forename: Sven
authors.initials: S
authors.lastname: Krieck
authors.affiliation: Center for Molecular Biomedicine (CMB), Department of Biophysics, Friedrich Schiller University Jena and Jena University Hospital , Hans-Knöll-Straße 2, D-07745 Jena, Germany.
authors.forename: Stefanie
authors.initials: S
authors.lastname: Quickert
authors.affiliation: Institute of Inorganic and Analytical Chemistry, Friedrich Schiller University Jena , Humboldtstraße, 8, D-07743 Jena, Germany.
authors.forename: Helmar
authors.initials: H
authors.lastname: Görls
authors.affiliation: Leibniz Institute of Photonic Technology (IPHT) , Albert-Einstein-Straße 9, D-07745 Jena, Germany.|Center for Sepsis Control and Care (CSCC), Friedrich Schiller University Jena and Jena University Hospital , Erlanger Allee 101, D-07747 Jena, Germany.
authors.forename: Ute
authors.initials: U
authors.lastname: Neugebauer
authors.affiliation: Institute of Physical Chemistry, Friedrich Schiller University Jena , Helmholtzweg 4, D-07743 Jena, Germany.
authors.forename: Michael
authors.initials: M
authors.lastname: Schmitt
authors.affiliation: Center for Molecular Biomedicine (CMB), Department of Biophysics, Friedrich Schiller University Jena and Jena University Hospital , Hans-Knöll-Straße 2, D-07745 Jena, Germany.
authors.forename: Guido
authors.initials: G
authors.lastname: Gessner
authors.affiliation: Center for Molecular Biomedicine (CMB), Department of Biophysics, Friedrich Schiller University Jena and Jena University Hospital , Hans-Knöll-Straße 2, D-07745 Jena, Germany.
authors.forename: Stefan H
authors.initials: SH
authors.lastname: Heinemann
authors.affiliation: Leibniz Institute of Photonic Technology (IPHT) , Albert-Einstein-Straße 9, D-07745 Jena, Germany.|Center for Sepsis Control and Care (CSCC), Friedrich Schiller University Jena and Jena University Hospital , Erlanger Allee 101, D-07747 Jena, Germany.|Institute of Physical Chemistry, Friedrich Schiller University Jena , Helmholtzweg 4, D-07743 Jena, Germany.
authors.forename: Jürgen
authors.initials: J
authors.lastname: Popp
authors.affiliation: Center for Sepsis Control and Care (CSCC), Friedrich Schiller University Jena and Jena University Hospital , Erlanger Allee 101, D-07747 Jena, Germany.
authors.forename: Michael
authors.initials: M
authors.lastname: Bauer
authors.affiliation: Institute of Inorganic and Analytical Chemistry, Friedrich Schiller University Jena , Humboldtstraße, 8, D-07743 Jena, Germany.
authors.forename: Matthias
authors.initials: M
authors.lastname: Westerhausen
mesh_terms: D008024:Ligands; D017895:Manganese Compounds / Q000737:chemistry*; D015394:Molecular Structure; D012995:Solubility; D013057:Spectrum Analysis / Q000379:methods; D014867:Water / Q000737:chemistry
chemical_list: D008024:Ligands; D017895:Manganese Compounds; D014867:Water