DOI: 10.5061/dryad.mcvdnck1f
title: Data from: Redox mediated carbon monoxide release from a manganese carbonyl—implications for physiological CO delivery by CORMs

description: We evaluated the dynamics of hydrogen peroxide reactions with
 metal carbonyls. specifically a water-soluble manganese
 carbonyl. These files are the raw data for the quantitative
 mechanistic investigation of the H2O2 oxidation of the water-soluble model
 complex fac-[Mn(CO)3(Br)(bpCO2)]2–, (A, bpCO22– =
 2,2’-bipyridine-4,4’-dicarboxylate dianion). The method of intial rates
 was utilized in the experimental studies thus raw spectral data
 for the figures and results presented in RSOS-211022 were
 included. These data demonstrated pH-dependent kinetics. All the raw
 absorbance data used to determine the initial reaction rates and observed
 rate constant from pH 6.1-7.4, 8-32 mM [H2O2]. and 19.5- 42oC are present.
 For soluble homogenous experiments, UV-Vis, Fluorescence assay, and FT-IR
 spectral data for conditions included in the manuscript. For insoluble
 products of the experiments, X-ray diffraction and ICP-AES raw data are
 included. There are several untested hypotheses about the mechanisms of
 the reaction of manganese carbonyl with reactive oxygen species. We found
 that intracellular pH greatly influences the reaction rate and may be a
 control for redox-mediated CO release from mangense CORMs. Since the
 lysosome is more acidic and mitochondrial matrix is more basic than the
 cytosol it is likely different local rates of CO release would be
 observed. Furthermore, in considering the localization and diffusion of
 H2O2 in biological systems, it is likely that a relatively slow
 reaction with manganese carbonyls (compared to catalase) can
 exhibit physiological effects. The cytotoxic effects of Mn(I)
 carbonyls have been associated with the generation of hydroxyl radicals,
 however we founs no appreciable quantities of hydroxyl radicals compared
 to known catalysts. Thus we conclude that these cytotoxic effects are more
 likely due to released CO interacting with heme-proteins vital to cellular
 respiration. Our mechanistic and kinetic findings provide
 literature precedence for researchers examining physiological effects of
 Mn(I) carbonyls.
description: The data was collected using primarily UV-Vis scpectroscopy. Some
 of the data was collected using XRD, NMR, EPR, and IR spectroscopy; as
 well as GC-TCD and voltammetry.
description: The data can be used entirely as is. The analyses the authors
 used is presented in the manuscript and should enable someone to
 re-analyze this raw data similarly. 
 ph7.4_8mMH2O2 absorbance data at 408 nm for
 the reaction of <b>A</b> (at var. concentration) with
 H<sub>2</sub>O<sub>2
 </sub>([H<sub>2</sub>O<sub>2</sub>]<sub>total</sub> = 8 mM) at pH 7.4 and 36.8°C. pH7.4_16mMH2O2 absorbance data at 408 nm for the reaction of <b>A</b> (at var. concentration) with H<sub>2</sub>O<sub>2 </sub>([H<sub>2</sub>O<sub>2</sub>]<sub>total</sub> = 16 mM) at pH 7.4 and 36.8°C. pH7.4_32mMH2O2 absorbance data at 408 nm for the reaction of <b>A</b> (at var. concentration) with H<sub>2</sub>O<sub>2 </sub>([H<sub>2</sub>O<sub>2</sub>]<sub>total</sub> = 32 mM) at pH 7.4 and 36.8°C. pH6.1_8mMH2O2 absorbance data at 408 nm for the reaction of <b>A</b> (at var. concentration) with H<sub>2</sub>O<sub>2 </sub>([H<sub>2</sub>O<sub>2</sub>]<sub>total</sub> = 8 mM) at pH 6.1 and 36.8°C. pH6.1_16mMH2O2 absorbance data at 408 nm for the reaction of <b>A</b> (at var. concentration) with H<sub>2</sub>O<sub>2 </sub>([H<sub>2</sub>O<sub>2</sub>]<sub>total</sub> = 16 mM) at pH 6.1 and 36.8°C. pH6.1_32mMH2O2 absorbance data at 408 nm for the reaction of <b>A</b> (at var. concentration) with H<sub>2</sub>O<sub>2 </sub>([H<sub>2</sub>O<sub>2</sub>]<sub>total</sub> = 32 mM) at pH 6.1 and 36.8°C. pH6.8_32mMH2O2 absorbance data at 408 nm for the reaction of <b>A</b> (at var. concentration) with H<sub>2</sub>O<sub>2 </sub>([H<sub>2</sub>O<sub>2</sub>]<sub>total</sub> = 32 mM) at pH 6.8 and 36.8°C. pH7.1_32mMH2O2 absorbance data at 408 nm for the reaction of <b>A</b> (at var. concentration) with H<sub>2</sub>O<sub>2 </sub>([H<sub>2</sub>O<sub>2</sub>]<sub>total</sub> = 32 mM) at pH 7.1 and 36.8°C. pH7.7_32mMH2O2 absorbance data at 408 nm for the reaction of <b>A</b> (at var. concentration) with H<sub>2</sub>O<sub>2 </sub>([H<sub>2</sub>O<sub>2</sub>]<sub>total</sub> = 32 mM) at pH 7.7 and 36.8°C. pH8_32mMH2O2 absorbance data at 408 nm for the reaction of <b>A</b> (at var. concentration) with H<sub>2</sub>O<sub>2 </sub>([H<sub>2</sub>O<sub>2</sub>]<sub>total</sub> = 32 mM) at pH 8 and 36.8°C. 19.5CvaryH2O2 absorbance data at 408 nm for the reaction of <b>A</b> with H<sub>2</sub>O<sub>2 </sub>([H<sub>2</sub>O<sub>2</sub>]<sub>total</sub> = variable) at pH 7.4 and 19.5°C. 25.5CvaryH2O2 absorbance data at 408 nm for the reaction of <b>A</b> with H<sub>2</sub>O<sub>2 </sub>([H<sub>2</sub>O<sub>2</sub>]<sub>total</sub> = variable) at pH 7.4 and 25.5°C. 31.5CvaryH2O2 absorbance data at 408 nm for the reaction of <b>A</b> with H<sub>2</sub>O<sub>2 </sub>([H<sub>2</sub>O<sub>2</sub>]<sub>total</sub> = variable) at pH 7.4 and 31.5°C. 33.9CvaryH2O2 absorbance data at 408 nm for the reaction of <b>A</b> with H<sub>2</sub>O<sub>2 </sub>([H<sub>2</sub>O<sub>2</sub>]<sub>total</sub> = variable) at pH 7.4 and 33.9°C. 42CvaryH2O2 absorbance data at 408 nm for the reaction of <b>A</b> with H<sub>2</sub>O<sub>2 </sub>([H<sub>2</sub>O<sub>2</sub>]<sub>total</sub> = variable) at pH 7.4 and 42°C. UV-Vis FigS1 UV-visible spectral data for<i> fac</i>-Mn(CO)<sub>3</sub>(Br)(bpCO<sub>2</sub>H) (90 µM) and bpCO<sub>2</sub>H (100 µM) in pH 7.4 phosphate buffered solution (0.118 M) at 25 °C. 100mMpyridineFigureS16 UV-visible spectral data recorded for a solution of<b> A</b> in pH 7.4 phosphate buffer before and after addition of pyridine. 32mMH2O2afterpyrFigureS17 UV-visible spectral data recorded for a solution of<b> A</b> substituted with pyridine in pH 7.4 phosphate buffer before and after addition of 32 mM H<sub>2</sub>O<sub>2</sub> XRDFigureS3 X-ray diffraction of white solid precipitate collected from the reaction of <b>A</b> with H<sub>2</sub>O<sub>2</sub> at in phosphate buffered solution ICP ICP-AES raw data of white solid precipitate collected from the reaction of <b>A</b> with H<sub>2</sub>O<sub>2</sub> at in phosphate buffered solution EmissionFigureS15 Emission spectral data of coumarin-3-carboxylic acid (345 µM) in phosphate buffer solution after a 3 h reactions under the following conditions: CuCl<sub>2</sub> (45 µM) plus H<sub>2</sub>O<sub>2 </sub>(32 mM). <b>A (</b>45 µM) plus H<sub>2</sub>O<sub>2 </sub>(32 mM). H<sub>2</sub>O<sub>2</sub> (32 mM) only. <b>A (</b>45 µM) only. CuCl<sub>2 </sub>(45 µM) only. (T = 25 °C). EPRFigureS5-6 Processed data for X-Band EPR spectrum of a phosphate buffered solution containing <b>A </b>and H<sub>2</sub>O<sub>2</sub> CVFigureS7-8 Cyclic voltammograms of <b>A</b> in deaerated phosphate buffer solution scanned from 0 to 1.3V and from 0 to -1.6 V using a glassy carbon electrode and of a pH 7.4 solution of <b>A</b> and H<sub>2</sub>O<sub>2</sub> in deaerated phosphate buffer at 37°C scanned from 0 to -0.85 V at different elapsed times after mixing indicating formation of O<sub>2</sub> IRFigureS10 Temporal<b> </b>infrared spectral changes of a DMSO solution of <b>A</b> and H<sub>2</sub>O<sub>2 </sub>and 5% aqueous phosphate buffer at 25°C. Variables for the columns in the sheets are as follows. Unless otherwise mentioned time values are in seconds, wavelength is in nm, and wavenumber is in cm<sup>-1</sup> "EX 1" through "EX 117" in sheets titled pHX.X_YmMH2O2 are absorbance values. "ligand" and "MnbpyCOOH" in sheet UV-vis FigS1 are absorbance values. "blank" and "100mMPyr_1" through "100mMPyr_68" in sheet 100mMpyridineFigureS16 are absorbance values. "298 nm" is the absorbance value for all the data at that wavelength. "32H2O2_100mMpyr_1" through "32H2O2_100mMpyr_100" in sheet 32mMH2O2afterpyrFigureS17 are absorbance values. "degrees" in sheet XRDFigureS3 are the 2 θ angle whiel the "counts" are the number representing intensity. The sheet ICP is the raw AES files. The wavelength and intensity of emission are reported. For examples 'Mn2576' had an emission intensity average(ave) = 328400 at wavelength 257.610 nm. The rest of the raw file is coded similarly. In sheet EmissionFigureS15, "wl6" is in wavelengh. "{Mn}", "H2O2", "{Mn} + H2O2", "CuCl", and "Cu + H2O2" are all emission intensity counts. "g" are magnetic field strength and all other columns are signl intensity in sheet EPRFigureS5-6. In sheet CVFigureS7-8, any column title that starts "I_" is current im amps. The columbs titled "potential" are the applied potential in volts. In sheet IRFigureS10, "WN1" through "WN15" are in cm<sup>-1</sup> and "ABS1" through "ABS15" are the corresponding absorbance values.