1549-88-8Relevant articles and documents
Electron Transfer Reactivity of the Aqueous Iron(IV)-Oxo Complex. Outer-Sphere vs Proton-Coupled Electron Transfer
Bataineh, Hajem,Pestovsky, Oleg,Bakac, Andreja
, p. 6719 - 6724 (2016)
The kinetics of oxidation of organic and inorganic reductants by aqueous iron(IV) ions, FeIV(H2O)5O2+ (hereafter FeIVaqO2+), are reported. The substrates examined include several water-soluble ferrocenes, hexachloroiridate(III), polypyridyl complexes M(NN)32+ (M = Os, Fe and Ru; NN = phenanthroline, bipyridine and derivatives), HABTS-/ABTS2-, phenothiazines, CoII(dmgBF2)2, macrocyclic nickel(II) complexes, and aqueous cerium(III). Most of the reductants were oxidized cleanly to the corresponding one-electron oxidation products, with the exception of phenothiazines which produced the corresponding oxides in a single-step reaction, and polypyridyl complexes of Fe(II) and Ru(II) that generated ligand-modified products. FeIVaqO2+ oxidizes even Ce(III) (E0 in 1 M HClO4 = 1.7 V) with a rate constant greater than 104 M-1 s-1. In 0.10 M aqueous HClO4 at 25 °C, the reactions of Os(phen)32+ (k = 2.5 × 105 M-1 s-1), IrCl63- (1.6 × 106), ABTS2- (4.7 × 107), and Fe(cp)(C5H4CH2OH) (6.4 × 107) appear to take place by outer sphere electron transfer (OSET). The rate constants for the oxidation of Os(phen)32+ and of ferrocenes remained unchanged in the acidity range 0.05 +] IVaqO2+ and further supporting the OSET assignment. A fit to Marcus cross-relation yielded a composite parameter (log k22 + E0Fe/0.059) = 17.2 ± 0.8, where k22 and E0Fe are the self-exchange rate constant and reduction potential, respectively, for the FeIVaqO2+/FeIIIaqO+ couple. Comparison with literature work suggests k22 -5 M-1 s-1 and thus E0(FeIVaqO2+/FeIIIaqO+) > 1.3 V. For proton-coupled electron transfer, the reduction potential is estimated at E0 (FeIVaqO2+, H+/FeIIIaqOH2+) ≥ 1.95 V.
Accelerated Forced Degradation of Pharmaceuticals in Levitated Microdroplet Reactors
Li, Yangjie,Liu, Yong,Gao, Hong,Helmy, Roy,Wuelfing, W. Peter,Welch, Christopher J.,Cooks, R. Graham
, p. 7349 - 7353 (2018/06/11)
Forced degradation is a method of studying the stability of pharmaceuticals in order to design stable formulations and predict drug product shelf life. Traditional methods of reaction and analysis usually take multiple days, and include LC-UV and LC-MS product analysis. In this study, the reaction/analysis sequence was accelerated to be completed within minutes using Leidenfrost droplets as reactors (acceleration factor: 23–188) and nanoelectrospray ionization MS analysis. The Leidenfrost droplets underwent the same reactions as seen in traditional bulk solution experiments for three chemical degradations studied. This combined method of accelerated reaction and analysis has the potential to be extended to forced degradation of other pharmaceuticals and to drug formulations. Control of reaction rate and yield is achieved by manipulating droplet size, levitation time and whether or not make-up solvent is added. Evidence is provided that interfacial effects contribute to rate acceleration.
A mechanistic study on the disproportionation and oxidative degradation of phenothiazine derivatives by manganese(III) complexes in phosphate acidic media
Wisniewska, Joanna,Rzesnicki, Pawel,Topolski, Adrian
scheme or table, p. 767 - 774 (2012/07/01)
The oxidative degradation of phenothiazine derivatives (PTZ) by manganese(III) was studied in the presence of a large excess of manganese(III)-pyrophosphate (P2O7 2-), phosphate (PO4 3-), and H+ ions using UV-vis. spectroscopy. The first irreversible step is a fast reaction between phenothiazine and manganese pyrophosphate leading to the complete conversion to a stable phenothiazine radical. In the second step, the cation radical is oxidized by manganese to a dication, which subsequently hydrolyzes to phenothiazine 5-oxide. The reaction rate is controlled by the coordination and stability of manganese(III) ion influenced by the reduction potential of these ions and their strong ability to oxidize many reducing agents. The cation radical might also be transformed to the final product in another competing reaction. The final product, phenothiazine 5-oxide, is also formed via a disproportionation reaction. The kinetics of the second step of the oxidative degradation could be studied in acidic phosphate media due to the large difference in the rates of the first and further processes. Linear dependences of the pseudo-first-order rate constants (k obs) on [Mn III] with a significant non-zero intercept were established for the degradation of phenothiazine radicals. The rate is dependent on [H+] and independent of [PTZ] within the excess concentration range of the manganese(III) complexes used in the isolation method. The kinetics of the disproportionation of the phenothiazine radical have been studied independently from the further oxidative degradation process in acidic sulphate media. The rate is inversely dependent on [PTZ+.], dependent on [H+], and increases slightly with decreasing H+ concentration. Mechanistic consequences of all these results are discussed.