Item request has been placed!
×
Item request cannot be made.
×
![loading](/sites/all/modules/hf_eds/images/loading.gif)
Processing Request
Aerobic reactions of antitumor active dirhodium(II) tetraacetate Rh2(CH3COO)4 with glutathione.
Item request has been placed!
×
Item request cannot be made.
×
![loading](/sites/all/modules/hf_eds/images/loading.gif)
Processing Request
- معلومة اضافية
- نبذة مختصرة :
Abstract: The aerobic reaction between glutathione (H3A) and dirhodium(II) tetraacetate, Rh2(AcO)4 (AcO− = CH3COO−), in aqueous solution (pH 7.4) breaks up the direct RhII–RhII bond and its carboxylate framework, as evidenced by UV–Vis spectroscopy. After purifying the reaction product using size exclusion chromatography, electrospray ionization mass spectrometry (ESI-MS) of the solution showed binuclear Rh2IIIHA42- and Rh2IIIHA54- ions. Evaporation yielded a solid compound, Na2Rh2IIIHA4·7H2On, for which Rh K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy revealed ~ 2 Rh-O (2.08 ± 0.02 Å) and ~ 4 Rh-S (2.33 ± 0.02 Å) bond distances around each RhIII center, and the RhIII··RhIII distance 3.11 ± 0.02 Å, close to that in dirhodium(III) complexes with three bridging thiolates connecting Rh2III units. The 13C CPMAS NMR spectrum of the RhIII–glutathione complex showed a change ∆δC > 6 ppm in the chemical shift of the COO− signal, indicating some carboxylate coordination to the Rh(III) ions. This study shows that under aerobic conditions glutathione enables oxidation of Rh2(AcO)4 and thus reduces its antitumor efficiency.Graphical Abstract: The reaction of Rh2(AcO)4 with glutathione was investigated by ESI-MS, UV–Vis, 13C NMR and X-ray absorption spectroscopy, revealing that glutathione breaks down the carboxylate framework enabling oxidization of the Rh24+ core to Rh(III) dimeric units, bridged by three thiolates.
[ABSTRACT FROM AUTHOR]
- نبذة مختصرة :
Copyright of Journal of Biological Inorganic Chemistry (JBIC) is the property of Springer Nature and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
No Comments.