Document Detail


Use of evolutionary factor analysis in the spectroelectrochemistry of Escherichia coli sulfite reductase hemoprotein and a Mo/Fe/S cluster.
MedLine Citation:
PMID:  10330905     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
The deconvolution of spectroelectrochemical data is often quite difficult if the spectra of intermediates are not known. Factor analysis, however, has been shown to be a powerful technique which can make it possible to deconvolute overlapping spectra. In this work, evolving factor analysis will be used to determine the number of intermediates and the spectra of those species for two typical spectroelectrochemical experiments: linear scan voltammetry and chronoabsorptometry in a thin-layer cell. The first system was the reduction of E. coli sulfite reductase hemoprotein (SiR-HP). Principal factor analysis indicated that three species were present. By using evolving factor analysis, the potential regions where each of the species were present were identified, and their concentrations and spectra were determined by the use of the mass balance equation. The spectra of the one-electron (SiR-HP1-) and two-electron (SiR-HP2-) reduced product were compared with previous work. The second experiment was the chronoabsorptometry of Cl2FeS2MoS2FeCl2(2-) in methylene chloride. This experiment indicated that five species were present during the experiment. The entire set of 61 spectra were fit by assuming that there were 4 species present during the electrolysis. The rate constant for the appearance of subsequent species fit quite well with the rate constant for the disappearance of previous species. The spectra of the intermediates and final product were obtained using evolving factor analysis and a mass balance equation. Identification of the fifth species, which was probably the initial reduction product, Cl2FeS2MoS2FeCl2(3-), was difficult due to its low concentration and the fact that it was present in the same time region as the starting material.
Authors:
R L Keesey; M D Ryan
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Publication Detail:
Type:  Journal Article; Research Support, U.S. Gov't, P.H.S.    
Journal Detail:
Title:  Analytical chemistry     Volume:  71     ISSN:  0003-2700     ISO Abbreviation:  Anal. Chem.     Publication Date:  1999 May 
Date Detail:
Created Date:  1999-06-21     Completed Date:  1999-06-21     Revised Date:  2007-11-14    
Medline Journal Info:
Nlm Unique ID:  0370536     Medline TA:  Anal Chem     Country:  UNITED STATES    
Other Details:
Languages:  eng     Pagination:  1744-52     Citation Subset:  IM    
Affiliation:
Chemistry Department, Marquette University, Milwaukee, Wisconsin 53201, USA.
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MeSH Terms
Descriptor/Qualifier:
Bacterial Proteins / chemistry,  metabolism
Electrochemistry / methods*
Escherichia coli / enzymology*
Factor Analysis, Statistical
Hemeproteins / chemistry*,  metabolism
Iron / chemistry*
Molybdenum / chemistry*
Organometallic Compounds / chemistry*
Oxidoreductases Acting on Sulfur Group Donors / chemistry*,  metabolism*
Sulfur / chemistry*
Grant Support
ID/Acronym/Agency:
R15 GM/OD55917/GM/NIGMS NIH HHS
Chemical
Reg. No./Substance:
0/Bacterial Proteins; 0/Hemeproteins; 0/Organometallic Compounds; 7439-89-6/Iron; 7439-98-7/Molybdenum; 7704-34-9/Sulfur; EC 1.8.-/Oxidoreductases Acting on Sulfur Group Donors

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine


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