Document Detail


A photochemical study of (E,E,E,E)-2-[9-(2-hydroxyethyl)imino-3,7-dimethyl-1,3,5,7-decatrien-1-yl]- 1,3,3-trimethylcyclohexene, a derivative of all-trans-retinal and ethanolamine.
MedLine Citation:
PMID:  14556318     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
A derivative of all-trans-retinal (RAL) and ethanolamine, A2-E, is the main fluorescent component of human retinal lipofuscin. The accumulation of lipofuscin has been correlated with exposure to ambient radiation and loss of photoreceptors. A possible precursor to A2-E is the imine formed from RAL and ethanolamine. This compound, (E,E,E,E)-2-[9-(2-hydroxyethyl)imino-3,7-dimethyl-1,3,5,7- decatrien-1-yl]-1,3,3-trimethylcyclohexene (HIDD), has been synthesized and structurally characterized. The photophysical and photochemical properties of HIDD and its protonated form, HIDD-H+, have been investigated using steady-state and time-resolved methods. Both HIDD and HIDD-H+ are weakly fluorescent, and the fluorescence lifetime and quantum yield for HIDD are ca 0.6 ns and 4.0 +/- 0.5 x 10(-4), respectively. HIDD forms a triplet excited state on direct excitation that decays with kd = 3.4 x 10(4) s-1. The extinction coefficient and quantum yield of intersystem crossing for the HIDD triplet are measured as 7.6 +/- 1.3 x 10(4) M-1 cm-1 and 0.055 +/- 0.006, respectively. The triplet excited state of HIDD-H+ can be sensitized by triplet energy transfer and has a decay rate constant of 1.6 x 10(4) s-1. The lifetime of the HIDD triplet excited state is observed to decrease with increasing concentration of the well-known electron or hydrogen atom donors, 2,3,5,6-tetramethyl-1,4-phenylenediamine and 2,3,5-trimethylhydroquinone, and the bimolecular rate constants for these reactions are approximately 5.4 x 10(6) M-1 s-1 and 1.7 x 10(8) M-1 s-1, respectively. These types of reactions may model photooxidative mechanisms of damage in the retina.
Authors:
Willa S Harper; Elizabeth R Gaillard
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Publication Detail:
Type:  Journal Article; Research Support, Non-U.S. Gov't; Research Support, U.S. Gov't, P.H.S.    
Journal Detail:
Title:  Photochemistry and photobiology     Volume:  78     ISSN:  0031-8655     ISO Abbreviation:  Photochem. Photobiol.     Publication Date:  2003 Sep 
Date Detail:
Created Date:  2003-10-14     Completed Date:  2003-12-11     Revised Date:  2007-11-14    
Medline Journal Info:
Nlm Unique ID:  0376425     Medline TA:  Photochem Photobiol     Country:  United States    
Other Details:
Languages:  eng     Pagination:  298-305     Citation Subset:  IM    
Affiliation:
Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115, USA.
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MeSH Terms
Descriptor/Qualifier:
Alkenes / chemistry*
Cyclohexanes / chemistry*
Ethanolamine / chemistry*
Fluorescence
Photochemistry*
Retinaldehyde / chemistry*
Grant Support
ID/Acronym/Agency:
EY12344/EY/NEI NIH HHS
Chemical
Reg. No./Substance:
0/(E,E,E,E)-2-(9-(2-hydroxyethyl)imino-3,7-dimethyl-1,3,5,7-decatrien-1-yl)- 1,3,3-trimethylcyclohexene; 0/Alkenes; 0/Cyclohexanes; 116-31-4/Retinaldehyde; 141-43-5/Ethanolamine

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


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