Document Detail


Controlled photochemical release of nitric oxide from O2-benzyl-substituted diazeniumdiolates.
MedLine Citation:
PMID:  12175240     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
An investigation of potential photosensitive protecting groups for diazeniumdiolates (R2N-N(O)=NO-) has been initiated, and here the effect of meta electron-donating groups on the photochemistry of O2-benzyl-substituted diazeniumdiolates (R2N-N(O)=NOCH2Ar) is reported. Photolysis of the parent benzyl derivative (Ar = Ph) results almost exclusively in undesired photochemistry-the formation of nitrosamine and an oxynitrene intermediate with very little, if any, photorelease of the diazeniumdiolate. We have been able to use meta substitution to tune the photochemistry of these benzylic systems. The desired diazeniumdiolate photorelease has been shown to become more substantial with stronger pi-donating meta substituents. This effect has been verified by direct observation of the photoreleased diazeniumdiolate with 1H NMR spectroscopy and by NO quantification measurements conducted in high- and low-pH solutions. In addition, the observed rates of NO release are consistent with that expected for normal thermal decomposition of the diazeniumdiolate in aqueous solutions and also show the same pH dependence.
Authors:
Patrick H Ruane; K Mani Bushan; Christopher M Pavlos; Raechelle A D'Sa; John P Toscano
Publication Detail:
Type:  Journal Article; Research Support, Non-U.S. Gov't; Research Support, U.S. Gov't, P.H.S.    
Journal Detail:
Title:  Journal of the American Chemical Society     Volume:  124     ISSN:  0002-7863     ISO Abbreviation:  J. Am. Chem. Soc.     Publication Date:  2002 Aug 
Date Detail:
Created Date:  2002-08-14     Completed Date:  2002-10-22     Revised Date:  2007-11-14    
Medline Journal Info:
Nlm Unique ID:  7503056     Medline TA:  J Am Chem Soc     Country:  United States    
Other Details:
Languages:  eng     Pagination:  9806-11     Citation Subset:  IM    
Affiliation:
Department of Chemistry, Johns Hopkins University, 3400 North Charles Street, Baltimore, Maryland 21218, USA.
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MeSH Terms
Descriptor/Qualifier:
Azo Compounds / chemistry*
Benzyl Compounds / chemistry*
Kinetics
Nitric Oxide / chemistry*
Photolysis
Grant Support
ID/Acronym/Agency:
R01 GM58109/GM/NIGMS NIH HHS
Chemical
Reg. No./Substance:
0/Azo Compounds; 0/Benzyl Compounds; 0/diazeniumdiolate; 10102-43-9/Nitric Oxide

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


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