Synthesis and characterization of photolabile o-nitrobenzyl derivatives of urea.
We present here the synthesis and characterization of four photolabile derivatives of urea in which alpha-substituted 2-nitrobenzyl groups are covalently attached to the urea nitrogen. These derivatives photolyze readily in aqueous solution to release free urea. The alpha-substituents of the 2-nitrobenzyl group strongly influence the rate of the photolysis reaction measured with transient absorption spectroscopy. Rates of photolysis at pH 7.5 and room temperature (approximately 22 degrees C) for N-(2-nitrobenzyl)urea, N-(alpha-methyl-2-nitrobenzyl)urea, N-(alpha-carboxymethyl-2-nitrobenzyl)urea, and N-(alpha-carboxy-2-nitrobenzyl)urea are, respectively, 1.7 x 10(4), 8.5 x 10(4), 4.0 x 10(4), and 1.1 x 10(5) s(-)(1). The quantum yields determined by measurement of free urea following irradiation by a single laser pulse at 308 nm were 0.81 for N-(2-nitrobenzyl)urea, 0.64 for N-(alpha-methyl-2-nitrobenzyl)urea, and 0.56 for N-(alpha-carboxy-2-nitrobenzyl)urea. The caged N-(alpha-carboxy-2-nitrobenzyl)urea is not a substrate of the enzyme urease, while the photolytically released urea is. Also, neither this caged urea nor its photolytic side products inhibit hydrolysis of free urea by urease. Thus, the alpha-carboxy-2-nitrobenzyl derivative of urea is suitable for mechanistic investigations of the enzyme urease.
Wieboldt
Raymond
R
Molecular Biology and Genetics, 217 Biotechnology Building, Cornell University, Ithaca, New York 14853-2703, USA.
Ramesh
Doraiswamy
D
Jabri
Evelyn
E
Karplus
P Andrew
PA
Carpenter
Barry K
BK
Hess
George P
GP
D002851:Chromatography, High Pressure Liquid; D021902:Enterobacter aerogenes / Q000201:enzymology; D007700:Kinetics; D015394:Molecular Structure; D009578:Nitrobenzenes / Q000032:analysis / Q000138:chemical synthesis / Q000737:chemistry; D010782:Photolysis; D013329:Structure-Activity Relationship; D014508:Urea / Q000031:analogs & derivatives / Q000032:analysis / Q000138:chemical synthesis / Q000737:chemistry; D014510:Urease / Q000737:chemistry / Q000378:metabolism
D009578:Nitrobenzenes; D014508:Urea; D014510:Urease