Intramolecular thiolysis of 4-mercaptobutyrate esters: developing a "traceless" linker for alcohol release from self-assembled monolayers on gold

被引:1
作者
Buchmann, MB [1 ]
Fyles, TM [1 ]
Mischki, T [1 ]
Sutherland, T [1 ]
Tong, CC [1 ]
Yip, VLY [1 ]
机构
[1] Univ Victoria, Dept Chem, POB 3065, Victoria, BC V8W 3V6, Canada
关键词
thiolysis; intramolecular; self-assembled monolayer; controlled release;
D O I
10.3998/ark.5550190.0002.c03
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
A series of esters of dithiobutyric acid was prepared using the carbodiimide coupling system. These esters were used to examine the kinetic feasibility of release of alcohols by reductive cleavage of the disulfide. Release of p-nitrophenol was rapid following reduction with dithiothreitol at pH similar to 10.5. Intramolecular thiolysis is at least one hundred-fold faster then base hydrolysis at this pH. NMR experiments established rapid alcohol release for phenolates and ethanolamine derivatives but alkyl substrates were found to release slowly. Self-assembled monolayers (SAMs) formed from nitrophenol or ethanolamine derivatives produce the expected quantity of alcohol following reductive release from gold powder.
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页数:8
相关论文
共 13 条
[1]   SYNTHESIS, STRUCTURE, AND PROPERTIES OF MODEL ORGANIC-SURFACES [J].
DUBOIS, LH ;
NUZZO, RG .
ANNUAL REVIEW OF PHYSICAL CHEMISTRY, 1992, 43 :437-463
[2]   HIGHLY EFFICIENT INTRAMOLECULAR NUCLEOPHILIC REACTIONS - CYCLIZATION OF P-NITROPHENYL N-(2-MERCAPTOPHENYL)-N-METHYLCARBAMATE AND PHENYL "N-(2-AMINOPHENYL)-N-METHYLCARBAMATE [J].
FIFE, TH ;
HUTCHINS, JEC ;
WANG, MS .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1975, 97 (20) :5878-5882
[3]  
HOUK J, 1987, METHOD ENZYMOL, V143, P129
[4]  
Imabayashi S, 1997, J ELECTROANAL CHEM, V428, P33
[5]   Electrochemical quartz crystal microbalance investigation of the reductive desorption of self-assembled monolayers of alkanethiols and mercaptoalkanoic acids on Au [J].
Kawaguchi, T ;
Yasuda, H ;
Shimazu, K ;
Porter, MD .
LANGMUIR, 2000, 16 (25) :9830-9840
[6]   FUNDAMENTAL-STUDIES OF THE CHEMISORPTION OF ORGANOSULFUR COMPOUNDS ON AU(111) - IMPLICATIONS FOR MOLECULAR SELF-ASSEMBLY ON GOLD SURFACES [J].
NUZZO, RG ;
ZEGARSKI, BR ;
DUBOIS, LH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (03) :733-740
[7]   ADSORPTION OF BIFUNCTIONAL ORGANIC DISULFIDES ON GOLD SURFACES [J].
NUZZO, RG ;
ALLARA, DL .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (13) :4481-4483
[8]  
SCHANBERG E, 1942, BER, V75, P468
[9]  
SCHNEIDER TW, 1992, ABSTR PAP AM CHEM S, V203, P34
[10]   REDUCTIVE DESORPTION OF ALKANETHIOLATE MONOLAYERS AT GOLD - A MEASURE OF SURFACE COVERAGE [J].
WALCZAK, MM ;
POPENOE, DD ;
DEINHAMMER, RS ;
LAMP, BD ;
CHUNG, CK ;
PORTER, MD .
LANGMUIR, 1991, 7 (11) :2687-2693