The hydrolysis of four alkoxysilane agents, gamma-methacryloxypropyl trimethoxysilane (MPS), gamma-mercaptopropyl trimetoxysilane (MRPS), octyl trimethoxysilane OS), and N-phenyl-gamma-aminopropyl trimethoxysilane (PAPS), was carried out in an ethanol/water (80/20) solution under both acid and basic conditions. H-1, C-13, and Si-29 NMR spectroscopy were used to provide quantitative analyses of the structural components during hydrolysis and condensation reaction. The analysis revealed that the acid-catalyzed hydrolysis of silane allows the formation of high amount of silanol groups, reduced the selfcondensation reaction among silanol groups and stabilized the propertion of intermediary hydrolyzed species for several days. However, under basic condition, condensation reactions proceed as soon as the hydrolysis reaction started leading to the rapid consumption of silanol groups through selfcondensation and to the growth of three-dimensional high molecular structures. The interaction of MPS and MRPS with cellulose fibers and the evolution of their surface properties were then investigated using adsorption isotherms and contact angle measurement. (c) 2008 Wiley Periodicals, Inc.