A reagent immobilized on a macroporous polymer support was prepared fo
r size selective derivatizations. These derivatization reagents showed
two distinct reaction zones, Sterically bulky analytes were denied ac
cess to some of the surface of the support, so that when reagent on th
e outer surface was exhausted from the support, only analytes that had
fun access to all regions of the support could react. These reagents
were applied to the derivatization of different amines in the presence
of a high concentration of a bulky analyte, adamantanamine, Pore size
measurements and determination of molecular dimensions also support a
size-selective derivatization mechanism, The reagents were also appli
ed to the derivatization of proteins, Proteins with several sites avai
lable for tagging shows a reduced number of products with size selecti
ve reagents, reflecting reactions only at sites accessible to the reag
ent. (C) 1997 by John Wiley & Sons, Ltd.