Articles and methods for the use of such articles are described for use in immobilizing nucleophile-containing materials. In one aspect, the invention provides an article comprising: a substrate having a first surface and a second surface; and a phosphonitrilic tethering group affixed to the first surface of the substrate, the phosphonitrilic tethering group comprising a reaction product of a complementary functional group on the first surface of the substrate with a phosphonitrilic tethering compound. A method of immobilizing a nucleophile-containing material to a substrate is also described, the method comprising: providing a phosphonitrilic tethering compound; providing a substrate having a complementary functional group capable of reacting with phosphonitrilic tethering compound; preparing a substrate-attached phosphonitrilic tethering group by reacting the phosphonitrilic tethering compound with the complementary functional group on the substrate resulting in an ionic bond, covalent bond, or combinations thereof; and reacting the substrate-attached phosphonitrilic tethering group with a nucleophile-containing material to immobilize the nucleophile-containing material.