A fibrous assembly is provided for performing site-specific chemistry. In general, the present invention provides a fibrous assembly comprising a first nanofiber that sequesters a first reactive component, wherein the first nanofiber is prepared by an electrospinning or gas-jet method, wherein the first nanofiber releases its reactive component when the nanofiber is in the presence of a releasing agent and the first reactive component and the releasing agent chemically react to produce a reaction product. Related methods of manufacture and use are also disclosed.