It depends a bit on the way you prepared the amino groups.
X-ray photoelectron spectroscopy XPS can do the job. However, if you are interested in primary amines (e.g. because they are supposed to be used for further reactions) it is hard to distinguish from secondary and tertiary amines and other groups which have only N-H and N-C bonds.
Derivatization/ labelling can help in this case. see DOI 10.1002/sia.2615, or 10.1002/sia.1828
Thanks for the suggestions. I am treating them with gold nanoparticles. But the binding of nanoparticles to the aminated substrate prepared on the first day is good compared to the same test performed on aminated substrate (used after 3 days of preparation). Does aging affect the stability of amine groups formed on the surface? Could there be any ways by which I can avoid this aging effect?
For example, plasma modified polymer surfaces have a wide spectrum of different groups which can undergo many reaction. If you just treated the PMMA surface with a diamine they can continue to aminolyze the ester. Or they can be split off by hydrolysis. There are many possibilities.