Raman
spectroscopy has drawn considerable attention in biomedical
sensing due to the promise of label-free, multiplexed, and objective
analysis along with the ability to gain molecular insights into complex
biological samples. However, its true potential is yet to be realized
due to the intrinsically weak Raman signal. Here, we report a simple,
inexpensive and reproducible signal enhancement strategy featuring
graphene as a substrate. Taking key blood constituent proteins as
representative examples, we show that Raman spectra acquired from
biomacromolecules can be reproducibly enhanced when these molecules
are placed in contact with graphene. In particular, we demonstrate
that hemoglobin and albumin display significant, but different, enhancement
with the enhancement factor depending on the Raman modes, excitation
wavelengths, and analyte concentrations. This technique offers a new
strategy for label-free biosensing owing to the molecular fingerprinting
capability, signal reliability, and simplicity of the enhancement
method.