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Infrared absorption spectroscopy is a powerful tool for structural and functional studies of biomolecules. The technique enables direct access to the vibrational fingerprints of molecular bonds in the mid-infrared spectral region (3-20μm). Although intrinsic absorption cross-sections are nearly ten orders of magnitude greater than corresponding Raman cross-sections, they are still small in comparison with those of fluorescent molecules. Sensitivity improvements are therefore required for the method to be applicable to single molecule / molecular layer studies. In this work, we demonstrate the use of lithographically patterned arrays of nanoantennas to enhance the absorption signature of the protein amide-I and II backbone vibrations. Strong absorption signals from monolayer thickness films are obtained. By arranging ensembles of tailored antennas in specific lattices, higher quality factor resonances and increased near-field intensities are possible. These features are leveraged to obtain 104-105 fold signal enhancements and the direct measurement of vibrational spectra of proteins at zepto-mole sensitivity levels.
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