Applications of Near-Infrared Raman Optical Activity to Biological Samples

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Many biological cofactors, such as light-absorbing chromophores in photoreceptors, are intrinsically planar molecules. A protein environment, however, causes structural distortions of the cofactor, and such structural changes can lead to a modulation of chemical properties of the cofactor to maximize its biological activity. We recently applied the near-infrared ROA to bacteriorhodopsin and photoactive yellow protein. These studies demonstrated that the near-infrared excitation allows us to measure the ROA spectra of a chromophore within a protein environment. Furthermore, calculations of the ROA spectra utilizing DFT provide detailed structural information, such as data about out-of-plane distortions of the chromophore. These findings extend the applicability of ROA to many biological cofactors.