The chemical and conformational structures of Bombyx mori silk were Studied with the complementary techniques of Fourier transforrn Raman spectroscopy and Fourier transform infrared spectroscopy. The Fourier transform Raman spectrum of silk showed strong bands for the photosensitive aromatic amino acids tyrosine, tryptophan, and phenylalamne. Intensive UV/ozone irradiation reduced the Raman intensities of the amide TII band and the tyrosine signals due to peptide chain scission of the silk polymer and the photochemical changes in the tyrosine residues on the silk molecules. However, the Raman spectroscopy changes for tryptophan were less clearly defined because of peak overlapping with other amino acid signals and the low concentration of tryptophan. The Fourier transform infrared (attenuated total reflectance) technique, coupled with second-derivative spectroscopy analysis, demonstrated a decrease in the crystallinity degree and tyrosine content of UV/ozone-irradiated silk, as indicated by changes in the Fourier transform infrared bands of amide III doublet and tvrosine sianals. (c) 2005 Wiley Periodicals, Inc.