Two-photon circular dichroism (TPCD) has been recognized for its exceptional spectroscopic ability for the structural and conformational analysis of chiral systems due to its high sensitivity to small peptide structural distortions. In 2008, Hernandez and co-workers demonstrated TPCD experimentally by the development of the Double L-scan technique. Since then, we have been working on a systematic theoretical-experimental study of chiral molecules using TPCD. In this dissertation, I present my contribution to the continuation to the study of the structure-property relationship of TPCD in molecules with axial chirality in solution, as well as the implementation of the TPCD measurements in the near- and far-UV regions. Employing a theoretical-experimental approach I will discuss: 1) the effect of the pulse width of the excitation source on the TPCD spectra of biaryl derivatives, 2) the theoretical study of the TPCD signal in the far-UV on molecular structures simulating aromatic amino acid residues in proteins with secondary structures, and 3) the pros and cons of the implementation of the FUV-TPCD spectrometer. The outcomes of my research reveal the potential of TPCD for the conformational analysis of relatively complex molecular systems such as peptides in the far-UV region, an area never accessed before. Additionally, we exposed the applicability of TPCD as a complimentary method to standard electronic circular dichroism (ECD) for the study of complex structures. Finally, I demonstrate for the very first time experimental evidence of TPCD in the near- to Far-UV region.
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Doctor of Philosophy (Ph.D.)
College of Sciences
Length of Campus-only Access
Doctoral Dissertation (Open Access)
Vesga Prada, Yuly Katherine, "Theoretical-Experimental Study of the Two-Photon Circular Dichroism of Helicenes and Aromatic Amino Acids in the UV Region: From the Structure-Property Relationship to the Final Implementation" (2016). Electronic Theses and Dissertations, 2004-2019. 5343.