TY - JOUR

T1 - Two-dimensional codistribution spectroscopy applied to UVRR and ROA investigations of biomolecular transitions

AU - Ramer, Georg

AU - Ashton, Lorna

N1 - This is the author’s version of a work that was accepted for publication in Journal of Molecular Structure. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Journal of Molecular Structure, 1124, 2016 DOI: 10.1016/j.molstruc.2016.02.056

PY - 2016/11/15

Y1 - 2016/11/15

N2 - The first Raman optical activity (ROA) two-dimensional correlation spectroscopy (2DCOS) study in 2006, monitoring the temperature-induced α-helix-to-β-sheet transition in poly(l-lysine), demonstrated the versatility of 2DCOS. The combination of ROA and 2DCOS provided new ROA band assignments, enabled a direct comparison between the simultaneously collected Raman and ROA data using heterocorrelations and probed sequential information. This study also confirmed that 2DCOS can be successfully used with bisignate data, although specific care is needed when interpreting the results. However, as time has passed, doubts have been raised about not only the sequential orders reported in the study but also the general reliability of sequential data. This issue has now been addressed with the introduction of 2D codistribution (2DCDS) which is specifically designed to provide the sequence of the distributed presence of species along the perturbation variable axis. In light of these new developments in 2D correlation techniques we have revisited the original ROA data and we present our updated results. Furthermore, we demonstrate how 2DCDS can be successfully applied to bisignate data using new spectral data sets of perturbation-induced transitions in polynucleotides.

AB - The first Raman optical activity (ROA) two-dimensional correlation spectroscopy (2DCOS) study in 2006, monitoring the temperature-induced α-helix-to-β-sheet transition in poly(l-lysine), demonstrated the versatility of 2DCOS. The combination of ROA and 2DCOS provided new ROA band assignments, enabled a direct comparison between the simultaneously collected Raman and ROA data using heterocorrelations and probed sequential information. This study also confirmed that 2DCOS can be successfully used with bisignate data, although specific care is needed when interpreting the results. However, as time has passed, doubts have been raised about not only the sequential orders reported in the study but also the general reliability of sequential data. This issue has now been addressed with the introduction of 2D codistribution (2DCDS) which is specifically designed to provide the sequence of the distributed presence of species along the perturbation variable axis. In light of these new developments in 2D correlation techniques we have revisited the original ROA data and we present our updated results. Furthermore, we demonstrate how 2DCDS can be successfully applied to bisignate data using new spectral data sets of perturbation-induced transitions in polynucleotides.

KW - Two-dimensional spectroscopy

KW - Codistribution

KW - Bisignate

KW - Sequential order

KW - ROA

U2 - 10.1016/j.molstruc.2016.02.056

DO - 10.1016/j.molstruc.2016.02.056

M3 - Journal article

VL - 1124

SP - 173

EP - 179

JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

SN - 0022-2860

ER -