K. Chruszcz-Lipska and E. W. Blanch
76
is considerably more accurate than has been found for analogous structural analyses
using protein electronic circular dichroism (ECd) spectra, as RoA is a vibrational
technique and so sensitive to far more structurally-sensitive bands.
4.4 Conclusions
No doubt, computational approaches to analysis of experimental RoA data can provide a great deal of information about the chiral structures of molecules. In the last
decade, the considerable progress in quantum chemical calculation of RoA spectra
has been achieved and the application of theoretical methods to better understand
experimentally measured RoA spectra is becoming more widely used. Nowadays,
not only are calculations of standard RoA spectra for various type of molecules
well developed but there also now appear in the literature some examples of theoretical modelling of surface enhanced RoA (SERoA) [105] and resonance RoA
(RRoA) spectra [106, 107]. Both of these techniques have considerable potential
for the investigation of biological samples because they combine chiral selectivity
with surface or resonance enhancement of a measured signal. Although SERoA and
RRoA are in the early stage of their experimental development, the calculations reported follow these developments quite closely and already demonstrate the insight
they can provide. It is also known in the literature that anharmonic effects can be
important for RoA [108] but regardless of successes in that field, the theoretical
calculation of RoA spectra can be still a challenging task.
Acknowledgements this research was partially supported by the British Council and the Polish
ministry of Science and higher Education in 2010 (grant to K. Ch-L. from the British-Polish
Young Scientist Programme). the authors thank the Academic Computer Centre ‘Cyfronet’ in
Kraków (Poland) for computer time (grant no. KBN/SgI_oRIgIN_2000/uJ/061/2000). the authors also thank Zofia Barto for help in Fig. 4.1 preparation.
References
1. Atkins PW, Barron Ld (1969) Rayleigh scattering of polarized photons by molecules. mol
Phys 16(5):453–466
2. Barron Ld, Bogaard mP, Buckingham Ad (1973) Raman scattering of circularly polarized
light by optically active molecules. J Am Chem Soc 95:603–605
3. Barron Ld, hecht L, Blanch EW, Bell AF (2000) Solution structure and dynamics of biomolecules from Ramam optical activity. Prog Biophys mol Biol 73:1–49
4. Barron Ld, Blanch EW, hecht L (2002) unfolded proteins studied by Raman optical activity.
Adv Protein Chem 62:51–90
5. Blanch EW, hecht L, Barron Ld (2003) vibrational Raman optical activity of proteins, nucleic
acids, and viruses. methods 29:196–209
6. hecht L, Phillips AL, Barron Ld (1995) determination of enantiomeric excess using vibrational Raman optical activity. J Raman Spectrosc 26:727–732
76
is considerably more accurate than has been found for analogous structural analyses
using protein electronic circular dichroism (ECd) spectra, as RoA is a vibrational
technique and so sensitive to far more structurally-sensitive bands.
4.4 Conclusions
No doubt, computational approaches to analysis of experimental RoA data can provide a great deal of information about the chiral structures of molecules. In the last
decade, the considerable progress in quantum chemical calculation of RoA spectra
has been achieved and the application of theoretical methods to better understand
experimentally measured RoA spectra is becoming more widely used. Nowadays,
not only are calculations of standard RoA spectra for various type of molecules
well developed but there also now appear in the literature some examples of theoretical modelling of surface enhanced RoA (SERoA) [105] and resonance RoA
(RRoA) spectra [106, 107]. Both of these techniques have considerable potential
for the investigation of biological samples because they combine chiral selectivity
with surface or resonance enhancement of a measured signal. Although SERoA and
RRoA are in the early stage of their experimental development, the calculations reported follow these developments quite closely and already demonstrate the insight
they can provide. It is also known in the literature that anharmonic effects can be
important for RoA [108] but regardless of successes in that field, the theoretical
calculation of RoA spectra can be still a challenging task.
Acknowledgements this research was partially supported by the British Council and the Polish
ministry of Science and higher Education in 2010 (grant to K. Ch-L. from the British-Polish
Young Scientist Programme). the authors thank the Academic Computer Centre ‘Cyfronet’ in
Kraków (Poland) for computer time (grant no. KBN/SgI_oRIgIN_2000/uJ/061/2000). the authors also thank Zofia Barto for help in Fig. 4.1 preparation.
References
1. Atkins PW, Barron Ld (1969) Rayleigh scattering of polarized photons by molecules. mol
Phys 16(5):453–466
2. Barron Ld, Bogaard mP, Buckingham Ad (1973) Raman scattering of circularly polarized
light by optically active molecules. J Am Chem Soc 95:603–605
3. Barron Ld, hecht L, Blanch EW, Bell AF (2000) Solution structure and dynamics of biomolecules from Ramam optical activity. Prog Biophys mol Biol 73:1–49
4. Barron Ld, Blanch EW, hecht L (2002) unfolded proteins studied by Raman optical activity.
Adv Protein Chem 62:51–90
5. Blanch EW, hecht L, Barron Ld (2003) vibrational Raman optical activity of proteins, nucleic
acids, and viruses. methods 29:196–209
6. hecht L, Phillips AL, Barron Ld (1995) determination of enantiomeric excess using vibrational Raman optical activity. J Raman Spectrosc 26:727–732