Abstract
Here we consider magnetic transition dipoles and magnetic-dipole transitions, using both semiclassical and quantum approaches. We introduce ellipticity and optical rotation, and derive the Rosenfeld equation, which shows how coupling of electric and magnetic transition dipoles results in circular dichroism. The circular dichroism of dimers and higher oligomers, including proteins and nucleic acids, is addressed in detail and is related to the theory of exciton interactions developed in Chap. 8. The chapter concludes with a discussion of magnetic circular dichroism.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Hansen, A.E.: On evaluation of electric and magnetic dipole transition moments in the zero differential overlap approximation. Theor. Chim. Acta 6, 341–349 (1966)
Král, M.: Optical rotatory power of complex compounds. Matrix elements of operators Del and R x Del. Collect. Czech. Chem. Commun. 35, 1939–1948 (1970)
Ham, J.S., Platt, J.R.: Far U.V. spectra of peptides. J. Chem. Phys. 20, 335–336 (1952)
Barnes, E.E., Simpson, W.T.: Correlations among electronic transitions for carbonyl and for carboxyl in the vacuum ultraviolet. J. Chem. Phys. 39, 670–675 (1963)
Callomon, J.H., Innes, K.K.: Magnetic dipole transition in the electronic spectrum of formaldehyde. J. Mol. Spectrosc. 10, 166–181 (1963)
Woody, R.W., Tinoco Jr., I.: Optical rotation of oriented helices. III. Calculation of the rotatory dispersion and circular dichroism of the alpha and 310-helix. J. Chem. Phys. 46, 4927–4945 (1967)
Hameka, H.: Advanced Quantum Chemistry. Addison-Wesley, Reading, MA (1965)
Schatz, G.C., Ratner, M.A.: Quantum Mechanics in Chemistry, p. 325. Prentice-Hall, Englewood Cliffs, NJ (1993)
Moffitt, W., Moscowitz, A.: Optical activity in absorbing media. J. Chem. Phys. 30, 648–660 (1959)
Moscowitz, A.: Theoretical aspects of optical activity part one: small molecules. Adv. Chem. Phys. 4, 67–112 (1962)
Rosenfeld, L.Z.: Quantenmechanische Theorie der natürlichen optischen Aktivität von Flüssigkeiten und Gasen. Z. Phys. 52, 161–174 (1928)
Hansen, A.E., Bak, K.L.: Ab-initio calculations of electronic circular dichroism. Enantiomer 4, 1024–2430 (1999)
Berova, N., Nakanishi, K., Woody, R.W. (eds.): Circular Dichroism. Principles and Applications. Wiley-VCH, New York, NY (2000)
Lightner, D.A., Gurst, J.E.: Organic Conformational Analysis and Stereochemistry from Circular Dichroism Spectroscopy. Wiley-VCH, New York, NY (2000)
Autschbach, J., Ziegler, T., van Gisbergen, S.J.A., Baerends, E.J.: Chirooptical properties from time-dependent density functional theory. I. Circular dichroism of organic molecules. J. Chem. Phys. 116, 6930–6940 (2002)
Diedrich, C., Grimme, S.: Systematic investigation of modern quantum chemical methods to predict electronic circular dichroism spectra. J. Phys. Chem. A 107, 2524–2539 (2003)
Hobden, M.V.: Optical activity in a nonenantiomorphous crystal silver gallium sulfide. Nature 216, 678 (1967)
Hobden, M.V.: Optical activity in a non-enantiomorphous crystal cadmium gallium sulfide. Nature 220, 781 (1968)
Claborn, K., Cedres, J.H., Isborn, C., Zozulya, A., Weckert, E., et al.: Optical rotation of achiral pentaerythritol. J. Am. Chem. Soc. 128, 14746–14747 (2006)
Kirkwood, J.G.: On the theory of optical rotatory power. J. Chem. Phys. 5, 479–491 (1937)
Moffitt, W.: Optical rotatory dispersion of helical polymers. J. Chem. Phys. 25, 467–478 (1956)
Tinoco Jr., I.: Theoretical aspects of optical activity part two: polymers. Adv. Chem. Phys. 4, 113–160 (1962)
Schellman, J.: Circular dichroism and optical rotation. Chem. Rev. 75, 323–331 (1975)
Charney, E.: The Molecular Basis of Optical Activity. Wiley-Interscience, New York, NY (1979)
Fasman, G.D. (ed.): Circular Dichroism and the Conformational Analysis of Macromolecules. Plenum, New York, NY (1996)
Condon, E.U.: Theories of optical rotatory power. Rev. Mod. Phys. 9, 432–457 (1937)
Greenfield, N., Fasman, G.D.: Computed circular dichroism spectra for the evaluation of protein conformation. Biochemistry 8, 4108–4116 (1969)
Saxena, V.P., Wetlaufer, D.B.: A new basis for interpreting the circular dichroic spectra of proteins. Proc. Natl. Acad. Sci. U. S. A. 68, 969–972 (1971)
Johnson Jr., W.C.: Analysis of circular dichroism spectra. Methods Enzymol. 210, 426–447 (1992)
Ramsay, G.D., Eftink, M.R.: Analysis of multidimensional spectroscopic data to monitor unfolding of proteins. Methods Enzymol. 240, 615–645 (1994)
Woody, R.W.: Circular dichroism. Methods Enzymol. 246, 34–71 (1995)
Plaxco, K.W., Dobson, C.M.: Time-resolved biophysical methods in the study of protein folding. Curr. Opin. Struct. Biol. 6, 630–636 (1996)
Whitmore, L., Wallace, B.A.: Protein secondary structure analyses from circular dichroism. Biopolymers 89, 392–400 (2008)
Wallace, B.A., Janes, R.W.: Modern Techniques for Circular Dichroism and Synchrotron Radiation Circular Dichroism Spectroscopy. IOS, Amsterdam (2009)
Pan, T., Sosnick, T.R.: Intermediates and kinetic traps in the folding of a large ribozyme revealed by circular dichroism and UV absorbance spectroscopies and catalytic activity. Nat. Struct. Biol. 4, 931–938 (1997)
Settimo, L., Donnini, S., Juffer, A.H., Woody, R.W., Marin, O.: Conformational changes upon calcium binding and phosphorylation in a synthetic fragment of calmodulin. Biopolymers 88, 373–385 (2007)
Bovey, F.A., Hood, F.P.: Circular dichroism spectrum of poly-L-proline. Biopolymers 5, 325–326 (1967)
Woody, R.W.: Circular dichroism of unordered polypeptides. Adv. Biophys. Chem. 2, 37–79 (1992)
Woody, R.W.: Circular dichroism spectrum of peptides in the polyPro II conformation. J. Am. Chem. Soc. 131, 8234–8245 (2009)
Manning, M.C., Illangasekare, M., Woody, R.W.: Circular dichroism studies of distorted α-helices, twisted β-sheets, and β-turns. Biophys. Chem. 31, 77–86 (1988)
Provencher, S.W., Glockner, J.: Estimation of globular protein secondary structure from circular dichroism. Biochemistry 20, 33–37 (1981)
van Stokkum, I.H., Spoelder, H.J., Bloemendal, M., van Grondelle, R., Groen, F.C.: Estimation of protein secondary structure and error analysis from circular dichroism spectra. Anal. Biochem. 191, 110–118 (1990)
Andrade, M.A., Chacon, P., Merelo, J.J., Moran, F.: Evaluation of secondary structure of proteins from UV circular dichroism spectra using an unsupervised learning neural network. Protein Eng. 6, 383–390 (1993)
Sreerama, N., Manning, M.C., Powers, M.E., Zhang, J.-X., Goldenberg, D.P., et al.: Tyrosine, phenylalanine, and disulfide contributions to the circular dichroism of proteins: circular dichroism spectra of wild-type and mutant bovine pancreatic trypsin inhibitor. Biochemistry 38, 10814–10822 (1999)
Whitmore, L., Wallace, B.A.: DICHROWEB, an online server for protein secondary structure analyses from circular dichroism spectroscopic data. Nucleic Acids Res. 32 (Web Server issue), W668–W673 (2004)
Gratzer, W.B., Holzwarth, G.M., Doty, P.: Polarization of the ultraviolet absorption bands in a-helical polypeptides. Proc. Natl. Acad. Sci. U. S. A. 47, 1785–1791 (1961)
Rosenheck, K., Doty, P.: The far ultraviolet absorption spectra of polypeptide and protein solutions and their dependence on conformation. Proc. Natl. Acad. Sci. U. S. A. 47, 1775–1785 (1961)
Tinoco Jr., I., Woody, R.W., Bradley, D.F.: Absorption and rotation of light by helical polymers: the effect of chain length. J. Chem. Phys. 38, 1317–1325 (1963)
Woody, R.W.: Improved calculation of the np* rotational strength in polypeptides. J. Chem. Phys. 49, 4797–4806 (1968)
Sreerama, N., Woody, R.W.: Computation and analysis of protein circular dichroism spectra. Methods Enzymol. 383, 318–351 (2004)
Hirst, J.D., Colella, K., Gilbert, A.T.B.: Electronic circular dichroism of proteins from first-principles calculations. J. Phys. Chem. B 107, 11813–11819 (2003)
Hirst, J.D.: Improving protein circular dichroism calculations in the far-ultraviolet through reparametrizing the amide chromophore. J. Chem. Phys. 109, 782–788 (1998)
Grishina, I.B., Woody, R.W.: Contributions of tryptophan side chains to the circular dichroism of globular proteins: exciton couplets and coupled oscillators. Faraday Discuss. 99, 245–267 (1994)
Cochran, A.G., Skelton, N.J., Starovasnik, M.A.: Tryptophan zippers: stable, monomeric beta-hairpins. Proc. Natl. Acad. Sci. U. S. A. 98, 5578–5583 (2001)
Ohmae, E., Matsuo, K., Gekko, K.: Vacuum-ultraviolet circular dichroism of Escherichia coli dihydrofolate reductase: insight into the contribution of tryptophan residues. Chem. Phys. Lett. 572, 111–114 (2013)
Matsuo, K., Hiramatsu, H., Gekko, K., Namatame, H., Taniguchi, M., et al.: Characterization of intermolecular structure of β2-microglobulin core fragments in amyloid fibrils by vacuum-ultraviolet circular dichroism spectroscopy and circular dichroism theory. J. Phys. Chem. B 118, 2785–2795 (2014)
Stephens, P.J.: Theory of magnetic circular dichroism. J. Chem. Phys. 52, 3489–3516 (1970)
Stephens, P.J.: Magnetic circular dichroism. Ann. Rev. Phys. Chem. 25, 201–232 (1974)
Thomson, A.J., Cheesman, M.R., George, S.J.: Variable-temperature magnetic circular dichroism. Methods Enzymol. 226, 199–232 (1993)
Solomon, E.I., Pavel, E.G., Loeb, K.E., Campochiaro, C.: Magnetic circular dichroism spectroscopy as a probe of the geometric and electronic structure of nonheme ferrous enzymes. Coord. Chem. Rev. 144, 369–460 (1995)
Kirk, M.L., Peariso, K.: Recent applications of MCD spectroscopy to metalloenzymes. Curr. Opin. Chem. Biol. 7, 220–227 (2003)
McMaster, J., Oganesyan, V.S.: Magnetic circular dichroism spectroscopy as a probe of the structures of the metal sites in metalloproteins. Curr. Opin. Struct. Biol. 20, 615–622 (2010)
Companion, A.L., Komarynsky, M.A.: Crystal field splitting diagrams. J. Chem. Ed. 41, 257–262 (1964)
Quadrifoglio, F., Urry, D.M.: Ultraviolet rotatory properties of peptides in solution. I. Helical poly-L-alanine. J. Am. Chem. Soc. 90, 2755–2760 (1968)
Riazance, J.H., Baase, W.A., Johnson Jr., W.C., Hall, K., Cruz, P., et al.: Evidence for Z-form RNA by vacuum UV circular dichroism. Nucleic Acids Res. 13, 4983–4989 (1985)
Author information
Authors and Affiliations
Rights and permissions
Copyright information
© 2015 Springer-Verlag Berlin Heidelberg
About this chapter
Cite this chapter
Parson, W.W. (2015). Circular Dichroism. In: Modern Optical Spectroscopy. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-662-46777-0_9
Download citation
DOI: https://doi.org/10.1007/978-3-662-46777-0_9
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-662-46776-3
Online ISBN: 978-3-662-46777-0
eBook Packages: Biomedical and Life SciencesBiomedical and Life Sciences (R0)