Coordination Properties of Magnesium in Chlorophyll from IR and NMR Spectra

  • Joseph J. Katz
Part of the Developments in Applied Spectroscopy book series (DAIS, volume 6)


The infrared (IR) and nuclear magnetic resonance (NMR) spectra of chlorophyll are best interpreted on the basis that the central magnesium atom of the chlorophyll always has a coordination number larger than 4. In electron-donor solvents, chlorophyll exists as monomer, with solvent molecules filling the axial position(s). In nonpolar solvents, the coordination unsaturation of the magnesium is relieved by coordination of the ketone oxygen function of one molecule of chlorophyll with the magnesium of another. This leads to dimer or higher aggregate formation in nonpolar media. Chlorophyll-ligand interactions can be studied by observing ring- current shielding effects on the chemical shifts of protons in ligands coordinated to the magnesium atom of chlorophyll. Chlorophyll is shown by this procedure to coordinate ethanol and lutein but not 0 carotene. With plant sulf olipid, chlorophyll probably dissolves in sulf olipid micelles present in CCI4 solution as a result of phytyl long-chain fatty acid interactions rather than as a primary result of coordination interactions involving magnesium. Deuterated chlorophyll is shown to be very useful for these NMR studies.


Nuclear Magnetic Resonance Spectrum Nuclear Magnetic Resonance Spectroscopy Nonpolar Solvent Upfield Shift Chlorophyll Molecule 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    J. J. Katz, G.L. Gloss, F.C. Pennington, M. R, Thomas, and H.H. Strain, J. Am. Chem. Soc. 85:3801 (1963).CrossRefGoogle Scholar
  2. 2.
    A.F.H. Anderson and M. Calvin, Arch. Biochem. Biophys. 107:251 (1964).CrossRefGoogle Scholar
  3. 3.
    L.J. Boucher, H.H. Strain, and J.J. Katz, J.Am. Chem. Soc. 88:1341 (1966).CrossRefGoogle Scholar
  4. 4.
    G.L. Gloss, J.J. Katz, F.C. Pennington, M. R. Thomas, and H.H. Strain, J. Am. Chem. Soc. 85:3809 (1963).CrossRefGoogle Scholar
  5. a. C.B. Storm and A.H. Corwin, J. Org. Chem. 29:3700 (1964); alsoCrossRefGoogle Scholar
  6. b. C.B. Storm, A.H. Corwin, R.R. Arellano, M. Martz, and R. Weintraub, J. Am. Chem. Soc. 88:2525 (1966).CrossRefGoogle Scholar
  7. 6.
    G.R. Seely and R.G. Jensen, Spectrochim. Acta 21:1835 (1965).CrossRefGoogle Scholar
  8. 7.
    G.R. Seely, Spectrochim. Acta 21:1847 (1965).CrossRefGoogle Scholar
  9. 8.
    K. Sauer. J.R.L. Smith, and A.J. Schultz, J. Am. Chem. Soc. 88 — 2681 (1966).Google Scholar
  10. 9.
    R.L. Amster and G. Porter, Proc. Roy. Soc. (London), A296:38–44 (1967).Google Scholar
  11. a.
    N.V. Sidgwick, The Chemical Elements, Vol. I, Oxford Press, Oxford (1950), p. 241 ff.; alsoGoogle Scholar
  12. a.
    F. Hein, Chemische Koordinationslehre, S.Hirzel Verlag, Zurich (1950), p. 380.Google Scholar
  13. 11.
    G.T. Byrne, R. P. Linstead, and A.R. Lowe, J. Chem. Soc. 1934:1017.Google Scholar
  14. 12.
    P.E. Wei, A.H. Corwin, and R. Arellano, J. Org. Chem. 27:3344 (1962).CrossRefGoogle Scholar
  15. 12a.
    a. E. Rabinowitch, Photosynthesis, Vol. I, Interscience Publishers, Inc. (John Wiley and Sons, Inc.), New York (1945), p. 450; alsoGoogle Scholar
  16. b. E.E. Jacobs and A.S. Holt, J. Chem. Phys. 20:1326 (1962).CrossRefGoogle Scholar
  17. 14.
    a. R. Livingston, Quart. Rev. (London) 14:174 (1960); alsoCrossRefGoogle Scholar
  18. b. R. Livingston and S. Weil, Nature 170:750 (1952).CrossRefGoogle Scholar
  19. 15.
    v. B. Evstigneev, V.A. Gavrilova, and A. A. Krasnovskii, Dokl. Akad. Nauk. S.S.S.R. 70:261 (1950).Google Scholar
  20. 16.
    J.J. Katz, R.C. Dougherry, and L. J. Boucher, “Infrared and Nuclear Magnetic Resonance Spectroscopy of Chlorophyll,” in: L. Vernon and G.R. Seely, eds.. The Chlorophylls, Chap. 7, Academic Press, Inc., New York (1966), pp. 185–251.Google Scholar
  21. a. J. Fernandez and R.S. Becker, J. Chem. Phys. 31:467 (1959); alsoCrossRefGoogle Scholar
  22. b. J. Franck, J.L. Rosenberg, and C. Weiss, Jr., in: H.P. Kollmann and C.M. Spruch, eds., Luminescence of Organic and Inorganic Materials, John Wiley and Sons, Inc., New York (1962), pp. 16 ff.; alsoGoogle Scholar
  23. c. R. S, Becker and M. Kasha, in: F.H. Johnson, ed., The Luminescence of Biological Systems, American Association for the Advancement of Science, Washington, D.C. (1955), pp. 30 ff.Google Scholar
  24. 18.
    a. E.I. Rabinowitch and Govindjee, Sci. Am. 213:74 (1965); alsoCrossRefGoogle Scholar
  25. Govindjee and E.l. Rabinowitch, J. Sci. Ind. Res. (India) 24:591 (1965).Google Scholar
  26. 19.
    Summarized by J.C. Goedheer, “Visible Absorption and Fluorescence of Chlorophyll and Its Aggregates in Solution,” Chap. 6, pp. 147–184, and W. L. Butler, “Spectral Characteristics of Chlorophyll in Green Plants,” Chap. 11, pp. 343–379, in: L. Vernon and G.R. Seely, eds.. The Chlorophylls, Academic Press, Inc., New York (1966).Google Scholar
  27. 20.
    A.S. Holt and E.E. Jacobs, Plant Physiol. 30:553 (1955).CrossRefGoogle Scholar
  28. 21.
    R.C. Dougherty, H.H, Strain, W.A. Svec, R.A. Uphaus, and J.J. Katz, J. Am. Chem. Soc. 88:5037 (1966).CrossRefGoogle Scholar
  29. 22.
    R.J. Abraham, Mol. Phys. 4:145 (1961).CrossRefGoogle Scholar
  30. a. J.J. Katz and H.L. Crespi, Science 151:1187 (1966); alsoCrossRefGoogle Scholar
  31. b. H.A. DaBoll, H.L. Crespi, and J.J. Katz, Biotechnol. Bioeng. 4:281–297 (1962); alsoCrossRefGoogle Scholar
  32. c. A. J. Williams, A.T. Morse, and R.S. Stuart, Can. J. Microbiol. 12:1167–1173 (1966).CrossRefGoogle Scholar
  33. 24.
    S. Aronoff and P. Kirk, Nature 213:722 (1967).CrossRefGoogle Scholar
  34. 25.
    B.C.L. Weedon, “Chemistry of the Carotenoids,” in: T.W. Goodwin, ed.. Chemistry and Biochemistry of Plant Pigments, Chap. 3, Academic Press, Inc., New York (1965), pp. 75–173.Google Scholar
  35. 26.
    A.A. Benson and I. Shibuya, “Surfactant Lipids,” in: R.A. Lewin, ed.. Physiology and Biochemistry of Algae. Chap. 22, Academic Press, Inc., New York (1962), pp. 371–383.Google Scholar
  36. 27.
    J.J. Katz, H.H. Strain, D.L. Leussing, and R.C. Dougherty, J. Am. Chem. Soc. 90:784 (1968).CrossRefGoogle Scholar

Copyright information

© Chicago Section of the Society for Applied Spectroscopy 1968

Authors and Affiliations

  • Joseph J. Katz
    • 1
  1. 1.Argonne National LaboratoryArgonneUSA

Personalised recommendations