Landmarks

XVII. A. Some Major Steps in the Understanding of the Chemical structure of porphyrins and Chl

In this historical section, emphasis is placed on important scientific discoveries that had a clear impact on the understanding of the chemical structure of porphyrins and Chl.
  1. 1818: Pelletier and Caventou first used the word chlorophyll to describe the pigment complex responsible for the green color of leaves.
  2. 1844: VerdeilSuggested a relationship between Chl and heme upon chemical conversion of Chl to a red pigment.
  3. 1860: Fremy partitioned the plastid pigments between a yellow ethereal solution containing carotenoids and an acidic aqueous solution of blue-green pheophytins and pheophorbides, which he called phyllocyanin.
  4. 1864: Stokes suggested as a result of his spectroscopic studies that even after extracting the yellow carotenoids, the Chl fraction consisted of two different, green, red-fluorescent substances.
  5. 1882: Borodin formed Chl crystals (actually ethyl chlorophyllide) by the action of ethyl alcohol on leaves.
  6. 1893: Monteverde isolated Chl crystals and determined their spectroscopic properties.
  7. 1896: Nencki established that porphyrins were made up of Pyrrole nuclei. He proposed that the similar chemical properties of hemin and chlorophyll denotes a common origin of plant and animal life and that comparison of similar compounds of flora and fauna provides insight into chemical and organismal evolution.
  8. 1906: Twsett separated blue Chl (i. e. Chl a) from yellow Chl (i. e. Chl b) using column chromatography, and called them chl alpha and beta, which later became a and b.
  9. 1907: Willstatter and Hocheder discovered and named pheophytin (Chl that has lost the central Mg atom).
  10. 1909: Willstatter and Fritzsche applied alkaline degradation to the study of the chemical structure of Chl.
  11. 1909: Willstatter and Asahina applied chromic acid oxidation to the study of the chemical structure of Chl.
  12. 1910: Willstatter and Stoll discovered and named chlorophyllide (Chl without esterification with phytol at position 7 of the macrocycle), pheophorbide (chlorophyllide without the central Mg-atom), chlorophyllase (the enzyme that deesterifies Chl).
  13. 1911: Willstatter and Stoll discovered and named Phytol (the major esterifying alcohol of Chl at position 7 of the macrocycle), pheophorbide (chlorophyllide without the central Mg-atom), chlorophyllase (the enzyme that deesterifies Chl) and allomerization.
  14. 1913: Kuster proposed a correct formula for the ring system of porphyrins in which four pyrrole rings are linked together into a macrocycle by 4 methine bridges.
  15. 1913: Willstattter and Stoll published a monograph that summarized most of the research findings of Willstatter and collaborators and ushered the modern era of the field of Chl chemistry.
  16. 1928, 1929: Fischer and Lowenberg established the structure of phytol (1928) and synthesized it form pseudoionone (1929).
  17. 1929, 1930: Noack and Kiessling (1929, 1930), initiated the study of the protochlorophyll chemistry of pumpkin seed coat.
  18. 1933: Noack and Schneider, started the study of bacteriochlorophyll
  19. 1935: Fischer and Stern, proposed a correct structure of Chl, except for the position of the two extra hydrogens which are now recognized to be located on ring IV at positions 7 and 8 of the macrocycle.
  20. 1937: Fischer and Orth published the first part of a monograph about chl chemistry that described the various research findings of Fischer and collaborators that resulted in our modern understanding of the structure of Chl and its degradation products.
  21. 1937, 1938 : Fischer and Lambrecht (1937, 1938) established the chemical relationship of bacteriochlorophyll to Chl by the preparation of common derivatives
  22. 1939: Fischer and Wenderoth, correctly assigned the two extra hydrogens of Chl to positions 7 and 8 on ring IV.
  23. 1939, 1940: Fischer and coworkers (1939, 1940) identified the protochlorophyll of pumpkin seed coat as a vinyl pheoporphyrin analog of chlorophyll.
  24. 1940: Fischer and Stern published the second part of a monograph about chl chemistry that described the various research findings of Fischer and collaborators that resulted in our modern understanding of the structure of Chl and its degradation products.
  25. 1942, 1943: Strain and coworkers (1942, 1943) showed that chlorofucine, later known as Chl c is not an artifact.
  26. 1943: Manning and Strain, discovered Chl d.
  27. 1954: Cookson and Rimington finalized their investigations of the chemical structure of porphobilinogen.
  28. 1959: Holt and Morley determined the chemical structure of Chl d
  29. 1960: Woodward and coworkers reported the total synthesis of chlorin e6 trimethyl ester, an important degradation product of chl. In the process the authors discovered the remarkable susceptibility of chl to electrophilic attack.
  30. 1963: Closs et al, and Katz and coworkers, applied infra-red and nuclear magnetic resonance techniques to the study of chl and some of its derivatives.
  31. 1970: Dougherty et al, determined the chemical structure of Chl c

    E. References

    1. Pelletier, P. J. and Caventou, J. B. (1818). Ann. Chim. et Phys. 9: 194-196.
    2. Verdeil, F. (1844). J. Prakt. Chem. 33: 478.
    3. Fremy E. Compt. Rend. 50: 405.
    4. Stokes, G. G. (1864). Proc. Roy. soc. 13: 144.
    5. Borodin, A. (1982). Botan. Ztg. 40: 608.
    6. Monteverde, N. A. (1893). Acta Horti Petropolitani. 13: 148.
    7. Nencki, M. (1896). Ber. Deut. Chem. Ges. 29: 2877.
    8. Twsett, M. (1906). Ber. Deut. Bot. Ges. 24: 384.
    9. Willstatter, R. and Hocheder, F. (1907). Ann. Chem. 354: 205.
    10. Willstatter, R. and Asahina, Y. Ann. Chem. 373: 227.
    11. Willstatter, R. and Fritzsche, H. Ann. Chem. 371: 33.
    12. Willstatter, R. and Stoll, A. Ann. Chem. 378: 18.
    13. Willstatter, R. and Stoll, A. Ann. Chem. 387: 317.
    14. Kuster, W. (1913). Z. Physiol. Chem. 82: 463-483.
    15. Willstatter, R. and Stoll, A. (1913). Untersuchungen uber Chlorophyll. Springer, Berlin, 1913.
    16. Fischer, F. G. and Lowenberg, K. (1928). Ann. Chem. 464: 69.
    17. Fischer, F. G. and Lowenberg, K. (1929). Ann. Chem. 475: 183.
    18. Noack K. and Kiessling, W. (1929). Z. Physiol. Chem. 182: 13.
    19. Noack K. and Kiessling, W. (1930). Z. Physiol. Chem. 182: 97.
    20. Noack, K. and Schneider, E. (1933). Naturwisswnchaften 21: 835
    21. Fischer H. and Stern, A. (1935). Ann. Chem. 520: 88.
    22. Fischer, H. and Orth, H. (1937). Die Chemie des Pyrrols. Vol 2, Part I. Akad. Verlagsges; Leipzig.
    23. Fischer, H. and Lambrecht, R. (1937). Z. Physiol. Chem. 249: I.
    24. Fischer, H. and Lambrecht, R. (1938). Z. Physiol. Chem. 253: I.
    25. Fischer, H. and Wenderoth, H. (1939). Ann. Chem. 537: 251.
    26. Fischer, H., Mittenzwei, H. and Oestreicher, A. (1939). Z. Physiol. Chem. 257: IV.
    27. Fischer, H., and Oestricher, A (1940). Z. Physiol. Chem. 262 : 243.
    28. Fischer, H. and Stern, A. (1940). Die Chemie des Pyrrols. Vol 2, Part II. Akad. Verlagsges; Leipzig.
    29. Strain, H. H. and Manning, W. M. (1942). J. Biol. Chem. 144: 625.
    30. Strain, H. H., Manning, W. M., and Hardin, G. (1943). J. Biol. Chem. 148: 655.
    31. Manning, W. M., and Strain, H. H. (1943). J. Biol. Chem. 151: 1.
    32. Cookson, G. H., and Rimington, C. (1954). Porphobilinogen. Biochem. J. 57: 476-484.
    33. Holt, A. S., and Morley, H. V. (1959). Can. J. Chem. 37: 507.
    34. Woodward, R. B., Ayer, W. A; Beaton, J. M., Bickelhaupt, F. Bonnet, R., Bushchacher, P. Closs, G. L., Dutler, H., Hannah, J., Hauck, F. P., Ito, S., Langemann, A., LeGoff, E., Leimgruber, W.,, Lwowski, W., Sauer, J., Valenta, Z. and Volz, H. (1960). J. Am. Chem. Soc. 82: 3800.
    35. Katz, J. J., Closs, G. L., Pennigton, F. C., Thomas, M. R. and Strain, H. H. (1963). J. Am. Chem. Soc. 85: 3801.
    36. Closs, G. L. Katz, J. J., Pennigton, F. C., Thomas, M. R. and Strain, H. H. (1963). J. Am. Chem. Soc. 85: 3809.
    37. Dougherty, R. C., Strain, H. H., Svec, W. A., Uphaus, R. A. and Katz, J. J. (1970). J. Am. Chem. Soc. 92: 2826.

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