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Articles

Protein Chemists Bypass the Colloid/Macromolecule Debate

Charles Tanford
&
Jacqueline Reynolds
Pages 33-51 | Published online: 18 Jul 2013

Notes and References

  • P. J. Flory, Principles of Polymer Chemistry (Ithaca: Cornell U. Press, 1953), pp. 3–28; H. Morawetz. Polymers: The Origins and Growth of a Science (New York: John Wiley, 1985); P. J. T. Morris, Polymer Pioneers (Philadelphia: Center for History of Chemistry, 1986); R. Olby, "The macromolecular concept," j Chem. Ed. 47 (1970), 168–174; Y. Furukawa, "Hermann Staudinger and the emergence of the macromolecular concept," Historia Scientiarum 22 (1982), 1–18; H. Eisenberg, "Birth of the macromolecule," Biophys. Chem. 59 (1996), 247–257. Also see Staudinger's own memoirs, H. Staudinger, Arbeitserrinerungen (Heidelberg: Hiithig, 1961), English translation entitled From Organic Chemistry to Macromolecules, (New York: John Wiley, 1970).
  • M. Florkin and E. H. Stotz, eds., Comprehensive Biochemistry (Amsterdam: Elsevier, 1972), vol. 32, pp. 279–284. The Florkin-Stotz position is substantially modified—protein chemists are given much more credit—in a subsequent volume of the same treatise: P. Laszlo, "The notion of macromolecules," ibid. (1986), vol. MA, pp. 12–22.
  • Words spoken in frustration at a lecture in 1925 at the Zurich Chemical Society. See Morawetz, op. cit. (1), P. 86.
  • W. H. Brock, The Fontana History of Chemistry (London: Fontana, 1992), P. 650.
  • P. J. Flory, op. cit. (1), p. 11; J. T. Edsall, "Proteins as macromolecules," Arch. Biochenz. Biophys., Supplement 1 (1962), 12–20.
  • G. J. Mulder, "Zusammensetzung von Fibrin, Albumin, Leimzucker, Leucin u.s.w.", Annalen der Pharmacie 28 (1838), 73–82.
  • H. B. Vickery, "The origin of the word protein," Yale J. Biol and Med 22 (1950), 387–393.
  • It was not till after 1840 that the famous confusion about atomic weights arose, which culminated in the 1860 Karslruhe conference decision effectively to have different sets of atomic weights for inorganic and organic chemistry. See J. R. Partington, History of Chemistry (London: Macmillan, 1961-1964), vol. 4, pp. 166,488.
  • J. Fruton, Molecules and Life (New York: Wiley-Interscience, 1972), pp. 95–101; E. Glas, "The protein theory of G. J. Mulder (1802–1880),"Janus 62 (1975), 289–308; E. Glas, "The Liebig-Mulder controversy. On the methodology of physiological chemistry," Janus 63 (1973), 27–46; J. B. Dumas and A. Cahours. "Sur les matieres azotées neutres de l'organisation," Ann. Chim. Phys. 6 (1842), 385–448; N. Laskowski. "Ueber die Proteintheorie," Annalen der Chemie 58 (1846), 129–166.
  • Distinction between primary and secondary bonds ultimately proved to be an important factor for protein structure, but in a different guise, as a force in what happens to macromolecular polypeptide chains post synthesis, i.e., folding to specific 3-dimensional structures and (sometimes) reversible association into oligomers.
  • J. L. W. Thudichum. A Manual of Chemical Physiology (London: Longmans, 1872). 'Atomic weight' was still used to represent the sum of the weights of atoms in the molecules. In fact, Mulder used the term where we have written 'molecular weight.'
  • O. Zinoffsky, "Ueber die Grosse des H5moglobinmolecills," Z. physiol. Chem. 10 (1885), 16–34; G. Hailer, "Neue Versuche zur Bestimmung der Sauerstoffcapacith des Blutfarbstoff', Archiv für Physiologie 1894, 130–176.
  • A. Kossel and F. Kutscher, "Beitrdge zur Kenntniss der Eiweisskörper," Z. physiol Chem. 31 (1900), 165–214; F. Hofmeister, "Ueber Bau und Gruppierung der Eiweisskörper," Ergebnisse der Physiologic 1(1902), 759–802.
  • H. Hlasiwetz and J. Habermann, "Ueber die Proteinstoffe," Annalen der Chemie 159 (1871), 304–333, 169 (1873), 150–166.
  • J. S. Fruton, "Contrasts in scientific style. Emil Fischer and Franz Hofmeister: their research groups and their theory of protein structure," Proceedings of the American Philosophical Society 129 (1985), 313–370; E. Fischer, "Uber die Hydrolyse der Proteinstoffe", Chemiker Zeitung 26 (1902), 939–940; F. Hofmeister, op. cit. (13). Fischer describes his synthetic experiments as the 'chaining of the amino acids' and suggests the names tripeptides, tetrapeptides', etc. for the products of his synthesis. Fischer was awarded a Nobel Prize in the same year (1902), but the award was for earlier work on sugars and purines.
  • E. Fischer, "Synthetical chemistry in its relation to biology" (Faraday Lecture), J. Chem. Soc. 91 (1907), 1749–1765.
  • B. Witkop, prologue to reprinted edition of E. Fischer, Aus meinen Leben (Berlin: Sprinter Verlag, 1987), P. xvi.
  • J. W. Servos, Physical Chemistry from Ostwald to Pauling (Princeton: Princeton U. Press, 1990); K. J. Laidler, The World of Physical Chemistry (Oxford: Oxford U. Press, 1993).
  • A. Sabanjeff, "Kryoskopische Untersuchung der Kolloide. Bestimmung des Moledkularge-wichtes von Kolloiden nach Raoult's Methode", Chem. Centralblatt 62 (1891), part 1, 10–12. (Abstract of earlier Russian paper).
  • G. B. Kauffman, Biography of Thomas Graham, DSB 5 (1972).
  • T. Graham, "Liquid diffusion applied to analysis," Phil. Trans. Roy. Soc. 151 (1861), 183–224. Graham quit his academic appointment at University College (London) in 1854 to become Master of the Mint, the last to hold that title, Isaac Newton having been the first. His 1861 paper dates from this late period in his career.
  • A. Kekulé, Inaugural lecture given at the Unviersity of Bonn, Nature 18 (1878), 210.
  • W. Ostwald, Lehrbuch der allgemeinen Chemie (Leipzig: W. Engelmann, 1884–85), vol. 1, p. 527.
  • J. M. van Bemmelen, "Sur las nature des colloides et leur teneur en eau," Rea Tray. Chem. Pays-Bas 7 (1888), 37–68. For English translation see E. Hatschek, ed., The foundations of colloid chemistry (London: Ernest Benn, 1925).
  • H. Picton & S. E. Linder, "Solution and Pseudo-solution," Part I, J. Chem. Soc. 61 (1892), 148–172; Part III, ibid. 71 (1897), 568–573. Neither Picton nor Linder kept on with their research after these papers were published, but they continued to be held in high esteem because their work laid the foundation for electrophoresis as an experimental tool. After World War 1 Picton became active in the peace movement and vigorously promoted good relations with Germany. In 1923 he was invited to address the 2nd general meeting of the Kolloidgesellschaft in Jena, where he gave a moving talk, describing himself as a 'phantom of the past'. See Report of the second general meeting of the Kolloidgesellschaft, Kollid Z. 33 (1923), 257-261; E. Hatschek, ed., "Klassische Arbeiten fiber kolloide Lösungen," Ostwald's Klassiker der Exakten Wissertschaften, vol. 217 (1926).
  • J. W. Servos, op. cit. (18), ch. 3; T. Hager, Force of Nature: the Life of Linus Pauling (New York: Simon & Schuster, 1995), pp. 77–84.
  • A. A. Noyes, "The preparation and properties of colloidal mixtures," J. Amer. Chem. Soc., 27 (1905), 85–104.
  • In that context see A. Muller, "Ober die Klassifikation der Kolloide," Z. anorganische Chem. 36 (1903), 340–345, who recognized the same division, but went on to suggest that theoretical insight into colloids could only be obtained by narrowing one's search to each groups separately.
  • A. Lumiere, Role des colloides chez les êtres vivants, essai de biocolloidologie (Paris: Masson et Cie, 1921); Wolfgang Ostwald & M. Fischer, An Introduction to Theoretical and Applied Colloid Chemistry (The world of neglected dimensions) (New York, John Wiley, 1917); Letter from Jacques Loeb to L. Michaelis, Jan 27,1921, in P. Werner, Otto Warburg's Beitrag zur Atmungstheorie (Marburg: Basiliken-Presse, 1996).
  • Philip Pauly, Controlling Life: Jacques Loeb and the Engineering Ideal in Biology (Oxford: Oxford Univ. Press, 1987).
  • First published in 1906 as Zeitschrift fiir Chemie und Industrie der Kolloide. Ostwald became editor in 1907.
  • Wolfgang Ostwald, "Zur Systematik der Kolloide", Z. fiir Chemie und Industrie der Kolloide (Kolloid Z.) 1 (1907), 291–300, 331-341.
  • Grete Ostwald, Wilhelm Ostwald, mein Vater (Stuttgart: Berliner Union, 1953).
  • Wolfgang Ostwald finally conceded the existence of true macromolecules in 1930. Colloid chemistry, of course, continues to flourish, mainly as applied to systems (like detergent micelles or inorganic colloids) where 'peculiar physical aggregation' is a legitimate concept; it also extended to aerosols and other situations remote from the original controversies. The Kolloid Zeitschrift changed its name to Kolloid Zeitschrift und Zeitschrift fiir Polymere in 1962.
  • R. Olby, op. cit. (1)
  • J. Needham and E. Baldwin, eds., Hopkins and Biochemistry (Cambridge: Helfer & Sons, 1949), p. 179.
  • W. Hausmann, "Ueber die Vertheilung des Stickstoffs von Eiweissmolekul," Z. physiol. Chem. 29 (1900), 136–145.
  • M. E. Jones, "Albrecht Kossel, a biographical sketch," Yale J. Biol. and Med. 26 (1953), 80–97. Kossel won a Nobel Prize in 1910 for his work on proteins and 'nucleic substances'.
  • A. Kossel and F. Kutscher, "Beitrdge zur Kenntniss der Eiweisskörper," Z. physiol. Chem. 31 (1900), 165–214; A. Kossel, "Lectures on the Herter Foundation," Johns Hopkins Hospital Bulletin 23 (1912), 65–76. The first actual determination of amino acid sequence had to wait until Sanger's work on insulin in 1953.
  • H. B. Vickery, Biographical memoir of T. B. Osborne, Biographical Memoirs of the National Academy of Sciences 14 (1931), 261–303.
  • T. B. Osborne, "Sulphur in protein bodies," J Amer. Chem. Soc. 24 (1902), 140–167; T. B. Osborne and I. F. Harris, "Nitrogen in protein bodies," J. Amer. Chem. Soc., 25 (1903), 323–353; T. B. Osborne, "On some definite compounds of protein bodies," J. Amer. Chem. Soc. 21 (1899), 486–493.
  • T. B. Osborne, The Vegetable Proteins (London: Longmans, 1909).
  • H. Holter and M. Moller (eds.), The Carlsberg Laboratories 1876/1976 (Copenhagen: Rhodos, 1976).
  • S. P. L. Sorensen, "Enzyme studies II. Measurement and significance of hydrogen ion concentration 117 enzyme processes", Comptes rendus treav. lab. Carlsberg 8 (1909), 1–168, in French; Biochem. Z. 21 (1909), 131–304, in German.
  • This measurement was repeated by Giintelberg and Linderstrom-Lang thirty years later. They obtained 45,000 for the molecular weight, essentially the value now known to be correct. Sorensen's smaller value was shown to arise mostly from uncertain extrapolation of his data to high dilution and not to error in the measurements per se. A. V. Gfintelberg and K. Linderstom-Lang, "Osmotic pressure of plakalbumin and ov-albumin solutions," Comptes rendus tray. lab. Carlsberg. Ser. chim. 27 (1949), 1–25.
  • S. P. L. Sorensen, M. Floyrup, M. & others, "Studies on proteins," Comptes rendus tray. lab Carlsberg 12 (1915–1917), 1–372. Important papers in this series include S. P. L. Sorensen and M. floyrup, "On the state of equilibrium between crystallised egg albumin and surrounding mother liquor, and on the application of Gibbs' phase rule to such systems," ibid. 12 (1917), 213–261, and S. P. L. Sorensen, "On the osmotic pressure of egg albumin solutions", ibid 12 (1917), 262–371.
  • E. Fischer, "Synthese von Depsiden, Flechtenstoffen und Gerbstoffen", Ber. Chem. Ges. 46 (1913), 3253–3289. The paper is the text of a lecture delivered in Vienna in September 1913.
  • Another puzzling backslider late in life was S. P. L. Sorensen, who (in 1930!) appears to disown his earlier (1915) criticism of colloid chemistry. Edsall has discussed the experimental fallacy that led to this, but no-one has explained why Sorensen chose to ignore all his own previous definitive experiments on the subject. See S. P. L. Sorensen, "The constitution of soluble proteins as reversibly dissociable component systems" Comptes rendus tray. lab. Carlsberg 18 (1930), no. 5,1–124; E. J. Cohn and J. T. Edsall, Proteins, Amino Acids and Peptides as Ions and Dipolar Ions (New York: Reinhold, 1943), pp. 576–585.
  • W. M. Bayliss, Principles of General Physiology (London: Longmans, 1914–1924; several editions).
  • F. G. Hopkins, "The dynamic side of biochemistry," reprinted in Hopkins and Biochemistry, op. cit. (36), p. 136–159.
  • J. Barcroft and A. V. Hill, "The nature of oxyhaemoglobin, with a note on its molecular weight," J. Physiol 39 (1910), 411–428.
  • William Hardy (1864–1934) made many valuable contributions to the study of the electrical properties of proteins. On the subject of protoplasm see W. B. Hardy, "Structure of cell proptoplasm," Physiol. 24 (1899), 158–210.
  • O. Cohnheim, Chemie der Eiweisskoerper (Braunschweig, Vieweg & Sohn, 1900; second edition, 1904); G. Mann, Chemistry of the Proteids (London: Macmillan, 1906).
  • E. Abderhalden, Lehrbuch de physiologischen Chemie in dreissig Vorlesungen (Berlin: Urban 8c Schwarzenberger, 1906); E. Abderhalden, Text-book of Physiological Chemistry in Thirty Lectures (New York: John Wiley, 1908).
  • E. Abderhalden, "Ueber die Beziehung der Kolloidchemie zur Physiologie," Kolloid Z. 31 (1922), 276–279, paper given at first meeting of the Kolloid-Gesellschaft.; E. Abderhalden and E. Komm, "Uber die Anhydridstruktur der Proteine", Z. physiol. Chem. 139 (1924), 181–204. For other Abderhalden aberrations see U. Deichmann and B. Mfiller-Hill, "The fraud of Abderhalden's enzymes", Nature 393 (1998), 109–111.
  • R. H. Aders Plinarner, The Chemical Constitution of the Proteins (London: Longmans 1908); S. B. Schryver, The General Characters of the Proteins (London: Longmans 1909). Both authors were on the faculty at the University College, London.
  • T. B. Roberston, Die physikalische Chemie der Proteine (Dresden: Steinkopff, 1912); T. B. Robertson, The Physical Chemistry of the Proteins (New York: Longmans, 1918); Wilhelm Ostwald's review of the German edition is in Z. fiir physikalische Chemie 81 (1912), 507–508.
  • Robertson's position must have been especially galling because he had been a doctoral student ofJacques Loeb and he and Wolfgang Ostwald were actually contemporaries in Loeb's laboratory—`two unforgettable years together with Robertson', in Ostwald's own words. See obituary by Wolfgang Ostwald in Kolloid Z 53 (1930), 384.
  • W. Pauli, Der kolloidale Zustand und die Vorgiinge in der lebendigen Substanz (Brauschweig, 1902); W. Pauli, Colloid Chemistry of Proteins (London: J 8c A Churchill, 1922).
  • A. Ede, "Colloids and quantification: the ultracentrifuge and its transformation of colloid chemistry", Ambix 43 (1996), 32–45. Data in Svedberg's dissertation on diffusion of particles of colloidal platinum prompted Albert Einstein to publish a classic note on the theory of Brownian motion: A. Einstein, "Theoretial observations on the Brownian motion," Z. föl-Elektrochemie 13 (1907), 41–42.
  • T. Svedberg, Herstellung kolloider Lösungen, (Dresden: Steinkopff, 1909); T. Svedberg, The Formation of Colloids (London: J 8c A Churchill, 1921).
  • Edwin J. Cohn (1892–1953) had studied with Osborne and Sorensen (see above) and subsequently became America's leading entrepreneur in the field of physical protein chemistry.
  • T. Svedberg and R. lahraeus, "A new method for the determination of the molecular weight of proteins," j. Amer. Chem. Soc. 48 (1926), 430–438.
  • H. G. Söderbaum, presentation speech for award to T. Svedberg, Nobel Lectures-Chemistry (Amsterdam: Elsevier, 1966); T. Svedberg, "Ultrazentrifugal Dispersitatsbestimungen an Eiweisslösungen," Kolloid Z. 51 (1930), 10–24.
  • See note (1). Yasu Furukawa, Inventing Polymer Science. Staudinger, Carothers and the Emergence of Macromolecular Chemistry (Philadelphia: Univ. of Pennsylvania Press, 1998) was not available to us at the time this paper was written.
  • See programme in Mitteilungen der Gesellschaft Deutscher Naturforscher und Arzte 3, no. 12 (1926).
  • Papers presented at the meeting were published: W. Waldschmidt-Leitz, "Zur Struktur der Proteine," Ber. chem. Ges. 59 (1926), 3000–3007. M. Bergmann, "Allgemeine Stukturchemie der komplexen Kohlenhydrate and der Protein," Ber. chem. Ges. 59 (1926), 2973–2981. The work of his own that Bergmann chiefly cites is not about proteins, but about inufin, a polysaccharide.
  • M. Bergmann and C. Niemann, "On the structure of proteins: cattle hemoglobin, egg albumin, cattle fibrin, and gelatin," J. Biol. Chem. 118 (1937), 301–314.
  • E. Waldschmidt-Leitz, "The chemical nature of enzymes," Science 78 (1933), 189–190.
  • H. Staudinger, "Die Chemie der hochmolekularen organischen Stoffe im Sinne der Kekulëschen Strukturlehre," Ber. chem. Ges. 59 (1926), 3019–3043.
  • T. Svedberg, Nobel Lectures-Chenzistry (Amsterdam: Elsevier, 1966). The physics prize also went to a colloid-oriented scientist in 1926, namely Jean Perrin.
  • R. Zsigmondy, Nobel Lectures-Chemistry (Amsterdam: Elsevier, 1966).
  • P. Werner, Otto Warburgs Beitrag zur Atmungstheorie, op. cit. (29).
  • E. J. Cohn, "The physical chemistry of the proteins," Physiol. Rev 5 (1925), 349–437.
  • H. Staudinger, Nobel Lectures-Chemistry (Amsterdam: Elsevier, 1966); H. Staudinger, op. cit. (1).
  • A. Ede, "When is a tool not a tool? Understanding the role of laboratory equipment in the early colloidal chemistry laboratory," Ambix 40 (1993), 11–24; A. Ede, op.cit. (60).

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