A lead user of instruments in Science: John D. Roberts and the adaptation of nuclear magnetic resonance to organic chemistry, 1955-1975

ISIS

Volumn 97, Issue 2, 2006, Pages 205-236

  Reinhardt, Carsten ^a  

^a UNIVERSITY OF REGENSBURG   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

ARTICLE; EQUIPMENT DESIGN; HISTORY; HUMAN; INSTRUMENTATION; MALE; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; ORGANIC CHEMISTRY; PROFESSIONAL STANDARD; UNITED STATES;

CHEMISTRY, ORGANIC; EQUIPMENT DESIGN; HISTORY, 20TH CENTURY; HUMANS; MAGNETIC RESONANCE SPECTROSCOPY; MALE; PROFESSIONAL ROLE; UNITED STATES;

EID: 33746331422     PISSN: 00211753     EISSN: 15456994     Source Type: Journal    
DOI: 10.1086/504732     Document Type: Article

References (148)

1. William von Eggers Doering to Geoffrey Keller, 1 Aug. 1962, National Archives and Records Administration (NARA), College Park, Maryland, Record Group (RG) 307, National Science Foundation (NSF), Office of the Director, General Records, 1949-1963, 1957-1959, box 76, folder "M, P, & E Chemistry Program." On the situation in 1953 see "Status Report on MPE (Mathematical, Physical, and Engineering) Sciences," 31 Jan. 1953, NARA, RG 307, NSF, Office of the Director, General Records, 1949-1963, 1951-1956, box 11. For circumstances by 1957 see MPE Divisional Committee, Chairman Thomas K. Sherwood, to Detlev Bronk and Alan T. Waterman, 21 Jan. 1957, NARA, RG 307, NSF, Office of the Director, General Records, 1949-1963, 1960-1961, box 48, folder "Division of M, P, and ES." The NSF budget for the fiscal year 1957 (Research & Development) was ca. $30.65 million. See National Science Foundation, Division of Science Resources Statistics, "Federal Funds for Research and Development, Detailed Historical Tables, Fiscal Years 1951-2000, Table B, Federal Obligations for Total Research and Development, by Major Agency," http://www.nsf.gov/ sbe/srs/nsf01308/htmstart.htm#sum (accessed 7 Mar. 2005).
2. Although the very definition of the chemical sciences rests on laboratory methods, historians have largely neglected the issue of instrumentation until recently. For new work see Peter J. T. Morris, ed., From Classical to Modern Chemistry: The Instrumental Revolution (Cambridge: Royal Society of Chemistry, 2002);
3. Ursula Klein, ed., Tools and Modes of Representation in the Laboratory Sciences (Dordrecht: Kluwer, 2001);
4. and Frederic L. Holmes and Trevor H. Levere, eds., Instruments and Experimentation in the History of Chemistry (Cambridge, Mass.: MIT Press, 2000).
5. See also Yakov Rabkin, "Uses and Images of Instruments in Chemistry," in Chemical Sciences in the Modern World, ed. Seymour H. Mauskopf (Philadelphia: Univ. Pennsylvania Press, 1993), pp. 25-42;
6. Davis Baird, "Analytical Chemistry and the 'Big' Scientific Instrumentation Revolution," Annals of Science, 1993, 50:267-290;
7. Leo Slater, "Instruments and Rules: R. B. Woodward and the Tools of Twentieth-Century Organic Chemistry," Studies in History and Philosophy of Science, 2002, 33:1-33;
8. and Jeffrey K. Stine, "Scientific Instrumentation as an Element of U.S. Science Policy: National Science Foundation Support of Chemistry Instrumentation," in Invisible Connections: Instruments, Institutions, and Science, ed. Robert Bud and Susan E. Cozzens (Bellingham, Wash.: SPIE Optical Engineering Press, 1992), pp. 238-263.
9. For a contemporary description of the impact of physical instrumentation on 1960s U.S. chemistry see National Academy of Sciences, National Research Council, Chemistry: Opportunities and Needs. A Report on Basic Research in U.S. Chemistry by the Committee for the Survey of Chemistry (Washington, D.C., 1965), pp. 86-102.
10. Yakov M. Rabkin, "Technological Innovation in Science: The Adoption of Infrared Spectroscopy by Chemists," Isis, 1987, 78.31-54;
11. and Timothy Lenoir and Christophe Lécuyer, "Intrument Makers and Discipline Builders: The Case of Nuclear Magnetic Resonance," Perspectives on Science, 1995, 3:276-345.
12. For a general history of NMR see Edwin D. Becker, Cherie Fisk, and C. L. Khetrapal, "The Development of NMR," in Encyclopedia of Nuclear Magnetic Resonance, 8 vols., ed. David M. Grant and Robin K. Harris, Vol. 1: Historical Perspectives (Chichester: Wiley, 1996), pp. 1-158.
13. For a history from a philosophical perspective see Henk Zandvoort, Models of Scientific Development and the Case of Nuclear Magnetic Resonance (Dordrecht: Reidel, 1986);
14. and Zandvoort, "Nuclear Magnetic Resonance and the Acceptability of Guiding Assumptions," in Scrutinizing Science: Empirical Studies a of Scientific Change, ed. Arthur Donovan et al. (Dordrecht: Kluwer, 1988), pp. 337-358.
15. For its early history see John S. Rigden, "Quantum States and Precession: The Two Discoveries of NMR," Reviews of Modern Physics, 1986, 58:433-448;
16. and Mark Gerstein, "Purcell's Role in the Discovery of Nuclear Magnetic Resonance: Contingency versus Inevitability," American Journal of Physics, 1994, 62:596-601.
17. Eric von Hippel, The Sources of Innovation (New York: Oxford Univ. Press, 1995), pp. 107 (quotation), 11-27, 133-163.
18. In the section on user-dominated innovation, von Hippel's book presents innovation histories of gas chromatography, ultraviolet spectroscopy, NMR, and electron microscopy. The borderline between user-innovators and lead users is fluid. Because my focus here is on the development of methods, their illustrative use, and their subsequent diffusion in science, the term "lead user" seems to be adequate. The concept became widely known in economics through von Hippel's efforts (in part with the companies 3M and Business Genetics) to establish it as a development and marketing tool. This even led to the founding of a company called Lead User Concepts, Inc. (LUCI). See "About lead user concepts," http://www.leaduser.com (accessed 30 Sept. 2003);
19. and "Lead user research," http://www.businessgenetics.com/ web_pdfs/leadUbrch.pdf (accessed 30 Sept. 2003).
20. Colin A. Russell, "The Changing Role of Synthesis in Organic Chemistry," Ambix, 1987, 34:169-180.
21. Leo B. Slater, "Woodward, Robinson, and Strychnine: Chemical Structure and Chemists" Challenge," Ambix, 2001, 48:161-189;
22. Peter J. T. Morris and Anthony S. Travis, "The Role of Physical Instrumentation in Structural Organic Chemistry," in Science in the Twentieth Century, ed. John Krige and Dominique Pestre (Amsterdam: Harwood, 1997), pp. 715-739, esp. pp. 717-719;
23. and Arthur J. Birch, To See the Obvious (Washington, D.C.: American Chemical Society, 1995), pp. 57-59, 67.
24. See Derek H. R. Barton, "Some Reflections on the Present Status of Organic Chemistry," in Science and Human Progress: Addresses at the Celebration of the Fiftieth Anniversary of the Mellon Institute (Pittsburgh: Mellon Institute of Industrial Research, 1964). pp. 85-100.
25. For a stronger view that connects the changeover in instrumentation to a change in the ontological status of structural formulas see Joachim Schummer, "The Impact of Instrumentation on Chemical Species Identity," in From Classical to Modern Chemistry, ed. Morris (cit n. 2), pp. 188-211;
26. and Leo B. Slater, "Organic Chemistry and Instrumentation: R. B. Woodward and the Reification of Chemical Structures," ibid., pp. 212-228.
27. Mary Jo Nye, From Chemical Philosophy to Theoretical Chemistry: Dynamics of Matter and Dynamics of Disciplines, 1800-1950 (Berkeley: Univ. California Press, 1993), pp. 1-2.
28. Peter Galison differentiated between the layers, or levels, of theory, experimentation, and instrumentation in twentieth-century physics. See Peter Galison, Image and Logic: A Material Culture of Microphysics (Chicago: Univ. Chicago Press, 1997). pp. 797-803.
29. For the importance of rules in the development and applications of instrumentation see Slater, "Instruments and Rules" (cit. n. 2).
30. Peter J. T. Morris, Anthony S. Travis, and Carsten Reinhardt, "Research Fields and Boundaries in Twentieth-Century Organic Chemistry," in Chemical Sciences in the Twentieth Century: Bridging Boundaries, ed. Reinhardt (Weinheim: Wiley-VCH. 2001), pp. 14-42, esp. pp. 14-20;
31. Nye, From Chemical Philosophy to Theoretical Chemistry (cit. n. 10), pp. 196-223;
32. and William H. Brock, The Fontana History of Chemistry (Hammersmith: Fontana, 1992), pp. 506-569.
33. For the coinage of the term "physical organic chemistry" and its description as a truly scientific, quantitative-mathematical enterprise see Louis P. Hammett, Physical Organic Chemistry: Reaction Rates, Equilibria, and Mechanisms (New York: McGraw-Hill, 1940).
34. Peter B. Dervan, "John D. Roberts," Aldrichimica Acta, 1988, 21:71-77, on p. 75.
35. Roberts's autobiography is John D. Roberts, The Right Place at the Right Time (Washington, D.C.: American Chemical Society, 1990) (hereafter cited as Roberts, Right Place at the Right Time).
36. For the transformation of MIT at large during this period see Christophe Lécuyer, "The Making of a Science-Based Technology University: Karl Compton, James Killian, and the Reform of MIT, 1930-1957," Historical Studies in the Physical and Biological Sciences, 1992, 23:153-180, and the literature cited therein.
37. For the first year, Roberts obtained the princely sum of $44,000; in the following years he was given half that amount. See Roberts, Right Place at the Right Time, p. 60.
38. For the work that resulted see J. D. Roberts and C. C. Lee, "The Nature of the Intermediate in the Solvolysis of Norbornyl Derivatives," Journal of the American Chemical Society, 1951, 73:5009.
39. See also Paul D. Bartlett, Nonclassical Ions: Reprints and Commentary (New York. Benjamin, 1965), p. v;
40. and, for a modern treatment, Jerry March, Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (New York: Wiley-Interscience, 1992), pp. 312-327.
41. Rachel Prud'homme, interview with John D. Roberts, Feb.-May 1985, Institute Archives, California Institute of Technology, Pasadena, California, Oral History Collection (hereafter cited as Prud'homme interview with Roberts), p. 53.
42. See also Stephen J. Weininger, "'What's in a Name?' From Designation to Denunciation - The Nonclassical Cation Controversy," Bulletin for the History of Chemistry, 2000, 25:123-131.
43. Roberts, Right Place at the Right Time, p. 141;
44. and Howard J. Lucas, Organic Chemistry (New York: American Book, 1935).
45. On Lucas and his succession by Roberts see California Institute of Technology, Chemistry and Chemical Engineering at the California Institute of Technology, 1952-1953: A Report of the Academic Year and Other Activities of the Division of Chemistry and Chemical Engineering, pp. 95-99.
46. Pauling's alpha-helix model of proteins was published in Linus C. Pauling and Robert E. Corey, "Atomic Coordinates and Structure Factors for Two Helical Configurations of Polypeptide Chains," Proceedings of the National Academy of Sciences, 1951, 37:235-240.
47. For literature on the history of NMR see note 4, above.
48. Roberts, Right Place at the Right Time, p. 152;
49. and Carsten Reinhardt, interview with John D. Roberts, 28 Jan. 1999.
50. Prud'homme interview with Roberts, p. 101.
51. On the chemical physicist E. Bright Wilson see Carsten Reinhardt, "Chemistry in a Physical Mode: Molecular Spectroscopy and the Emergence of NMR," Ann. Sci, 2004, 61:1-32;
52. and George B. Kistiakowsky, "Edgar Bright Wilson, Jr., Theodore William Richards Professor of Chemistry," Journal of Physical Chemistry, 1979. 83:5A-7A.
53. For the beginning of Yost's work on NMR see his annual report to Linus Pauling, 7 July 1950, Yost Papers, Institute Archives, California Institute of Technology, Pasadena, California, folder 10.6; for the grant from Newmont Exploration see Fred Searls, Jr., to Lee A. DuBridge, 14 Sept. 1954, Yost Papers, folder 2.2.4; for Yost's interest in mathematics see his annual report to Linus Pauling, 7 June 1954, Yost Papers, folder 10.6.
54. Reinhardt interview with Roberts, 28 Jan. 1999;
55. Roberts, Right Place at the Right Time, p. 153;
56. and Prud'homme interview with Roberts, p. 103.
57. See also Carl Niemann to DuBridge, memorandum, 24 Feb. 1955, Roberts Papers (in private possession), folder "Varian Correspondence through 1969." Among Roberts's colleagues, R. M. Badger (physical chemistry), W. Corcoran (chemical engineering), Norman Davidson (chemistry/molecular biology), Verner Schomaker (electron diffraction methods), and Carl Niemann (organic chemistry) expressed interest in the use of NMR.
58. For a detailed description of this work see Roberts, Right Place at the Right Time, pp. 162-167;
59. Prud'homme interview with Roberts, pp. 105-106;
60. and P. Madhavan Nair and John D. Roberts, "Nuclear Magnetic Resonance Spectra: Hindered Rotation and Molecular Asymmetry," J. Amer. Chem. Soc., 1957, 79:4565-4566.
61. Prud'homme interview with Roberts, p. 106. J. J. Drysdale and William Phillips of the DuPont Experimental Station in Wilmington, Delaware, embarked on very similar studies.
62. See J. J. Drysdale and W. D. Phillips, "Restricted Rotation in Substituted Ethanes as Evidenced by Nuclear Magnetic Resonance," J. Amer. Chem. Soc., 1957, 79:319-322. Drysdale had been a student of Roberts at MIT.
63. Lenoir and Lécuyer, "Instrument Makers and Discipline Builders" (cit. n. 3), p. 287;
64. Stuart W. Leslie and Robert H. Kargon, "Selling Silicon Valley: Frederick Terman's Model for Regional Advantage," Business History Review, 1996, 70:435-472;
65. and Rebecca S. Lowen, Creating the Cold War University: The Transformation of Stanford (Berkeley: Univ. California Press, 1997), pp. 103-109, passim.
66. The first was either Magnolia Petroleum of Dallas, Texas (Magnolia was a predecessor of Mobil Oil), or Phillips Petroleum, joined in 1953 by Humble Oil in Baytown, Texas (later Exxon), Shell Development Company in Emeryville, California, and the chemical company DuPont of Wilmington, Delaware. See Shannon Mercer, interview with Ralph Kane, Nov. 1989, Varian Associates, Inc., Oral History Project, Department of Special Collections, Stanford University Libraries, Stanford, California, SCM 708, box 1;
67. Don Woessner, "Early Days of NMR at Mobil in Dallas," TAMU NMR Newsletter 1995, 449.33-37, copy in Richard R. Ernst Papers (in private possession);
68. and Raymond C. Ferguson, "William D. Phillips and Nuclear Magnetic Resonance Spectroscopy at DuPont," in Encyclopedia of Nuclear Magnetic Resonance, ed. Grant and Harris (cit n. 4), Vol. 1, pp.309-313.
69. Martin Packard, "The Varian Story: As Presented at the 1980 Pittsburgh Conference on Analytical Chemistry," p. 9, Department of Special Collections, Stanford University Libraries, Stanford, California, SC 345, series Varian Associates, box 4, folder 23.
70. See also Hugh D. Graham and Nancy Diamond, The Rise of American Research Universities: Elites and Challenges in the Postwar Era (Baltimore: Johns Hopkins Univ. Press, 1997), Ch. 2: "The Revolution in Federal Science Policy";
71. and Roger L. Geiger, "Science, Universities, and National Defense," Osiris, 2nd Ser., 1992, 7:26-48.
72. On Shoolery's role in promoting NMR see James N. Shoolery, "NMR Spectroscopy in the Beginning," Analytical Chemistry, 1993, 65:731A-741A;
73. and Carsten Reinhardt, interview with James N. Shoolery, 23 Jan. 1999.
74. On Varian's laboratory and workshops see Lenoir and Lécuyer, "Instrument Makers and Discipline Builders" (cit. n. 3).
75. Roberts, Right Place at the Right Time, p. 170 ("stellar salesman").
76. On Varian's relations with the academic world see Sharon Mercer, interview with Martin Packard, Dec. 1989, Varian Associates, Inc., Oral History Project (cit. n. 25), SC M 708, box 1.
77. John D. Roberts to James N. Shoolery, 3 Jan. 1956, and Shoolery to Roberts, 6 Jan. 1956,
78. Roberts Papers (in private possession), folder "Varian Correspondence through 1969";
79. and Varian Instrument Division, announcement of upgrade possibilities with field/frequency control for the HR-60, DP-60, and HP-100 models, 24 Feb. 1964, Roberts Papers, folder "Varian Correspondence through 1969." For an in-depth study of the "Living Instrument" policy, with the interesting remark that it referred to both the adding of new hardware and the service provided by the Varian Associates Applications Laboratory, see Jody A. Roberts, "Instruments and Domains of Knowledge: The Case of Nuclear Magnetic Resonance Spectroscopy, 1956-1969" (M.Sc. thesis, Virginia Polytechnic Institute and State University, 2002), p. 45. I thank Roberts for providing me with a copy of his thesis.
80. Roberts to Shoolery, 11 Jan. 1956; Shoolery to Roberts, 6 Jan. 1956; and W. C. Dersch (Service Manager) to Roberts, 15 Feb. 1956: Roberts Papers, folder "Varian Correspondence through 1969."
81. Regarding Roberts's initial query about temperature control see Emery Rogers to Roberts, 18 Jan. 1955, Roberts Papers, folder "Varian Correspondence through 1969." The publication that premiered the new device was James N. Shoolery and John D. Roberts, "High Resolution Nuclear Magnetic Resonance Spectroscopy at Elevated Temperatures," Review of Scientific Instruments, 1957, 28:61-62.
82. Roberts describes his contribution in Reinhardt interview with Roberts, 28 Jan. 1999; see also Roberts to Shoolery, 11 Jan. 1956, Roberts Papers, folder "Varian Correspondence through 1969."
83. Roberts to Shoolery, 11 Jan. 1956, Roberts Papers, folder "Varian Correspondence through 1969."
84. Regarding Roberts's first NMR paper see Roberts to Shoolery, 21 June 1956, 20 July 1956, and Shoolery to Roberts, 6 July 1956, Roberts Papers, folder "Varian Correspondence through 1969." The paper is J. D. Roberts, "Temperature Effects on Nuclear Magnetic Resonance Absorption of Hydrogens Attached to Nitrogen," J. Amer. Chem. Soc., 1956, 78:4495. On the incident involving Rogers see Roberts to Shoolery, handwritten letter, 2 Nov. [1956]. Roberts Papers, folder "Varian Correspondence through 1969" (emphasis in the original).
85. J. N. Shoolery and M. T. Rogers, "Nuclear Magnetic Resonance Spectra of Steroids," J. Amer Chem. Soc., 1958, 80:5121-5135.
86. See also Norman S. Bhacca and Dudley H. Williams, Applications of NMR Spectroscopy in Organic Chemistry: Illustrations from the Steroid Field (San Francisco: Holden-Day, 1964), p. 14;
87. and Becker et al., "Development of NMR" (cit. n. 4), pp. 23-24.
88. Shoolery to Roberts, 18 June 1957, Roberts Papers, folder "Varian Correspondence through 1969."
89. The paper is Nair and Roberts, "Nuclear Magnetic Resonance Spectra: Hindered Rotation and Molecular Asymmetry" (cit. n. 22).
90. Reinhardt interview with Shoolery, 23 Jan. 1999.
91. Becker et al., "Development of NMR" (Cit. n. 4), p. 23;
92. Shoolery, "NMR Spectroscopy in the Beginning" (Cit. n. 27), pp. 734A, 736A; and Reinhardt interview with Shoolery, 23 Jan. 1999.
93. For the appearance of the NMR series in the Journal of Organic Chemistry and its role in this community see J. Roberts, "Instruments and Domains of Knowledge" (cit. n. 29).
94. This paragraph is based on a search done with SciFinder Scholar.
95. Compare this with the influence that RCA of Camden, New Jersey, a manufacturer of electron microscopes, had on standards in biological electron microscopy. See Nicolas Rasmussen, Picture Control: The Electron Microscope and the Transformation of Biology in America, 1940-1960 (Stanford, Calif.: Stanford Univ. Press, 1997), Ch. 1.
96. Ray Freeman to Bernard L. Shapiro, 13 Aug. 1990, TAMU NMR Newsletter, 1990, 384:15 (special section on Shollery's retirement), copy in Roberts Papers.
97. See D. Chapman and P.D. Magnus, Introduction to Practical High Resolution Nuclear Magnetic Resonance Spectroscopy (London: Academic, 1966, pp. 36-39, where the acetaldehyde spectrum is described as a standard.
98. John D. Roberts, report of the NIH grant GM 11072-19, "Nitrogen-15 and Carbon-13 NMR Spectroscopy," period 1 May 1981-30 April 1982, Roberts Papers, folder "NSF."
99. See also the summary in John D. Roberts, "Final Project Report," 9 Dec. 1983, NSF CHE81-20508, period 1 May 1979-31 October 1983. Roberts Papers, folder "NSF·:
100. Carbon and nitrogen are, with hydrogen and oxygen, the elements most widely present in organic compounds. While the abundant isotopes of carbon and nitrogen, carbon-12 and nitrogen-14, do not give a signal in NMR experiments, the less abundant isotopes, carbon-13 and nitrogen-15, do. The problem was the low concentration of these isotopes, which led to a dramatic decrease in sensitivity. Though one could work with carbon-13 and nitrogen-15 enriched compounds, this was not an ideal solution to the problem. To be of real use for mainstream organic chemists and biochemists, carbon-13 and nitrogen-15 NMR had to be run at the natural abundance level. This was a considerable challenge in terms of sensitivity. The carbon-12 isotope has a natural abundance of 98.892 percent, carbon-13 an abundance of only 1.108 percent; the ratio of nitrogen-14 (99.635 percent) to nitrogen-15 (0.365 percent) is even worse. For the history of carbon-13 NMR see Becker et al., "Development of NMR" (cit. n.4), pp.28-29, 49.
101. On the initial design for both spectra see Roberts to Forrest Nelson, 19 Jan. 1965, and Roberts to Shoolery, 21 July 1965, Roberts Papers, folder "Varian Correspondence through 1969"; and Roberts, Right Place at the Right Time, pp. 193-197. On Varian's wish to focus on the carbon-13 NMR market see Shoolery to Roberts, 16 July 1965, Roberts Papers, folder "Varian Correspondence through 1969"; for the quotation see Roberts to Shoolery, 21 July 1965, Roberts Papers, folder "Varian Correspondence through 1969." On the incorporation of features into later instruments see Roberts, Right Place at the Right Time, pp. 194-195.
102. In the Journal of Organic Chemistry (year/no. of articles): 1956/6, 1957/ 5, 1958/14, 1959/16, 1960/21, 1961/83, 1962/151, 1963/202, 1964/263, 1965/352, 1966/368, 1967/198.... 1976/171.
103. In the Journal of the American Chemical Society: 1955/5, 1956/15, 1957/ 33, 1958/45, 1959/72, 1960/115, 1961/149, 1962/206, 1963/279, 1964/ 324.... 1976/339.
104. The data were acquired by a SciFinder search for publications with the keyword "NMR," restricted to time period and analyzed by journal and year. These figures differ considerably from the numbers published in Lenoir and Lécuyer, "Instrument Makers and Discipline Builders" (cit. n. 3), figs. 4 and 8 (pp. 323, 327).
105. However, they support the main thesis of Lenoir and Lécuyer in attributing significant impact to the A-60 spectrometer in the quantitative breakthrough and their claim that the year 1966 marks the end of the "quantum-leap" of NMR, at least in organic chemistry (see pp. 329-330). For the numbers of instruments in chemistry departments, and for graphs showing the use rate, see National Academy of Sciences, Chemistry: Opportunities and Needs (cit. n. 2), pp. 88, 90, 207.
106. Before 1960, not more than twenty-six NMR spectrometers suited for organic chemical research existed in those 101 departments. For more information about the impact of physical methods on organic chemistry and the complementarity of infrared spectroscopy and NMR see Morris and Travis, "Role of Physical Instrumentation in Structural Organic Chemistry" (cit. n. 7);
107. and Rabkin, "Technological Innovation in Science" (cit. n. 3).
108. Roberts describes his own difficulties in learning to operate the NMR spectrometer and in obtaining reliable results in Right Place at the Right Time, pp. 154-159.
109. On Eliel and NMR see Ernest L. Eliel, "Conformational Equilibria by Nuclear Magnetic Resonance Spectroscopy," Chemistry and Industry, 1959, p. 568;
110. Eliel et al.. Conformational Analysis (New York: Interscience, 1965), pp. 152-156;
111. and Eliel, From Cologne to Chapel Hill (Washington, D.C.: American Chemical Society, 1990), pp. 41-42.
112. The cubane and bullvalene examples are from National Academy of Sciences, Chemistry: Opponunities and Needs, p. 94.
113. This was the case for "Shoolery's rules" on the additivity of the chemical shift. Reinhardt interview with Shoolery, 23 Jan. 1999.
114. John D. Roberts, "Chemistry 246b - Nuclear Magnetic Resonance," lecture manuscript, undated [1956], p. 1, Roberts Papers.
115. Roberts cited George Pake, "Fundamentals of Nuclear Magnetic Resonance Absorption: I, II," Amer. J. Phys., 1950, 18:438-452, 473-486;
116. John E. Wertz, "Nuclear and Electronic Spin Magnetic Resonance," Chemical Reviews, 1955, 55:829-955;
117. and J. A. S. Smith, "Nuclear Magnetic Resonance Absorption," Quarterly Reviews, 1953, 7:279-306.
118. Prud'homme interview with Roberts, p. 77 (quotation);
119. and Roberts, Right Place at the Right Time, pp. 169-170 (lectures).
120. The books in the new series were Charles A. MacDowell, ed., Mass Spectrometry (New York: McGraw-Hill, 1963);
121. Klaus Biemann, Mass Spectrometry: Organic Chemical Applications (New York: McGraw-Hill, 1962);
122. J. A. Pople, W. G. Schneider, and H. J. Bernstein, High-Resolution Nuclear Magnetic Resonance (New York: McGraw-Hill, 1959);
123. and John D. Roberts, Nuclear Magnetic Resonance: Applications to Organic Chemistry (New York. McGraw-Hill, 1959).
124. Roberts, Nuclear Magnetic Resonance, p. 3.
125. In style, Roberts's figure closely resembles the drawing of a simplified NMR apparatus given by Varian Associates in Technical Information from the Laboratories of Varian Associates, 1953, 1(1):1 - though in the Bulletin illustration the dimensions of the test tube and the spectrometer served to emphasize the former even more. Copy in Roberts Papers.
126. Prud'homme interview with Roberts, p. 78.
127. For an example of such a review see Robert I. Walter, "Nuclear Magnetic Resonance," Journal of Chemical Education, 1959, 36:531.
128. See Technical Information from the Laboratories of Varian Associates, 1953, 1(1), copy in Roberts Papers.
129. Linus Pauling, The Nature of the Chemical Bond and the Structure of Molecules and Crystals (Ithaca, N.Y.: Cornell Univ. Press, 1939).
130. See Mary Jo Nye, "From Student to Teacher: Linus Pauling and the Reformulation of the Principles of Chemistry in the 1930s," in Communicating Chemistry: Textbooks and Their Audiences, ed. Anders Lundgren and Bernadette Bensaude-Vincent (Canton, Mass.: Science History Publications, 2000), pp. 397-414.
131. Kostas Gavroglu and Ana Simões, "One Face or Many? The Role of Textbooks in Building the New Discipline of Quantum Chemistry," in Communicating Chemistry, ed. Lundgren and Bensaude-Vincent, pp. 415-449.
132. See also David Kaiser, ed., Pedagogy and the Practice of Science: Historical and Contemporary Perspectives (Cambridge, Mass.: MIT Press, 2005).
133. John D. Roberts and Marjorie C. Caserio, Basic Principles of Organic Chemistry (New York: Benjamin, 1964), p. ix.
134. An abbreviated version of the book was published three years later: Roberts and Caserio, Modern Organic Chemistry (New York: Benjamin, 1967).
135. On the decision to join the Benjamin board see Prud'homme interview with Roberts, p. 79; he also notes (p.84) that there were financial reasons to relinquish this position.
136. John D. Roberts, An Introduction to the Analysis of Spin-Spin-Splitting in High-Resolution Nuclear Magnetic Resonance Spectra (New York: Benjamin, 1961); on p. 5 he promises to explain the quantitative theory behind NMR in a manner comprehensible to chemists.
137. See also, on this point, Roberts, "Applications of Nuclear Magnetic Resonance Spectroscopy in Organic Chemistry," rev. of Lloyd Jackman, Applications of Nuclear Magnetic Resonance Spectroscopy in Organic Chemistry (1959), J. Amer Chem Soc., 1960, 82:5767.
138. Roberts, Right Place at the Right Time, p. 174 (on sales);
139. and Becker et al., "Development of NMR" (cit. n. 4), pp. 25-27.
140. Aksel A. Bothner-By, "Nuclear Magnetic Resonance: Applications to Organic Chemistry," J. Amer. Chem. Soc., 1959, 81:5013-5014, on p. 5013.
141. Robert B. Bates and John P. Schaefer, Research Techniques in Organic Chemistry (Englewood Cliffs, NJ.: Prentice-Hall, 1971), p. 123.
142. John D. Roberts, Supplemental equipment proposal for support of research by the NSF, "Nuclear Magnetic Resonance Spectroscopy, Structures and Reaction Mechanisms of Organic Compounds," 1 July 1970, Roberts Papers, folder "NSF."
143. Roberts, Right Place at the Right Time, pp. 197-198. The basic idea behind Fourier transform (FT) NMR is the excitation of all resonance frequencies in a spectrum at the same time rather than sequentially, as in the "normal" continuous wave techniques, where either the magnetic field or the radiofrequency field was swept through. This traditional mode led to a reduced sensitivity per time unit, because only a narrow frequency band brought about the signal at one time. In FT NMR, the spectrum is excited all at once by a pulsed radiofrequency. Using a mathematical method first developed by Jean Baptiste Fourier in the early nineteenth century, the time-dependent impulse response (called free induction decay, or FID) is transformed to the frequency-domain spectrum - thus, the familiar NMR spectrum. Richard R. Ernst at Varian Associates invented FT NMR in the mid 1960s. Its breakthrough came in the late 1960s and early 1970s with carbon-13 NMR. FT NMR soon became the standard measuring procedure and the basis for subsequent developments.
144. See Sunney I. Chan, memorandum to the chemistry faculty, research fellows, and graduate students, 21 Aug. 1968, Roberts Papers, folder "Varian Correspondence through 1969."
145. For a description of the Bruker instmment - the WH-180 - see Roberts, Right Place at the Right Time, pp. 203-205.
146. On the decision to give the order to Bruker see Roberts to Peter Llewellyn of Varian, 30 Nov. 1972, Roberts Papers, folder "Varian Correspondence, 1970-1972."
147. Reinhardt interview with Roberts, 28 Jan. 1999.
148. A recent overview is Carsten Reinhardt and Harm G. Schröter, "Academia and Industry in Chemistry: The Impact of State Intervention and the Effects of Cultural Values." Ambix. 2004, 51:99-106.