New Insight into the “Fortuitous Error” that Led to the 2000 Nobel Prize in Chemistry
Published 2021-03-01
Keywords
- polyacetylene,
- plastic films,
- Nobel Prize 2020,
- polymerization conditions,
- Ziegler-Natta catalysis
How to Cite
Copyright (c) 2020 Seth C Rasmussen
This work is licensed under a Creative Commons Attribution 4.0 International License.
Abstract
In 2000, the Nobel Prize in Chemistry was awarded to Hideki Shirakawa, Alan G. MacDiarmid, and Alan J. Heeger “for the discovery and development of electrically conductive polymers.” While this award was in reference to their collaborative efforts on conducting polyacetylene in the mid-to-late 1970s, the narrative leading up to these efforts began in 1967 with the production of polyacetylene plastic films via what has been called a "fortuitous error." At the heart of this discovery were Shirakawa and a visiting Korean scientist, Hyung Chick Pyun. The current report provides background on Pyun and, for the first time, presents his version of the events leading to the discovery of polyacetylene films in order to provide new insight into this important historical event.
References
- Press Release. NobelPrize.org. Nobel Media AB 2020. https://www.nobelprize.org/ prizes/chemistry/2000/press-release (accessed February 9, 2020).
- H. Shirakawa, E. J. Louis, A. G. MacDiarmid, C. K. Chiang, A. J. Heeger, Synthesis of Electrically Conducting Organic Polymers: Halogen Derivatives of Polyacetylene, (CH)x. Chem. Commun. 1977, 578-580.
- C. K. Chiang, C. R. Fincher, Jr., Y. W. Park, A. J. Heeger, H. Shirakawa, E. J. Louis, S. C. Gau, A. G. MacDiarmid, Electrical Conductivity in Doped Polyacetylene. Phys. Rev. Lett. 1977, 39, 1098-1101.
- C. K. Chiang, S. C. Gau, C. R. Fincher, Jr., Y. W. Park, A. G. MacDiarmid, A. J. Heeger, Polyacetylene, (CH)x: n-type and p-type doping and compensation. Appl. Phys. Lett. 1978, 33, 18-20.
- C. K. Chiang, Y. W. Park, A. J. Heeger, H. Shirakawa, E. J. Louis, A. G. MacDiarmid, Conducting polymers: Halogen doped polyacetylene. J. Chem. Phys. 1978, 69, 5098-5104.
- M. M. Maricq, J. S. Waugh, A. G. MacDiarmid, H. Shirakawa, A. J. Heeger, Carbon-13 Nuclear Magnetic Resonance of cis- and trans-Polyacetylenes. J. Am. Chem. Soc. 1978, 100, 7729-7730.
- C. R. Fincher, Jr., D. L. Peebles, A. J. Heeger, M. A. Druy, Y. Matsumura, A. G. MacDiarmid, H. Shirakawa, S. Ikeda, Anisotropic Optical Properties of Pure and Doped Polyactylene. Solid State Commun. 1978, 27, 489-494.
- C. K. Chiang, M. A. Druy, S. C. Gau, A. J. Heeger, E. J. Louis, A. G. MacDiarmid, Y. W. Park, H. Shirakawa, Synthesis of Highly Conducting Films of Derivatives of Polyacetylene, (CH)x. J. Am. Chem. Soc. 1978, 100, 1013-1015.
- Y. W. Park, M. A. Druy, C. K. Chiang, A. G. MacDiarmid, A. J. Heeger, H. Shirakawa, S. Ikeda, Anisotropic Electrical Conductivity of Partially Oriented Polyactylene. J. Polym. Sci. Polym. Lett. Ed. 1979, 17, 195-201.
- H. Shirakawa, The Discovery of Polyacetylene Film: The Dawning of an Era of Conducting Polymers. In Les Prix Nobel, The Nobel Prizes 2000, T. Frängsmyr, Ed. Nobel Foundation: Stockholm, 2000, pp. 217-226.
- H. Shirakawa, The Discovery of Polyacetylene Film: The Dawning of an Era of Conducting Polymers (Nobel Lecture). Angew. Chem. Int. Ed. 2001, 40, 2574-2580.
- H. Shirakawa, Nobel Lecture: The Discovery of Polyacetylene Film?The Dawning of an Era of Conducting Polymers. Rev. Modern Phys. 2001, 73, 713-718.
- H. Shirakawa, The Discovery of Polyacetylene Film. The Dawning of an Era of Conducting Polymers. Synth. Met. 2002, 125, 3-10.
- H. Shirakawa, Hideki Shirakawa. In Les Prix Nobel, The Nobel Prizes 2000 (Ed: T. Frängsmyr) Nobel Foundation: Stockholm, 2000, pp. 213-216.
- H. Shirakawa, Reflections on “Simultaneous Polymerization and Formation of Polyacetylene Film on the Surface of Concentrated Soluble Ziegler-Type Catalyst Solution,” by Takeo Ito, Hideki Shirakawa, and Sakuji Ikeda, J. Polym. Sci.: Polym. Chem. Ed., 12, 11 (1974). J. Polym. Sci. A Polym. Chem. 1996, 34, 2529-2530.
- R. B. Kaner, A. G. MacDiarmid, Plastics That Conduct Electricity. Sci. Am. 1988, 258(2), 106-111.
- J. S. Miller, The 2000 Nobel Prize in Chemistry?A Pesonal Accolade. ChemPhysChem 2000, 1, 229-230.
- M. Brennan, Electrifying Plastics. Chem. Eng. News 2000, 78(42), 4-5.
- A. G. MacDiarmid, Alan G. MacDiarmid. In Les Prix Nobel, The Nobel Prizes 2000 (Ed.: T. Frängsmyr) Nobel Foundation: Stockholm, 2000, pp. 183-190.
- N. Hall, Twenty-five years of conducting polymers. Chem. Commun. 2003, 1-4.
- B. Hargittai, I. Hargittai, Candid science V: Conversations with Famous Scientists. Imperial College Press: London, 2005, pp. 401-409.
- B. Hargittai, I. Hargittai, Candid science V: Conversations with Famous Scientists. Imperial College Press, London, 2005, pp. 411-427.
- C. Scott, History of Conductive Polymers. In Nanostructured Conductive Polymers (Ed: A. Eftekhari) John Wiley & Sons, Chichester, 2010, pp. 3-17.
- I. Hargittai, Drive and Curiosity: What Fuels the Passion for Science. Prometheus Books: Amherst, NY, 2011, pp. 173-190.
- S. C. Rasmussen, Electrically Conducting Plastics: Revising the History of Conjugated Organic Polymers. In 100+ Years of Plastics. Leo Baekeland and Beyond (Eds: E. T. Strom, S. C. Rasmussen) American Chemical Society, Washington, DC, 2011, pp. 147–163.
- S. C. Rasmussen, The Path to Conductive Polyacetylene. Bull. Hist. Chem. 2014, 39, 64-72.
- S. C. Rasmussen, Early History of Conductive Organic Polymers. In Conductive Polymers: Electrical Interactions in Cell Biology and Medicine (Eds: Z. Zhang, M. Rouabhia, S. E. Moulton) CRC Press, Boca Raton, FL, 2017, pp. 1-21.
- S. C. Rasmussen. Acetylene and Its Polymers. 150+ Years of History. Springer Briefs in Molecular Science: History of Chemistry. Springer: Heidelberg, 2018, pp. 85-108.
- S. C. Rasmussen, Early History of Conjugated Polymers: From their Origins to the Handbook of Conducting Polymers. In Handbook of Conducting Polymers, 4th Ed. (Eds.: J. R. Reynolds, T. A. Skotheim, B. Thompson) CRC Press, Boca Raton, FL, 2019, pp. 1-35.
- G. Natta, P. Pino, G. Mazzanti, Polimeri ad elevato peso molecolore degli idrocarburi acetilenici e procedimento per la loro preparozione. Italian Patent 530,753 (July 15, 1955); Chem. Abst. 1958, 52, 15128b.
- G. Natta, G. Mazzanti, P. Pino, Hochpolymere von Acetylen-Kohlenwasserstoffen, erhalten mittels Organometall-Komplexen von Zwischenschalenelementen als Katalysatoren. Angew. Chem. 1957, 69, 685-686.
- G. Natta, G. Mazzanti, P. Corradini, Polimerizzazione stereospecifica dell’acetilene. Atti Accad. Naz. Lincei, Rend., Cl. Sci. Fis., Mat. Nat. 1958, 25, 3-12.
- M. Hatano, S. Kanbara, S. Okamoto, Paramagnetic and electric properties of polyacetylene. J. Polym. Sci. 1961, 51, S26–S29
- S. Kanbara, M. Hatano, T. Hosoe, ??????????????-??????????????????????? (Polymerization of acetylene by transition metal acetylacetonate-triethylaluminum system). J. Soc. Chem. Ind. Japan 1962, 65, 720-723.
- S. Ikeda, M. Hatano, Polymerization reaction by organic transition metal complexes. Ko?gyo? kagaku zasshi. 1963, 66(8), 1032-1037.
- K. Shimamura, M. Hatano, S. Kanbara, I. Nakada, Electrical Conduction of Poly-Acetylene under High Pressure. J. Phys. Soc. Japan 1967, 23, 578-581.
- M. Hatano, ????????????????? (Structures and electrical properties of acetylene polymers). Tanso 1967, 1967(50), 26-31.
- S. Ikeda, Recent Development in Polymer Synthesis. J. Synth. Org. Chem. Jpn 1962, 20, 76-86.
- S. Ikeda, T. Akihiro, Y. Akira, Measurement of C2 component in acetylene-14C polymerization system by Ziegler catalyst by radio gas chromatography. Radioisotopes 1964, 13, 415-417.
- S. Ikeda, T. Akihiro, On the mechanism of the cyclization reaction of acetylene polymerization. J. Polym. Sci. B Polym. Lett. Ed. 1966, 4, 605-607.
- S. Ikeda, ???????????????????????????? (Stereochemistry of ethylene and acetylene polymerization by Ziegler catalyst). J. Soc. Chem. Ind. Japan 1967, 70, 1880-1886.
- H. Shirakawa, S. Ikeda, Infrared Spectra of Poly(acetylene). Polym. J. 1971, 2, 231-244.
- Byun Hyung Jik, The Chosun Ilbo (chosun.com), http://focus.chosun.com/people/people-01.jsp?id=20494 (accessed October 6, 2017).
- J. Byun, Personal communication with the son of Pyun, 2018.
- H. C. Pyun, Pre-equilibrium in the Schmidt Reaction of Benzhydrols. J. Korean Chem. Soc. 1964, 8, 25-29.
- H. C. Pyun, J. R. Kim, Isotopic Exchange 5-bromouracil-Br82. J. Korean Chem. Soc. 1964, 8, 39-42.
- H. J. Byun, What is a Nobel Prize? 2013.
- H. J. Byun, I can't doubt the facts… KAERI Magazine 2002, 10, 7-8.
- H. C. Pyun, Pre-equilibrium in the Schmidt reaction of benzhydrols. Ph.D. Dissertation, Seoul National University, 1970.
- H. C. Pyun, J. Kim, W.-M. Lee, Copolymerization of Phenyl Acetylene with Stryrene. J. Korean Chem. Soc. 1969, 13, 387-393.
- T. Ito, H. Shirakawa, S. Ikeda, Simultaneous Polymerization and Formation of Polyactylene Film on the Surface of Concentrated Soluble Ziegler-Type Catalyst Solution. J. Polym. Sci. Polym. Chem. Ed. 1974, 12, 11-20.
- A. Munardi, R. Aznar, N. Theophilou, J. Sledz, F. Schue, H. Naarnann, Morphology of Polyacetylene Produced in the Presence of the Soluble Catalyst Ti(OnBu)4-n-BuLi. Eur. Polym. J. 1987, 23, 11-14.
- W. P. Hoen, H. C. Walvoort, J. P. M. Overbeke, What are the Factors Determining Authorship and the Order of the Author Names? JAMA 1998, 280, 217-218.
- S. P. DiBartola, K. W. Hinchcliff, Deciding on Authorship: Giving Credit Where It Is Due (and Only Where It Is Due). J. Vet. Intern. Med. 2006, 20, 803-804.
- V. Venkatraman, Conventions of scientific authorship. Science Magazine, April 16, 2010. http://www.sciencemag.org/careers/2010/04/conventions-scientific-authorship (accessed August 13, 2020).