Substantia. An International Journal of the History of Chemistry 6(1): 121-127, 2022 Firenze University Press www.fupress.com/substantia ISSN 2532-3997 (online) | DOI: 10.36253/Substantia-1426 Citation: Shirakawa H. (2022) Path to the Synthesis of Polyacetylene Films with Metallic Luster: In Response to Rasmussen’s Article. Substantia 6(1): 121-127. doi: 10.36253/Substan- tia-1426 Received: Oct 07, 2021 Revised: Jan 15, 2022 Just Accepted Online: Jan 16, 2022 Published: Mar 07, 2022 Copyright: © 2022 Shirakawa H. This is an open access, peer-reviewed article published by Firenze University Press (http://www.fupress.com/substantia) and distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distri- bution, and reproduction in any medi- um, provided the original author and source are credited. Data Availability Statement: All rel- evant data are within the paper and its Supporting Information files. Competing Interests: The Author(s) declare(s) no conflict of interest. Historical Article Path to the Synthesis of Polyacetylene Films with Metallic Luster: In Response to Rasmussen’s Article Hideki Shirakawa Professor Emeritus, University of Tsukuba, Tennodai, Tsukuba, Ibaraki 305-8577, Japan Abstract. The 2000 Nobel Prize in Chemistry was awarded jointly to Alan J. Heeger, Alan G. MacDiarmid, and Hideki Shirakawa “for the discovery and development of conductive polymers.” Unlike metals, organic polymers or plastics do not conduct elec- tricity. The three laureates found that polyacetylene can be doped on a film, which was initially synthesized by Shirakawa following a failed experimental trial by a Korean sci- entist, Hyung Chick Pyun. Later, Pyun insisted that he was the discoverer of polyacety- lene films with silvery sheen. This note sheds light on the true history of the synthesis of polyacetylene films. Keywords: polyacetylene film, Nobel Prize 2000, polymerization, Ziegler-Natta cata- lyst, fortuitous error, serendipity. INTRODUCTION On October 10, 2000, the Royal Swedish Academy of Sciences announced that plastic can indeed, under certain circumstances, be made to behave like a metal – a discovery for which Professor Alan J. Heeger, Profes- sor Alan G. MacDiarmid, and I, Hideki Shirakawa, received the Nobel Prize in Chemistry in 2000. This public announcement was followed by a story about the initial discovery of polyacetylene films: “once – by mistake – a thousand-fold too much catalyst was added.”1 Professor Bengt Nordén, chair- man of the Nobel Committee for Chemistry, also used the term “mistake” in the prize announcement.2 Commenting on a trigger of our achievements, he stated that the road to the discovery had started in 1967, when Shirakawa found that “by mistake” “a student [Pyun] had taken a thousand times too much catalyst” when polymerizing acetylene gas to make something called polyacetylene. At the beginning of my Nobel lecture entitled “The Discov- ery of Polyacetylene Film: The Dawning of an Era of Conducting Polymers,” given on December 8, 2000 at Aula Magna, Stockholm University, I acknowl- edged Dr. Hyung Chick Pyun (1926–2018), among other important contribu- tors, for sharing a “fortuitous error” that motivated further work toward the discovery of polyacetylene films.6 http://www.fupress.com/substantia http://www.fupress.com/substantia 122 Hideki Shirakawa In his recent article,3 Professor Seth C. Rasmus- sen discussed the event leading to the discovery of pol- yacetylene films by fortuitous error, based mainly on a “working English translation” of Pyun’s account writ- ten in Korean. Carefully reading Pyun’s two original documents written in 2002 and 2013 (through Japanese translation), 4,5 I found numerous factual errors, distor- tions, and assumptions. In this note, I would like to cor- rect them and present what happened regarding the syn- thesis of polyacetylene films with metallic luster, based on my memory and my laboratory notebooks. PYUN’S EXPERIMENTAL TRIAL In his article,3 Rasmussen asserts that the core of the discovery of polyacetylene films resulted from the performance of both myself and Pyun, a scientist visit- ing Japan from South Korea, quoting the “fortuitous error” that I mentioned in the Nobel Prize lecture6 and is described in the Les Prix Nobel: The Nobel Prizes 2000 and its reprints.7 This description is acceptable if the core of the discovery is interpreted as an important trig- ger for the synthesis of the metallic polyacetylene films. I repeat that the occurrence of the “fortuitous error” was a trigger for the subsequent synthesis of metallic polya- cetylene films but not the successful synthesis itself. However, Rasmussen does not present the discov- ery in this manner. Most descriptions in the article are based on Pyun’s accounts5 and third-party records, such as press reports by the Nobel Foundation and Royal Swedish Academy of Sciences at the time of the Nobel Prize announcement and award. The article lacks any of my own input, except for my printed Nobel Lecture and scientific papers. As a result, it depicts a biased account that contains serious errors. In his document,5 Pyun insists that he was an actual discoverer of polyacetylene films and not Shirakawa. He states, “A good result will be anticipated with the stirring speed reducing as much as possible during the polymeri- zation process. One day, when I tried an experiment on acetylene polymerization with this idea, it happened that a stirring motor stopped suddenly, presumably due to setting the rotation speed too slow. I was very panicked at first, but with careful inspection of the reaction flask, I found that a silvery membrane had formed on a surface of the catalyst solution, to my surprise.” He adds, “On this day, for some reason, the then assistant [Research Associate] Shirakawa was not in the laboratory.” These descriptions contain the two following factual errors: 1) “a silvery membrane had formed” and 2) “On this day, for some reason, the then assistant Shirakawa was not in the laboratory.” The exact date of “this day” is not clear because the trial run was not recorded on my laboratory notebook as the trial run was not mine. According to my memory, what happened on “this day” is as follows. One of Pyun’s two academic supervisors was Professor Yoneho Tabata (1928–2019) of Tokyo Uni- versity, Faculty of Nuclear Engineering. Due to Tabata’s prolonged trip to the United States, Pyun could not per- form any primary research during the period, which he described as his free time. The “this day” that Pyun refers to likely occurred in August 1967 considering these circumstances. One day, Pyun came to my office and asked to try acetylene polymerization as he was interested in acetylene polymerization and polyacety- lene. I provided an experimental protocol for perform- ing acetylene polymerization as a trial experiment at my research laboratory (room number 404) at the Research Laboratory for Resources Utilization, Tokyo Institute of Technology. As mentioned above, because this trial run was not my own research work, any relevant data, including the date and conditions for the polymerization, were not recorded in my laboratory notebook. I gave Pyun nor- mal guidelines for the polymerization process, such as a solvent, species of the catalyst components, and their concentrations. I expected that the product would be in a powdered form as usual. After briefly instructing Pyun on the handling of lab wares and equipment, I returned to my office, a preparatory room next to the No. 404 lab. The No. 404 lab, which I used as my own lab, was designed by Professor Sakuji Ikeda (1920–1984) as a tracer experiment for handling radioisotopes. When you enter the room from the passageway, you enter my office, a small preparatory room that students and I used as a study room. The No. 404 lab is accessible from the pre- paratory room. According to the lab rule, study desks were not placed in the No. 404 lab, so researchers and students spent their time in the preparatory room and only entered the lab to perform experimental work. At that time, the lab was freely open only to graduate and undergraduate students who were under my guidance. Therefore, Pyun could not carry out experiments for acetylene polymerization in my absence. On that day, after some time, Pyun came to my office to say that the polymerization had stopped. As this experiment should have been easy to perform, I was puzzled by what could have gone wrong. I checked the apparatus carefully with him, the occurrence being inconceivable. I then found that the magnetic stirrer had stopped and, after watching for a while, the mercury manometer, which indicates the acetylene’s pressure, did not decrease. 123Path to the Synthesis of Polyacetylene Films with Metallic Luster: In Response to Rasmussen’s Article We confirmed that the acetylene monomer had not polymerized, meaning that the reaction had not taken place. The reaction flask was, therefore, detached from the vacuum line, and we looked carefully inside the flask. If the reaction had proceeded normally, we would have observed a powdery product, but instead, we found that a black flappy or spongy matter had formed on the surface of the catalyst solution. The product, which was extracted using a pair of tweezers, was like a black rag. It was not “the silvery membrane” that Pyun described. If the reaction had proceeded normally, the product would have been a powder. The trial was clearly a failure, and Pyun was in agreement. I remember the result of the run clearly, even now. SUCCESSFUL SYNTHESIS OF POLYACETYLENE FILM WITH METALLIC LUSTER I still do not fully understand why Pyun’s trial run failed. However, because the product was not a pow- der but a quite different form, I thought that it might be possible to synthesize polyacetylene into a thin film by changing the polymerization conditions. I was also strongly motivated to clarify the cause of the failure. Immediately after Pyun’s failure, I started a series of polymerization experiments with graduate students under my guidance by changing the concentration of the catalysts and other conditions. Pyun was not involved in this series of experiments. Within one to two weeks, my students and I could successfully synthesize films of polyacetylene that were self-standing and could be easily handled by increasing the concentration of the catalysts by 1,000 or more times the normal condition. The self-standing film was such that it did not need lining. By improving the polym- erization conditions and methods, we also found that a thin film with a silvery metallic sheen could be obtained by polymerizing acetylene on the glass surface of a reac- tion f lask when a concentrated catalyst solution was applied to the glass surface of the flask. The side stuck to the glass surface of the reaction flask displayed a metal- lic luster, while the other side facing the acetylene gas took on a black color and a matted texture. The difference in the appearance of the two sides was clarified by observations made through transmis- sion and scanning electron microscopic observations. Scanning electron microscopic observations of a surface of the polyacetylene film revealed that the film was com- posed of entangled fiber-like long microcrystals (fibrils) with a diameter of ca. 200 Å. The morphology of an extremely thin film with several micrometers in thick- ness observed by a transmission electron microscope was also found to have the same microstructure. From these observations, it was clear that the whole film was composed of entangled fibrils. Because these films are composed of loosely entan- gled fibrils and inevitably lead to low bulk density, the incident light on the surface of the fibrils scattered ran- domly. Consequently, both surfaces of these films appear matted black due to random ref lections. The films formed on an interfacial surface of vapor/liquid (catalyst solution) reflect the trend strongly. Therefore, both sides of such films are the same matted black and show no metallic silverly luster. However, on the side of the film that touches the glass wall of the reaction flask applied by the catalyst layer, the growing fibrils are forced onto the glass wall during the polymerization reaction. Thus, the surface of the film facing the glass wall becomes flat with a higher density than the other surface. When inci- dent light shines on this side of the film, the light reflects in the same direction, and the surface presents a silverly metallic sheen. Following this process, cis-polyacetylene synthesized at a very low temperature (as low as -78 degrees centigrade) has a copper-like reflection color. All double bonds in the cis-polyacetylene have a cis form of geometric isomeric double bonds through the conjugated molecular chain. The cis form of polyacetylene results in a reflection spectrum shift to higher energy than that of trans form, because the bandgap of the cis form is larger than the trans form, which has a silvery sheen. THE FORTUITOUS ERROR I referred to Pyun’s trial run as a “fortuitous error” because, as a result of that failure, a black flappy or spongy matter was formed instead of the powdery prod- uct that should have formed under normal conditions. This accident became a trigger for the successful syn- thesis of films with a metallic sheen. Immediately after Pyun’s trial run, while continuing experimental trials to clarify the reason for the failure, we found that films formed on the surface of a much more concentrated catalyst solution – a thousand times more – instead of the traditional mmol/liter order of concentration. Using these films as a specimen for infrared spectroscopy, Raman scattering spectroscopy, X-ray diffraction, and normal vibrational analysis, among other tests, our pri- mary intention to clarify the mechanism of acetylene polymerization reactions with Ziegler-Natta catalysts was accomplished within an unexpectedly short period (just less than two years). Because the unforeseen fail- ure of Pyun’s test run had triggered the successful syn- 124 Hideki Shirakawa theses of polyacetylene films, and I thought of this for- tuitous error as a result of “serendipity,” I introduced this occurrence as a typical example of fortuitous error at domestic academic meetings and workshops, as well as international conferences and institutions. However, our polyacetylene study, published in academic journals internationally or domestically received little attention at the time.8 As context, it may be pointed out that research activities on organic and polymeric semiconductors declined globally after the 1960s, after being very active from the early 1950s to the 1960s. In particular, Natta et al. succeeded in synthesizing polyacetylene by the polymerization of acetylene using so-called Ziegler- Natta catalysts in 1958.9 The product was an intractable black powder used for the elucidation of various chemi- cal and physical properties of polyacetylene. Several years after our successful synthesis of polya- cetylene films, I was invited to conduct collaborative research with MacDiarmid, Department of Chemis- try, University of Pennsylvania. MacDiarmid had been intrigued by the silvery metallic luster of the polya- cetylene film (with a silvery sheen) when he visited and gave a seminar at the Tokyo Institute of Technology in 1975. In September 1976, we began joint research on the chemical and physical properties of polyacetylene with Heeger, a solid-state physicist of the Physics Depart- ment at the University of Pennsylvania. On November 23, 1976, when we tried to add a small amount of bro- mine to a piece of polyacetylene film, we found, to our surprise, that the electrical conductivity of the polya- cetylene film increased a hundred thousand times. This epoch-making result was reported at an international conference held in New York City in May 1977, and we followed up with two consecutive communications.11 The result initiated considerable interest among many researchers around the world. The newborn field was named conductive (conducting) polymers and synthetic metals, and a new journal entitled Synthetic Metals was born in October 1979. With increasing research activ- ity in this field, the episode of the successful synthesis of the silvery films of polyacetylene was shared widely among researchers. When I delivered talks at academic meetings and lectures at universities and institutions, I referred to the episode as a typical serendipitous event. As Pyun’s trial run was unsuccessful, I did not mention his name in view of his honor. To avoid embarrassing him, I referred to him in evasive terms, such as “a foreign research- er,” “a visiting researcher,” and sometimes simply “a researcher,” “a student,” or “a graduate student.” I now regret not mentioning his name. The episode resulted in gossip among researchers about how this “foreign researcher” did not understand Japanese and could not follow directions. I am very sorry that Pyun had to endure this. PYUN’S RESEARCH SUBJECT I do not remember the exact date of Pyun’s visit as a foreign researcher to the lab of Ikeda, Division of Macromolecular Materials, Research Laboratories for Resources Utilization, Tokyo Institute of Technology, as I have no written record of his visit. However, his visit occurred one year after I started my post as a research associate in the division in April 1966. According to Pyun’s document,5 he visited Japan in May 1967 and returned to Korea in March 1968. I am unsure when I first met Pyun in person or at labora- tory meeting. However, I have a vivid memory of how he first introduced himself as he told me that his family name was “HEN 邊” – that is, the side (hen) of a trian- gle. I knew that he grew up in the era of Japanese colo- nization, and he was forced to be educated in Japanese. Later, he struggled through the Korean War (1950–1953). However, he never communicated about his difficult life in Korea. He was always easy to work with and he never expressed any inability to understand Japanese. As I had only recently joined the lab, I was not informed about how and why Pyun had joined the Ike- da lab as a foreign associate. However, I knew vaguely that his research purpose was the clarification of certain polymerization mechanisms using isotopes as one of his supervisors was Tabata, Department of Atomic Engi- neering, University of Tokyo. I found out only recently that, as mentioned above, Pyun’s research in Tabata’s lab was interrupted for some time because Tabata’s return from his visit to the United States was delayed. During this period, Pyun visited my lab to conduct the trial run on the polymerization of acetylene, feeling that he had free time to work on subjects outside his main focus during Tabata’s absence. According to Rasmussen’s article and Pyun’s docu- ments, Pyun’s research subject was the copolymerization of ethylene and tetrafluoroethylene and the analysis of its molecular structure by infrared spectroscopy. There was no discussion at the lab meeting that Pyun had joined the research group to study acetylene polymeriza- tion. At that time, I was unaware of whether Ikeda was unwilling for Pyun to deviate from his primary subject of interest, and I did not know that Tabata’s return had been delayed. However, I accepted his offer to perform a trial run without hesitation. It was very clear that the 125Path to the Synthesis of Polyacetylene Films with Metallic Luster: In Response to Rasmussen’s Article trial run was an experience test for him, and he did not undertake it as a research collaborator in the ongoing work in Ikeda’s lab. It turns out that, as described below, Pyun con- ducted two or more related tests after this initial test. However, I am sure that his additional experiments were performed after our group’s establishment of the syn- thesis of self-standing polyacetylene films with a silvery luster. I was hired as a research associate in the Division of Macromolecular Materials, Research Laboratory for Resources Utilization, Tokyo Institute of Technology, on April 1, 1966, and I continued my research work in the same lab for five years during my graduate student days. At that time, Dr. Shu Kambara (1906-1999) was the pro- fessor, and Ikeda was the associate professor of the divi- sion. Soon after, Kambara retired on March 31, 1967, and subsequently, Ikeda was promoted to the position of pro- fessor on August 1, 1967. Ikeda had been engaged in research on the vulcan- izing mechanism of natural and synthetic rubber using radio isotopes from his associate professor days. After becoming professor of the division, he then continued to work on the mechanism of ethylene and acetylene polymerization with Ziegler-Natta catalysts using tracer techniques. When I became a research associate, Ikeda was very close to his work on ethylene polymerization and had just started research on acetylene polymeriza- tion, and I participated in this work. When Pyun came to my lab to request permission to perform a trial run on acetylene polymerization, his intention, I later realized, was quite different from what he originally stated. When I was a graduate student, Dr. Masahiro Hatano (1930–, who later moved to the Chemical Research Institute of Non-Aqueous Solutions, Tohoku University) was a research associate under Kam- bara and undertook research on the polymerization of compounds with carbon-carbon and carbon-nitrogen triple bonds for the synthesis of polymer semiconduc- tors. The Kambara and Ikeda Lab has a long history of research on acetylene polymerization and polyacety- lene, and Hatano developed acetylene polymerization for many years and accumulated relevant techniques. Pyun was interested in related research work on semiconducting polymers, which he sought to learn more about by joining Ikeda’s group. In fact, he wrote in his document5 that “I thought of spending my unexpected free time carrying out acetylene polymerization as I learned from various reports in the lab that this lab [the Kambara and Ikeda Lab] had conducted related studies for nearly ten years, and I was much interested in such work.” Regarding his research purpose, he also writes, “I thought that even if acetylene polymers are powder, if the polymerization can be controlled to produce particles larger in size, various properties [of acetylene polymers], such as conductivity, would be closer to true values.” As mentioned above, he writes that it would be better to decrease the stirring speeds as much as possible during the polymerization reaction to increase the size of the particles. I never heard such a clear idea from him at that time and only learned of it after reading his document. It is worth noting that while he writes that it would be bet- ter to increase the size of particles, he provides no idea of how to produce polyacetylene in film form. As mentioned above, Pyun’s trial run was not recorded in my laboratory notebook. While it would be best to check Pyun’s notebook regarding the trial run, I learned from reading his documents that he was unable to bring the notebook home following Ikeda’s instruc- tions. His laboratory notebook went missing after that. His document5 include many inconsistent descrip- tions of his stay in Japan. The following is one example: “About two weeks after starting my work at Professor’s Tabata lab at the University of Tokyo, I went to the Tokyo Institute of Technology to take the deuterated stocked ethylene in the Ikeda lab. There I encountered Profes- sor Kambara’s retirement memorial lecture, which had started just then in the auditorium.” He continued with the following observations: “The audience was full in the auditorium, and the title was ‘A History of the Develop- ment of Polymer Science and Engineering in Japan.’ I was staggered on hearing Professor Kambara’s words in the last part of his lecture in front of such a large audi- ence. He disclosed ‘a long-awaited method of produc- ing polyacetylene in the form of polyacetylene film had been attained in Japan, and the inventor is the assistant [Research Associate] Shirakawa of the Ikeda lab.’” Kambara’s retirement date was March 31, 1967, and by custom, lectures by retiring professors were held just before their retirement. If the date of Pyun’s visit to Japan was May 1967, as noted in Rasmussen’s article, it would be impossible for him to attend Kambara’s final lecture as it was before his visit to Japan. Therefore, this must be a continuity error. Pyun further infers that the abovementioned audi- ences provided information to the mass media in Japan and that the media caused a media circus immediately after the announcement of Shirakawa’s Nobel Prize in Chemistry. Soon after the announcement by the Nobel Committee on October 10, 2000, three young journalists visited my home and questioned me closely as to why Pyun was not a joint prize winner, which left me with an unpleasant memory. The journalists were from one of three big presses in Korea; if my memory is correct, the press was The Dong-a Ilbo. From this, I learned for 126 Hideki Shirakawa the first time that Pyun was known as a leading scien- tist in the synthesis of polyacetylene in Korea, and thus he missed receiving what would have been Korea’s first Nobel Prize in Chemistry. I have no memory of any discussion with Pyun regarding research, especially on acetylene polymeri- zation and the properties of polyacetylene during his one-year stay at the Tokyo Institute of Technology and the University of Tokyo. However, I realized that Pyun was highly interested in polyacetylene as an impor- tant candidate in semiconducting polymer by reading related articles before visiting Japan. In his document, he describes that while in Japan “my study of polyacety- lene study was stopped after all…,” calling up for me his strong emotion toward polyacetylene study. RECORD OF PYUN’S WORK IN MY LABORATORY NOTEBOOKS To refresh my memory to write this note, I checked my 15 laboratory notebooks used during my period at the Tokyo Institute of Technology and more than 20 notebooks related to my research works. These showed me that Pyun conducted several experiments on acety- lene polymerization. The date of these experiments can- not be specified, but presumably, it was in mid-Septem- ber 1967, after we established the synthetic method of self-standing polyacetylene films with a silvery sheen. The first assumable description was a series of runs in which Pyun carried out three polymerizations of deu- terated acetylene by changing the polymerization tem- perature. The results of the elemental analyses of the deuterated polyacetylenes are recorded in my notebook No. 3, page 442, as Pe-1 polymerization temperature 60 degrees centigrade, Pe-2 polymerization temperature 20 degrees centigrade, and Pe-3 polymerization tempera- ture -78 degrees centigrade, respectively. The code “Pe” can be understood as Pyun’s initial. He synthesized deu- terated acetylene by himself as precursors for the syn- thesis of deuterated ethylene, such as C2H2D2 and C2D4, as monomers for deuterated polyethylene. It was my assumption that he tried to polymerize the deuterated acetylene prior to his primary purpose. The next record was on the mass-spectroscopy anal- ysis of ethylene-d4, synthesized by Pyun. The result is described in my notebook No. 3, page 444, October 13, 1967. The ethylene-d4 was synthesized by an additional reaction of deuteron to acetylene-d2 for the copolymeri- zation of ethylene and tetrafluoroethylene. For his pri- mary purpose, Pyun synthesized acetylene-d2 himself as an intermediate for the synthesis of ethylene-d4. Pre- sumably, he attempted to polymerize the acetylene-d2 as a monomer. His experimental results, mentioned above, were recorded twice in my notebook because I was familiar with the application procedures for elemental analysis and mass-spectroscopy. Thus, his products, acetylene-d2 and ethylene-d4, were passed to each analytical lab via me, and the data were, necessarily, recorded in my note- book. The first appearance of the term “polyacetylene film” is recorded clearly in my notebook No. 3, page 452, on November 8, 1967, as X-ray scattering analysis was car- ried out in the X-ray analysis room of the Department of Textile Engineering. The measurements were performed at two different temperatures – 21 and 80 degrees cen- tigrade – to measure the estimated thermal expansion coefficient of polyacetylene films. It should be noted that these analyses were carried out for a series of measure- ments of the various physical properties of polyacetylene films, and there was no relation to Pyun’s research. CLOSING REMARKS The Nobel Committee announced that our Nobel Prize in Chemistry in 2000 was awarded “for the discov- ery and development of conductive polymers” based on the doping of polyacetylene attained by the three laure- ates. It should be noted that it was not for the synthesis of polyacetylene films. However, there is no doubt that the synthesis of polyacetylene films was a key factor in the discovery of conducting polymers. In this account, I have presented the truth to the best of my ability, based upon my memories and my notebooks. I further want to stress that Pyun’s contribution was minimal and that his claims that he was the discoverer of the synthesis of polyacetylene were his strong belief, but they were not supported by the truth of what happened. However, his one-year stay in Japan was not satisfactory, and as one of the concerned personnel, I regret that his research work was not attained fully due to several unfavorable events during his stay in Japan. ACKNOWLEDGEMENTS I wish to thank Dr. Yasu Furukawa for alerting me to the historical article by Rasmussen and its supporting information. My special thanks go to doctoral graduate student Lee Jinyoung, Graduate School of Interdiscipli- nary Information Studies, The University of Tokyo, and her supervisor, Associate Professor Dr. Ken Ito, Interfac- 127Path to the Synthesis of Polyacetylene Films with Metallic Luster: In Response to Rasmussen’s Article ulty Initiative in Information Studies, Graduate School of Interdisciplinary Information Studies, The University of Tokyo, who translated Pyun’s Korean documents into Japanese. Lastly, I would like to thank Dr. Naresh Pan- dya, Kapiolani Community College, and Associate Pro- fessor Dr. Katsuro Anazawa, The University of Tokyo, for their suggestions on a draft of this paper. REFERENCES 1. The Nobel Prize in Chemistry 2000, 2021, https:// www.nobelprize.org/prizes/chemistry/2000/ popular- information / 2. Nobel Media AB 2021, 2021, https://www.nobelprize. org/prizes/chemistry/2000/prize-announcement/ 3. S. C. Rasmussen, New Insight into the “Fortuitous Error” that Led to the 2000 Nobel Prize in Chemis- try. Substantia. 2021, 5, 91–97. 4. H. J. Pyun, I can’t doubt the facts…, (in Korean). KAERI Magazine. 2002, 10, 7–8. This is a shorter version of the document in note 5. 5. H. J. Pyun, What is a Nobel Prize? (in Korean). 2013. (An unpublished document provided by Professor Rasmussen). 6. H. Shirakawa, The Discovery of Polyacetylene Film: The Dawning of an Era of Conducting Polymers. in Les Prix Nobel, The Nobel Prizes 2000 (Ed.: Nobel Foundation), Stockholm, 2000, pp. 217–226. Original speech: https://www.nobelprize.org/prizes/chemis- try/2000/shirakawa/lecture/ 7. H. Shirakawa, Nobel Lecture: The discovery of polya- cetylene film – the dawning of an era of conducting polymers. Rev. Mod. Physics. 2001, 73, 713 – 718; H. Shirakawa, The discovery of polyacetylene film – the dawning of an era of conducting polymers. Angew. Chem. Int. Ed. 2001, 40, 2575-2580. 8. H. Shirakawa, S. Ikeda, Infrared Spectra of Poly(acetylene). Polym. J. 1971, 2, 231–244; H. Shi- rakawa, T. Ito, S. Ikeda, Raman Scattering and Elec- tronic Spectra of Poly(acetylene). Polym. J. 1973, 4, 460–462; T. Ito, H. Shirakawa, S. Ikeda, Simultaneous Polymerization and Formation of Polyacetylene Film on the Surface of Concentrated Soluble Ziegler-Type Catalyst Solution. J. Polym. Sci. Polym. Chem. Ed. 1974, 12, 11–20. 9. G. Natta, G. Mazzanti, P. Corradini, Polimerizazione stereospecifica dell’acetilene. Atti Accad. Naz. Lincei, Rend., Cl. Sci. Fis., Mat. Nat. 1958, 25, 3-12. 10. M. Akhtar, C.K. Chiang, M. J. Cohen, J. Kleppinger, A. J. Heeger, E. J. Louis, A. G. MacDiarmid, J. Mil- liken, M. J. Molan, D. L. Peebles, H. Shirakawa, Syn- thesis and Properties of Halogen Derivatives of (SN)X and (CH)X. Ann. N. Y. Acad. Sci. 1978, 313, 726–736. 11. H. Shirakawa, E. J. Louis, A. G. MacDiarmid, C. K. Chiang, A. J. Heeger, Synthesis of Electrically Con- ducting Organic Polymers: Halogen Derivatives of Polyacetylene. (CH)X. JCS Chem. Commun. 1977,16, 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. Substantia An International Journal of the History of Chemistry Vol. 6, n. 1 - 2022 Firenze University Press To Print or not to Print? Preprints and publication: how the Covid-19 pandemic affected the quality of scientific production Pierandrea Lo Nostro Faraday’s Dogma Stephen T. Hyde Creativity in the Art, Literature, Music, Science, and Inventions Singlet Dioxygen 1O2, its Generation, Physico-chemical Properties and its Possible Hormetic Behavior in Cancer Therapy Marc Henry1, Miro Radman2, Luc Benichou3, Khalid O. Alfarouk4, Laurent Schwartz5,* Is the Second Law of Thermodynamics Able to Classify Drugs? Laurent Schwartz1,*, Luc Benichou2, Jules Schwartz1, Maxime Pontié3, Marc Henry4 History of Research on Phospholipid Metabolism and Applications to the Detection, Diagnosis, and Treatment of Cancer Peter F. Daly1, Jack S. Cohen2,* Capillary Electrophoresis (CE) and its Basic Principles in Historical Retrospect. Part 3. 1840s –1900ca. The First CE of Ions in 1861. Transference Numbers, Migration Velocity, Conductivity, Mobility Ernst Kenndler The Early History of Polyaniline II: Elucidation of Structure and Redox States† Seth C. Rasmussen Path to the Synthesis of Polyacetylene Films with Metallic Luster: In Response to Rasmussen’s Article Hideki Shirakawa Comments on Shirakawa’s Response Seth C. Rasmussen Lipids, Chloroform, and Their Intertwined Histories Carlos A. Ramírez Professor Alexander Kessenikh (1932-2021) Andrey V. Andreev1, Vadim A. Atsarkin2, Konstantin V. Ivanov1, Gennady E. Kurtik1, Pierandrea Lo Nostro3, Vasily V. Ptushenko4,5, Konstantin A. Tomilin1, Natalia V. Vdovichenko1, Vladimir P. Vizgin1