Looking Back the Most Beautiful Molecule C60 after Quarter Century of Discovery Insert

On the occasion of silver anniversary of the C60 discovery, the present situation of C60 research is briefly analyzed from three distinct angles: molecule, solid and nanoparticle. With regard to molecular angle, the long pending problem of formation mechanism is almost solved by molecular dynamics a...

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Published in:Вісник НАН України
Date:2012
Main Author: Ōsawa, Eiji
Format: Article
Language:English
Published: Видавничий дім "Академперіодика" НАН України 2012
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Online Access:https://nasplib.isofts.kiev.ua/handle/123456789/38963
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Journal Title:Digital Library of Periodicals of National Academy of Sciences of Ukraine
Cite this:Looking Back the Most Beautiful Molecule C60 after Quarter Century of Discovery Insert / Eiji Ōsawa // Вісн. НАН України. — 2012. — № 9. — С. 30-38. — Бібліогр.: 34 назв. — англ.

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Digital Library of Periodicals of National Academy of Sciences of Ukraine
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author Ōsawa, Eiji
author_facet Ōsawa, Eiji
citation_txt Looking Back the Most Beautiful Molecule C60 after Quarter Century of Discovery Insert / Eiji Ōsawa // Вісн. НАН України. — 2012. — № 9. — С. 30-38. — Бібліогр.: 34 назв. — англ.
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container_title Вісник НАН України
description On the occasion of silver anniversary of the C60 discovery, the present situation of C60 research is briefly analyzed from three distinct angles: molecule, solid and nanoparticle. With regard to molecular angle, the long pending problem of formation mechanism is almost solved by molecular dynamics approach hinted by Prigogine’s nonequilibrium thermodynamics. The C60 research is at the moment most active in chemistry, and some of the recent results are discussed here. Though C60 is closer to molecule than to the smallest nanoparticle in its outlook, a big future seems hidden in its application in nanotechnology. З нагоди срібної річниці з часу відкриття фулеренів коротко проаналізовано нинішню ситуацію з їх дослідженням. C60 розглянуто в трьох різних аспектах — молекула, тверде тіло та наночастинка. Стосовно молекулярного аспекту варто зазначити, що давню проблему механізму утворення фулеренів майже розв’язано за допомогою молекулярно-динамічного підходу, підказаного нерівноважною термодинамікою І. Пригожина. Нині найактивніше досліджують хімію C60. У статті розглянуто деякі з нещодавніх результатів у цій галузі. Хоча за своїми характеристиками C60 ближчий до молекул, ніж до найдрібніших наночастинок, його застосування в нанотехнологіях, схоже, таїть у собі великі перспективи. По случаю серебряной годовщины со времени открытия фуллеренов кратко проанализирована нынешняя ситуация с их исследованием. C60 рассматривается в трех различных аспектах — молекула, твердое тело и наночастица. Касательно молекулярного аспекта нельзя не отметить, что давно занимавшая умы ученых проблема механизма образования фуллеренов почти решена с помощью молекулярно-динамического подхода, подсказанного неравновесной термодинамикой И. Пригожина. Сегодня наиболее активно изучаются химические свойства C60. В статье обсуждаются некоторые последние результаты в этой области. Хотя по своим характеристикам C60 ближе к молекулам, чем к мельчайшим наночастицам, его применение в нанотехнологиях, похоже, таит в себе большие перспективы.
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fulltext 30 ISSN 0372-6436. Вісн. НАН України, 2012, № 9 СТАТТІ ТА ОГЛЯДИ On the occasion of silver anniversary of the C60 discovery, the present situation of C60 research is briefly analyzed from three distinct angles: molecule, solid and nanoparticle. With regard to molecular angle, the long pending problem of forma- tion mechanism is almost solved by molecular dynamics approach hinted by Prigogine’s nonequilibrium thermodynamics. The C60 research is at the moment most active in chemistry, and some of the recent results are discussed here. Though C60 is closer to molecule than to the smallest nanoparticle in its outlook, a big future seems hidden in its application in nanotech- nology. Keywords: buckminsterfullerene, formation mechanism, dyadic electronic system, fullerenol polisher, elixir. UDC 546.26 EIJI ŌSAWA NanoCarbon Research Institute Limited Ueda, Nagano, 386-8567, Japan, osawaeiji@aol.com LOOKING BACK THE MOST BEAUTIFUL MOLECULE C60 AFTER QUARTER CENTURY OF DISCOVERY © Eiji Ōsawa, 2012 INTRODUCTION C60 (Fig. 1, see insert) was first found in 1985 [1] and then isolated in 1990 [2] as a new mol- ecule and aroused tremendous interests from chemists. Next year, physicists found super- conductivity in alkali-doped C60 films [3]. Ex- citement quickly spread to engulf scientists and engineers of all disciplines, and enormous surge of research on buckminsterfullerene be- gan. In addition to the scientific novelty, C60 is also called as the most beautiful molecule [4] with perfect symmetry [5]. Everyone seemed to like it. The fever continued to about 1996, when the discoverers were awarded Nobel Prize for Chemistry. Then, all of sudden inter- ests of scientists shifted to carbon nanotubes, the tubular kin of C60. CNT fever continued somewhat longer, until about 2010, but then graphene took over the leading position of in- ternational scientific race, after Nobel Prize for Physics went to the re-discoverers of graphene. Graphene is a lengthwise opened and extended carbon nanotube. Where do we go after graph- ene in the journey on sp2-networks? Clearly, carbon research is undergoing Sturm und Drang period in the past 20 years. For just an example of the intensity of impact, the Na- ture paper by Kroto and others [1] that started all these research activities has been cited about 8,800 times by June 2012 according to Google Scholar statistics. Iijima’s first paper on CNT [6] obtained still higher citations of about 24,900! Scientists are working hard every- where as if they are driven by strong force, and with high enthusiasm in one or the others of these new carbons. We would like to know why the popular targets of carbon research change so quickly. What would be the next target? Will any of the recognized targets produce use- ful products some day? In this short review, we will try to answer at least some of the above questions. For personal reason, we will limit our discussion to C60, and analyze the reason for its rise and fall. We hope that the fall in the number of research outputs of fullerene is temporary and will recover in due time. FORMATION MECHANISM A persistent weak point of C60 as the raw in- dustrial material is the high production cost (end price = ¥30,000/2.5 g). Actually not only C60 but also all the breeds of new carbon net- works including single-walled carbon nano- tubes and graphenes have the same problem of forbiddingly high price. In order to bring down price, we must improve the production method. These are new carbons are being produced by one or the other variations of bottom-up me- thods that involve generation of carbon plasma at extremely high temperatures like 5000 K. 31ISSN 0372-6436. Вісн. НАН України, 2012, № 9 СТАТТІ ТА ОГЛЯДИ These conditions are different from those which chemists used to work in the past two- centuries, thus posing us an entirely new and difficult task when we want to probe into their formation mechanism. In spite of hard work for a quarter of century, none of the known bottom-up nanocarbons has yielded atomistic details in the formation mechanism. If we do not know the mechanism of formation, we cannot improve the production process. Let us start looking at the formation mechanism of C60. In the beginning only the traditional, deter- ministic, equilibrium and multi-step approach was earnestly followed [7, 8]. This approach as- sumes that nature knows the shortest possible but energetically most economical pathway of building up carbon atoms step by step to C60 with eicosahedral symmetry, where the surface pattern of soccer ball or truncated dodecahe- drane is reproduced with a bewildering net- work of 12 pentagons and 20 hexagons. In the absence of techniques to study phenomena oc- curring at 5000 K, we had to guess what nature knows and confirm the guess by some objective means. Many people including ourselves felt challenged and were adsorbed in the puzzle (Fig. 2), but this traditional approach turned out to be surprisingly futile: about a dozen of seemingly reasonable mechanisms have been suggested but neither experimental nor com- putational support could be obtained [9]. Then the second, non-traditional approach surfaced from about the turn of century. This method is essentially non-empirical simulation with the help of molecular dynamics algorithm as the basic tool. Namely a few hundreds of C1 or C2 species are confined in a small space of nanometer size, and heated at 2000–3000 K as long as one can afford, generally up to pico se- conds, to see what happens in computer. As the number of carbon atoms must be large enough so as to reproduce real phenomena, the load of computation became quite large, hence ener- gies were at first calculated by fast empirical potential functions like Brenner’s reactive bond order types [10]. However, no C60 was formed. It was finally felt that energy must be evaluated by quantum chemical method. At this point, Irle – Morokuma group began using NCC-DFTB level of theory in 2003 [10]. Even with this lowest possible level, they succeeded to observe hot C2 species self-assemble into a hot giant fullerene consisting of 100 to 200 car- bon atoms, which then releases C2 species to shrink close to C60 [7]. However, this remarkable breakthrough is still incomplete as they have hardly reached C60 itself. It seems that some unknown but cru- cial condition is missing to accelerate the strongly endothermic shrinking step. Addition of helium, carbon monoxide and oxygen did not work, even though He did occasionally lead to C60 but not so often as to reproduce the Fig. 2. An example of traditional mechanistic pathway from an arbitrary C60 isomer (2) to buckminsterfullerene (1) as obtained by a combined topological and semi-empirical quantum mechanical approach using only Stone — Wales rearrangement as the elementary step. Four integers above arrow indicate the four adjacent rings participating in the rearrangement, wherein the central C–C bond (bold) formally rotates by a right angle. Taken from [4] 32 ISSN 0372-6436. Вісн. НАН України, 2012, № 9 СТАТТІ ТА ОГЛЯДИ high yields observed in experiments, ca 20% in arc discharge and 100% in combustion methods [12, 13]. Nevertheless, their Shrinking Hot Giant Fullerene Road avoids difficulties in the tradi- tional approach, like including a number of un- stable intermediates, passing through high tran- sition states of Stone — Wales rearrangements and compensating large entropy loss in forming closed systems. We believe that the SHGFR theo ry is the most likely among all the other the- ories of C60 formation. When eventually com- pleted, the mechanism will be the most re ma r k- able examples of Prigogine’s non-equilibrium and irreversible physics, where a highly orde red structure like C60 emerges from completely disordered starting mixture by dynamic self- assembling process at very high temperature. The Irle — Morokuma theory explains at least one well-observed but so far enigmatic experimental observation: initial formation of large amounts of high-mass peaks and their subsequent disappearance in MS. Their simu- lation results strongly support a long-held in- terpretation that each of the large cluster peaks represents a giant fullerene. Giant fullerenes should be practically strain-free but kinetically highly unstable at such high temperatures of 2,000 to 3,000 K, hence it is perfectly reason- able that they release C2 to shrink into smaller and smaller fullerenes until it reaches the dis- tinguished kinetic energy minimum of C60. This picture fits to the absence of mass peaks below C58 fullerenes and appearance of several inter- mediates below C100 like C70. If closed network growth mechanism holds, the distribution pat- tern around C60 must be the other way around. The most likely places of C2 expulsion will be the central bond of abutting pentagons, or the places with high curvatures in very large giant fullerenes. Failure to reproduce the shrinking process by computer simulation is likely caused by the neglect of vibronic coupling outside the Born — Oppenheimer approximation. Elec- tronic states of giant fullerenes in very high vibrational excited states must be greatly in- fluenced by non-adiabatic nuclear movements. Accordingly bonds are the more readily broken as the curvature of surface increases. In other words, C2 expulsion will become faster and faster as the fullerene shell shrinks smaller and smaller towards C60, which is an outstanding kinetic energy minimum. If we assume that the Irle – Morokuma the- ory will be sooner or later completed along the direction they proposed, we can then proceed to improve the yield of C60 production. Some more details of the production process will be given later in this review. MOLECULE OR NANOPARTICLE? C60 is often referred as the first member of nanoparticles. However, this statement should be taken with some reservation. According to the formal definition of nanoparticle (1–100 nm in diameter), C60 with its nuclear-nuclear dis- tance of 0.71 nm, or van der Waals diameter of 1.0 nm, only marginally qualifies as the small- est nanoparticle. In more general terms like amenability to purification (Table I, see insert), C60 is closer to molecule rather than nanoparti- cle. It would be more appropriate to categorize C60 as a borderline case between molecule and nanoparticle. Mass production and cost reduction of ma- terial are not necessarily as important in nano- technology as in modern chemical technology. This assessment came out in the course of com- parison between the two technologies (Table I). As far as the classification of a material to ei- ther molecule or nanoparticle is concerned, the most pertinent criteria would be the ways of application (origin of function) and the units used (the lowest two lines in Table I). Nano- particles are generally used as individual par- ticles, hence counted by the number, whereas chemical substances are treated as a collection of molecules and counted by the weight (actu- ally in terms of mole numbers). C60 may be used, if used at all, either as individual particle or as a mass of molecules depending on the pur- pose due to its border-line nature. In the latter case, mass production and low cost is certainly an important asset. In that case, combustion method is by far the most advantageous. 33ISSN 0372-6436. Вісн. НАН України, 2012, № 9 СТАТТІ ТА ОГЛЯДИ Production of C60 by combustion. Forma- tion of C60 in the flame of hydrocarbon com- bustion was discovered by J. Howard of MIT [14] and K.-H. Homann of Darmstadt TH [15] immediately after the first isolation of C60 from carbon vapor by Krätchmer et al. [2]. It has long been considered that the two methods fol- low different mechanisms. However, Homann and his coworkers have long recognized the formation of large variety of giant carbon clus- ters just below fullerene formation zone in flame, and named it as aromers for aromatic oligomers and thought the smaller of them as fullerene precursors (Fig. 3, see insert) [15]. In the light of Irle – Morokuma theory, aromers could well be giant fullerenes. Then an inevita- ble conclusion is that the two C60 syntheses, arc discharge and combustion, follow the same mechanism. Independently, Howard continued to im- prove the combustion synthesis of C60, almost single-handedly after Homann retired. The yield of C60 in the solid black product from combustion increased from 1% in the earliest period, to 20% by the effort of Mitsui Chem. Co., which built a plant with this yield level, then Howard reached 100% before 2003. By this time Howard had set up a venture compa- ny and stopped publishing his results even though he continued to keep his teaching post at MIT. Unfortunately, he suffered from brain cancer and died on July 7, 2008. Thus, the most precious records on the optimum conditions of combustion synthesis of C60 remained in secre- cy and will never be published. Nevertheless, it would be challenging for us to take the best ad- vantage of Irle – Morokuma mechanism and to reproduce the Howard conditions posthu- mously. It appears important to keep the flame temperature very high near 3000 K even at the end of long flame. External heating may be necessary. RECENT DEVELOPMENTS On the industrial sector and investment market, activities around C60 have long dimin- ished. Some of the continuing moves in the commercial sector will be briefly touched at the end of this section. However, in the academia, C60 research is still going on rather strong. Here again we need a small remark on its relation to the fullerene fever. As a molecule, or chemical reagent, C60 is definitely one of the most favored companions among chemists. Its outstanding chemical features include strong electron-withdrawing property, high reactivity to addition reactions, and high symmetry. For this reason, C60 is still a very popular topic in chemistry. Electron acceptors in dyadic systems. One of the most favored strategies in current scenes of green energy is to arrange a pair of electropositive and electronegative molecules or their fragments in nano-vicinity, let light absorbed by the former to excite its frontier electrons, to migrate them to the latter by or- bital interactions through bonds (OITB) or through space (OITS), and to take them out as electric current. Here skill in the organic synthesis is required in order to construct elaborate molecular architecture. Graphene is a classical electron acceptor but C60, which is a spherical graphene, is preferred due to high electronegativity (the low energy va- cant molecular orbitals are in the bonding en- ergy levels), and reactivity. For these reasons, C60 and a simple derivative [6,6]PCBM (phe- nyl-C61-butyric acid methyl ester) has been the best-used electron acceptors (or n-type semiconductor as physicists prefer to call) in the research of photosynthesis and photo- voltaic cells [16, 17]. About the turn of cen- tury, porphyrin-fullerene dyad systems have been extensively studied, but the light-har- vesting efficiency still cannot compete with natural systems [18]. 34 ISSN 0372-6436. Вісн. НАН України, 2012, № 9 СТАТТІ ТА ОГЛЯДИ Designer syntheses. Due to its high symme- try (Ih, next only to sphere), C60 can be deriva- tized to novel polyfunctional structures while still retaining many of its symmetry elements [19, 20]. These novel structures are at the mo- ment one of the attractive playgrounds of syn- thetic organic chemists. It is fascinating to see that such a large and complicated structure like C60 are incorporated at will into intricate molecular architectures like fashion designers creating original costumes one after the other. Interested readers are referred to the original publications. Surgery on C60 cage. The C60 cage is large enough to cut open, place foreign atoms or even a molecule into the inside of cage, then close the opened mouth by stitching together by means of chemical bonds. Komatsu and Murata succeeded in encapsulating a H2 molecule in- side C60 through a 13-membered ring orifice and then closing it again [21]. In reality, the opening and closing of cage involve many steps of elaborate chemical transformations and it will need a lot more work to simplify and ge- neralize the technique. Nevertheless, this is a flexible and valuable approach to the novel en- dohedral C60 derivatives. Endohedral metallofullerenes. An alterna- tive physical method of encapsulation of fo- reign matters in C60 cage structure has been explored since soon after the discovery of C60. Still now, synthesis of M@C60 (M = metal atoms or ions) is achieved only with extremely low yields, and the type of M strictly limited (Fig. 4, see insert) [22]. Clearly metal encapsu- lation into C60 comprises one of the most chal- lenging subjects in the C60 research. It is hoped that QM/MD simulation will be able to solve many mysteries in M@C60 that cannot be solved by experimental approaches. Fullerenols. One other type of fullerene de- rivatives of C60 that has attracted much atten- tion of chemists is those exhaustively substitut- ed with small heteroatoms like C60H60 and C60F60, wherein cage skeleton will be still a perfect sphere but inflated due to sp3 hybridization, with longer and equal C–C bonds and smaller angle strain. However, the reaction stopped af- ter 44 substituents have entered, due to steric crowding. Beyond this limit, the cage skeleton starts to break apart [23]. Exactly the same situ- ation was observed when OH radicals were forced to add to C60 as many as possible [24]. In these C60X60 systems, C–X bonds are supposed to be considerably elongated due to severe steric crowding with the neighboring X atoms. Thus, there will be a hard and rigid spherical shell consisting of spherically aligned, non-bonded X-atoms concentrically enclosing above the spherical C60. Thus, from the outside the C60X60 molecule will look like a very hard sphere filled with X atoms on the surface. Such a molecule must be very unique and new, chemically inert and show highly positive surface potential. Originally, the synthesis of C60X60 was sug- gested by Kroto as ideal nanolubricants in analogy with the known lubrication proper- ty of poly(tetrafluoroethylene). No frictional constant has been reported for C60X44 (X = H, F, OH) so far, but we can easily guess that these are too small for solid spacers with approxi- mate diameter of only about 1 nm to perform effective lubrication for usual surfaces. Perhaps super-lubrication may be realized for the C60X44/PTFE systems. However, this is not the whole story. Surprisingly enough, C60(OH)44 (and C60(OH)36 as well) proved to be an excellent and practi- cable polisher for copper surface of multi-lay- ered integrated circuits [25, 26]. Fullerenol is dissolved in water and the copper device is treated in agitating fullerenol solution only for a few minutes to achieve the novel me- chano-chemical polishing. Mechanism of the MCP action is still not well understood. Al- though vicinal surface OH groups may act like ethylene glycol to form pentagonal chelate ring, a chelating agent is already ad- ded in the polishing liquid from the begin- ning. We imagine that hard and rigid ball of C60(OH)44 plays some unknown but critical role to smooth out the copper surface by chopping off tiny asperities only one or two atomic layers thick. We imagine that this ful- lerenol/copper polishing system will be the beginning of polishing in the atomic scale. 35ISSN 0372-6436. Вісн. НАН України, 2012, № 9 СТАТТІ ТА ОГЛЯДИ Radical sponge for elixir. Remarkable suc- cess in polyhydroxylation of C60 confirms its high capacity to absorb radicals. The «radical sponge» characteristics of C60 have been used for photodynamic therapy of skin cancer and for scavenging harmful singlet oxygen [27]. For the same reason, when a French research group found that olive oil dissolves small but certain amount of C60, they tested the effect of daily dose of 1.2 mg C60/kg·day to mice upon their life [28]. Astonishingly the life-length of C60-treated group proved almost doubled than that of un-treated group. On the other hand, Cataldo and Braun [29] have already reported that C60 could be dissolved in many kinds of unsaturated plant oils but only to much smal l- er saturation concentrations. Damage of cells by C60 is also known to occur in vivo [cited in 29]. PERSPECTIVES AND CONCLUDING REMARKS The result of explosive expansion of C60 re- search on unprecedented scale produced thou- sands of publications, which led to a new prob- lem: it is impossible to write a comprehensive review or book, simply because the volume of literature on C60 grew too large to be handled by a single person or even by a small group of authors. The same remark will also apply to carbon nanotubes. For this reason I picked up the topics in the foregoing section from among those papers which I happened to come across. Hence this and the preceding sections must be taken as very subjective and intuitive, but here I have to answer the questions I posed to myself at the outset. I better start with an interpretation of a new social phenomenon called «research fever». This interpretation may be already obvious to many, but quite fast propagation of news by in- ternet, e-mails and on-line publications must be largely responsible to the sudden breakout of feverish research activities. Nowadays big scientific discoveries propagate almost instant- ly around the earth. An inevitable consequence of such efficient information flow is that we are always chased by the news, but not the other way around as it used to be. Life and time are moving faster and faster. It is partly true that one research topic will be soon digested and overworked in a matter of few months. In the case of C60, it has three faces due to of its special shape and functions. One is the face of a molecule for chemists, the second one the face of a solid for physicists, and the last one that of a nanoparticle for material scientists. Molecular face is still being explored among chemists as shown above [30]. Solid face is al- most lost as exemplified by the disappointingly small increase in the superconductive transi- tion temperature by only 2 K in 20 years [31]. However, nano face is still mostly hidden as il- lustrated by the less well-known case of unique polishing ability of fullerenol with atomic pre- cision. It is hoped that more and more examples of C60’s performance as the smallest nanoparticle will appear, but the development is still slow. Once the basic rules and concepts of nano-sci- ence and technology are better understood [32–34], we are sure C60 will come back to the front scene. Large specific number density and surface area are the definitive advantages of C60 like the primary particles of detonation nanodiamond, other typical smaller nanopar- ticle (Table II, the lowest two lines). 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Touhara H., Okino F. Fluorinated fullerenes // Ad- vanced Inorganic Fluorides: Synthesis, Characteri- zation and Applications / Nakajima T., Žemva B., Tressaud A. (eds.). — Amsterdam: Elsevier, 2000. — P. 555–590. 24. Kokubo K., Matsubayashi K., Tategaki H. et al. Facile synthesis of highly water-soluble fullerenes more than half-covered by hydroxyl groups // ACS Nano. — 2008. — V. 2. — P. 327–333. 25. Takaya Y., Tachika H., Hayashi T. et al. Performance of water-soluble fullerenol as novel functional mo- lecular abrasive grain for polishing nanosurfaces // CIRP Annals. Manuf. Technol. — 2009. — V. 58. — P. 495–498. 26. Takaya Y., Kishida H., Hayashi T. et al. Chemical me- chanical polishing of patterned copper wafer surface using water-soluble fullerenol slurry // CIRP Annals. Manuf. Technol. — 2011. — V. 60. — P. 567–570. 27. Tabata Y., Ikada Y. Biological functions of fullerene // Pure Appl. Chem. — 1999. — V. 71. — P. 2047–2053. 28. Baati T., Bourasset F., Gharbi N. et al. The prolonga- tion of the lifespan of rats by repeated oral adminis- tration of [60]fullerene // Biomater. — 2012. — V. 33. — P. 4936–4946. 29. Cataldo F., Braun T. The Solubility of C60 Fullerene in Long Chain Fatty Acids Esters // Fullerenes, Nanotubes and Carbon Nanostructures. — 2007. — V. 15, N 5. — P. 331–339. 30. Ōsawa E. Formation Mechanism of C60 under Non- equilibrium and Irreversible Conditions — An An- notation // Fullerenes, Nanotubes and Carbon Nano- structures. — 2012. — V. 20, N 4–7. — P. 299–309. 31. Matsushita E. Attempt at extending BCS-like theory to explain fullerene superconductors // Prog. Theor. Phys. — 2011. — V. 125, N 5. — P. 1021–1034. 32. Ōsawa E., Ho D. Nanodiamond and its application to drug delivery // J. Med. Allied Sci., in press. 33. Ōsawa E. Nanodiamond — an Emerging Nanocar- bon Material // Handbook of Advanced Ceramics / S. Soumiya (ed.). — 2nd Edition. — Elsevier, 2012, in press. 34. Barnard A., Sasaki S., Ōsawa E. Statistical modelling of ensembles of nanoparticles: approaches to diversity and polydispersivity // Cryst. Growth & Design, submitted for publication. Received 02.07.2012 37ISSN 0372-6436. Вісн. НАН України, 2012, № 9 СТАТТІ ТА ОГЛЯДИ Ейджі Осава NanoCarbon Research Institute Limited Ueda, Nagano, 386-8567, Japan, osawaeiji@aol.com ПОГЛЯД НА НАЙКРАСИВІШУ МОЛЕКУЛУ C60 ЧЕРЕЗ ЧВЕРТЬ СТОЛІТТЯ ПІСЛЯ ВІДКРИТТЯ З нагоди срібної річниці з часу відкриття фулеренів коротко проаналізовано нинішню ситуацію з їх дослі- дженням. C60 розглянуто в трьох різних аспектах — молекула, тверде тіло та наночастинка. Стосовно молекулярного аспекту варто зазначити, що давню проблему механізму утворення фулеренів майже розв’язано за допомогою молекулярно-динамічного підходу, підказаного нерівноважною термодинамікою І. Пригожина. Нині найактивніше досліджують хімію C60. У статті розглянуто деякі з нещодавніх результа- тів у цій галузі. Хоча за своїми характеристиками C60 ближчий до молекул, ніж до найдрібніших наночасти- нок, його застосування в нанотехнологіях, схоже, та- їть у собі великі перспективи. Ключові слова: бакмінстерфулерен, механізм утворення, діадна електронна система, полі ру валь- ний фулеренол, еліксир життя. Эйджи Осава NanoCarbon Research Institute Limited Ueda, Nagano, 386-8567, Japan, osawaeiji@aol.com ВЗГЛЯД НА САМУЮ КРАСИВУЮ МОЛЕКУЛУ C60 ЧЕРЕЗ ЧЕТВЕРТЬ ВЕКА ПОСЛЕ ОТКРЫТИЯ По случаю серебряной годовщины со времени от- крытия фуллеренов кратко проанализирована нынеш- няя ситуация с их исследованием. C60 рассматривается в трех различных аспектах — молекула, твердое тело и наночастица. Касательно молекулярного аспекта нель- зя не отметить, что давно занимавшая умы ученых проблема механизма образования фуллеренов почти решена с помощью молекулярно-динамического под- хода, подсказанного неравновесной термодинамикой И. Пригожина. Сегодня наиболее активно изучаются химические свойства C60. В статье обсуждаются неко- торые последние результаты в этой области. Хотя по своим характеристикам C60 ближе к молекулам, чем к мельчайшим наночастицам, его применение в нанотех- нологиях, похоже, таит в себе большие перспективы. Ключевые слова: бакминстерфуллерен, механизм образования, диадная электронная система, полиро- вочный фуллеренол, эликсир жизни. 38 ISSN 0372-6436. Вісн. НАН України, 2012, № 9 СТАТТІ ТА ОГЛЯДИ Я народився в місті Тояма в Японії в 1935 році. 1960 року на факультеті промислової хімії в Уні- верситеті Кіото здобув ступінь магістра за спеці- альністю «промислова хімія». Кілька років пра- цював інженером на виробництві. Щасливий для мене збіг обставин стався в 1961 році — Радянський Союз запустив перший космічний корабель «Восток», пілотований Юрі- єм Гагаріним. Він здійснив виток навколо Землі і благополучно приземлився. Ця подія спровоку- вала посилення холодної війни між СРСР і США, причому останні явно програвали в ній. Незаба- ром США і Японія подвоїли кількість студентів природничих спеціальностей у великих універ- ситетах. У результаті виникла гостра нестача ви- кладачів природничих наук. У такий спосіб я діс- тав можливість повернутися в академічний світ. Проте невдовзі я зрозумів, що експериментальні дослідження — це не моя стезя. Хоча пошук свого місця в науці був для мене досить складним, інший щасливий випадок до- поміг мені: у 1985 році Г. Крото, Р. Смоллі і Р. Керл відкрили фулерен C60. З цього моменту я усвідо- мив себе як ученого і творчу особистість, оскіль- ки ще в 1970 році я передбачив можливість існу- вання молекули C60 та її високу стабільність. Удача ще раз усміхнулася мені в 2002 році — врешті-решт було виділено первинні частинки наноалмазів, отримані детонаційним способом. Цей об’єкт виявився «найтвердішим горішком», з яким я будь-коли мав справу в своєму житті. З цієї причини я все ще продовжую працювати над цією темою. Науковий шлях 1960–1964 — науковий співробітник Teijin Co. Ltd., Осака 1964–1967 — асистент кафедри синтетичної хімії, Університет Кіото, Кіото 1966–1967 — докторантура Університету Віс- консина (професор R. West) 1967–1969 — докторантура Принстонського університету (професор P.v.R. Schleyer) 1970–1990 — доцент кафедри хімії Університе- ту Хоккайдо, Саппоро 1990–2001 — професор кафедри Knowledge- Based Information, Технологічний університет Тойохасі 2001 — донині — президент NanoCarbon Re- search Institute Limited, Уеда, Нагано Наукові інтереси Останнім часом: дисперсні наноалмази (діа- метром 3,7±0,6 нм) та їх застосування. Раніше: наука і технології нановуглецевих сполук, у тому числі С60 та інших фулеренів, на- но цибулинки (nano-onions), Маккей-кристали (McKay crystals) та детонаційні наноалмази. У минулому: хімія вуглеводнів, обчислюваль- на хімія. Публікації 336 наукових статей у журналах з імпакт-фак- тором, 71 книг/розділів у книгах; 108 публікацій за матеріалами міжнародних конференцій, 24 па- тенти і патентні заявки, 208 статей у науково- популярних журналах (станом на липень 2010). h-індекс — 35. ЕЙДЖІ ОСАВА МОЯ КОРОТКА НАУКОВА БІОГРАФІЯ
id nasplib_isofts_kiev_ua-123456789-38963
institution Digital Library of Periodicals of National Academy of Sciences of Ukraine
issn 0372-6436
language English
last_indexed 2025-11-24T11:50:33Z
publishDate 2012
publisher Видавничий дім "Академперіодика" НАН України
record_format dspace
spelling Ōsawa, Eiji
2012-11-26T15:32:28Z
2012-11-26T15:32:28Z
2012
Looking Back the Most Beautiful Molecule C60 after Quarter Century of Discovery Insert / Eiji Ōsawa // Вісн. НАН України. — 2012. — № 9. — С. 30-38. — Бібліогр.: 34 назв. — англ.
0372-6436
https://nasplib.isofts.kiev.ua/handle/123456789/38963
546.26
On the occasion of silver anniversary of the C60 discovery, the present situation of C60 research is briefly analyzed from three distinct angles: molecule, solid and nanoparticle. With regard to molecular angle, the long pending problem of formation mechanism is almost solved by molecular dynamics approach hinted by Prigogine’s nonequilibrium thermodynamics. The C60 research is at the moment most active in chemistry, and some of the recent results are discussed here. Though C60 is closer to molecule than to the smallest nanoparticle in its outlook, a big future seems hidden in its application in nanotechnology.
З нагоди срібної річниці з часу відкриття фулеренів коротко проаналізовано нинішню ситуацію з їх дослідженням. C60 розглянуто в трьох різних аспектах — молекула, тверде тіло та наночастинка. Стосовно молекулярного аспекту варто зазначити, що давню проблему механізму утворення фулеренів майже розв’язано за допомогою молекулярно-динамічного підходу, підказаного нерівноважною термодинамікою І. Пригожина. Нині найактивніше досліджують хімію C60. У статті розглянуто деякі з нещодавніх результатів у цій галузі. Хоча за своїми характеристиками C60 ближчий до молекул, ніж до найдрібніших наночастинок, його застосування в нанотехнологіях, схоже, таїть у собі великі перспективи.
По случаю серебряной годовщины со времени открытия фуллеренов кратко проанализирована нынешняя ситуация с их исследованием. C60 рассматривается в трех различных аспектах — молекула, твердое тело и наночастица. Касательно молекулярного аспекта нельзя не отметить, что давно занимавшая умы ученых проблема механизма образования фуллеренов почти решена с помощью молекулярно-динамического подхода, подсказанного неравновесной термодинамикой И. Пригожина. Сегодня наиболее активно изучаются химические свойства C60. В статье обсуждаются некоторые последние результаты в этой области. Хотя по своим характеристикам C60 ближе к молекулам, чем к мельчайшим наночастицам, его применение в нанотехнологиях, похоже, таит в себе большие перспективы.
en
Видавничий дім "Академперіодика" НАН України
Вісник НАН України
Статті та огляди
Looking Back the Most Beautiful Molecule C60 after Quarter Century of Discovery Insert
Погляд на найкрасивішу молекулу С60 через чверть століття після відкриття
Взгляд на самую красивую молекулу C60 через четверть века после открытия
Article
published earlier
spellingShingle Looking Back the Most Beautiful Molecule C60 after Quarter Century of Discovery Insert
Ōsawa, Eiji
Статті та огляди
title Looking Back the Most Beautiful Molecule C60 after Quarter Century of Discovery Insert
title_alt Погляд на найкрасивішу молекулу С60 через чверть століття після відкриття
Взгляд на самую красивую молекулу C60 через четверть века после открытия
title_full Looking Back the Most Beautiful Molecule C60 after Quarter Century of Discovery Insert
title_fullStr Looking Back the Most Beautiful Molecule C60 after Quarter Century of Discovery Insert
title_full_unstemmed Looking Back the Most Beautiful Molecule C60 after Quarter Century of Discovery Insert
title_short Looking Back the Most Beautiful Molecule C60 after Quarter Century of Discovery Insert
title_sort looking back the most beautiful molecule c60 after quarter century of discovery insert
topic Статті та огляди
topic_facet Статті та огляди
url https://nasplib.isofts.kiev.ua/handle/123456789/38963
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