Generation of Broader Impact of Research Activities through International Partnering and Collaborations NSF’s Broader Impact review criteria encourage its research force to engage in activities that partner with researchers from international institutions. Da Silva Portugal Zapata Mexico Feringa Holland Scaiano Canada International partnering and exchanges produce enhancement of the training of faculty, students and postdoctoral associates, exposing researchers to a powerful diversity of ideas, methods and mentoring. Ottaviani Italy Zecca Italy Jin China Flohr Adam Braun Germany Inoue Japan Locations of International Collaborators Horeswill Levitt Whittaker England Australia England Komatsu Japan Murata Japan Arsu Turkey Yagci Turkey Nicholas J. Turro Columbia University The PI at Columbia University has established a user friendly Colaboratory for a range of topics of fundamental and technological interests in areas such as molecular and supramolecular photochemical and photophysical investigations. The senior international collaborators participating in these collaborations are shown in this slide. Kraeutler Austria Room Estonia Buchachenko Russia The success of the project can be evaluated by the fact that in the last three years coauthored publications have resulted or are in press with each of the senior collaborators indicated. The support of the National Science Foundation through the following grants is gratefully acknowledged: Understanding Chemical Complexity & Diversity Through Collaboration and Integration (CHE 07 -17518).
Can a H 2 molecule, incarcerated in a buckyball, communicate with the outside world? Imagine the simplest molecule, H 2, permanently incarcerated inside one of the loveliest molecule, buckyball, C 60. Can the incarcerated H 2 communicate with molecules in the outside world? The question (see below) was probed by a combination of nuclear magnetic resonance (NMR) spectroscopy and spin chemistry in collaborations with scientists in Russia and in Japan. The Russia collaborator assisted in theoretical interpretation of the NMR relaxation of H 2 and of H 2@C 60. The Japanese collaborators developed the synthesis of. H 2@C 60. Russia: Prof. Anatoly Buchachenko, Moscow State U. The NMR relaxation of H 2@C 60, the simplest molecule incarcerated in a buckyball, in the presence of relaxants was measured for the first time. The experiments (Figure right) demonstrate that the H 2 inside C 60 can “communicate” with paramagnetic molecules in the “outside world”. Reference: J. Am. Chem. Soc. , 130, 2221 (2008). Japan: Prof. Koichi Komatsu and Prof. Yosujiro Murata, Kyoto U. The simplest molecule, H 2 exists as two completely distinct species with its nuclear spins are parallel ( ) or antiparallel ( ). The interconversion of two spin isomers of H 2 inside a buckyball was achieved (Figure left) with oxygen as a spin catalyst, showing that the H 2 inside C 60 can communicate with the outside world. Reference: J. Am. Chem. Soc. , 130, 10506 (2008). International Symposium on H 2@C 60 held at Columbia on August 15, 2008. N. J. Turro, Columbia U. , Organizer. International participants (Figure right): Malcolm Levitt (U. Southampton, UK), Toomas Room (Ins. Chem. Phys. , Tallinn, Estonia). Anthony Horsewill (U. Nottingham, UK), Yasujiro Murata (U. Kyoto, Japan), Martin Saunders (Yale U. , USA), Zlatko Bacic (NYU, USA), Stephen Fitzgerald (Oberlin U. ). Ron Lawler (Brown U. , USA).
Green diaper production, fluorescent bananas and tracking molecules adsorbed on porous catalytic solids Germany. Collaborator: Andreas Flohr, Proctor & Gamble, Schwalbach. A novel method for the surface cross-linking (Figure left) of superabsorbent polymer particles used for manufacturing diapers has been developed. Polymer materials produced have superior properties such as liquid flow thought the fluid particle bed and capacity. In addition, the process is projected to be more energy efficient (through green chemistry) than the current thermal method for cross-linking. Reference: J. Appl. Polymer Sci. , 111, 2163 -2170 (2009). Austria. Collaborator; Prof. Bernhard Kraeutler, U. Innsbruck. The decomposition of chlorophyll in banana was found to produce a blue fluorescent species (Figure right) whose concentration tracks the ripening of the bananas. Such species are also found as those in degreened leaves, suggest that chlorophyll degrades through a related pathway in leaf senescence and fruit ripening. Reference: Angew. Chem. , 47, 8954 (2008). white light (400 -800 nm) UV light (366 nm) Italy. Collaborator: Prof. M. F. Ottaviani, U. Urbino. An understanding of the supramolecular structure and dynamics of absorption of molecules on the external and internal surface of porous solids is of critical importance in a range of solid state catalysis. Electron spin resonance (Figure left) has been employed to quantitatively determine the surface structure and dynamics of organic molecules adsorbed on the external surface of the important MFI family of catalysts. Reference: J. Am. Chem. Soc. , 130, 11344 -11354 (2008).
Photochemistry at a tool for the synthesis and study of polymers: perfluorocarbons for photolithography, the mechanism of polymer synthesis and synthesis of thin conducting polymer films. Germany. Collaborator: Dr. Andre Braun, U. Karlsruhe The photolithographic industry has considered the use of 157 nm lasers as a means of making smaller features in the manufacture of computer chips. Perfluorpolymers are critical materials to protect computer chips from contaminants. The photochemistry of these materials at very short wavelengths was investigated and elucidated for the first time (Figure left). Reference: J. Am. Chem. Soc. , 127, 8320 -8327 (2005). Turkey. Collaborator, Prof. N. Arsu, Yildiz U. , Istanbul Acylphosphines are widely used as photoinitiators for the incustrial important process of radical polymerization. Mercaptothioxanthone was shown to act as sensitizer and coinitiator for acylphosphine photoinitiators in free radical polymerization (Figure right). Reference: Macromolecules, 41, 4631 (2008). h polymer (O 2) Turkey. Collaborator, Prof. N. Yusuf Yagci, Istanbul Tech. University. Organic thin films of conjugated polymers such as polythiophene (Figure left) are of current interest because of their potential use in electronics and electro-optical devices. The mechanism of the photoinduced polymerization of thiophene using onium ions as photoinitiators was elucidated employing laser flash photolysis methods. Reference: Macromolecules, 40, 4481 (2007).
Controlling the selectivity of oxidation reactions, producing high refractive index materials for photolithography and cleaning up environmental pollutants with light Japan: Yoshihiro Inoue, Osaka U. A novel mechanism for controlling the selectivity of reactions of singlet oxygen, an electronically excited state of normal oxygen (Figure left). The addition of singlet oxygen to certain double bonds was found to be extremely selective. The selectivity was found to be very dependent on conditions such as solvents and temperature. Reference: Tetrahedron, 62, 6707 -6717 (2006). Australia: Andrew Whittaker, U. Queensland Producing immersion fluids that are transparent at 193 nm and that possess a high refractive index is an important goal for producing smaller features in making computer chips by photolithography. An empirical correlation (Figure right) was developed that allows an accurate prediction of the best candidates for such immersion fluids. Importantly, the correlation revealed that cyclic saturated hydrocarbons possess a significantly higher refractive index than linear hydrocarbons of comparable molecular weight. Reference: J. Photochem. Sci. Tech. , 20, 643 -650 (2007). Portugal: Jose P. Da Silva, U. Algarve Chlorinated aromatic compounds are environmental pollutants that have the potential to be mineralized to environmentally acceptable materials by photochemical reactions. Substitution, reduction and oxidation mechanisms of aryl chloride photoreactions were probed and elucidated with oxygen as a competitive quencher (Figure left). Reference: Photochem. Photobiol. Sci. , 8, 210 -216 (2009).
International graduate student exchange: Students add undergraduates. Salvo, French, Australia, Columbia Portugal + Italy + Israel + England Columbia Netherlands Columbia Japan M. Francesca Ottaviani Judy Chen Columbia Portugal + Italy + Israel + England Prof. Da. Silva U. Algarve, Portugal Prof. M. Francesca Ottaviani U. Urbino, Italy Japan Columbia Hideaki Saito U. Osaka, Japan Columbia U. Prof. Yoshi Inoue U. Osaka Greg Carroll Columbia U. Groningen Prof. Ben Feringa, Jeremiah Johnson Prof. Yasujiro U. Groningen Columbia Murata, U. Kyoto U. Osaka Germany Columbia Melissa Sojka U. Karlsruhe, Germany Columbia U. Prof. Andre Braun U. Karlsruhe Germany Columbia Sarah Bosio U. Wuerzburg, Germany Columbia U. Prof. Waldemar Adam, U. Wuerzburg,
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