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 Germany Germany
Inoue
Japan
Locations of
International
Collaborator
s
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 H2 molecule, incarcerated in a buckyball, communicate with the outside world?
Imagine the simplest molecule, H2, permanently incarcerated inside one of the loveliest
molecule, buckyball, C60. Can the incarcerated H2 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 the theoretical
interpretation of the NMR relaxation of H2 and of H2@C60. The Japanese
collaborators developed the synthesis ofH2@C60 .
Russia: Prof. Anatoly Buchachenko, Moscow State U.
The NMR relaxation of H2@C60, 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 H2 inside C60 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, H2 exists as two completely distinct species
with its nuclear spins are parallel ( ) or antiparallel (). The
interconversion of two spin isomers of H2 inside a buckyball was
achieved (Figure left) with oxygen as a spin catalyst, showing that the
H2 inside C60 can communicate with the outside world.
Reference: J. Am. Chem. Soc., 130, 10506 (2008).
International Symposium on H2@C60 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 (400-800nm)
UV light (366nm)
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).
O O
h
polymer
C P Ph
O
Ph
O
O
SH
S
O
O
C
P Ph
(O2)
Ph
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
A
H
H3C
N
H
high enantioselectivty
O
(up to 97% ee)
O
E isomer
conformationally
controlled
2 stereoselective
quenching by CH vibrations
3O
O
sterically
controlled
stereoselective
photooxidative
cleavage
1O
2
Z isomer
O
H
H3C
(R/S)
MDB
O
N
H
low enantioselectivty
(up to 30% ee)
H3C
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).
A
Australia: Andrew Whittaker, U. Queensland
H
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
Cl
h
Cl
- Cl
+ R-H
-R
H
+ O2
O
O
H
H
H
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. DaSilva
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
Murata,
Columbia 
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,