Project No.:22003
Core Institution in Japan:Tokyo Institute of Technology
JSPS Core-to-Core Program
–Integrated Action InitiativesFY2011　Research Report
Project No.
22003
Research Theme
Photoionisation-induced switch in aromatic molecule-solvent recognition
Duration of Project
April 1, 2010 ― March 31, 2012
Core Institution in Japan
Tokyo Institute of Technology
( 24 months)
Implementing Organizations
Japan
Country
Tokyo Institute of Technology
Core Institution
Masaaki FUJII, Professor
Co-Chair (name and title)
Number of Cooperating Institutions 2
Cooperating Institutions
Yokohama city University
Tokyo Metropolitan University
Country
Core Institution
Co-Chair (name and title)
Number of Cooperating Institutions
Germany
TU Berlin
Otto DOPFER, Professor
1
Cooperating Institutions
University of Düsseldorf
Matching Fund
1) Photoionisation-induced switch in aromatic molecule –
solvent recognition (DO 729/4)
2) Electronic structure of protonated aromatic molecules (DO
729/3)
3) Geometric and electronic structure of silicon- containing
aggregates (DO 729/5)
4) Reactivity and Structure of isolated and solvated flavin ions
under cryogenic temperatures in a 22-pole ion trap (DO 729/6)
Country
Core Institution
Co-Chair (name and title)
Number of Cooperating Institutions
England
The University of Manchester
Klaus MÜLLER-DETHLEF, Professor
2
Cooperating Institutions
The University of York
The University of Oxford
Matching Fund
Photon science institute and school of chemistry
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Result of Program Implementation
This year we have continued the collaborative researches on three following themes.
(Germany) Structural analysis of ionic cluster studied by EI-IR spectroscopy.
(UK) Structural analysis of neutral and ionic cluster studied by ZEKE photoelectron spectroscopy.
(Japan) Analysis of photoionization dynamics studied by photoionization-IR spectroscopy.
Many young scientists and students have gone to England and Germany, and carried out joint experiments.
We organized three seminars: "Symposium on Aromatic Recognition Phenomena" on Nov. 3rd, 2011 at TU
Berlin (Germany), "Integration of experiment and theory in aromatic molecule-solvent recognition" on Nov.
17th, 2011 at Tokyo Institute of Technology (Japan), and "Seminar of Core-to-Core Program on Aromatic
Cluster Spectroscopy" on Mar. 1-2, 2012 at TU Berlin (Germany).
Many students presented the latest advances in aromatic interactions including photoionization-induced
switching.
We also encouraged young scientists/students to make an English presentation at international conferences
such as Isolated Biomolecules and Biomolecular Interactions (IBBI 2012) and the Gordon Research
Conference on Molecular and Ionic Cluster (GRC-MIC 2012).
Achievements in FY2011 (Self Review)
It is very important that we understand interaction between molecules such as van der Waals forces and
vibronic interactions (hydrogen bond), and the understanding interaction between molecules can solve higher
order structure of biologically relevant molecule such as protein and DNA. This year we aimed at the IR
spectroscopic and quantum chemical characterization of not only phenol-rare gas/methane clusters but also
aromatic molecule-solvent recognition system, through the formation of EU-Japan collaborative research
network.
As a result, the switching of a single water around the peptide bond in trans-acetanilide was observed in real
time by picosecond time-resolved IR spectroscopy of trans-acetanilide-H2O (1:1) cluster cation for the first
time. In the neutral state of trans-acetanilide-H2O (1:1) cluster, the H2O is hydrogen-bonded to the CO site
of the peptide bond. Triggered by photoionization, the H2O is released from this binding site and eventually
trapped after a switching time of 5 picoseconds at the NH site of the same peptide bond. Picosecond timeresolved IR spectra reveal that this water switching is not a simple elementary process but involves an
intermediate state, in which H2O is binding neither to the CO nor the NH site.
This result is very important as a first step toward the direct measurement of solvent dynamics around
proteins.
Future Plan (Measures toward Achieving Research Objectives)
The goals of this project can be summarized as follows.
In a collaborative effort, a variety of spectroscopic techniques, such as nanosecond and picosecond UVUV-IR spectroscopy (Japan), ZEKE, MATI, and PIE spectroscopy (UK), and nanosecond EI-IR spectroscopy
(Germany) with quantum chemical calculations, shall be applied to some types of neutral and ionic aromatic
molecule-solvent clusters in order to investigate the effects of ionization on the intermolecular potential
energy surface. This joint application of spectroscopic techniques is required to obtain a full understanding
of photoionisation-induced switch in aromatic molecule-solvent recognition involved the dynamical
processes. The aromatic molecule-solvent systems to be studied also involve aromatic molecules with
relevance to biophysical interactions. These include simple benzene derivatives, like phenol (residue of
tyrosine), catechol and tyramine (aromatic core of neurotransmitters), the amino acid phenylglycine, and the
aromatic amides formanilide and phenylamide (mimicking peptide bonds in proteins). The ligands involve raregas atoms and water molecules, which represent nonpolar (hydrophobic) and polar (hydrophilic) solvent
molecules. However, for example, the pico-second experiments in Japan are quite challenging and cannot be
carried out for all species listed. Therefore, the initial focus will be on the simple systems. Later, we will
concentrate on the more complex species, with the selection strongly depending on the success of
generating the species, and the feedback from theory and the experimental results of the other groups.
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