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-./01" Molecular structure of jet-cooled thioanisole
studied by laser-induced fluorescence spectroscopy and ab
initio calculations: Planar and/or perpendicular
conformation?"
231Mariko Nagasaka-Hoshino, Tasuku Isozaki, Tadashi
Suzuki, Teijiro Ichimura, Susumu Kawauchi
45671Chem. Phys. Lett. 457, 58–61 (2007)
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[1] T. Isozaki et al., J. Chem. Phys., 126, 214304-11 (2007).
[2] H. Iga et al., J. Phys. Chem. A, 111, 5981-5987 (2007).
[3] T. Isozaki et al., Chem. Phys. Lett., 449, 63-66 (2007).
[4] R. Matsumoto et al., J. Mol. Struct., 735-736, 153
(2005).
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6 7 8 9 : "Heterodyne-Detected Electronic Sum
Frequency Generation: 'Up' versus 'Down' Alignment of
Interfacial Molecules"
;.:Shoichi Yamaguchi and Tahei Tahara
<=>?:J. Chem. Phys. 129, 101102 (2008)
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@ABCD "Ultrafast Pump-Probe Study of Primary
Photoreaction Dynamics in pharaonis Halorhodopsin:
Halide-Ion Dependence and Isomerization Dynamics"
E.DTakumi Nakamura, Satoshi Takeuchi, Mikihiko
Shibata, Makoto Demura, Hideki Kandori, and Tahei
Tahara
FGHIDJ. Phys. Chem. B, 112, 12795-12800 (2008)
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[1] T. Arlt et al, Chem. Phys. Lett. 241, 559-565 (1995).
[2] F. Peters et al, Chem. Phys. 323, 109-116 (2006).
[3] M. Shibata et al, Biochemistry. 44, 12279-12286 (2005).
3
!"#$%&'()*+,-./0123452 No. 13
67 20 8 10 9
"A long-lived M-like state of phoborhodopsin
that mimics the active state"
Yuki Sudo, Tatsuya Nishihori, Masayuki Iwamoto,
Kazumi Shimono, and Naoki Kamo
Biophys. J. 95, 753-760 (2008)
"Structural changes in the O-decay accelerated
mutants of pharaonis phoborhodopsin"
Yuki Sudo, Yuji Furutani, Masayuki Iwamoto, Naoki
Kamo, and Hideki Kandori
Biochemistry 47, 2866-2874 (2008)
” ”
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[1] , 46, 330-336 (2006).
[2] B. Yan, T. Takahashi, R. Johnson and J. L. Spudich,
Biochemistry 30, 10686-10692 (1991).
[3] Y. Sudo, M. Yamabi, S. Kato, C. Hasegawa, M.
Iwamoto, K. Shimono and N. Kamo, J. Mol. Biol. 357,
1274-1282 (2006).
[4] M. Iwamoto, Y. Sudo, K. Shimono, T. Araiso and N.
Kamo, Biophys. J. 88. 1215-1223 (2005).
.
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