T.Majima et al.
FULL PAPER
5-(4-Methylthiophenyl)pentanoic acid (MTC4): A solution of n-butyl
lithium (Nakarai Tesque, about 1.6m (15%) in hexane) (26 mL) under an
argon atmosphere was dropwise added to a solution of 4-bromothioani-
sole (Tokyo Kasei) (4.06 g) in anhydrous Et2O (50 mL).The mixture was
stirred for 2 h.The reaction mixture was then dropwise added to a so-
lution of 1,4-dibromobutane (Tokyo Kasei, 98%) (21.6 g) in anhydrous
Et2O (15 mL) for 30 min with a syringe under an argon atmosphere, and
Acknowledgments
This work has been partly supported by a Grant-in-Aid for Scientific Re-
search on Priority Area (417), 21st Century COE Research, and others
from the Ministry of Education, Culture, Sports, Science and Technology
(MEXT) of the Japanese Government.
the mixture was stirred overnight.An ether solution of an NH Cl saturat-
4
ed aqueous solution was dropped into the reaction mixture and the mix-
ture was extracted with Et2O.The extract was washed with a saturated
aqueous NaCl solution, and dried over anhydrous sodium sulfate.The
solvent and an excess of 1,4-dibromobutane were removed under
vacuum, and the residue was distilled under reduced pressure (175–
1858C).The product was purified by column chromatography (hexane)
to yield of pale yellow liquid (bromide, 4a) (1.843 g). MTC4 (150 mg) as
a colorless solid was prepared from the bromide (907.2 mg) following the
same procedure as MTC3: M.p. 79.0–80.08C; 1H NMR (270 MHz,
CDCl3, 208C, TMS): d = 7.14 (AA’BB’ type signals, 4H, ArH), 2.60 (t,
J=6.9 Hz, 2H, CH2), 2.47 (s, 3H, SCH3), 2.38 (t, J=6.9 Hz, 2H, CH2),
1.66 (m, 4H, CH2CH2); MS: m/z: calcd for C12H16O2S: 224.32, found
224.2; elemental analysis calcd (%) for C12H16O2S: C 64.25, H 7.19, S
14.29; found: C 64.12, H 7.07, S 14.26.
[1] A.Fujishima, K.Honda, Nature 1972, 238, 37–38.
[2] A.Fujishima, TN. .Rao, DA. .Tryk,
2000, 1, 1–21.
J. Photochem. Photobiol. C
[3] a) A.Mills, RH. .Davies, D.Worsley,
Chem. Soc. Rev. 1993, 22,
417–425; b) A.Mills, S.L.Hunte, J. Photochem. Photobiol. A 1997,
108, 1–35.
[4] M.R.Hoffmann, S.T.Martin, W.Choi, D.W.Bahnemann,
Chem.
Rev. 1995, 95, 69–96.
[5] a) M.A.Fox, M.T.Dulay, Chem. Rev. 1993, 93, 341–357; b) M.A.
Fox, Electron Transfer in Chemistry, Vol. 1 (Ed.: V. Balzani), Wiley,
New York, 2001, pp.271–311.
[6] A.L.Linsebigler, G.Lu, Y.T.Yates, Jr,.
758.
Chem. Rev. 1995, 95, 735–
[7] a) R.Wang, K.Hashimoto, A.Fujishima, M.Chikuni, E.Kojima, A.
Cyclic voltammetry measurements: Cyclic voltammograms were obtained
Kitamura, M.Shimohigoshi, T.Watanabe, Nature 1997, 388, 431–
by using
a conventional three-electrode system (BAS, CV-50W) in
432; b) N.Sasaki, A.Fujishima, T.Watanabe, K.Hashimoto,
J. Phys.
MeCN solution at room temperature.A platinum electrode was used as
the working electrode and an Ag/AgNO3 electrode was used as the refer-
ence electrode.
Chem. B 2003, 107, 1028–1035.
[8] a) RF. .Howe, M.Grätzel,
J. Phys. Chem. 1985, 89, 4495–4499;
Inorg. Chem. 1985, 24, 2253–
b) U.Kölle, J.Moser, M.Grätzel,
Steady-state UV/Vis absorption and diffuse reflectance spectral measure-
ments: The steady-state UV/Vis absorption and diffuse reflectance spec-
tra were measured by UV/Vis-NIR spectrophotometers (Shimadzu, UV-
3100 and Jasco, V-570, respectively) at room temperature.The sample
solutions containing TiO2 powder (20 gdmꢀ3) were sonicated for 10 min,
and the TiO2 particles in solution were then completely removed by cen-
trifugation (10000 rpm, 10 min) using a high-speed microcentrifuge (Hi-
tachi, himac CF16RX) at 228C for the UV absorption measurements.All
procedures for the sample preparation were performed with shielding
from the UV light.
2258; c) G.Rothenberger, J.Moser, M.Grätzel, N.Serpone, D.K.
Sharma, J. Am. Chem. Soc. 1985, 107, 8054–8059; d) N.Serpone, D.
Lawless, R.Khairutdinov, E.Pelizzetti,
16655–16661.
J. Phys. Chem. 1995, 99,
[9] a) A.Yamakata, T.Ishibashi, H.Onishi,
Chem. Phys. Lett. 2001,
333, 271–277; b) A.Yamakata, T.Ishibashi, H.Onishi,
Chem. 2001, 105, 7258–7262; c) S.H. Szczepankiewicz, J.A.
Moss, M.R.Hoffmann, J. Phys. Chem. B 2002, 106, 2922–2927.
J. Phys.
B
[10] a) D.Bahnemann, A.Henglein, J.Lilie, L.Spanhel,
J. Phys. Chem.
1984, 88, 709–711; b) D.W.Bahnemann, M.Hilgendorff, R.Memm-
ing, J. Phys. Chem. B 1997, 101, 4265–4275; c) X.Yang, N.Tamai,
Phys. Chem. Chem. Phys. 2001, 3, 3393–3398; d) D.P.Colombo, Jr.,
R.M.Bowman, J. Phys. Chem. 1995, 99, 11752–11756; e) D.P.Co-
lombo, Jr., R. M. Bowman, J. Phys. Chem. 1996, 100, 18445–18449;
The concentrations of the adsorbates in MeCN containing TiO2 powder
(20 gdmꢀ3) after reaching an adsorption equilibrium ([S]eq) were deter-
mined from the steady-state UV absorption measurements.The amounts
of adsorbates (nad, in molgꢀ1) were estimated by using Equation (15),
f) A.Furube, T.Asahi, H.Masuhara, H.Yamashita, M.Anpo,
J.
Phys. Chem. B 1999, 103, 3120–3127; g) A.Furube, T.Asahi, H.
Masuhara, H.Yamashita, M.Anpo, Res. Chem. Intermed. 2001, 27,
177–187; h) T.Yoshihara, R.Katoh, A.Furube, Y.Tamaki, M.
Abs:ꢀAbs:TiO
2
ð15Þ
nad ¼ ½S Â
Abs:
Murai, K.Hara, S.Murata, H.Arakawa, M.Tachiya,
B 2004, 108, 3817–3823.
J. Phys. Chem.
where [S] is the concentration of S in the bulk MeCN, and Abs.and
Abs.TiO2 represent the absorbances of S in the absence and presence of
the TiO2 powder, respectively.
[11] a) T.Tatsuma, S.Tachibana, A.Fujishima,
J. Phys. Chem. B 2001,
105, 6987–6992; b) T.Tatsuma, W.Kubo, A.Fujishima,
2002, 18, 9632–9634.
[12] a) K.Ishibashi, Y.Nosaka, K.Hashimoto, A.Fujishima,
Langmuir
Time-resolved diffuse reflectance (TDR) measurements: The TDR meas-
urements were performed using the third harmonic generation (355 nm,
5 ns full width at half-maximum) from a Q-switched Nd3+:YAG laser
(Continuum, Surelite II-10) for the excitation operated with temporal
control by a delay generator (Stanford Research Systems, DG535).In
these experiments, the spot irradiated on the sample cell with a thickness
of 2 mm was approximately 1 cm“2.The reflected analyzing light from a
pulsed 450-W Xe-arc lamp (Ushio, XBO-450) was collected by a focusing
lens and directed through a grating monochromator (Nikon, G250) to a
silicon APD (Hamamatsu Photonics, S5343).The transient signals were
recorded by a digitizer (Tektronix, TDS 580D).The reported signals are
averages of 20–30 events.
J. Phys.
Chem. B 1998, 102, 2117–2120; b) K.Ishibashi, A.Fujishima, T.
Watanabe, K.Hashimoto, J. Phys. Chem. B 2000, 104, 4934–4938;
c) Y.Nosaka, M.Nakamura, T.Hirakawa, Phys. Chem. Chem. Phys.
2002, 4, 1088–1092.
[13] D.Lawless, N.Serpone, D.Meisel,
5170.
J. Phys. Chem. 1991, 95, 5166–
[14] a) RF. .Howe, M.Grätzel,
J. Phys. Chem. 1987, 91, 3906–3909;
b) O.I.Micic, Y.Zhang, K.R.Cromack, A.D.Trifunac, M.C.Thur-
nauer, J. Phys. Chem. 1993, 97, 7277–7283; c) M.A.Grela, M.E.J.
Coronel, A.J. Colussi, J. Phys. Chem. 1996, 100, 16940–16946;
d) P.F.Schwarz, N.J.Turro, S.H.Bossmann, A.M.Braun, A-.M.A.
Abdel Wahab, H.Dꢂrr, J. Phys. Chem. B 1997, 101, 7127–7134;
e) Y.Nakaoka, Y.Nosaka, J. Photochem. Photobiol. A 1997, 110,
299–305.
The absorption values (% absorption) were obtained by subtracting the
absorption value observed in the absence of S from that observed in the
presence of S.Here,%absorption (%abs). is given by Equation (16),
[15] a) Y.Nosaka, M.Kishimoto, J.Nishio,
J. Phys. Chem. B 1998, 102,
Langmuir 2002, 18,
R0 ꢀ R
10279–10283; b) T.Hirakawa, Y.Nosaka,
3247–3254.
ð16Þ
%abs: ¼
 100
R0
[16] a) R.Nakamura, A.Imanishi, K.Murakoshi, Y.Nakato,
J. Am.
where R and R0 represent intensities of the diffuse reflected monitor
Chem. Soc. 2003, 125, 7443–7450; b) R.Nakamura, Y.Nakato, J.
Am. Chem. Soc. 2004, 126, 1290–1298.
light with and without excitation, respectively.[16]
5352
ꢀ 2004 Wiley-VCH Verlag GmbH & Co.KGaA, Weinheim
Chem. Eur. J. 2004, 10, 5345 – 5353