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DOI: 10.1002/adma.200501839
Highly Stabilized b-Carotene in Carbon Nanotubes**
By Kazuhiro Yanagi,* Yasumitsu Miyata, and Hiromichi Kataura
Producing the next generation of photonics-related technol-
ogies, such as all-optical switching devices, data processing by
optical–neural networks, etc., requires the development of
materials that have the following three features: 1) large third-
order optical nonlinearity, 2) ultrafast optical response, and
3) sufficient robustness for device applications.[1] p-Conjugat-
ed polyene molecules have great potential for such future
photonics applications, since they satisfy the first and second
requirements,[2–9] i.e., they exhibit an ultrafast optical re-
sponse[2,7] and a dramatic increase in third-order optical nonlin-
earity upon the introduction of an electron-withdrawing group
at one end of the polyene chain.[9] However, as Marder et al.
have pointed out,[9] p-conjugated polyene molecules are not
stable enough for use as nonlinear optical device materials.
These molecules are easily degraded under ambient conditions
by reaction with radical species (such as singlet oxygen);[10]
also, trans-to-cis isomerization occurs under illumination by
light or as a result of heat treatment.[10,11] Thus, the use of poly-
ene molecules as device materials in photonics technologies re-
quires the development of an innovative technique that can
overcome this degradation problem.
Encapsulation of organic molecules inside single-walled car-
bon nanotubes (SWCNTs) has recently been reported.[12–16]
Air-stable n-type SWCNTs are produced by encapsulating tet-
rathiafulvalene (TTF) or tetramethyl-tetraselenafulvalene
(TMTSF) inside the tubes.[15] Takenobu et al. have proposed
that the organic molecules inside the tubes will be protected
from any external reactive species by the surrounding nano-
tube wall.[15] Therefore, we expect that the degradation of
p-conjugated molecules might be overcome by encapsulating
them inside carbon nanotubes.
Carotenoids are very important natural pigments in plants
and animals and have been used extensively as model systems
for the study of p-conjugated polyene molecules.[17] Figure 1a
shows the chemical structure of b-carotene. Although b-caro-
tene shows large third-order optical nonlinearity,[4] it has not
been used as a photonic device material since it degrades easi-
ly under ambient conditions.[10,11] Our hypothesis is that if
– enough for b-carotene to be encapsulated, we expect that
[*] Dr. K. Yanagi, Y. Miyata, H. Kataura
Nanotechnology Research Institute
National Institute of Advanced Industrial Science
and Technology (AIST)
1-1-1 Higashi, Tsukuba, Ibaraki, 305-8562 (Japan)
E-mail: k-yanagi@aist.go.jp
[**] K.Y. acknowledges a Grand-in-Aid from the Advanced Technology
Institute Foundation and The Sumitomo Foundation (Grant
No. 050 645). This study was supported in part by the Industrial
Technology Research Grant Program in ’03 from the New Energy and
Industrial Technology Development Organization (NEDO) of Japan.
Adv. Mater. 2006, 18, 437–441 © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
(a)
(b)
Figure 1. a) Chemical structure of b-carotene, and b) a schematic illus-
tration of b-carotene inside a (12,8) SWCNT (where (12,8) denotes the
chiral vector of the SWCNT).
b-carotene can be encapsulated in SWCNTs, its degradation
will be suppressed. Although there are no reports about en-
capsulating b-carotene in SWCNTs, from a structural point of
view, encapsulation is possible. Figure 1b shows a schematic
illustration of a b-carotene molecule inside a SWCNT. We
have thus attempted to encapsulate b-carotene in SWCNTs to
verify the above hypothesis.
We have prepared and procured three types of SWCNTs:
a) SWCNTs manufactured by the laser vaporization (LV) of
carbon rods doped with Co/Ni in an argon atmosphere (here-
after referred to as LV tubes), b) high-pressure CO SWCNTs
(HiPco, Carbon Nanotechnologies Inc., USA, Lot. 79), and
c) purified HiPco tubes. The LV tubes are purified with H2O2,
HCl, and NaOH. The details of the purification procedure
have been published previously.[12] Since fullerenes can be en-
capsulated in these LV tubes with high yields,[12] the terminal
ends of the tubes are left open to enable molecules to enter the
tubes. It is worth noting that raw-soot HiPco tubes are capped
with hemifullerenes.[18] Therefore, although the HiPco tubes
range from 0.79 to 1.20 nm in diameter,[18,19] which is large
b-carotene should not be encapsulated inside the raw-soot
HiPco tubes due to the presence of caps at their terminal ends.
Yang et al. have reported that the caps of HiPco tubes can be
opened by heat treatment and HCl acid etching.[20] We have
prepared purified HiPco tubes (p-HiPco) according to a purifi-
cation procedure previously described in the literature to clari-
fy the effect of the caps on the encapsulation of b-carotene.[20]
To encapsulate b-carotene inside the SWCNTs, b-carotene
(100 mg, Wako) was dissolved in hexane (100 mL), and the
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SWCNTs (1 mg) were added to the solution. Before adding to

the solution, the SWCNTs were annealed at 350 °C for
20 min. The mixture was then refluxed for 10 h in a N2 atmo-
sphere. Subsequently, the solution was filtered and washed
with tetrahydrofuran (THF, 100 mL) to produce a sheet of
SWCNT paper. To remove the b-carotene coating on the
SWCNT surface, the paper was dispersed in THF (10 mL) by
sonicating it for 10 min. Finally, the solution was filtered and
washed again with THF (100 mL) to obtain a sheet of
SWCNT paper. We repeated this purification process three
times to completely remove any b-carotene that might be at-
tached to the outside of the tube walls. We applied this proce-
dure to the HiPco, p-HiPco, and LV tubes.
First, we verified whether b-carotene can be encapsulated in-
side the SWCNTs. It is known that Raman scattering is one of
the most useful techniques for confirming the encapsulation of
organic molecules inside the tubes.[12,15] Thus we have used this
spectroscopic technique to characterize our samples (details of
the experimental setup for our optical measurements are de-
scribed in the Experimental). Figure 2 shows the Raman spectra
of the HiPco and p-HiPco tubes. Figures 2a,d show the Raman
spectra of b-carotene in acetone solution. Figures 2b,c show the
Figure 2. Raman spectra of a) b-carotene in acetone solution and
Raman spectra of the HiPco tubes before and after the b,c) HiPco tubes before and after the encapsulation–purification proce-
encapsulation procedure, respectively. The Raman spectra of dure, respectively. Raman spectra of d) b-carotene in acetone solution
the p-HiPco tubes before and after the procedure are shown in and e,f) p-HiPco tubes before and after the encapsulation–purification
Figures 2e,f, respectively. No significant difference is noted procedure, respectively.
between Figures 2b,c. However, quite remarkably, we observe
Raman signals originating from b-carotene in Figure 2f (p-HiP- tubes and the Car@SWCNT tubes, we can more easily identify
co tubes). The difference between the HiPco and p-HiPco tubes several Raman peaks originating from b-carotene in the
is whether or not their terminal ends are capped. Thus, these Car@SWCNTs.
results indicate that the Raman peaks
originate from b-carotene existing inside
the tubes. We can thus conclude the
following: 1) b-carotene attached to the
external surface of the tubes has been
completely removed by the purification
process, and 2) b-carotene cannot enter
the HiPco tubes due to the caps at the ter-
minal ends of the tubes. However, upon
removal of the caps, b-carotene is able to
enter the tubes.
We hypothesize that b-carotene should
be able to enter the LV tubes more effi-
ciently than the p-HiPco tubes as a) the
diameter of the LV tubes is larger than
that of the p-HiPco tubes and b) the LV
tubes used in this study are of higher pur-
ity. Figure 3 shows the Raman spectra of
the LV tubes. Figure 3a is the Raman
spectrum of b-carotene in acetone solu-
tion. Figures 3b,c show the Raman spec-
tra of the LV tubes before and after the
encapsulation–purification procedure Figure 3. Raman spectra of a) b-carotene in acetone solution and b,c) LV tubes before and after the
encapsulation–purification procedure, respectively. The post-processed LV tubes are referred to as
(hereafter we refer to these post-pro-
Car@SWCNTs. d) Radial breathing mode (RBM) Raman spectra of LV (solid line) and Car@SWCNT
cessed LV tubes as Car@SWCNTs). tubes (dotted line). Both spectra in (d) are normalized at their peak frequencies. e) Raman spec-
Comparing the spectra for the p-HiPco trum of Car@SWCNTs (solid line) in dimethylformamide (DMF; dotted line) solution.

438 www.advmat.de © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2006, 18, 437–441
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In the Raman spectrum of Car@SWCNTs, there are four Ra- The absorption spectra of LV and Car@SWCNT tubes in di-
man peaks (m1, m2, m3, and m4) that can be attributed to the char- methylformamide (DMF) solution are shown in Figures 4a,b,
acteristic Raman signals from b-carotene. These peaks can be respectively. The two spectra are normalized at 1030 nm to fa-
attributed as follows:[21] m1 originates from the stretching modes cilitate comparison. The solid line in Figure 4c indicates the
of the conjugated C苷C bonds, m2 arises from a mixture of C苷C
and C–C bond stretching modes with C–H bending modes, m3 is
attributed to the stretching modes of C–CH3 bonds between
the main-chain and the side methyl carbons, and m4 can be at-
tributed to out-of-plane C–H wagging modes. Raman signals
from the encapsulated molecules are usually quite small com-
pared to that of the G-band from carbon nanotubes;[12] how-
ever, the four Raman peaks observed in Car@SWCNTs are re-
markably intense. As discussed below, this reflects the fact that
the 488 nm excitation wavelength matches the absorption band
of b-carotene in Car@SWCNTs, leading to a resonance en-
hancement of the Raman signals from b-carotene.
When carotenoids form a particular cis conformation, char-
acteristic Raman peaks of the cis conformation can be clearly
observed.[21,22] For example, a strong band at about 1245 cm–1
can be observed in the Raman spectra of all isomers of b-caro-
tene containing a C15苷C15′ bond in a cis conformation. Also,
when a C13苷C14 bond of b-carotene exhibits a cis conforma-
tion, its Raman spectrum exhibits an intense band at about
1138 cm–1.[21] However, in the spectrum of Car@SWCNTs, we
cannot identify any Raman peaks that clearly indicate the
presence of a cis conformation.
The presence of the m4 peak is one of the most remarkable
features of the Raman spectrum of Car@SWCNTs. This peak
indicates that the b-carotene in Car@SWCNTs adapts a Figure 4. Absorption spectra of a) LV and b) Car@SWCNT tubes in DMF
solution (both spectra are normalized at 1030 nm), and c) the difference
twisted conformation, since the m4 mode is forbidden for pla- absorption spectrum between (a) and (b).
nar molecules.[21] The reason why the m4 peak is not observed
in acetone solution (Fig. 3a) is that non-planar configurations
of carotenoids involving rotations around C–C bonds are not difference spectrum between (a) and (b), and the absorption
stable in solution at room temperature.[23] It is well known spectrum of b-carotene in DMF solution is shown as a dotted
that the intensity of the m4 peak is enhanced only when the line. We can clearly identify the absorption band originating
carotenoid is bound inside photosynthetic pigment–protein from b-carotene in Car@SWCNTs. The 488 nm excitation
complexes.[23] Thus, the large intensity of the signal from the wavelength in the Raman measurements matches the absorp-
m4 mode provides strong evidence that b-carotene is stabilized tion band of b-carotene in Car@SWCNTs. This is the reason
inside the carbon nanotubes. From these two remarkable ob- for the intense Raman signals of b-carotene in Car@SWCNTs.
servations, a) that there are no Raman peaks that clearly indi- The absorption peak energy of b-carotene becomes lower
cate the presence of the cis conformation and b) that the m4 when it is encapsulated in the nanotubes. In general, there are
Raman line is present, we conclude that b-carotene in three different kinds of shifts in absorption spectra:[25] charge-
Car@SWCNTs adopts a twisted trans conformation. induced energy shifts, dispersion interaction shifts, and exci-
It is noteworthy that the encapsulation of b-carotene does not ton interaction shifts. SWCNTs and b-carotene are not polar
affect the peak position of the G-band (1592 cm–1) of the LV materials, thus charge-induced shifts can be ruled out as the
tubes. Shifts of the G-band peak are caused by charge transfer origin of the red-shift in Car@SWCNTs. As Andersson et al.
between the encapsulated molecules and the SWCNTs.[15] Thus, have pointed out,[25] dispersion interactions are primarily re-
since there is no change in the peak position of the G-band dur- sponsible for spectral shifts in carotenoids. They found that
ing the encapsulation process, we conclude that charge transfer the refractive index n of the surrounding environment affects
does not occur in Car@SWCNTs. This result agrees well with the peak frequency of the carotenoids.[21,25,26] Pichler et al. re-
the fact that b-carotene is not a polar molecule. ported the dielectric function of SWCNTs, measured by
Figure 3d shows the radial breathing mode (RBM) Raman means of electron energy loss spectroscopy.[27] According to
spectra of the LV tubes (solid line) and the Car@SWCNT their results, the real part of the refractive index of SWCNTs
tubes (dotted line). As is seen with other peapod materi- can be estimated to be about 1.6 at 500 nm (this value is de-
als,[15,24] the RBM Raman spectrum shows a slight change duced from the figures depicted in the paper).[27] The value of
after the encapsulation of b-carotene. n for the DMF solution is 1.431;[28] thus, the difference in n be-

Adv. Mater. 2006, 18, 437–441 © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.advmat.de 439
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tween SWCNTs and DMF could cause a change of the ab-
sorption peak energy. It has been reported that the peak ener-
gy of b-carotene in non-polar solvents has the following rela-
tionship with n:[25]
m = [24 900 – 11 800 R(n)] ± 700 cm–1
n2 1 beam radiation is strong enough to damage the encapsulated
R…n† ≡
n2 ‡ 2
This relationship is not directly applicable to Car@SWCNTs be-
cause the surrounding environment of b-carotene in
Car@SWCNTs is quite different from that in the solvents.[26]
However, we use this relationship to roughly estimate the contri-
bution of the dispersive interaction to the red-shift observed in
Car@SWCNTs. The derived m value using the n value reported
for SWCNTs is 20 800 ± 700 cm–1. This is still much larger than
the absorption peak frequency of b-carotene in Car@SWCNTs,
19 710 ± 80 cm–1. Therefore, although a dispersion interaction
could be one of the possible origins for the observed red-shift,
the presence of an additional mechanism seems likely.
The exciton interaction becomes important when b-carotene
is in the solid state.[29] In the solid state, apart from the shift of
the peak energy of the absorption band, another remarkable
feature of b-carotene is the shift of the m1 Raman line.[29] The m1
frequency as well as the peak energy of the absorption band de-
creases in the order: crystal < film < solution (here crystal, film,
and solution mean b-carotene as a crystal, in a spin-coated
film, and in a solution, respectively). Figure 3e shows the m1
frequency, 1523 cm–1, for Car@SWCNTs in DMF solution.
This frequency is significantly lower than in acetone solu-
tion, 1525 cm–1 (Fig. 3a), and is the same as in a sheet of
Car@SWCNT paper (Fig. 3c). It is noteworthy that the m1 fre-
quency is independent of differences in the solvent.[30] There-
fore, these optical characteristics, i.e., the red-shifts seen for both
the peak energy of the absorption band and the m1 frequency,
indicate that b-carotene in Car@SWCNTs appears to be in the
solid state even when Car@SWCNT is dispersed in solution.
The weight percent of b-carotene inside the SWCNTs can be
derived from the absorbance of b-carotene in Car@SWCNTs.
The derived weight percent is approximately 3 %. The filling
rate of b-carotene in the SWCNTs can be evaluated from its
weight percent. Thus, assuming that the b-carotene molecules
are arranged in a straight line inside a 1.4 nm diameter SWCNT,
we estimate that the filling rate is approximately 30 %.
There is a possibility that additional defects caused by the
purification process affect the Raman signals from b-carotene
in Car@SWCNTs. However, it is quite unlikely that the fol-
lowing three phenomena are caused only by additional de-
fects: 1) large red-shift of the absorption peak of b-carotene
in Car@SWCNTs, 2) change in the line shape of the RBM
mode of Car@SWCNTs, which is similar to previously ob-
served effects in C60 peapods (the encapsulation of C60 in
SWCNTs has been widely confirmed),[24] and 3) the 30 % fill-
ing rate of b-carotene in Car@SWCNTs. We therefore con-
clude that b-carotene is encapsulated inside the SWCNTs.
Encapsulated b-carotene is not a robust molecule like C60
(the Raman and absorption peaks originating from b-carotene
440 www.advmat.de © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
inside the SWCNTs disappear at approximately 150 °C in vac-
uum). Therefore, although high-resolution transmission elec-
tron microscopy (HRTEM) measurements have been used to
directly probe encapsulation inside SWCNTs, it is difficult to
determine the detailed structure of the encapsulated b-caro-
(1) tene only from HRTEM measurements, since the electron-
(2)
b-carotene. Further study is needed to determine the detailed
structure of b-carotene inside SWCNTs.
The color and optical quality of the solution and film of
Car@SWCNTs is shown in Figure 5. Figures 5a,b show SWCNTs
and Car@SWCNTs dispersed in DMF solution, respectively, and
Figure 5c shows a Car@SWCNT film on the surface of a fused-
silica plate. Car@SWCNTs in DMF solution have a deep-red col-
or due to the presence of the encapsulated b-carotene.
( ) ( ) ()
Figure 5. a) SWCNTs and b) Car@SWCNTs dispersed in DMF solution.
c) Car@SWCNT film on the surface of a fused-silica plate.
Finally, we have compared the UV irradiation stabilities of
b-carotene and Car@SWCNTs. The two samples in DMF so-
lution were irradiated with UV light (365 nm, Vilber Lour-
mat, TFX-20LC) for 30 min, and their absorption spectra
were recorded. Figures 6a,b show the absorption spectra of
b-carotene and Car@SWCNTs, respectively, in DMF solution
before (solid line) and after (dotted line) irradiation with UV
light. To highlight the absorption band of b-carotene in
Car@SWCNTs, the spectra shown in Figure 6b are the differ-
ence absorption spectra between the LV tubes and
Car@SWCNTs. The absorption band of b-carotene in the
DMF solution almost disappears after UV irradiation; how-
ever, the absorption band of b-carotene in Car@SWCNTs is
still retained after irradiation. This clearly indicates that en-
capsulation can suppress the light degradation of b-carotene.
It is known that the light degradation of carotenoids occurs
for two reasons:[10,11] 1) reaction with radical species (e.g., sin-
glet oxygen) and 2) isomerization. We expect that the pres-
ence of a surrounding tube wall will protect b-carotene from
attack by radical species existing outside the wall and that
isomerization will not occur, as there is not enough space for
b-carotene to change its conformation inside the nanotube.
In conclusion, we have verified that b-carotene can be en-
capsulated inside carbon nanotubes. b-Carotene is a model
system for p-conjugated molecules and shows large third-or-
der optical nonlinearity.[4] Degradation of p-conjugated mole-
Adv. Mater. 2006, 18, 437–441

Figure 6. a) Absorption spectra of b-carotene in DMF solution before
(solid line) and after (dotted line) UV irradiation. b) Difference absorp-
tion spectra between Car@SWCNTs and LV tubes before (solid line) and
after (dotted line) UV irradiation.
cules is a bottleneck impeding their application in photonic
devices. Here, we have found that encapsulation inside a
nanotube can protect b-carotene from reacting with radical
species and also suppress its isomerization. Thus, this protec-
tion technique will open the door for the application of p-con-
jugated molecules in photonic devices. It is known that the sta-
bility of polyene molecules can be improved by adsorption
inside zeolites.[31] However, the encapsulation of polyene mol-
ecules inside SWCNTs can change the physical properties of
the SWCNTs as well as those of the encapsulated mole-
cules.[32] Thus, the encapsulation technique reported here will
contribute to various applications of SWCNTs because it can
be used not only to stabilize the polyene molecules but also to
optimize the electronic and optical properties of the SWCNTs.
It is noteworthy that carbon nanotubes can serve as nanocon-
tainers and b-carotene is quite easily encapsulated in carbon
nanotubes. It is known that carotenoids can be functionalized
by attaching various kinds of organic groups.[33] We expect
that functionalized carotenoids will also be able to easily enter
SWCNTs. As with functionalized fullerene peapods,[34] simple
chemical transformations of the organic groups would enable
us to introduce different chemical functionalities into the cav-
ity of SWCNTs, forming functionalized carotenoid peapods.
Experimental
We used a triple monochromator system equipped with a charge-
coupled device (CCD) detector for Raman measurements (Photon
Design Co., PDPT3-640S). Our light source was an Ar ion laser (Spec-
tra Physics, model 2016). The excitation wavelength was fixed at
488 nm in the measurements. The absorption spectra were recorded
using a spectrophotometer (Shimazu Co., SolidSpec-3700DUV).
Received: September 1, 2005
Final version: November 8, 2005
Published online: January 18, 2006
Adv. Mater. 2006, 18, 437–441 © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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