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Highly Stabilized B-Carotene in Carbon Nanotubes : by Kazuhiro Yanagi, Yasumitsu Miyata, and Hiromichi Kataura
Highly Stabilized B-Carotene in Carbon Nanotubes : by Kazuhiro Yanagi, Yasumitsu Miyata, and Hiromichi Kataura
DOI: 10.1002/adma.200501839
Adv. Mater. 2006, 18, 437–441 © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 437
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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- inside the SWCNTs disappear at approximately 150 °C in vac-
sorption peak energy. It has been reported that the peak ener- uum). Therefore, although high-resolution transmission elec-
gy of b-carotene in non-polar solvents has the following rela- tron microscopy (HRTEM) measurements have been used to
tionship with n:[25] directly probe encapsulation inside SWCNTs, it is difficult to
determine the detailed structure of the encapsulated b-caro-
m = [24 900 – 11 800 R(n)] ± 700 cm–1 (1) tene only from HRTEM measurements, since the electron-
n2 1 beam radiation is strong enough to damage the encapsulated
R
n ≡ (2)
n2 2 b-carotene. Further study is needed to determine the detailed
This relationship is not directly applicable to Car@SWCNTs be- structure of b-carotene inside SWCNTs.
cause the surrounding environment of b-carotene in The color and optical quality of the solution and film of
Car@SWCNTs is quite different from that in the solvents.[26] Car@SWCNTs is shown in Figure 5. Figures 5a,b show SWCNTs
However, we use this relationship to roughly estimate the contri- and Car@SWCNTs dispersed in DMF solution, respectively, and
bution of the dispersive interaction to the red-shift observed in Figure 5c shows a Car@SWCNT film on the surface of a fused-
Car@SWCNTs. The derived m value using the n value reported silica plate. Car@SWCNTs in DMF solution have a deep-red col-
for SWCNTs is 20 800 ± 700 cm–1. This is still much larger than or due to the presence of the encapsulated b-carotene.
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
Figure 5. a) SWCNTs and b) Car@SWCNTs dispersed in DMF solution.
frequency, 1523 cm–1, for Car@SWCNTs in DMF solution. c) Car@SWCNT film on the surface of a fused-silica plate.
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- Finally, we have compared the UV irradiation stabilities of
quency is independent of differences in the solvent.[30] There- b-carotene and Car@SWCNTs. The two samples in DMF so-
fore, these optical characteristics, i.e., the red-shifts seen for both lution were irradiated with UV light (365 nm, Vilber Lour-
the peak energy of the absorption band and the m1 frequency, mat, TFX-20LC) for 30 min, and their absorption spectra
indicate that b-carotene in Car@SWCNTs appears to be in the were recorded. Figures 6a,b show the absorption spectra of
solid state even when Car@SWCNT is dispersed in solution. b-carotene and Car@SWCNTs, respectively, in DMF solution
The weight percent of b-carotene inside the SWCNTs can be before (solid line) and after (dotted line) irradiation with UV
derived from the absorbance of b-carotene in Car@SWCNTs. light. To highlight the absorption band of b-carotene in
The derived weight percent is approximately 3 %. The filling Car@SWCNTs, the spectra shown in Figure 6b are the differ-
rate of b-carotene in the SWCNTs can be evaluated from its ence absorption spectra between the LV tubes and
weight percent. Thus, assuming that the b-carotene molecules Car@SWCNTs. The absorption band of b-carotene in the
are arranged in a straight line inside a 1.4 nm diameter SWCNT, DMF solution almost disappears after UV irradiation; how-
we estimate that the filling rate is approximately 30 %. ever, the absorption band of b-carotene in Car@SWCNTs is
There is a possibility that additional defects caused by the still retained after irradiation. This clearly indicates that en-
purification process affect the Raman signals from b-carotene capsulation can suppress the light degradation of b-carotene.
in Car@SWCNTs. However, it is quite unlikely that the fol- It is known that the light degradation of carotenoids occurs
lowing three phenomena are caused only by additional de- for two reasons:[10,11] 1) reaction with radical species (e.g., sin-
fects: 1) large red-shift of the absorption peak of b-carotene glet oxygen) and 2) isomerization. We expect that the pres-
in Car@SWCNTs, 2) change in the line shape of the RBM ence of a surrounding tube wall will protect b-carotene from
mode of Car@SWCNTs, which is similar to previously ob- attack by radical species existing outside the wall and that
served effects in C60 peapods (the encapsulation of C60 in isomerization will not occur, as there is not enough space for
SWCNTs has been widely confirmed),[24] and 3) the 30 % fill- b-carotene to change its conformation inside the nanotube.
ing rate of b-carotene in Car@SWCNTs. We therefore con- In conclusion, we have verified that b-carotene can be en-
clude that b-carotene is encapsulated inside the SWCNTs. capsulated inside carbon nanotubes. b-Carotene is a model
Encapsulated b-carotene is not a robust molecule like C60 system for p-conjugated molecules and shows large third-or-
(the Raman and absorption peaks originating from b-carotene der optical nonlinearity.[4] Degradation of p-conjugated mole-
440 www.advmat.de © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2006, 18, 437–441
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Adv. Mater. 2006, 18, 437–441 © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.advmat.de 441