Chemical Physics Letters
Chemical Physics Letters
Chemical Physics Letters
a r t i c l e i n f o a b s t r a c t
Article history: We report on the theoretical–experimental analysis of the two-photon absorption (TPA) and two-photon
Received 20 June 2013 circular-linear dichroism (TPCLD) spectra of (1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadi-
In final form 30 July 2013 ene-3,5-dione (curcumin) in Tetrahydrofuran (THF) solution. The measurement of the full TPA spectrum
Available online 6 August 2013
of this molecule reveals a maximum TPA cross-section at 740 nm, i.e. more than 10 times larger than the
maximum reported in the literature at 800 nm for the application of curcumin in bioimaging. The TPCLD
spectrum exposes the symmetry of the main excited-states involved in the two-photon excitation pro-
cess. TD-DFT calculations support the experimental results. These outcomes are expected to expand
the application of natural-occurring dyes in bioimaging.
Ó 2013 Elsevier B.V. All rights reserved.
0009-2614/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cplett.2013.07.080
J.A. Tiburcio-Moreno et al. / Chemical Physics Letters 583 (2013) 160–164 161
and effective penetration into the cells. Although, curcumin has al- [23], employing the Becke’s three-parameter exchange, Lee, Yang
ready been tested as a multiphoton fluorophore, its maximum TPA and Parr correlation (B3LYP) hybrid functional [24–26] and the
cross-section (dTPA ðkÞ) between 780 and 900 nm, the investigated 6-31++G⁄⁄ basis set [27]. The TPA response (for the degenerate
spectral region, [2,19] is only few Goeppert–Mayer, i.e. <6 GM case) for the first 18 electronic excited states was computed with
(1 GM = 1 1050 cm4 s photons1) [20]. Consequently, the TPA ac- DALTON2011, [28] employing Time-Dependent DFT (TD-DFT) [29]
tion cross-section defined as dTPA ðkÞ ¼ dTPA ðkÞ uF , which is the at the same level of theory as for the geometry optimization. All
parameter that serves to evaluate specific chromophores for two- theoretical calculations were performed in THF within the polariz-
photon fluorescence microscopy, is still relatively low due to the able continuum model (PCM) [30].
very modest dTPA ðkÞ. In order to unveil the full potential of this nat- The TPA spectra were obtained through, [31–33]
ural dye as a two-photon biomarker, a systematic characterization of
the two-photon absorption (TPA) of curcumin in solution is in great 4p3 aa50 X 2
dTPA
0f ðxÞ ¼ ðhxf Þ dTPA
0f ðx0f Þgð2x; x0f ; CÞ; ð1Þ
need. In light of these recent finding we have engaged in the study of c f
the TPA of this important molecule.
In this article, we report on the theoretical–experimental anal- 2 2
X
dTPA
0f ðxÞ 1:25273 10 ðhxÞ gð2x; x0f ; CÞ dTPA
0f ðx0f Þ: ð2Þ
ysis of the TPA and two-photon circular-linear dichroism (TPCLD)
f
spectra of (1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-hept-
adiene-3,5-dione (curcumin) in Tetrahydrofuran (THF) solution In Eq. (1), c is the speed of light in vacuum, a0 is the Bohr’s ra-
(curcumin/THF). Using a tunable 90 fs amplified OPA-femtosec- dius, a is the fine structure constant, E ¼ hx is the photon energy
ond system working at 50 Hz repetition rate and over a broad spec- (half of the transition energy for the degenerate case) and dTPA
0f ðx0f Þ
tral range (600–900 nm), we measured the full TPA spectra of this is the orientational averaged two-photon probability for the
dye with linear and circular polarization employing the double L- degenerate case. A Lorentzian line-shape gð2x; x0f ; CÞ was used
scan technique [21]. Our results reveal a maximum TPA cross-sec- to broaden electronic transitions (Eq. (3)),
tion of at 740 nm and unveil the position and symmetry of the
main excited states involved in this process. Time-dependent den- 1 Cgf =2
gð2x; x0f ; CÞ ¼ ; ð3Þ
sity functional theory (TD-DFT) calculations, carried out using re- p ðxgf 2xÞ2 þ ðCgf =2Þ2
sponse theory at the B3LYP level with the 6-31++G⁄⁄ basis set,
solidly certify the experimental results. The outcomes of this Letter where C (in s1) is the full width at half-maximum (FHWM) line-
are expected to motivate further studies on this molecule and open width for all transitions. A value of C ¼ 0.15 eV was applied to better
a new road for the application of this bio-friendly natural dye in reproduce the experimental spectra. Partially solving Eq. (1) yields
the biomedical and pharmaceutical field. Eq. (2), which contemplates the necessary conversion factors to obtain
the TPA spectra in Göppert-Mayer units (GM), i.e. 1050 cm4 s
1 1
2. Experimental methods mol photon , when all the parameters are introduced in atomic
units.
Curcumin (98%) and THF (spectroscopic grade) were purchased The polarization dependent dTPA
0f ðx0f Þ (in atomic units) is ob-
from Sigma–Aldrich and used without further purification. The lin- tained from [31].
ear absorption spectrum of curcumin in THF was taken using a sin- X
dTPA ðx0f Þ ¼ 1 F S0f 0f
þ ðG þ HÞ S0f 0f
gle-beam spectrophotometer (Agilent 8453 Diode Array UV–Vis), 0f aa Sbb ab Sab ; ð4Þ
30 a;b
from 190 nm to 1100 nm, in a 1.0 cm quartz cuvette at a concen-
tration of 3 105 M. Contributions from the solvent and the x
here, S0f
ab is the transition matrix element which is a function of 2 ;
0f
Figure 3. Molecular orbitals of curcumin calculated using Gaussian 0920 at the B3LYP/6–31++G⁄⁄ level of theory in THF. The arrows represent one- and two-photon
transitions between S0 ? S1 (99%_HOMO ? LUMO) and S0 ? S2 (97%_HOMO-1 ? LUMO), respectively, at their corresponding maximum absorption. Inset – Normalized OPA
and TPA spectra.
Table 1
Results summary for the TPA theoretical calculation. n is the excited state number;
dTPA TPA
0f ;LP ðx0f ÞðGMÞ and d0f ;CP ðx0f ÞðGMÞ are the TPA cross-sections for LPL and CPL,
respectively and DdTPCLD is the TPCLD.
n
dTPA
dTPA DdTPCLD
0f ;LP ðx0f Þ 0f ;CP ðx0f Þ
k
(nm) (GM) (GM)
S1 921.816 9.66 1001 1.15 1002 0.087
S2 802.487 4.58 1003 3.02 1003 0.205
S3 692.649 1.73 1003 2.59 1003 0.200
S4 683.109 2.07 1001 2.88 1001 0.167
S5 654.270 8.66 1002 5.60 1002 0.212
S6 618.375 1.12 1003 7.59 1002 0.190
S7 610.760 1.83 1002 1.35 1002 0.156
S8 586.214 2.72 1001 1.85 1001 0.190
S9 536.728 1.79 1002 1.24 1002 0.183
S10 532.121 8.56 1001 6.16 1001 0.163
S11 509.176 6.48 1002 4.40 1002 0.190
S12 507.093 2.12 1002 1.52 1002 0.163
S13 506.058 7.37 1001 1.11 1000 0.200
S14 499.936 2.86 1001 4.30 1001 0.200
S15 492.001 6.18 1002 4.13 1002 0.198
S16 490.056 1.73 1000 2.59 1000 0.200
S17 489.090 9.52 1001 9.78 1001 0.015
Figure 4. Log–Log plot of the normalized transmittance change vs. input irradiance
S18 485.261 3.41 1002 5.11 1002 0.200
at 600 (black squares), 740 (blue spheres) and 840 nm (red triangles). (For
interpretation of the references to color in this figure legend, the reader is referred
to the web version of this article.)
the theoretical spectra, dTPA ðk < 600 nmÞ of curcumin, in the visible
spectral region, remains below the maximum value obtained at nitude between the two spectra is attributed to the same factors
740 nm. In order to corroborate TPA within the studied spectral described above on the TPA spectra analysis. Second, according
range we measured the normalized transmittance change vs. input to theoretical results reported by Nascimento [36] on the polariza-
at 600, 740 and 840 nm (see Figure 4). A slope equal to one, in the tion dependence of TPA rates for randomly oriented molecules and
log–log plot, evidences the typical quadratic law with respect to those by De Boni and co-workers on TPA polarization dependence
the input irradiance for TPA processes [42]. of perylene [37], a negative TPCLD value (DdTPCLD < 0) throughout
Finally, we analyze the experimental and theoretical TPCLD the whole spectral region indicates that the main TPA transitions
spectra of curcumin/THF (Figure 5). This novel spectroscopic tech- take place between states of the same symmetry. This can be cor-
nique can be utilized to determine the symmetry of the excited roborated by carefully inspecting values of DdTPCLD in Table 1.
states and the relative orientation between transition electric di- Although, excitations to excited states S1, S3 and S4 present
pole moments [37]. First thing to notice in Figure 5 is the spectral 0 < DdTPCLD 6 0:2, and to S13, S14, S16, S17 and S18 DdTPCLD ¼ 0:2,
agreement between theory and experiment. The difference in mag- which correspond to transitions between states of different
164 J.A. Tiburcio-Moreno et al. / Chemical Physics Letters 583 (2013) 160–164
References
Acknowledgements