Nonlinear Optical Studies of Curcumin Metal

Derivatives with cw Laser



F. Z. Henaria) and S. Cassidy

Department of Basic Medical Sciences, Royal College of Surgeons in Ireland,

Medical University of Bahrain, Kingdom of Bahrain
a)
fzhenari@rcsi-mub.com

Abstract. We report on measurements of the nonlinear refractive index and nonlinear absorption
coefficients for curcumin and curcumin metal complexes of boron, copper, and iron at different
wavelengths using the Z-scan technique. These materials are found to be novel nonlinear media. It
was found that the addition of metals slightly influences its nonlinearity. These materials show a
large negative nonlinear refractive index of the order of 10 -7 cm2/W and negative nonlinear
absorption of the order of 10-6 cm/W. The origin of the nonlinearity was investigated by comparison
of the formalism that is known as the Gaussian decomposition model with the thermal lens model.
The optical limiting behavior based on the nonlinear refractive index was also investigated.
Keywords: Nonlinear refractive index, nonlinear absorption, optical limiting, metal complexes of
curcumin, z-scan.
PACS: 42.65k, 42.70.JK

INTRODUCTION
There has been considerable interest in searching for materials exhibiting nonlinear
optical effects. These effects are of great technological importance for use in future
applications within electronic and photonic devices [1, 2]. The nonlinear optical
effects include: laser induced grating, soliton pulse propagation in waveguides, optical
switching, self-focusing, self-defocusing, self-phase modulation, saturation absorption,
reverse saturation absorption and optical limiting [3-7]. Many materials such as photo
refractive materials [8], Buckminster-fullerenes [9], fluoride glasses [10], and
polymers [11] have been investigated for these applications.
In this work, we report the experimental measurements of the nonlinear refractive
index n2, and nonlinear absorption E of metal complexes of curcumin with a
continuous wave (cw) laser beam using the Z- scan technique. The optical limiting
based on the nonlinear refractive index of the metal complexes of curcumin was
investigated. The origin of the nonlinearity was investigated by comparison the
Gaussian beam composition [12, 13] and the thermal lens model [14].

4th International Congress in Advances in Applied Physics and Materials Science (APMAS 2014)
AIP Conf. Proc. 1653, 020044-1–020044-10; doi: 10.1063/1.4914235
© 2015 AIP Publishing LLC 978-0-7354-1295-8/$30.00

020044-1
 MATERIALS
Curcumin is a yellow pigment which is a natural component of rhizome called
turmeric, of the plant Curcuma Longa L. The powdered rhizome of this plant is called
turmeric. In addition to its use in curries for the flavouring and colouring of the diet,
curcumin has been used as a medicine for treatments of inflammation, skin wound and
cough. However its anticancer properties have generated a greater interest, resulting in
many publications. Chemical analysis of the extraction products of this powder by a
variety of solvent mixtures has shown the principal components to be Curcumin [1,7-
bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione], demethoxycurcumin [1-
(4-hydroxyphenyl)-7-(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione] and
bisdemethoxycurcumin [1,7-bis(4-hydroxyphenyl)-1,6-heptadiene-3,5-dione] [15].
Curcumin [1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione] was
synthesized from vanillin and acetylacetone using boric acid as a protecting group and
1-butylamine as a base in a solvent mixture of toluene and dimethylformamide. The
synthetic curcumin was complexed with boron, copper and iron respectively. Metal
complexes of curcumin have generated a great interest resulting in many publications
on their anticancer properties.
The general synthetic procedure of the metal complexes involved dissolution of
synthesized curcumin in methanol followed by addition of an aqueous solution of the
relevant metal. For boron and copper the reactant molar ratios were curcumin: metal
1:2 while for iron a ratio of curcumin: iron 1:3 was used. The mixture was refluxed for
a period of 3 hours. The precipitated complexes were filtered washed with cold water,
followed by ethanol, then dried and purified. The structures of the metal complexes
of curcumin are shown in Fig. 1.

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Fig.1. Chemical structure of the Curcumin metal complexes formed between Curcumin and the relevant
metals.

The linear absorption spectrum of the metal complexes of curcumin in ethyl acetate
with 0.25g/l concentration is shown in Fig.2. The absorption spectrum of the samples
was recorded using by a UV-1800 Shimadzu UV-3600 double beam
spectrophotometer. The absorption spectrum of the sample shows an absorption peak
around 418nm and a small ground state absorption at 488 nm, 514 nm.

020044-3
 3.5

3.0 B
CU
2.5 Fe
Curc
Absorbance

2.0

1.5

1.0

0.5

0.0

300 400 500 600

Wavelength (nm)

Fig.2. Linear absorption of the spectra of metal complexes of curcumin in ethyl acetate.

EXPERIMENTS and RESULTS

The experimental technique used in this measurement was the Z-scan technique
[13]. In this technique, the transmittance of a tightly focused Gaussian Beam in the far
field is measured with and without an aperture as a function of the sample position z
with respect to the focal plane. The nonlinear refraction of the sample causes a spatial
beam broadening or narrowing in the far field and thus modifies the fraction of light
that passes through the aperture as the sample position is changed. The nonlinear
absorption causes the change in the transmission of the beam as function of the z-
position. The transmission is maximum at a focus for materials that exhibit saturation
absorption and the transmission is minimum at the focus for materials that exhibit
reverse saturation absorption.
The experiment was performed with an air-cooled multiline cw argon-ion laser (λ=
488 nm, 514 nm with a power range of 4-20 mW. The laser beam was focused by a
lens of 50 mm focal length to a spot size of 20μm at a 1mm cuvette sample. The
sample cell was placed on the translation stage and moved forward and backward by a
computer-controlled stepping motor. The transmission for the sample was measured
with and without an aperture in the far-field of the lens, as the sample moved through
the focal point. This enables the nonlinear refractive index (closed aperture) to be
separated from that of the nonlinear absorption (open aperture). Figure 3 shows typical
normalized transmission for wavelengths 418 nm (closed Z-scan), as a function of the
sample position for different metal complexes of curcumin at concentration 0.25g/l.

020044-4
The peak valley configuration (peak then valley) of the Z-scan data indicates that the
sign of the nonlinear refractive index is negative (self-defocusing). The nonlinear
refractive index arises from local variation of the refractive index with temperature.
The absorption of the focused beam propagating through the sample leads to a spatial
variation of temperature in the sample and, consequently spatial variation of refractive
index that acts as thermal lens resulting in the phase distortion of the beam.

3.0

2.5
Normalized Transmission

Fe
2.0 Cu
Cur
B
1.5

1.0

0.5

0.0

-10 -5 0 5 10
Z (mm)

Fig. 3. Normalized transmittance (closed aperture) of different metal complexes of curcumin at

incident intensity of 2x107W/m2.

It is possible from the peak to valley variation of the measured transmittance curve
to measure the nonlinear refractive index. The difference between normalized peak –
valley transmittance 'Tp-v is given by [16]

'T p v 0.40(1  s) 0.25 'I (1)

whereο‫ ׎‬is the on axis nonlinear phase shift at focus and S is the linear transmittance
of the aperture and is given by

2
2ra
s 1  exp(  2
) (2)
wa

where ra is the radius of the aperture and Wa is the radius of the laser at the entrance of
the aperture. The nonlinear phase shift is given by [13]

020044-5
 'IDO
n2 (3)
2SI o (1  e Dl )

where n2 is the nonlinear refractive index, P is the laser power, wo is the laser
wavelength, wo is the beam waist at focus and Leff (1  exp(D o d )) / D o with D is
the linear absorption coefficient, d is the sample thickness and Leff is the effective
thickness of the sample. The above equations were used to determine the value of
refractive index n2 of the metal complexes of curcumin at two different wavelengths
488nm and 514nm at average intensity 7.6x106 W/m2. The results are summarized in
Table 1.
Fig. 4 shows the normalize transmittance without an aperture as a function of the
distance along the lens axis z, for the boron complex of curcumin. The transmission is
symmetric with respect to the focus (z=0), where it has a maximum transmission. This
is indicative that the sample exhibits saturation absorption, SA.
The normalized transmission for open aperture is given by [13]

'M
'T 1 (4)
1 x2

Where x = z/zo with ‫ݖ‬௢  ൌ ߨ‫ݓ‬௢ଶ Ȁߣ is the diffraction length of the Gaussian beam, wo is
the beam waist, and ο߮ is the phase change. At focus (z=o), maximum transmission is
To related to E by

2 2 (1  To )
E (5)
I o Leff

Where, Leff is the effective thickness of the sample and Io is the intensity of beam at
focus. The above equations were used to determine the value of refractive index E of
the metal complexes of curcumin at two different wavelengths 488nm and 514nm at
average intensity 7.6x106 W/m2. The results are summarized in Table1. The value
obtained in the experiment is two orders higher than the value 1.2x10-3 cm/W for C60
and C1A1Pc [10, 19] and of the same order when compared to the value 2.8x10-5
cm/W for Fast green FCF dye [20].

020044-6
 1.7

1.6

1.5

Normalized Transmission
1.4

1.3

1.2

1.1

1.0

0.9
-10 -5 0 5 10

Z(mm)

Fig. 4. Normalized transmittance (open aperture) of Boron complexes of curcumin at incident intensity
of 2x107 W/m2.

In general, the mechanisms involved in the nonlinear response can be divided into
two groups, local and nonlocal. For the former the nonlinearity depends on the
instantaneous intensity within the medium, which in this case the Gaussian
decomposition method [13, 14] can be used for analysis the nonlinear response.
Nonlocal nonlinearities typically depend on energy density deposited in the medium.
The energy absorbed by the medium gives rise to local heating which diffuses within
the medium resulting in a spatial variation of temperature in the sample, and,
consequently spatial variation of refractive index that acts as a thermal lens resulting in
the phase distortion of the beam. In this case the thermal lens model can be used to
investigate the nonlinear response [16]. Fig. 5 showed the normalised transmission as
a function of position for a closed case at incident power of 10mW for the boron
complex of curcumin at 488 nm .The blue line is a fit to the data using Gaussian
decomposition model, and the red line is a fit to the data using the thermal lens model.
In the figure you may notice the best fit to the data is accomplished with thermal
model along with asymmetric nature of the scan and cw nature of the laser used
suggests that the nonlinear refractive index observed is nonlocal and of thermal origin.
Also the observed asymmetric nature of the closed scan along with the fact that the
nonlinear refractive index depends on the linear absorption suggests that the nonlinear
refractive index observed in this experiment is of thermal origin.

020044-7
 2.4

2.2

2.0

Normalized Trnasmission
1.8

1.6

1.4

1.2

1.0

0.8

0.6

0.4

0.2
-10 -5 0 5 10

Z (mm)

Fig.5. Closed z scan of the boron complex of curcumin at 488 nm at incident power of 10mW, solid red
line is a fit from thermal lens model, blue line is a fit from Gaussian decomposition method.

The thermal nonlinear refractive index can be used for the determination of the
ௗ௡
thermal conductivity ݇and the temperature coefficient of the refractive index, ௞ௗ் the
thermal origin n2 depends on the linear absorption of the medium and the beam waist
wo of the beam at the focus through the relation

Dw 2 dn
n2 o
(6)
4k dT
Using the data given in Table and assuming that all energy is absorbed by the
ௗ௡
sample, the value of ௞ௗ் , was calculated and found to be around 0.00189 m/W.
Optical limiting is a nonlinear optical process in which the transmitted intensity of
the material increases at low incident intensities and at the certain threshold intensity
value the transmission remains constant. It has been shown that the optical limiting
can be used for the protection of eyes and sensors from high intensity laser beams. In
this work the optical limiting experiment based on aperture limited geometry was
performed by placing the sample at post focus position and measuring the transmitted
power through the aperture for different incident laser powers. Fig.6 shows the optical
limiting curve where the transmission is plotted as a function of input power for
0.25g/l solution for all samples. As can be seen from Fig.6, at a low power region, the
output power is increased with an increase in input power. At a certain threshold value
the defocusing effect occurs, which results in a greater cross section area and reduces
the proportional intensity of the beam passing the aperture. Thus the transmittance
recorded by the detector remained reasonably constant showing a plateau region. The

020044-8
limiting effect of the samples occurred at a threshold power value measured from the
deviation from linearity and the values are given in Table 1. The values obtained here
depend on the experimental setup parameters such as the focusing lens and the
distance between the sample and the detector and the concentration of the sample.

12
11
10 B
9 Cu
Fe
Output Power (mW)

8
Cur
7
6
5
4
3
2
1
0

0 5 10 15 20 25
Input Power (mW)

Fig.6. Optical limiting effect of metal complexes of curcumin in ethyl acetate.

Table 1: Shows the values nonlinear refractive index and nonlinear absorption for metal complexes of
curcumin at wavelengths 488nm and 514 nm.
Compounds n2 (cm2/W) E (cm/W) n2 (cm2/W) E (cm/W) Opt. limiting
O=488nm O=488nm O=514nm O=514nm power (mW)
Curcumin 2.43x10-7 7.71 x10-3 - - 12
Boron(B) 1.65x10-7 5.05x10-3 - - 2.5
Copper(Cu) 2.79x10-7 4.56x10-3 2.55x10-7 4.76x10-3 6
Iron(Fe) 2.38x10-7 7.71x10-3 2.23x10-7 6.68x10-3 6

CONCLUSIONS
In conclusion the nonlinear refractive index and nonlinear absorption coefficients
for metal complexes of curcumin at two different wavelengths using cw laser were
measured by a Z-scan technique. All metal complexes show large nonlinearities with
slight change in nonlinearities influenced by the metal. The observed nonlinear
refractive index is attributed to a thermal nonlinearity resulting from the absorption of
incident beam by the medium. The nonlinear absorption is attributed to saturation
absorption. The calculated nonlinear refractive index used to determine dn/k5T=

020044-9
0.00189m/W. Based on nonlinear refraction the complexes behaved as optical limiters
over a wide range spectrum band indicating that this type of materials find potential
applications in optical limiting and signal processing applications.

ACKNOWLEDGMENT
We are thankful to RCSI-Bahrain for the financial support for this work.

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