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Nonlinear optical properties of Rose Bengal: Effect of environment
Accepted Manuscript Nonlinear optical properties of Rose Bengal: Effect of environment
Sahar Peyghami, Soheil Sharifi, Forough Rakhshanizadeh, Khalil Alizadeh PII: DOI: Reference:
S0167-7322(17)32903-3 doi: 10.1016/j.molliq.2017.09.058 MOLLIQ 7895
To appear in:
Journal of Molecular Liquids
Received date: Revised date: Accepted date:
1 July 2017 2 September 2017 16 September 2017
Please cite this article as: Sahar Peyghami, Soheil Sharifi, Forough Rakhshanizadeh, Khalil Alizadeh , Nonlinear optical properties of Rose Bengal: Effect of environment, Journal of Molecular Liquids (2017), doi: 10.1016/j.molliq.2017.09.058
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ACCEPTED MANUSCRIPT Nonlinear Optical Properties of Rose Bengal: Effect of Environment Sahar peyghami1, Soheil Sharifi1*, Forough Rakhshanizadeh2*, Khalil Alizadeh1 1
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Department of Physics, Faculty of Science, Ferdowsi Ferdowsi University of Mashhad, Mashhad, Iran Department of Pediatrics, Faculty of Medicine, Mashhad University of Medical Sciences, Mashhad, Iran
Abstract:
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The dye with strong two photon absorption (2PA) at low concentration has application in Photodynamic therapy. For this reason, the nonlinear optical properties of Rose Bengal in
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various solvents, water-surfactant solution and water-in-ionic liquid microemulsion (MEs)
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was studied by Z-scan technique with a CW Diode laser at 532nm wavelength and 50mW
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power to study the effect of environment on Rose Bengal (RB). The dipole moment of RB in MEs was determined by using a spectrophotometer and fluorometer and the quantum
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perturbation theory. The results disclose that the nonlinear refractive index and 2PA of RB reduce with the increase of dielectric constant of the medium. Moreover, the NLO properties
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and dipole moment of RB depend on the formation of anionic surfactant and MEs.
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Keywords: Rose Bengal, Two Photon Absoprtion, Nonlinear Optic, fluorescence, nano-droplets, dipole moment.
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Corresponding author: Soheil Sharifi (Email: [email protected] ,[email protected] ) and Forough Rakhshanizadeh (Email: [email protected] )
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1. Introduction: Rose Bengal (RB) is a Xanthene type dye with a high quantum yield and triplet state formed, [1,2]. RB is active in the visible region with high absorption, which makes it suitable for the
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study of linear and nonlinear optical properties. The singlet oxygen (1O2) produces under illumination of RB which is known to Photodynamic therapy (PDT) that in PDT, cancer is
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killed by singlet oxygen [3].
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The scope of PDT could be using materials that can absorb light in lower energy and produce singlet oxygen, because the light with lower energy can provide deep penetration in tissue
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[4,5]. Usually, the synthesis of materials that absorb light in the low energy of light are
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difficult. One way is to produce materials with strong two-photon absorption (2PA) [6,7]. RB has application in ophthalmology, waste water treatment, while being due to quantum yield, good solubility in water and active in the visible region.
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In the Xanthene family, the red shift in fluorescence spectra depends on increasing the number of the halogen group in molecular structure. The heavier halogens change the rate of intersystem crossing of the dye, which is an important scale for a photosensitizer. For this
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reason, rose Bengal is more efficient than other Xanthene molecules [8,9].
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Because of dye aggregation, most photosensitizer's molecules have low emission quantum yields and poor solubility in aqueous solutions. Usually, these effects reduced generation of 1O2 that it can affect the PDT. One way in the reduction of dye aggregation deals with the use of dye in nano-particles or nano-droplets. It is easy to change nanomaterials size and optimize the ratio of surface to volume in having higher fluorescence quantum yields or better optical properties. The absorption of two photons with the same or different frequency in order to excite from ground to excited state is called two-photon absorption (2PA). 2PA can excite dye by lower energy or higher wavelength. The higher wavelength can influence 2
ACCEPTED MANUSCRIPT the depth of tissue. In the PDT two parameters are important firstly increase of 2PA and secondly increase of fluorescence of dye or photosensitizer.
By z-scan technique, 2PA of different molecules have been characterized. The z-scan technique is the way to find nonlinear optic of materials [10,11]. One way for reduction of
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aggregation and increase of fluorescence intensity is mixed dye with surfactants or microemulsion. The microemulsion (MEs) are a mixture of water, oil and surfactant which
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are stable and transparent. The AOT is an anionic surfactant that AOT MEs is an ionic liquid
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[12,13]. The mixture of AOT/Water/Hexane and AOT/Water/Heptane was studied in several works [14-16]. In this works, the Microemulsion prepared AOT surfactant and Heptane and
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Hexane with X=3 and 8 are spherical droplet, [14-16]. From the previous studied the
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water/AOT/oil (Oils are Heptane and Hexane), with increasing water to the surfactant molar ratio (X), the three different phases (monomeric, transient and oligomeric phase) appear for
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microemulsion, [14] that the microemulsion with X≤8 have a monomeric phase.[14] The
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microemulsion in this phase is optically transparent without turbidity. In our samples, the AOT/Water/Oil/Rose Begnal is optically transparent without any turbidity.
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In this paper, the effect of solvents (water, ethanol and methanol), surfactant (Bis(2ethylhexyl) sulfosuccinate sodium salt) and MEs on 2PA and dipole moment of Rose Bengal
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(RB) dyes was studied by Z scan instrument. By quantum perturbation theory[17,18], dipole moment of Rose Bengal was extracted in MEs. The main points of this work is to find a method for enhancement of NLO properties of RB, because of application in PDT. For this reason, the NLO properties of RB with three types of solutions were studied. (a) The effect of polarity of solvent (water, ethanol and methanol) on NLO properties of Rose Bengal. (b) The effect of AOT surfactant and the micelle on NLO properties of RB that from our knowledge it was not studied before. (c) The effect of electro-static interaction of the droplet on
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ACCEPTED MANUSCRIPT nonlinear optical of Rose Bengal. It is well known that with the increase of droplet concentration electrostatic interaction between droplets is increasing. In the MEs, the size of droplet defined by the molar ratio of water to surfactant (X) and the droplet concentration in MEs can control by mass fraction. It is very interesting to see what is the effect of droplet concentration in 2PA or the nonlinear refractive index at constant dye concentration. We have
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proven in this work, that by the increase of droplet concentration 2PA of RB enhancement at
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constant dye concentration. So, the electro-static interaction between droplets can change
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2PA of RB. We have proven in this study, the 2PA of RB in microemulsion with lower droplet size is higher than other type of solvent. So, the mixture of dye with lower size of
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droplet is suitable systems for PDT.
2. Experiment:
Materials and preparation:
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2.1.
Rose Bengal (RB), AOT (Bis(2-ethylhexyl) sulfosuccinate sodium salt) and Hexane, were
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obtained from Sigma-Aldrich. Three types of solution were prepared: (a) The mixture of Rose Bengal with different dye concentration in water, ethanol and methanol. The
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concentration of dye in solution was described by (Cdye). (b) The mixture of aqueous solutions of Rose Bengal with different AOT surfactant concentration on this part the effect of AOT on optical properties of Rose Bengal was studied. The concentration of dye in solution (AOT/Water/RB) was described by (Cdye) and the concentration of AOT in solution (AOT/Water/RB) was described by (CAOT). (c) The microemulsion was prepared with a mixture of AOT, water, oil (Heptane and Hexane) and Rose Bengal. The MEs is prepared by mixing mass value, at the fixed the molar ratio of surfactant to water, X=[H2O]/[AOT], (X=3,
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ACCEPTED MANUSCRIPT 8) and the different mass fraction of droplets (mf,drop=(mmass of droplet)/(mTotal)). Rose Bengaldroplet solutions were prepared by a mixture of dye-water solution (1mM) with surfactant-oil solutions.
2.2.
Methods:
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The Z-scan equipment is a way to investigate the NLO values. The continuous wave diode
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laser (λ=532nm, with 80mW) with a Gaussian beam was used. The two detectors (close and
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open) were measured the light intensity during the motion of the sample in the direction of light. The data of closed and open aperture are used for calculating n2 and ß. Raman spectra
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were measured with the AvaSpec-ULS 2048x64TEC Raman spectrometer. The UV-1650 PC and Jasco FP-6200 spectrofluorimeter was used to study of absorption and fluorescence
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spectra.
Solvent Effect:
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3.1.
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3. Results and discussion:
The nonlinear optical nature of molecules can depend on media polarity and the molecular
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interaction,[19,20]. The solvent plays important role in optical properties in the liquid state,
molecules.
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and the interactions and aggregation, leading to the change of the dipole moment of the
The open and close aperture curve of different concentration of Rose Bengal in methanol, ethanol and water presented in fig. 1. In fig. 1 (a, b, c), the intensity of light reduces when the sample is near from the focus and the open aperture curve shows a minimum transmittance at the focus (Z=0) that the minimum decrease by reduction of droplet mass fractions. The open aperture curve is analyzed using the methods explained by Sheik-Bahae et al in order to
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ACCEPTED MANUSCRIPT characterize the NLO parameters of the Rose Bengal. The 2PA is extracted from open an aperture curve fitted by equation 1. [21] TOA(Z,S=1)=∑[(-q0(Z,0))]m/(m+1)3/2
(1)
That q0 is q0(Z,0)=βI0Leff/(1+(Z/Z0)2)
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(2)
laser intensity of focus and the β is 2PA coefficient.
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Where Leff and z0 are the effective thickness and the Rayleigh length of the sample [22]. I0 is
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The normalized intensity of transmission of the close aperture display in fig. 1 (d, e, f). The figure shows asymmetric peak followed by a valley and so the sign of the refractive
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nonlinearity is negative. In fig. 1 (d, e, f), the solid line is fitted by equation 2. The difference
value of ΔTp-v is given by [22]
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between the normalized transmittances of close aperture can be determined as ΔTp-v that the
∆TP-V=0.406(1-S)0.25∆ɸ0
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(3)
That ΔΦ0 is the phase distortion, and S is aperture transmittance,[22]. The n2, can calculate
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from the ΔTp–v of the close z-scan curve by (4)
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n2=(λ∆TP-V)/(2πLeffI0(0.406)(1-S)0.25)
The real part of third order susceptibility is pertaining to n2 and it was appraised using the following equations:
χR(3)=2 n2 n02ε02c
(5)
Where n0 an c are refractive index and light velocity. The real part of molecular hyperpolarizabilities γR is given by equation 6. γR= χR(3)/(L4N) Where L is the Lorenz correction factor. 6
(6)
ACCEPTED MANUSCRIPT The n2, ß, χR and γR for the Rose Bengal solutions were done using Z-scan techniques and the data was analyzed by equations 1-6 and the result are presented in the Table 1. The nonlinear absorption coefficient, ß, was observed of the order of 10-8cm2/W in higher dye concentration. The n2, was observed in the order of 10-12cm2/W in lower dye concentration. The ß and n2 as a function of dye concentration is presented in the figure 2 (a and b). The
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NLO value of RB in methanol and ethanol was observed in lower dye concentration than
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aqueous solutions of RB. At the same value of dye concentration the nonlinear optical
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parameters of ethanol and methanol are higher that water. Moreover, the γR and χR depends
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on the dye concentration in solution. In general, the cross section of 2PA is defined as [23,24]
σ2PA=(4π2 a05 α)(ω2g(ω))δ2PA/(15c0Γf)
(7)
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Here a0, c0 , α, g(ω) and Γf are the radius of Bohr, the speed of light, a constant, the profile of
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spectral line and the level broadening, respectively. δ2PA is defined as follows:
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δ2PA=24[2(μe-μg) μge/ωf]2
(8)
Where μge , μe , μg and ωf are the dipole moment of the transition, excited state, ground state
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and different between the energy of the excited and ground state, respectively. Equations 7 and 8 show the 2PA are related to the dipole moment of molecular. In general, the dipole
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moment of molecule change with the medium polarity, [25]. So, the change of 2PA with solvent is due to change of dipole moment. From quantum perturbation theory and solvent effect, [25], the medium with higher polarity produces an external field that it can reduce the ground state dipole moment of molecule. So, the 2PA in water less than other solvent because the aqueous solutions of RB, have smaller ground state dipole moment. In general, the type of dye aggregation is another reason for change of dipole moment. A previous studied shows
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ACCEPTED MANUSCRIPT that the RB forms H-type aggregates in water, ethanol and methanol, [26]. So, the 2PA value or the dipole moment of RB in solution is not depends on the type of dye aggregation. Table 1. The values of , n2, χR and γR of Rose Bengal at different solvent (water, Ethanol and Methanol) and different dye concentration (Cdye).
Methanol
0.1
2.26288
0.12
3.89705
0.18
4.90137
χR (×10-3m2V-2)
γR (×10-24m5V-2)
2.6 4.04 7.02
0.354303 0.269183 0.234027
1.16 6.9 7.51
7.71625 9.2044 7.14828
7.36175
5.05
8.41712
10.7653 12.4944
7.39
8.20573
8.57
7.14279
3.79602 5.88579 10.2342 0.37314 1.24427 2.19753
1.68719 10.0629 10.941 0.352016 0.58319 1.33318
0.0004
Surfactant effect:
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3.2.
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0.0006 0.0008
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1.3635
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0.005 0.01 0.02 0.003 0.0035 0.004 0.0001 0.0005 0.0007 0.001 0.0012 0.0016
n2 (×10-12cm2/W)
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Ethanol
β (×10-7cm/W)
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Water
Cdye (×10-2mM) 0.08
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Solvent
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The surfactant and micelle formation can change the optical properties of dye molecules [27,28,29,30]. For this reason, the mixture of RB in a solution of water-AOT was studied by Z-Scan. For study the effect of AOT on the 2PA of Rose Bengal dye molecules, three concentrations of AOT (1, 2 and 4mM) are prepared in a different dye concentration (between 0.004-0.01mM). The open aperture of three AOT concentrations is presented in fig. 3 (a) CAOT=1mM, fig. 3 (b) CAOT=2mM and fig. 3 (c) CAOT=4mM. The 2PA of RB-AOTWater is presented in table 2. The 2PA increase with addition of AOT concentration in AOTWater solutions. It is well known that the critical micelle concentration of AOT is 2mM and 8
ACCEPTED MANUSCRIPT the surfactant has micelle formation, in the higher AOT concentration (4mM). So, the 2PA of Rose Bengal depends on the formation of AOT-Water solutions.
β (×10-7cm/W)
0.08 0.1 0.12 0.08 0.1 0.12 0.08 0.1 0.12
0.60398 1.14355 2.45211 0.62264 0.83479 1.04566 0.44937 0.62826 1.46456
2
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Effect of Microemulsion:
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3.3.
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1
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Cdye (mM)
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CAOT (mM)
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Table 2. Calculated values of β of Rose Bengal at three AOT concentrations (CAOT) and different dye concentration (Cdye).
The Z-Scan instrument was used to study the RB-water to oil AOT microemulsion that it
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prepared at different droplet concentration (mass fraction, mf) and two droplet size (X=3 and
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8). The Heptane and Hexane was used as oil in MEs. The opened-aperture transmitted intensity of the RB-mesh is presented in the fig. 4 and the results of analyzes are presented in the table 3. The results indicated that the values of ß reduce linearly with the decrease of dye
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concentrations. The closed-aperture data of Z-scan instrument are displayed in the fig. 5. The
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n2 is obtained from analyzing and presented in the table 3. The results indicated that the 2PA of RB-MEs enhanced compared to the dye inside of other prepared solutions (ethanol, methanol and water).
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ACCEPTED MANUSCRIPT Table. 3. Calculated values of β, n2, χR and γR of RB-MEs at different dye concentration (Cdye) and molar ratio and RB/Water ratio.
0.4 8
3 1 8 Heptane
3 0.4 8
0.95877 1.65001 5.07375 7.02871 3.83904 5.90964 7.86734
1.83033 5.20448 5.79405 6.28974 1.32324 4.86771 6.4209
χR (×10-3m2V-2)
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2.131 2.520 2.873 5.082 3.257 4.842 6.482 1.729 1.894 0.467 0.626 1.076 3.340 6.269 7.332 2.886 4.337 5.839 1.051 1.464 1.712 0.680 0.758
γR (×10-24m5V-2)
4.96709 9.48669 6.91947 9.2298
3.41 6.51 4.75 6.33
6.76531 6.73636 6.76531 6.73636
5.26157 6.84434 9.72533 4.3826 5.89253 10.6208
3.61 4.7 6.67 3.01 4.04 7.29
2.28846 2.13734 2.59693 2.94694 3.55527 6.03968
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3
0.03 0.035 0.04 0.07 0.02 0.03 0.04 0.045 0.05 0.006 0.008 0.04 0.05 0.06 0.07 0.01 0.015 0.02 0.05 0.06 0.07 0.008 0.009 0.009 5
n2 (×10-12cm2/W)
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8
Hexane
β (×10-7cm/W)
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1
Cdye (×10-2mM)
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3
mfd
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X
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RB/water ratios (mM)
oil
0.804
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The n2 versus dye concentration is displayed in the figure 6. The results show at the same dye
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concentration, the value of n2 at X=8 is higher than X=3. So, the nonlinear refractive index depends on structure formation of MEs. It is well known that the nonlinear refractive index produce by thermal effects [31,32]. So, the thermal effect in MEs depends on structure formation of structure formation of MEs (molar ratio or size). The ß versus of mass fraction at constant RB concentration is presented in the figure 7. The results indicated that the 2PA, increase with addition of droplet concentration (mass fraction). It is well known that the number of droplet can change the interaction between droplets [33,34,35]. So, the interaction between droplets can affect the NLO parameters. The ß and n2 10
ACCEPTED MANUSCRIPT as a function of the dielectric constant of bulk solution at a constant dye concentration (Cday=0.1mM for 2PA and Cday=0. 005mM for n2) is presented in the figure 8. In the case of RB-MEs solutions, the oil was considered as the bulk. The results indicated that ß and n2 reduce with the increase of dielectric constant. From our results, the NLO parameters of RB depend on the dielectric constant of solution,
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structure formation of microemulsion or surfactant that these can affect dipole moment of RB
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molecules. For this reason, the theory was applied to find the dipole moment of RB-MEs. The
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absorption of RB-MEs for preparing samples shows a broad peak at 557.6nm, fig. 9. The fluorescence spectra of RB-MEs at different droplet concentrations (mf=0. 04–0.3) at two
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molar ratios (X=3 and 8) and constant RB/water (1mM) is demonstrated in fig.10. The wavelength of fluorescence spectra peak, has a red shift with the increase of mass fraction
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(droplet concentration).
The relation between absorption and fluorescence spectra can be described by the following
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equations [36,37].
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νa-νf=m1×f(ε,n)+const (9)
νa+νf=-m2×(f(ε,n)+2g(n))+const (10)
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The νa and νf are absorption and fluorescence peak and the f(ε,n) and g(n) are polarity values
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[36,37]. The ratio of dipole moment can described by the following equations,[36,37]:
μe/μg=(m2+m1)/(m2-m1)
(11)
For studied the polarity of solutions, the Raman spectra was used. The Raman Spectra of Rose Bengal/AOT/Water/Hexane at X=3 and mf=0. 04 shows in fig. 11 (a) and Raman Spectra of Rose Bengal/AOT/Water/Hexane at X=8 and mf=0. 07 shows in fig. 11 (b). In the spectra two peaks at 1890 and 1773 (1/cm) was observed that it becomes of dye-water inside of the droplet. These peaks haven’t changed to increase of droplet or molar ratio. The
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ACCEPTED MANUSCRIPT position and intensity of Raman spectra depend on the polarity of mediums. So, in our samples, the medium polarity doesn't change and the dielectric constant and refractive index was considered constant at different droplet size and concentration. The spectral shifts νaνb(
) and νa+νb(
) was founded from figs.9-10. From equation 8-10, the value of
μe/μg was evaluated and the results were presented in the table 4. In general, the ratio of
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dipole moment increase by increase of dye concentration. That it could be reason of change
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of NLO properties of RB. For Rose Bengal/AOT/Water/hexane, the ratio of dipole moment
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increase by reduce of molar ratio at the same dye concentration. The formation of
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AOT/Water/hexane can change the dipole moment of the molecule.
Hexane 8
Heptane
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3
0.3 0.1 0.07 0.04 0.3 0.07 0.04 0.3 0.1 0.07 0.04 0.3 0.1 0.07
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Cdye (mM) 0.02409 0.00736 0.005082 0.002873 0.05485 0.01161 0.006482 0.024827 0.00762 0.005241 0.002956 0.056007 0.01722 0.01193
abs
(nm) 557.6 557.6 557.6 557.6 557.6 557.6 557.6 557.6 557.6 557.6 557.6 557.6 557.6 557.6
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3
mfd
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X
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oil
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Table 4. The wavelength maximum of the absorption and emission (λabs, λem) of RB inside droplet for varied droplet concentrations,νa-νf(cm-1), νa-νf(cm-1), ratio of dipole moments (μe/μg) with dye/water=1mM. em
(nm) 577.7 573.2 570.5 567.7 581.6 573 572.4 577.2 571.7 570.5 570.5 585.1 576 573.9
νa –νf ( −1 ) 623.98037 488.08521 405.51908 319.0654 740.05514 481.99589 463.70238 608.98554 442.31142 405.51908 405.51908 842.90733 572.89176 509.36443
νa+νb ( −1 ) 35244.02537 35379.92052 35462.48666 35548.94034 35127.9506 35386.00985 35404.30336 35259.02019 35425.69432 35462.48666 35462.48666 35025.09841 35295.11398 35358.64131
3.54655 2.74374 2.32514 1.93235 4.37551 2.71126 2.61527 3.44996 2.50599 2.32514 2.32514 5.25578 3.2261 2.85942
Moreover, the fluorescence intensity of peak versus dye concretion presented in the fig. 12. The results indicated that the fluorescence intensity depends on the formation of MEs (molar ratio and oil type).
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ACCEPTED MANUSCRIPT The fluorescence spectrum of Rhodamine B (RhB) and Fluorescein sodium salt (FSS) in a water to oil MEs was studied before, [38]. The fluorescence of RhB is higher than FSS that it is due to the reduction aggregation of RhB inside of MEs, [38]. Probably, The Rose Bengal aggregation in MEs reduce by change of formation of MEs (Molar ratio and mass fraction) and it can change the fluorescence intensity and dipole moment of RB. So, The change of
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2PA of RB-MEs is due to change of dipole moment.
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4. Conclusion:
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The magnitude of NLO parameters in the Rose Bengal dye, prepared in three solutions (water, ethanol and methanol) and different RB-AOT-Water and RB-MEs, have been
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determined, by the Z-scan. The values of NLO are measured at 532nm with diode laser light. A negative nonlinear refractive index of the order of 10-12 cm2/W for all the samples. It was
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shown that dielectric constant, formation structure of droplet (size of droplets) and mass
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fraction of droplet can affect the NLO parameters. The 2PA of RB was enhanced by MEs that it makes suitable system of Photodynamic therapy. The ratio of the dipole moment of the
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Rose Bengal molecule in MEs was investigated by quantum perturbation theory. Moreover,
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the fluorescence intensity of RB depends on the oil type and droplet size.
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ACCEPTED MANUSCRIPT 35. Behzadi, N. B., & Sharifi, S. (2014). “Light scattering and SAXS of spherical to cylindrical transition of AOT/H2O/cyclohexane/PI,” Physics and Chemistry of Liquids. 52(3), 428-435 (2014). 36. Raikar, U. S., Renuka, C. G., Nadaf, Y. F., Mulimani, B. G., Karguppikar, A. M., & Soudagar, M. K. “Solvent effects on the absorption and fluorescence spectra of coumarins 6
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Xanthene type dyes in nano-confined liquid, Journal of Physics D: Applied Physics J. Phys.
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D: Appl. Phys. 50, 155301-155310 (2017)
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Fig.1. (a, b, c) open aperture curve of different Rose Bengal concentration (Cdye) in water, ethanol and methanol, (d, e, f) close aperture curve of different concentration of Rose Bengal .in water, ethanol and methanol. Insert numbers is dye concentration in solutions
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Fig.3. Open aperture curves of Zscan at three AOT concentrations (a) CAOT=1mM , (b) CAOT=2mM and (c) CAOT=4mM and three Rose Bengal concentration (Cdye=0.08, 0.1 and 0.12mM).
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Fig.4. Open aperture curves of RB/AOT/Water/Heptane at X=3 (a) and X=8 (b) and RB/AOT/Water/Hexane at X=3 (c) and X=8 (d) for different droplet mass fraction (mf) with RB/Water=1mM.
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Fig.6. The nonlinear refractive index of RB/AOT/Water/Oil with X=8 (Up-triangle) and X=3 (Cubic) that open points are heptane and close points are hexane as function of dye concentration.
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Fig.7. The two photon absorption of RB/AOT/Water/Oil with X=8 (Up-triangle) and X=3 (Cubic) that open points are heptane and close points are hexane as a function of droplet mass fraction at a constant dye concentration (Cdye=3. 34×10-3 mm).
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Water AOT(1mM) AOT(2mM) AOT(4mM) Ethanol Methanol Hexane(x=8) Hexane(x=3) Heptane(x=8) Heptane(x=3)
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Fig.8. The (a) two photon absorption and (b) nonlinear refractive index of RB in different solution, surfactant concentration and microemulsion at constant dye concentration (Cdye=0. 1 mm for two photon absorption) and (Cdye=0. 005 mm for nonlinear refractive index).
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Graphical abstract
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The Two Photon Absorption as function of Rose Bengal Concentration in different mediums.
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Sahar Peyghami, Soheil Sharifi, Forough Rakhshanizadeh, Khalil Alizadeh PII: DOI: Reference:
S0167-7322(17)32903-3 doi: 10.1016/j.molliq.2017.09.058 MOLLIQ 7895
To appear in:
Journal of Molecular Liquids
Received date: Revised date: Accepted date:
1 July 2017 2 September 2017 16 September 2017
Please cite this article as: Sahar Peyghami, Soheil Sharifi, Forough Rakhshanizadeh, Khalil Alizadeh , Nonlinear optical properties of Rose Bengal: Effect of environment, Journal of Molecular Liquids (2017), doi: 10.1016/j.molliq.2017.09.058
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ACCEPTED MANUSCRIPT Nonlinear Optical Properties of Rose Bengal: Effect of Environment Sahar peyghami1, Soheil Sharifi1*, Forough Rakhshanizadeh2*, Khalil Alizadeh1 1
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Department of Physics, Faculty of Science, Ferdowsi Ferdowsi University of Mashhad, Mashhad, Iran Department of Pediatrics, Faculty of Medicine, Mashhad University of Medical Sciences, Mashhad, Iran
Abstract:
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The dye with strong two photon absorption (2PA) at low concentration has application in Photodynamic therapy. For this reason, the nonlinear optical properties of Rose Bengal in
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various solvents, water-surfactant solution and water-in-ionic liquid microemulsion (MEs)
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was studied by Z-scan technique with a CW Diode laser at 532nm wavelength and 50mW
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power to study the effect of environment on Rose Bengal (RB). The dipole moment of RB in MEs was determined by using a spectrophotometer and fluorometer and the quantum
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perturbation theory. The results disclose that the nonlinear refractive index and 2PA of RB reduce with the increase of dielectric constant of the medium. Moreover, the NLO properties
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and dipole moment of RB depend on the formation of anionic surfactant and MEs.
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Keywords: Rose Bengal, Two Photon Absoprtion, Nonlinear Optic, fluorescence, nano-droplets, dipole moment.
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Corresponding author: Soheil Sharifi (Email: [email protected] ,[email protected] ) and Forough Rakhshanizadeh (Email: [email protected] )
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1. Introduction: Rose Bengal (RB) is a Xanthene type dye with a high quantum yield and triplet state formed, [1,2]. RB is active in the visible region with high absorption, which makes it suitable for the
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study of linear and nonlinear optical properties. The singlet oxygen (1O2) produces under illumination of RB which is known to Photodynamic therapy (PDT) that in PDT, cancer is
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killed by singlet oxygen [3].
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The scope of PDT could be using materials that can absorb light in lower energy and produce singlet oxygen, because the light with lower energy can provide deep penetration in tissue
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[4,5]. Usually, the synthesis of materials that absorb light in the low energy of light are
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difficult. One way is to produce materials with strong two-photon absorption (2PA) [6,7]. RB has application in ophthalmology, waste water treatment, while being due to quantum yield, good solubility in water and active in the visible region.
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In the Xanthene family, the red shift in fluorescence spectra depends on increasing the number of the halogen group in molecular structure. The heavier halogens change the rate of intersystem crossing of the dye, which is an important scale for a photosensitizer. For this
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reason, rose Bengal is more efficient than other Xanthene molecules [8,9].
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Because of dye aggregation, most photosensitizer's molecules have low emission quantum yields and poor solubility in aqueous solutions. Usually, these effects reduced generation of 1O2 that it can affect the PDT. One way in the reduction of dye aggregation deals with the use of dye in nano-particles or nano-droplets. It is easy to change nanomaterials size and optimize the ratio of surface to volume in having higher fluorescence quantum yields or better optical properties. The absorption of two photons with the same or different frequency in order to excite from ground to excited state is called two-photon absorption (2PA). 2PA can excite dye by lower energy or higher wavelength. The higher wavelength can influence 2
ACCEPTED MANUSCRIPT the depth of tissue. In the PDT two parameters are important firstly increase of 2PA and secondly increase of fluorescence of dye or photosensitizer.
By z-scan technique, 2PA of different molecules have been characterized. The z-scan technique is the way to find nonlinear optic of materials [10,11]. One way for reduction of
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aggregation and increase of fluorescence intensity is mixed dye with surfactants or microemulsion. The microemulsion (MEs) are a mixture of water, oil and surfactant which
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are stable and transparent. The AOT is an anionic surfactant that AOT MEs is an ionic liquid
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[12,13]. The mixture of AOT/Water/Hexane and AOT/Water/Heptane was studied in several works [14-16]. In this works, the Microemulsion prepared AOT surfactant and Heptane and
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Hexane with X=3 and 8 are spherical droplet, [14-16]. From the previous studied the
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water/AOT/oil (Oils are Heptane and Hexane), with increasing water to the surfactant molar ratio (X), the three different phases (monomeric, transient and oligomeric phase) appear for
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microemulsion, [14] that the microemulsion with X≤8 have a monomeric phase.[14] The
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microemulsion in this phase is optically transparent without turbidity. In our samples, the AOT/Water/Oil/Rose Begnal is optically transparent without any turbidity.
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In this paper, the effect of solvents (water, ethanol and methanol), surfactant (Bis(2ethylhexyl) sulfosuccinate sodium salt) and MEs on 2PA and dipole moment of Rose Bengal
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(RB) dyes was studied by Z scan instrument. By quantum perturbation theory[17,18], dipole moment of Rose Bengal was extracted in MEs. The main points of this work is to find a method for enhancement of NLO properties of RB, because of application in PDT. For this reason, the NLO properties of RB with three types of solutions were studied. (a) The effect of polarity of solvent (water, ethanol and methanol) on NLO properties of Rose Bengal. (b) The effect of AOT surfactant and the micelle on NLO properties of RB that from our knowledge it was not studied before. (c) The effect of electro-static interaction of the droplet on
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ACCEPTED MANUSCRIPT nonlinear optical of Rose Bengal. It is well known that with the increase of droplet concentration electrostatic interaction between droplets is increasing. In the MEs, the size of droplet defined by the molar ratio of water to surfactant (X) and the droplet concentration in MEs can control by mass fraction. It is very interesting to see what is the effect of droplet concentration in 2PA or the nonlinear refractive index at constant dye concentration. We have
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proven in this work, that by the increase of droplet concentration 2PA of RB enhancement at
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constant dye concentration. So, the electro-static interaction between droplets can change
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2PA of RB. We have proven in this study, the 2PA of RB in microemulsion with lower droplet size is higher than other type of solvent. So, the mixture of dye with lower size of
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droplet is suitable systems for PDT.
2. Experiment:
Materials and preparation:
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2.1.
Rose Bengal (RB), AOT (Bis(2-ethylhexyl) sulfosuccinate sodium salt) and Hexane, were
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obtained from Sigma-Aldrich. Three types of solution were prepared: (a) The mixture of Rose Bengal with different dye concentration in water, ethanol and methanol. The
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concentration of dye in solution was described by (Cdye). (b) The mixture of aqueous solutions of Rose Bengal with different AOT surfactant concentration on this part the effect of AOT on optical properties of Rose Bengal was studied. The concentration of dye in solution (AOT/Water/RB) was described by (Cdye) and the concentration of AOT in solution (AOT/Water/RB) was described by (CAOT). (c) The microemulsion was prepared with a mixture of AOT, water, oil (Heptane and Hexane) and Rose Bengal. The MEs is prepared by mixing mass value, at the fixed the molar ratio of surfactant to water, X=[H2O]/[AOT], (X=3,
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2.2.
Methods:
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The Z-scan equipment is a way to investigate the NLO values. The continuous wave diode
RI
laser (λ=532nm, with 80mW) with a Gaussian beam was used. The two detectors (close and
SC
open) were measured the light intensity during the motion of the sample in the direction of light. The data of closed and open aperture are used for calculating n2 and ß. Raman spectra
NU
were measured with the AvaSpec-ULS 2048x64TEC Raman spectrometer. The UV-1650 PC and Jasco FP-6200 spectrofluorimeter was used to study of absorption and fluorescence
MA
spectra.
Solvent Effect:
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3.1.
D
3. Results and discussion:
The nonlinear optical nature of molecules can depend on media polarity and the molecular
CE
interaction,[19,20]. The solvent plays important role in optical properties in the liquid state,
molecules.
AC
and the interactions and aggregation, leading to the change of the dipole moment of the
The open and close aperture curve of different concentration of Rose Bengal in methanol, ethanol and water presented in fig. 1. In fig. 1 (a, b, c), the intensity of light reduces when the sample is near from the focus and the open aperture curve shows a minimum transmittance at the focus (Z=0) that the minimum decrease by reduction of droplet mass fractions. The open aperture curve is analyzed using the methods explained by Sheik-Bahae et al in order to
5
ACCEPTED MANUSCRIPT characterize the NLO parameters of the Rose Bengal. The 2PA is extracted from open an aperture curve fitted by equation 1. [21] TOA(Z,S=1)=∑[(-q0(Z,0))]m/(m+1)3/2
(1)
That q0 is q0(Z,0)=βI0Leff/(1+(Z/Z0)2)
RI
PT
(2)
laser intensity of focus and the β is 2PA coefficient.
SC
Where Leff and z0 are the effective thickness and the Rayleigh length of the sample [22]. I0 is
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The normalized intensity of transmission of the close aperture display in fig. 1 (d, e, f). The figure shows asymmetric peak followed by a valley and so the sign of the refractive
MA
nonlinearity is negative. In fig. 1 (d, e, f), the solid line is fitted by equation 2. The difference
value of ΔTp-v is given by [22]
D
between the normalized transmittances of close aperture can be determined as ΔTp-v that the
∆TP-V=0.406(1-S)0.25∆ɸ0
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(3)
That ΔΦ0 is the phase distortion, and S is aperture transmittance,[22]. The n2, can calculate
CE
from the ΔTp–v of the close z-scan curve by (4)
AC
n2=(λ∆TP-V)/(2πLeffI0(0.406)(1-S)0.25)
The real part of third order susceptibility is pertaining to n2 and it was appraised using the following equations:
χR(3)=2 n2 n02ε02c
(5)
Where n0 an c are refractive index and light velocity. The real part of molecular hyperpolarizabilities γR is given by equation 6. γR= χR(3)/(L4N) Where L is the Lorenz correction factor. 6
(6)
ACCEPTED MANUSCRIPT The n2, ß, χR and γR for the Rose Bengal solutions were done using Z-scan techniques and the data was analyzed by equations 1-6 and the result are presented in the Table 1. The nonlinear absorption coefficient, ß, was observed of the order of 10-8cm2/W in higher dye concentration. The n2, was observed in the order of 10-12cm2/W in lower dye concentration. The ß and n2 as a function of dye concentration is presented in the figure 2 (a and b). The
PT
NLO value of RB in methanol and ethanol was observed in lower dye concentration than
RI
aqueous solutions of RB. At the same value of dye concentration the nonlinear optical
SC
parameters of ethanol and methanol are higher that water. Moreover, the γR and χR depends
NU
on the dye concentration in solution. In general, the cross section of 2PA is defined as [23,24]
σ2PA=(4π2 a05 α)(ω2g(ω))δ2PA/(15c0Γf)
(7)
MA
Here a0, c0 , α, g(ω) and Γf are the radius of Bohr, the speed of light, a constant, the profile of
D
spectral line and the level broadening, respectively. δ2PA is defined as follows:
PT E
δ2PA=24[2(μe-μg) μge/ωf]2
(8)
Where μge , μe , μg and ωf are the dipole moment of the transition, excited state, ground state
CE
and different between the energy of the excited and ground state, respectively. Equations 7 and 8 show the 2PA are related to the dipole moment of molecular. In general, the dipole
AC
moment of molecule change with the medium polarity, [25]. So, the change of 2PA with solvent is due to change of dipole moment. From quantum perturbation theory and solvent effect, [25], the medium with higher polarity produces an external field that it can reduce the ground state dipole moment of molecule. So, the 2PA in water less than other solvent because the aqueous solutions of RB, have smaller ground state dipole moment. In general, the type of dye aggregation is another reason for change of dipole moment. A previous studied shows
7
ACCEPTED MANUSCRIPT that the RB forms H-type aggregates in water, ethanol and methanol, [26]. So, the 2PA value or the dipole moment of RB in solution is not depends on the type of dye aggregation. Table 1. The values of , n2, χR and γR of Rose Bengal at different solvent (water, Ethanol and Methanol) and different dye concentration (Cdye).
Methanol
0.1
2.26288
0.12
3.89705
0.18
4.90137
χR (×10-3m2V-2)
γR (×10-24m5V-2)
2.6 4.04 7.02
0.354303 0.269183 0.234027
1.16 6.9 7.51
7.71625 9.2044 7.14828
7.36175
5.05
8.41712
10.7653 12.4944
7.39
8.20573
8.57
7.14279
3.79602 5.88579 10.2342 0.37314 1.24427 2.19753
1.68719 10.0629 10.941 0.352016 0.58319 1.33318
0.0004
Surfactant effect:
CE
3.2.
PT E
D
0.0006 0.0008
PT
1.3635
RI
0.005 0.01 0.02 0.003 0.0035 0.004 0.0001 0.0005 0.0007 0.001 0.0012 0.0016
n2 (×10-12cm2/W)
SC
Ethanol
β (×10-7cm/W)
NU
Water
Cdye (×10-2mM) 0.08
MA
Solvent
AC
The surfactant and micelle formation can change the optical properties of dye molecules [27,28,29,30]. For this reason, the mixture of RB in a solution of water-AOT was studied by Z-Scan. For study the effect of AOT on the 2PA of Rose Bengal dye molecules, three concentrations of AOT (1, 2 and 4mM) are prepared in a different dye concentration (between 0.004-0.01mM). The open aperture of three AOT concentrations is presented in fig. 3 (a) CAOT=1mM, fig. 3 (b) CAOT=2mM and fig. 3 (c) CAOT=4mM. The 2PA of RB-AOTWater is presented in table 2. The 2PA increase with addition of AOT concentration in AOTWater solutions. It is well known that the critical micelle concentration of AOT is 2mM and 8
ACCEPTED MANUSCRIPT the surfactant has micelle formation, in the higher AOT concentration (4mM). So, the 2PA of Rose Bengal depends on the formation of AOT-Water solutions.
β (×10-7cm/W)
0.08 0.1 0.12 0.08 0.1 0.12 0.08 0.1 0.12
0.60398 1.14355 2.45211 0.62264 0.83479 1.04566 0.44937 0.62826 1.46456
2
4
Effect of Microemulsion:
MA
3.3.
SC
1
RI
Cdye (mM)
NU
CAOT (mM)
PT
Table 2. Calculated values of β of Rose Bengal at three AOT concentrations (CAOT) and different dye concentration (Cdye).
The Z-Scan instrument was used to study the RB-water to oil AOT microemulsion that it
D
prepared at different droplet concentration (mass fraction, mf) and two droplet size (X=3 and
PT E
8). The Heptane and Hexane was used as oil in MEs. The opened-aperture transmitted intensity of the RB-mesh is presented in the fig. 4 and the results of analyzes are presented in the table 3. The results indicated that the values of ß reduce linearly with the decrease of dye
CE
concentrations. The closed-aperture data of Z-scan instrument are displayed in the fig. 5. The
AC
n2 is obtained from analyzing and presented in the table 3. The results indicated that the 2PA of RB-MEs enhanced compared to the dye inside of other prepared solutions (ethanol, methanol and water).
9
ACCEPTED MANUSCRIPT Table. 3. Calculated values of β, n2, χR and γR of RB-MEs at different dye concentration (Cdye) and molar ratio and RB/Water ratio.
0.4 8
3 1 8 Heptane
3 0.4 8
0.95877 1.65001 5.07375 7.02871 3.83904 5.90964 7.86734
1.83033 5.20448 5.79405 6.28974 1.32324 4.86771 6.4209
χR (×10-3m2V-2)
PT
2.131 2.520 2.873 5.082 3.257 4.842 6.482 1.729 1.894 0.467 0.626 1.076 3.340 6.269 7.332 2.886 4.337 5.839 1.051 1.464 1.712 0.680 0.758
γR (×10-24m5V-2)
4.96709 9.48669 6.91947 9.2298
3.41 6.51 4.75 6.33
6.76531 6.73636 6.76531 6.73636
5.26157 6.84434 9.72533 4.3826 5.89253 10.6208
3.61 4.7 6.67 3.01 4.04 7.29
2.28846 2.13734 2.59693 2.94694 3.55527 6.03968
RI
3
0.03 0.035 0.04 0.07 0.02 0.03 0.04 0.045 0.05 0.006 0.008 0.04 0.05 0.06 0.07 0.01 0.015 0.02 0.05 0.06 0.07 0.008 0.009 0.009 5
n2 (×10-12cm2/W)
SC
8
Hexane
β (×10-7cm/W)
NU
1
Cdye (×10-2mM)
MA
3
mfd
D
X
PT E
RB/water ratios (mM)
oil
0.804
CE
The n2 versus dye concentration is displayed in the figure 6. The results show at the same dye
AC
concentration, the value of n2 at X=8 is higher than X=3. So, the nonlinear refractive index depends on structure formation of MEs. It is well known that the nonlinear refractive index produce by thermal effects [31,32]. So, the thermal effect in MEs depends on structure formation of structure formation of MEs (molar ratio or size). The ß versus of mass fraction at constant RB concentration is presented in the figure 7. The results indicated that the 2PA, increase with addition of droplet concentration (mass fraction). It is well known that the number of droplet can change the interaction between droplets [33,34,35]. So, the interaction between droplets can affect the NLO parameters. The ß and n2 10
ACCEPTED MANUSCRIPT as a function of the dielectric constant of bulk solution at a constant dye concentration (Cday=0.1mM for 2PA and Cday=0. 005mM for n2) is presented in the figure 8. In the case of RB-MEs solutions, the oil was considered as the bulk. The results indicated that ß and n2 reduce with the increase of dielectric constant. From our results, the NLO parameters of RB depend on the dielectric constant of solution,
PT
structure formation of microemulsion or surfactant that these can affect dipole moment of RB
RI
molecules. For this reason, the theory was applied to find the dipole moment of RB-MEs. The
SC
absorption of RB-MEs for preparing samples shows a broad peak at 557.6nm, fig. 9. The fluorescence spectra of RB-MEs at different droplet concentrations (mf=0. 04–0.3) at two
NU
molar ratios (X=3 and 8) and constant RB/water (1mM) is demonstrated in fig.10. The wavelength of fluorescence spectra peak, has a red shift with the increase of mass fraction
MA
(droplet concentration).
The relation between absorption and fluorescence spectra can be described by the following
D
equations [36,37].
PT E
νa-νf=m1×f(ε,n)+const (9)
νa+νf=-m2×(f(ε,n)+2g(n))+const (10)
CE
The νa and νf are absorption and fluorescence peak and the f(ε,n) and g(n) are polarity values
AC
[36,37]. The ratio of dipole moment can described by the following equations,[36,37]:
μe/μg=(m2+m1)/(m2-m1)
(11)
For studied the polarity of solutions, the Raman spectra was used. The Raman Spectra of Rose Bengal/AOT/Water/Hexane at X=3 and mf=0. 04 shows in fig. 11 (a) and Raman Spectra of Rose Bengal/AOT/Water/Hexane at X=8 and mf=0. 07 shows in fig. 11 (b). In the spectra two peaks at 1890 and 1773 (1/cm) was observed that it becomes of dye-water inside of the droplet. These peaks haven’t changed to increase of droplet or molar ratio. The
11
ACCEPTED MANUSCRIPT position and intensity of Raman spectra depend on the polarity of mediums. So, in our samples, the medium polarity doesn't change and the dielectric constant and refractive index was considered constant at different droplet size and concentration. The spectral shifts νaνb(
) and νa+νb(
) was founded from figs.9-10. From equation 8-10, the value of
μe/μg was evaluated and the results were presented in the table 4. In general, the ratio of
PT
dipole moment increase by increase of dye concentration. That it could be reason of change
RI
of NLO properties of RB. For Rose Bengal/AOT/Water/hexane, the ratio of dipole moment
SC
increase by reduce of molar ratio at the same dye concentration. The formation of
NU
AOT/Water/hexane can change the dipole moment of the molecule.
Hexane 8
Heptane
AC
3
0.3 0.1 0.07 0.04 0.3 0.07 0.04 0.3 0.1 0.07 0.04 0.3 0.1 0.07
8
Cdye (mM) 0.02409 0.00736 0.005082 0.002873 0.05485 0.01161 0.006482 0.024827 0.00762 0.005241 0.002956 0.056007 0.01722 0.01193
abs
(nm) 557.6 557.6 557.6 557.6 557.6 557.6 557.6 557.6 557.6 557.6 557.6 557.6 557.6 557.6
D
3
mfd
PT E
X
CE
oil
MA
Table 4. The wavelength maximum of the absorption and emission (λabs, λem) of RB inside droplet for varied droplet concentrations,νa-νf(cm-1), νa-νf(cm-1), ratio of dipole moments (μe/μg) with dye/water=1mM. em
(nm) 577.7 573.2 570.5 567.7 581.6 573 572.4 577.2 571.7 570.5 570.5 585.1 576 573.9
νa –νf ( −1 ) 623.98037 488.08521 405.51908 319.0654 740.05514 481.99589 463.70238 608.98554 442.31142 405.51908 405.51908 842.90733 572.89176 509.36443
νa+νb ( −1 ) 35244.02537 35379.92052 35462.48666 35548.94034 35127.9506 35386.00985 35404.30336 35259.02019 35425.69432 35462.48666 35462.48666 35025.09841 35295.11398 35358.64131
3.54655 2.74374 2.32514 1.93235 4.37551 2.71126 2.61527 3.44996 2.50599 2.32514 2.32514 5.25578 3.2261 2.85942
Moreover, the fluorescence intensity of peak versus dye concretion presented in the fig. 12. The results indicated that the fluorescence intensity depends on the formation of MEs (molar ratio and oil type).
12
ACCEPTED MANUSCRIPT The fluorescence spectrum of Rhodamine B (RhB) and Fluorescein sodium salt (FSS) in a water to oil MEs was studied before, [38]. The fluorescence of RhB is higher than FSS that it is due to the reduction aggregation of RhB inside of MEs, [38]. Probably, The Rose Bengal aggregation in MEs reduce by change of formation of MEs (Molar ratio and mass fraction) and it can change the fluorescence intensity and dipole moment of RB. So, The change of
RI
PT
2PA of RB-MEs is due to change of dipole moment.
SC
4. Conclusion:
NU
The magnitude of NLO parameters in the Rose Bengal dye, prepared in three solutions (water, ethanol and methanol) and different RB-AOT-Water and RB-MEs, have been
MA
determined, by the Z-scan. The values of NLO are measured at 532nm with diode laser light. A negative nonlinear refractive index of the order of 10-12 cm2/W for all the samples. It was
D
shown that dielectric constant, formation structure of droplet (size of droplets) and mass
PT E
fraction of droplet can affect the NLO parameters. The 2PA of RB was enhanced by MEs that it makes suitable system of Photodynamic therapy. The ratio of the dipole moment of the
CE
Rose Bengal molecule in MEs was investigated by quantum perturbation theory. Moreover,
AC
the fluorescence intensity of RB depends on the oil type and droplet size.
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NU
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19
(d)
0.5
Water -45 0 45 Z (mm )
2.0
RI 0.0005 0.0004
1.5 1.0
Ethanol -40 0 40 Z (mm )
AC
0.5
Normalized Transmittance (a.u. )
Ethanol -50 0 50 Z (mm ) (e) 0.0007
PT E
1.0
0.003 0.0035 0.004
D
0.02 0.01 0.0049
SC
0.8 0.7
0 50 Z (mm ) Normalized Transmittance (a.u. )
1.5
0.9
80
1.0 (c)
0.9 0.001 0.0012 0.0016
2.4 Normalized Transmittance (a.u. )
0.4 Water -50
0.08 0.1 0.12 0.16
(b)
NU
0.6
1.0
MA
0.8
Normalized Transmittance (a.u. )
1.0 (a)
CE
Normalized Transmittance (a.u. )
Normalized Transmittance (a.u. )
PT
ACCEPTED MANUSCRIPT
Methanol -50 0 50 Z (mm ) (f)
1.8
0.0008 0.0006 0.0004
1.2 0.6 0.0 Methanol -40 0 40 Z (mm)
80
Fig.1. (a, b, c) open aperture curve of different Rose Bengal concentration (Cdye) in water, ethanol and methanol, (d, e, f) close aperture curve of different concentration of Rose Bengal .in water, ethanol and methanol. Insert numbers is dye concentration in solutions
20
ACCEPTED MANUSCRIPT
1.5
(a)
2
4.0
n2(×10 cm /W)
(b) 1.0
Ethanol Methanol Water
0.8
0.5
RI
1.6
SC
2.4
PT
-11
3.2
0.0
Ethanol Methanol Water
0.0 0.00
0.05
0.10
0.15
0.000
NU
Cdye(mM )
0.009
0.018
Cdye(mM )
CE
PT E
D
MA
Fig.2. (a) Two photon absorption and (b) nonlinear refractive index as function of dye concentration in water (open circle), Methanol (up-triangle) and ethanol (Cubic).
AC
-7
(×10 cm/W)
4.8
21
0.8
-80
0.08 0.1 0.12 -40
0 Z (mm )
40
80
(b)
AOT+water=2mM 1.0
0.9 0.08 0.1 0.12 0.8 -80
-40
0
40
80
Z (mm )
(c)
AOT+water=4mM 1.0
0.9
0.8
0.08 0.1 0.12
PT
(a)
Normalized Transmittance (a.u. )
AOT+water=1mM 1.0
Normalized Transmittance (a.u. )
Normalized Transmittance (a.u. )
ACCEPTED MANUSCRIPT
-40
0 40 Z (mm )
AC
CE
PT E
D
MA
NU
SC
RI
Fig.3. Open aperture curves of Zscan at three AOT concentrations (a) CAOT=1mM , (b) CAOT=2mM and (c) CAOT=4mM and three Rose Bengal concentration (Cdye=0.08, 0.1 and 0.12mM).
22
80
0.6 mf=0.05 0.4 mf=0.06
x=3
0.2
mf=0.07
Heptane 0.0 -80
-40
0
40
80
Z (mm ) (c ) mf=0.03
1.0
mf=0.035
mf=0.04
x=3 Hexane
0.0 -80
mf=0.07
-40
0
D
0.2
MA
0.6 0.4
0.8
mf=0.01
0.6 0.4
mf=0.015
x=8
0.2
Heptane 0.0 -80
-40
40
80
Z (mm )
mf=0.02 0
40
80
40
80
Z (mm )
1.2
(d )
1.0 0.8
NU
0.8
1.0
PT
0.8
(b )
RI
mf=0.04
1.2
SC
1.0
Normalized Transmittance (a.u. )
1.2
(a )
Normalized Transmittance (a.u. )
Normalized Transmittance (a.u. )
1.2
Normalized Transmittance (a.u. )
ACCEPTED MANUSCRIPT
mf=0.02
0.6
mf=0.03
0.4 0.2
x=8
Hexane 0.0 -80 -40
mf=0.04 0
PT E
Z (mm )
AC
CE
Fig.4. Open aperture curves of RB/AOT/Water/Heptane at X=3 (a) and X=8 (b) and RB/AOT/Water/Hexane at X=3 (c) and X=8 (d) for different droplet mass fraction (mf) with RB/Water=1mM.
23
1.5
1.0
0.5
Heptane x=3
0.0 -70
-35
0
35
Normalized Transmittance (a.u.)
mf=0.055 mf=0.05 mf=0.045
(c )
-70
MA
1.0
0.5
1.5
1.0
Heptane x=8
0.5
-35
0
35
70
Z (mm )
(d )
1.5
mf=0.008 mf=0.006
NU
1.5
Hexane x=3 -35
0
35
D
Normalized Transmittance (a.u.)
2.0
mf=0.0095 mf=0.009 mf=0.008
(b )
0.0 -70
70
Z (mm )
2.0
PT
mf=0.07 mf=0.06 mf=0.05
(a )
SC
2.0
RI
Normalized Transmittance (a.u.)
Normalized Transmittance (a.u.)
ACCEPTED MANUSCRIPT
70
1.0
0.5
Hexane x=8 0.0 -70
-35
0
35
70
Z (mm )
PT E
Z (mm )
AC
CE
Fig.5. Close aperture curves of RB/AOT/Water/Heptane at X=3 (a) and X=8 (b) and RB/AOT/Water/Hexane at X=3 (c) and X=8 (d) for different droplet mass fraction (mf) with RB/Water=1mM.
24
PT
ACCEPTED MANUSCRIPT
RI SC
2
cm /W)
10
MA
6
D
n2(×10
-12
NU
8
4
PT E
0.0008
0.0016 Cdye (mM )
Hexane (x=8) Hexane (x=3) Heptane(x=8) Heptane(x=3)
0.0024
AC
CE
Fig.6. The nonlinear refractive index of RB/AOT/Water/Oil with X=8 (Up-triangle) and X=3 (Cubic) that open points are heptane and close points are hexane as function of dye concentration.
25
ACCEPTED MANUSCRIPT
-3
cdye=3.34×10 mM
PT
4
-7
(×10 cm/W)
5
RI
3
SC
Hexane(x=8) Hexane(x=3) Heptane(x=8) Heptane(x=3)
0.01
0.02
NU
2 0.03
0.04
0.05
MA
mf
AC
CE
PT E
D
Fig.7. The two photon absorption of RB/AOT/Water/Oil with X=8 (Up-triangle) and X=3 (Cubic) that open points are heptane and close points are hexane as a function of droplet mass fraction at a constant dye concentration (Cdye=3. 34×10-3 mm).
26
ACCEPTED MANUSCRIPT
Water AOT(1mM) AOT(2mM) AOT(4mM) Ethanol Methanol Hexane(x=8) Hexane(x=3) Heptane(x=8) Heptane(x=3)
150 100
PT
-7
(×10 cm/W)
200
0 (a) 20
40
60
80
MA
NU
0
SC
RI
50
D
CE
100
Water Ethanol Methanol Hexane(x=8) Hexane(x=3) Heptane(x=8) Heptane(x=3)
PT E
150
50
0 (b) 0
AC
n2(×10
-12
2
cm /W)
200
30
60
90
Fig.8. The (a) two photon absorption and (b) nonlinear refractive index of RB in different solution, surfactant concentration and microemulsion at constant dye concentration (Cdye=0. 1 mm for two photon absorption) and (Cdye=0. 005 mm for nonlinear refractive index).
27
ACCEPTED MANUSCRIPT
3.0 mf=0.3 mf=0.1 mf=0.07 mf=0.04
1.2 Hexane 0.8
x=3 \
0.4
500
550
MA
Absorbance (a.u. )
PT E
D
1.2
Heptane
x=3 \
CE
Absorbance (a.u. )
(c)
mf=0.3 mf=0.1 mf=0.04
0.4
0.0 450
PT
1.5
Hexane
1.0
x=8
500
0.0 450
600
Wavelength(nm )
0.8
2.0
0.5
0.0 450
1.6
(b)
RI
1.6
2.5
SC
Absorbance (a.u. )
2.0
mf=0.3 mf=0.07 mf=0.04
(a )
NU
Absorbance (a.u. )
2.4
550
3.0
500
550
600
Wavelength(nm ) mf=0.3 mf=0.1 mf=0.07
(d)
2.4 1.8 1.2
Heptane
x=8 0.6
600
Wavelength(nm )
0.0 450
500
550
600
AC
Wavelength(nm )
Fig.9. The absorption spectra of RB/AOT/Water/Oil at two molar ratio (X=3 and 8) and two oil type (a, b) Hexane and (c, d) Heptane.
28
ACCEPTED MANUSCRIPT
250 200 150 100
Hexane
50
x=3
0 500
550
600
650
250 200 150 100 50 0 500
700
550
600
Hexane
x=8 650
700
Wavelength(nm )
Wavelength(nm )
25
(d)
mf=0.3 mf=0.1 mf=0.07 mf=0.04
25
MA
20 15 10
D
Heptane
5
550
600
650
mf=0.3 mf=0.1 mf=0.07
20
15
10 Heptane 5
x=3
PT E
0 500
fluorescence(a.u. )
(c)
NU
30
fluorescence(a.u. )
mf=0.3 mf=0.07 mf=0.04
(b)
PT
fluorescence(a.u. )
fluorescence(a.u. )
300
300
RI
mf=0.3 mf=0.1 mf=0.07 mf=0.04
(a) 350
SC
400
700
0 500
x=8 550
600
650
700
Wavelength(nm )
Wavelength(nm )
AC
CE
Fig.10. The fluorescence spectra of RB/AOT/Water/Oil at two molar ratio (X=3 and 8) and two oil type (a, b) Hexane and (c, d) Heptane.
29
ACCEPTED MANUSCRIPT
4
10
(a )
3
Counts
10
Hexane (x=3 )
2
10
mf=0.04
PT
Cdye=1 mM 1
10
(b )
RI
3
Heptane (x=8 ) 2
10
SC
Counts
10
mf=0.07
NU
Cdye=1 mM 1
10
0
1500
3000
MA
Raman shift (1/cm)
AC
CE
PT E
D
Fig.11. The Raman spectra of (a) RB/AOT/Water/Hexane (b) RB/AOT/Water/Heptane.
30
400
Hexane (x=3) Hexane (x=8) Heptane (x=3) Heptane (x=8)
300
PT
200 100 0
SC
0.02 0.04 Cdye (mM)
RI
fluorescence intensity (a.u.)
ACCEPTED MANUSCRIPT
0.06
AC
CE
PT E
D
MA
NU
Fig.12. RB/AOT/Water/Oil at two molar ratio (X=3 and 8) and two oil type (Hexane and Heptane) at RB/Water=1mM.
31
ACCEPTED MANUSCRIPT
D
MA
NU
SC
RI
PT
Graphical abstract
AC
CE
PT E
The Two Photon Absorption as function of Rose Bengal Concentration in different mediums.
32