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Spectrochimica Acta Part A 70 (2008) 615–618

Fluorescence quenching of meso-tetrakis (4-sulfonatophenyl)

porphyrin by colloidal TiO2
A. Kathiravan, V. Anbazhagan, M. Asha Jhonsi, R. Renganathan ∗
School of Chemistry, Bharathidasan University, Tiruchirappalli 620 024, Tamil Nadu, India
Received 27 June 2007; received in revised form 7 August 2007; accepted 13 August 2007

Abstract
A stable colloidal TiO2 has been prepared. The interaction of meso-tetrakis (4-sulfonatophenyl) porphyrin (TSPP) with colloidal TiO2 was studied
by absorption and fluorescence spectroscopy. Upon excitation of its absorption band, the fluorescence emission of TSPP was quenched by colloidal
TiO2 . The bimolecular quenching rate constant (kq ) is 1.78 × 1011 M−1 s−1 . The porphyrin can participate in the quenching process by injecting
electrons from its excited states into the conduction band of TiO2 . The quenching mechanism is discussed on the basis of the quenching rate constant
as well as the reduction potential of the colloidal TiO2 . Rehm–Weller equation was applied for the calculation of free energy change (Get ).
© 2007 Elsevier B.V. All rights reserved.

Keywords: TSPP; Fluorescence quenching; Photoinduced electron transfer; TiO2

1. Introduction Rahman and Harmon reported recently, absorbance change

Application of porphyrins and porphyrin-like compounds in
medicine has increased significantly over the last decade due
to interesting properties of natural and synthetic porphyrins and
their derivatives, especially due to their efficacy in photodynamic
therapy (PDT) of cancer [1,2]. A synthetic water-soluble meso-
tetrakis (4-sulfonatophenyl) porphyrin was studied and used in
clinical experiments as a promising sensitizer for PDT [3,4].
and static quenching of fluorescence of meso-tetrakis (4-
sulfonatophenyl) porphyrin (TPPS) by trinitrotoluene [5].
Goncalves et al. reported, effect of protonation on the photophys-
ical properties of meso-tetrakis (4-sulfonatophenyl) porphyrin
[6]. Sensitization of large band-gap semiconductor electrode
with organic dye molecules has been a field of extensive
research over past decades due to its potential applications in
solar energy conversion [7,8]. Wu et al. reported, hypocrellin
B (HB) as a sensitizer to study electron injection in col-
loidal TiO2 particles [9]. Recently we have reported interaction
between xanthene dyes and colloidal TiO2 via electron transfer
mechanism [10].
The present study involves the use of water soluble meso-
tetrakis (4-sulfonatophenyl) porphyrin as a sensitizer to study
electron injection to the conduction band of the semiconductor
TiO2 at pH ∼3.5.

2. Experimental

2.1. Materials

meso-tetrakis (4-sulfonatophenyl) porphyrin and tita-

nium(IV) 2-propoxide were purchased from Aldrich. The
doubly distilled water was used for preparing the solu-
∗ Corresponding author. Tel.: +91 431 2407053; fax: +91 431 2407045. tions. All measurements were performed at room temperature
E-mail address: rrengas@gmail.com (R. Renganathan). (28 ◦ C).

1386-1425/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2007.08.007
616 A. Kathiravan et al. / Spectrochimica Acta Part A 70 (2008) 615–618
2.2. Preparation of colloidal TiO2
The colloidal TiO2 suspension was prepared by the hydroly-
sis of titanium(IV) 2-propoxide in water, as described earlier
[11]. Titanium(IV) 2-propoxide in 2-propanol (10%, 0.5 ml)
was injected by syringe into 40 ml of water kept stirred under
N2 atmosphere. Freshly prepared colloidal TiO2 stock solution
(1 × 10−2 M) was diluted with water to obtain the desired con-
centration of TiO2 . No attempts were made to exclude the traces
of 2-propanol (∼0.4%) present in the colloidal semiconductor
suspension and it was confirmed separately that the presence of
2-propanol did not affect the photophysical and photochemical
measurements [12].
2.3. Instrumentation
The steady state fluorescence quenching measurements were
carried out with JASCO FP-6500 spectrofluorometer. The exci-
tation wavelength was 434 nm and the emission was monitored
at 664 nm. The excitation and emission slit widths (each
3 nm) and scan rate (500 nm/s) were kept constant for all the
experiments. Absorption spectra were recorded using Cary300
UV–vis spectrophotometer. Samples were prepared by dis-
solving TSPP in doubly distilled water and administering the
appropriate amounts of colloidal TiO2 . The samples were care-
fully degassed using pure nitrogen gas for 30 min. Quartz cells
(4 cm × 1 cm × 1 cm) with high vacuum Teflon stopcocks were
used for degassing.
3. Results and discussion
The absorption and emission spectra of TSPP (Fig. 1 ) were
recorded in the absence and in presence of colloidal TiO2
(Figs. 2 and 3 ). The following observations were made: (i) the
shape and band maxima of absorption and fluorescence spectra
of TSPP remain unchanged, (ii) no other new emission band of
the TSPP is noticed, and (iii) absorbance of the TSPP does not
change during the course of experiment.
The above observations suggest that (i) the TSPP–TiO2 inter-
action does not change the absorption and fluorescence spectral
properties and (ii) the formation of any emissive exciplex may
be ruled out.
Fig. 1. Absorption (A) and emission (B) spectrum of TSPP at pH ∼3.5.
Fig. 2. Absorption spectrum of TSPP in presence of colloidal TiO2 in the
concentration range of (0–5) × 10−4 M in water.
The Stern–Volmer constant (Ksv ) and the quenching rate
constant (kq ) for the fluorescence quenching of TSPP were
determined from Stern–Volmer plots using emission intensity
data,
I0
= 1 + Ksv [Q] (1)
I
where
Ksv = kq τ (2)
where I0 and I correspond to the intensities of the sensitizer
in the absence and presence of the quencher, respectively, [Q]
the concentration of the quencher and τ 0 is the emission life-
time of TSPP in the absence of quencher, i.e., 3.6 ns in water
[6]. The Stern–Volmer plot in the quenching of TSPP is linear
with a correlation coefficient (R2 ) of greater than 0.9976 indi-
cating the dynamic nature of quenching process and absence
of static quenching (Fig. 4 ). From the slope of the above
plot, the Ksv values obtained is 6.42 × 104 M−1 and using Eq.
(2) namely Ksv = kq τ, the kq value calculated is found to be
1.78 × 1011 M−1 s−1 .
3.1. Calculation of free energy changes (Get ) for the
electron transfer reactions
The nature of the electron transfer pathway (i.e., oxidative
or reductive quenching) can be understood by examining the
free energy of the corresponding reactions. Thermodynamics
Fig. 3. Steady state fluorescence quenching of TSPP (2 × 10−6 M) with colloidal
TiO2 in the concentration range of (0–7) × 10−4 M in water at pH ∼3.5.
 A. Kathiravan et al. / Spectrochimica Acta Part A 70 (2008) 615–618 617

transfer from excited TSPP to TiO2 ) and hence there is no energy

transfer.

3.2. Schematic diagram describing the electron transfer

quenching process

Upon excitation of TSPP, it goes to excited state and an elec-

tron transfer from excited TSPP to conduction band of TiO2
occurs.

Fig. 4. Stern–Volmer plot for the fluorescence quenching of TSPP with various
concentrations of TiO2 ((0–7) × 104 M) in water.

Table 1
Photophysical properties of TSPP
S. No. Parameters TSPP

1 Eox vs. SCE (V) 1.10a

2 E(0,0) (eV) 1.92a
3 Get (eV) −0.72b
a From Ref. [17].
(ox) (red)
b Calculated by Rhem–Weller equation Get = E1/2 − E1/2 − E(0,0) + C.
4. Conclusions
of electron transfer from the sensitizer to the quencher can be
calculated by the well-known Rehm–Weller equation [13]. The fluorescence quenching of singlet excited TSPP by col-
loidal TiO2 was carried out in water. Based on the results
(ox) (red)
Get = E1/2 − E1/2 − E(0,0) + C (3) obtained, it is suggested that: (i) the fluorescence quenching
involves electron transfer mechanism. TSPP serves as electron
(ox) (red)
where E1/2 is the oxidation potential of the donor, E1/2 the donor and TiO2 as electron acceptor. (ii) No ground-state com-
reduction potential of the acceptor, E(0,0) the singlet state energy plex is formed between the fluorophore and quencher.
of the sensitizer and C is the coulombic term. Since one of the
species is neutral and the solvent used is polar in nature, the Acknowledgements
coulombic term in the above expression is neglected [14]. The
oxidation potential, excited singlet state energy (E(0,0) ) and the R.R. and V.A thank DST (Ref: SP/S1/H-41/2001, dt: 12-09-
calculated Get value for the TSPP is shown in Table 1 . The 2002) (Government of India) for the Project and fellowship,
conduction band potential of TiO2 is −0.1 V versus SCE [15]. respectively. Authors also thank DST-FIST for the spectrofluo-
By using Rehm–Weller equation negative value of Get was rometer facility.
obtained. The absence of any overlap between the emission spec-
tra of the TSPP and the absorption spectrum of TiO2 (Fig. 5 ) References
and the well established electron accepting nature of e− cb of TiO2
(in presence of excited electron donors namely the dyes [16]) [1] R. Bonnett, Chem. Soc. Rev. 19 (1995).
[2] M. Ochsner, J. Photochem. Photobiol. 39 (1997) 1–18.
coupled with the above observation support that the quenching
[3] E. Ben-Hur, B. Horowitz, Photochem. Photobiol. 62 (1995) 383–388.
mechanism in this work involves electron transfer (i.e., electron [4] D.E. Lewis, R.E. Utecht, M.M. Judy, L.J. Matthews, T.C. Chanh, Spectrum
6 (1993) 8–14.
[5] M. Rahman, H.J. Harmon, Spectrochim. Acta A 65 (2006) 901–906.
[6] P.J. Goncalves, L. De Boni, N.M. Barbosa Neto, J.J. Rodrigues, S.C. Zilio,
I.E. Borissevitch, Chem. Phys. Lett. 407 (2005) 236–241.
[7] B. O’Regan, J. Moser, M. Anderson, M. Gratzel, J. Phys. Chern. 94 (1990)
8720–8726.
[8] B. O’Regan, M. Gratzel, Nature 253 (1991) 737–740.
[9] T. Wu, S.J. Xu, J.Q. Shen, S. Chen, M.H. Zhang, T. Shen, J. Photochem.
Photobiol. A: Chem. 137 (2000) 191–196.
[10] A. Kathiravan, V. Anbazhagan, M. Asha Jhonsi, R. Renganathan, Z. Phys.
Chem. 221 (2007) 941–948.
[11] D. Bahnemann, A. Henglein, J. Lilie, L. Spanhel, J. Phys. Chem. 88 (1984)
709–711.
[12] P.V. Kamat, J.P. Chauvet, R.W. Fessenden, J. Phys. Chem. 90 (1986)
1389–1394.
Fig. 5. Absorption spectrum of TiO2 and the emission spectrum of TSPP. [13] D. Rehm, A. Weller, Isr. J. Chem. 8 (1970) 259–271.
618 A. Kathiravan et al. / Spectrochimica Acta Part A 70 (2008) 615–618

[14] S. Parret, F.M. Savary, J.P. Fouassier, P. Ramamurthy, J. Photochem. Pho- [16] Q. Dai, J. Rabani, J. Photochem. Photobiol. A: Chem. 148 (2002) 17–
tobiol. A: Chem. 83 (1994) 205–209. 24.
[15] S.L. Murov, I. Carmichael, G.L. Hug, Handbook of Photochemistry, 2nd [17] K. Kalyanasundaram, M. Neumann-Spallart, J. Phys. Chem. 86 (1982)
ed., M. Dekker Inc., New York, 1993, pp. 269–273. 5163–5169.