Abstract

We demonstrate the use of the Z-scan technique as a method to measure a chemical parameter, the pKa value, that characterizes the equilibrium constant in acid–base reactions. The measurements were performed with picosecond pulses at 532 nm in Fe(III)-meso-tetrakis(4-N-methyl-pyridyl) porphyrin. The results were compared with linear absorption measurements and electron paramagnetic resonance, the usual techniques employed to determine pKa values in aqueous solutions, and showed excellent agreement.

© 2000 Optical Society of America

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  1. N. Bloembergen, Nonlinear Optics (Benjamin, Reading, Mass., 1965).
  2. Y. R. Shen, The Principles of Nonlinear Optics (Wiley, New York, 1984).
  3. M. Sheik-Bahae, A. A. Said, and E. W. Van Stryland, Opt. Lett. 14, 955 (1989).
    [CrossRef] [PubMed]
  4. D. Dolphin, ed., The Porphyrins (Academic, New York, 1978), Vol. I.
  5. Ö. Almarsson and T. C. Bruice, J. Am. Chem. Soc. 117, 4533 (1995).
    [CrossRef]
  6. V. E. Yushmanov, H. Imasato, T. T. Tominaga, and M. Tabak, Inorg. Biochem. 61, 233 (1996).
    [CrossRef]
  7. P. K. Shantha and A. L. Verma, Inorg. Chem. 35, 2723 (1996).
    [CrossRef]
  8. S. Guha, K. Kang, P. Porter, J. F. Roach, D. E. Remy, F. J. Aranda, and D. V. G. L. N. Rao, Opt. Lett. 17, 264 (1992).
    [CrossRef] [PubMed]
  9. S. R. Mishra, H. S. Rawat, and M. Laghat, Opt. Commun. 147, 328 (1998).
    [CrossRef]
  10. K. Kandasamy, P. N. Puntambekar, B. P. Singh, S. J. Shetty, and T. S. Srivastava, J. Nonlin. Opt. Phys. Mater. 6, 361 (1997).
    [CrossRef]
  11. W. Sun, C. C. Byeon, C. M. Lawson, G. M. Gray, and D. Wang, Appl. Phys. Lett. 74, 3254 (1999).
    [CrossRef]
  12. H. Ma, A. S. L. Gomes, and C. B. de Araújo, Appl. Phys. Lett. 59, 2666 (1991).
    [CrossRef]
  13. T. Xia, D. J. Hagan, M. Sheik-Bahae, and E. W. Van Stryland, Opt. Lett. 19, 317 (1994).
    [CrossRef] [PubMed]
  14. D. V. Petrov, A. S. L. Gomes, and C. B. de Araújo, Appl. Phys. Lett. 65, 1067 (1994).
    [CrossRef]
  15. J. Castilo, V. P. Kozich, and A. O. Marcano, Opt. Lett. 19, 171 (1994).
    [CrossRef]
  16. J. Wang, M. Sheik-Bahae, A. A. Said, D. J. Hagan, and E. W. Van Stryland, J. Opt. Soc. Am. B 11, 1009 (1994).
    [CrossRef]
  17. N. J. Patronas, J. S. Cohen, R. H. Knop, A. J. Dwyer, D. Colcher, J. Lundy, F. Mornex, P. Hambright, M. Sohn, and C. E. Myers, Cancer Treat. Rep. 70, 391 (1986).
    [PubMed]
  18. P. N. Prasad and D. J. Williams, Introduction to Nonlinear Optical Effects in Molecules and Polymers (Wiley, New York, 1991).
  19. Z. Gryczynski, R. Paolesse, K. M. Smith, and E. Bucci, Chem. Phys. Lett. 69, 71 (1997).
  20. A. G. Bezerra, I. E. Borissevitch, R. E. de Araujo, A. S. L. Gomes, and C. B. de Araújo, “Investigation of picosecond optical nonlinearity in porphyrin metal complexes derivatives,” Chem. Phys. Lett. (to be published).

1999

W. Sun, C. C. Byeon, C. M. Lawson, G. M. Gray, and D. Wang, Appl. Phys. Lett. 74, 3254 (1999).
[CrossRef]

1998

S. R. Mishra, H. S. Rawat, and M. Laghat, Opt. Commun. 147, 328 (1998).
[CrossRef]

1997

K. Kandasamy, P. N. Puntambekar, B. P. Singh, S. J. Shetty, and T. S. Srivastava, J. Nonlin. Opt. Phys. Mater. 6, 361 (1997).
[CrossRef]

Z. Gryczynski, R. Paolesse, K. M. Smith, and E. Bucci, Chem. Phys. Lett. 69, 71 (1997).

1996

V. E. Yushmanov, H. Imasato, T. T. Tominaga, and M. Tabak, Inorg. Biochem. 61, 233 (1996).
[CrossRef]

P. K. Shantha and A. L. Verma, Inorg. Chem. 35, 2723 (1996).
[CrossRef]

1995

Ö. Almarsson and T. C. Bruice, J. Am. Chem. Soc. 117, 4533 (1995).
[CrossRef]

1994

1992

1991

H. Ma, A. S. L. Gomes, and C. B. de Araújo, Appl. Phys. Lett. 59, 2666 (1991).
[CrossRef]

1989

1986

N. J. Patronas, J. S. Cohen, R. H. Knop, A. J. Dwyer, D. Colcher, J. Lundy, F. Mornex, P. Hambright, M. Sohn, and C. E. Myers, Cancer Treat. Rep. 70, 391 (1986).
[PubMed]

Almarsson, Ö.

Ö. Almarsson and T. C. Bruice, J. Am. Chem. Soc. 117, 4533 (1995).
[CrossRef]

Aranda, F. J.

Bezerra, A. G.

A. G. Bezerra, I. E. Borissevitch, R. E. de Araujo, A. S. L. Gomes, and C. B. de Araújo, “Investigation of picosecond optical nonlinearity in porphyrin metal complexes derivatives,” Chem. Phys. Lett. (to be published).

Bloembergen, N.

N. Bloembergen, Nonlinear Optics (Benjamin, Reading, Mass., 1965).

Borissevitch, I. E.

A. G. Bezerra, I. E. Borissevitch, R. E. de Araujo, A. S. L. Gomes, and C. B. de Araújo, “Investigation of picosecond optical nonlinearity in porphyrin metal complexes derivatives,” Chem. Phys. Lett. (to be published).

Bruice, T. C.

Ö. Almarsson and T. C. Bruice, J. Am. Chem. Soc. 117, 4533 (1995).
[CrossRef]

Bucci, E.

Z. Gryczynski, R. Paolesse, K. M. Smith, and E. Bucci, Chem. Phys. Lett. 69, 71 (1997).

Byeon, C. C.

W. Sun, C. C. Byeon, C. M. Lawson, G. M. Gray, and D. Wang, Appl. Phys. Lett. 74, 3254 (1999).
[CrossRef]

Castilo, J.

Cohen, J. S.

N. J. Patronas, J. S. Cohen, R. H. Knop, A. J. Dwyer, D. Colcher, J. Lundy, F. Mornex, P. Hambright, M. Sohn, and C. E. Myers, Cancer Treat. Rep. 70, 391 (1986).
[PubMed]

Colcher, D.

N. J. Patronas, J. S. Cohen, R. H. Knop, A. J. Dwyer, D. Colcher, J. Lundy, F. Mornex, P. Hambright, M. Sohn, and C. E. Myers, Cancer Treat. Rep. 70, 391 (1986).
[PubMed]

de Araujo, R. E.

A. G. Bezerra, I. E. Borissevitch, R. E. de Araujo, A. S. L. Gomes, and C. B. de Araújo, “Investigation of picosecond optical nonlinearity in porphyrin metal complexes derivatives,” Chem. Phys. Lett. (to be published).

de Araújo, C. B.

D. V. Petrov, A. S. L. Gomes, and C. B. de Araújo, Appl. Phys. Lett. 65, 1067 (1994).
[CrossRef]

H. Ma, A. S. L. Gomes, and C. B. de Araújo, Appl. Phys. Lett. 59, 2666 (1991).
[CrossRef]

A. G. Bezerra, I. E. Borissevitch, R. E. de Araujo, A. S. L. Gomes, and C. B. de Araújo, “Investigation of picosecond optical nonlinearity in porphyrin metal complexes derivatives,” Chem. Phys. Lett. (to be published).

Dwyer, A. J.

N. J. Patronas, J. S. Cohen, R. H. Knop, A. J. Dwyer, D. Colcher, J. Lundy, F. Mornex, P. Hambright, M. Sohn, and C. E. Myers, Cancer Treat. Rep. 70, 391 (1986).
[PubMed]

Gomes, A. S. L.

D. V. Petrov, A. S. L. Gomes, and C. B. de Araújo, Appl. Phys. Lett. 65, 1067 (1994).
[CrossRef]

H. Ma, A. S. L. Gomes, and C. B. de Araújo, Appl. Phys. Lett. 59, 2666 (1991).
[CrossRef]

A. G. Bezerra, I. E. Borissevitch, R. E. de Araujo, A. S. L. Gomes, and C. B. de Araújo, “Investigation of picosecond optical nonlinearity in porphyrin metal complexes derivatives,” Chem. Phys. Lett. (to be published).

Gray, G. M.

W. Sun, C. C. Byeon, C. M. Lawson, G. M. Gray, and D. Wang, Appl. Phys. Lett. 74, 3254 (1999).
[CrossRef]

Gryczynski, Z.

Z. Gryczynski, R. Paolesse, K. M. Smith, and E. Bucci, Chem. Phys. Lett. 69, 71 (1997).

Guha, S.

Hagan, D. J.

Hambright, P.

N. J. Patronas, J. S. Cohen, R. H. Knop, A. J. Dwyer, D. Colcher, J. Lundy, F. Mornex, P. Hambright, M. Sohn, and C. E. Myers, Cancer Treat. Rep. 70, 391 (1986).
[PubMed]

Imasato, H.

V. E. Yushmanov, H. Imasato, T. T. Tominaga, and M. Tabak, Inorg. Biochem. 61, 233 (1996).
[CrossRef]

Kandasamy, K.

K. Kandasamy, P. N. Puntambekar, B. P. Singh, S. J. Shetty, and T. S. Srivastava, J. Nonlin. Opt. Phys. Mater. 6, 361 (1997).
[CrossRef]

Kang, K.

Knop, R. H.

N. J. Patronas, J. S. Cohen, R. H. Knop, A. J. Dwyer, D. Colcher, J. Lundy, F. Mornex, P. Hambright, M. Sohn, and C. E. Myers, Cancer Treat. Rep. 70, 391 (1986).
[PubMed]

Kozich, V. P.

Laghat, M.

S. R. Mishra, H. S. Rawat, and M. Laghat, Opt. Commun. 147, 328 (1998).
[CrossRef]

Lawson, C. M.

W. Sun, C. C. Byeon, C. M. Lawson, G. M. Gray, and D. Wang, Appl. Phys. Lett. 74, 3254 (1999).
[CrossRef]

Lundy, J.

N. J. Patronas, J. S. Cohen, R. H. Knop, A. J. Dwyer, D. Colcher, J. Lundy, F. Mornex, P. Hambright, M. Sohn, and C. E. Myers, Cancer Treat. Rep. 70, 391 (1986).
[PubMed]

Ma, H.

H. Ma, A. S. L. Gomes, and C. B. de Araújo, Appl. Phys. Lett. 59, 2666 (1991).
[CrossRef]

Marcano, A. O.

Mishra, S. R.

S. R. Mishra, H. S. Rawat, and M. Laghat, Opt. Commun. 147, 328 (1998).
[CrossRef]

Mornex, F.

N. J. Patronas, J. S. Cohen, R. H. Knop, A. J. Dwyer, D. Colcher, J. Lundy, F. Mornex, P. Hambright, M. Sohn, and C. E. Myers, Cancer Treat. Rep. 70, 391 (1986).
[PubMed]

Myers, C. E.

N. J. Patronas, J. S. Cohen, R. H. Knop, A. J. Dwyer, D. Colcher, J. Lundy, F. Mornex, P. Hambright, M. Sohn, and C. E. Myers, Cancer Treat. Rep. 70, 391 (1986).
[PubMed]

Paolesse, R.

Z. Gryczynski, R. Paolesse, K. M. Smith, and E. Bucci, Chem. Phys. Lett. 69, 71 (1997).

Patronas, N. J.

N. J. Patronas, J. S. Cohen, R. H. Knop, A. J. Dwyer, D. Colcher, J. Lundy, F. Mornex, P. Hambright, M. Sohn, and C. E. Myers, Cancer Treat. Rep. 70, 391 (1986).
[PubMed]

Petrov, D. V.

D. V. Petrov, A. S. L. Gomes, and C. B. de Araújo, Appl. Phys. Lett. 65, 1067 (1994).
[CrossRef]

Porter, P.

Prasad, P. N.

P. N. Prasad and D. J. Williams, Introduction to Nonlinear Optical Effects in Molecules and Polymers (Wiley, New York, 1991).

Puntambekar, P. N.

K. Kandasamy, P. N. Puntambekar, B. P. Singh, S. J. Shetty, and T. S. Srivastava, J. Nonlin. Opt. Phys. Mater. 6, 361 (1997).
[CrossRef]

Rao, D. V. G. L. N.

Rawat, H. S.

S. R. Mishra, H. S. Rawat, and M. Laghat, Opt. Commun. 147, 328 (1998).
[CrossRef]

Remy, D. E.

Roach, J. F.

Said, A. A.

Shantha, P. K.

P. K. Shantha and A. L. Verma, Inorg. Chem. 35, 2723 (1996).
[CrossRef]

Sheik-Bahae, M.

Shen, Y. R.

Y. R. Shen, The Principles of Nonlinear Optics (Wiley, New York, 1984).

Shetty, S. J.

K. Kandasamy, P. N. Puntambekar, B. P. Singh, S. J. Shetty, and T. S. Srivastava, J. Nonlin. Opt. Phys. Mater. 6, 361 (1997).
[CrossRef]

Singh, B. P.

K. Kandasamy, P. N. Puntambekar, B. P. Singh, S. J. Shetty, and T. S. Srivastava, J. Nonlin. Opt. Phys. Mater. 6, 361 (1997).
[CrossRef]

Smith, K. M.

Z. Gryczynski, R. Paolesse, K. M. Smith, and E. Bucci, Chem. Phys. Lett. 69, 71 (1997).

Sohn, M.

N. J. Patronas, J. S. Cohen, R. H. Knop, A. J. Dwyer, D. Colcher, J. Lundy, F. Mornex, P. Hambright, M. Sohn, and C. E. Myers, Cancer Treat. Rep. 70, 391 (1986).
[PubMed]

Srivastava, T. S.

K. Kandasamy, P. N. Puntambekar, B. P. Singh, S. J. Shetty, and T. S. Srivastava, J. Nonlin. Opt. Phys. Mater. 6, 361 (1997).
[CrossRef]

Sun, W.

W. Sun, C. C. Byeon, C. M. Lawson, G. M. Gray, and D. Wang, Appl. Phys. Lett. 74, 3254 (1999).
[CrossRef]

Tabak, M.

V. E. Yushmanov, H. Imasato, T. T. Tominaga, and M. Tabak, Inorg. Biochem. 61, 233 (1996).
[CrossRef]

Tominaga, T. T.

V. E. Yushmanov, H. Imasato, T. T. Tominaga, and M. Tabak, Inorg. Biochem. 61, 233 (1996).
[CrossRef]

Van Stryland, E. W.

Verma, A. L.

P. K. Shantha and A. L. Verma, Inorg. Chem. 35, 2723 (1996).
[CrossRef]

Wang, D.

W. Sun, C. C. Byeon, C. M. Lawson, G. M. Gray, and D. Wang, Appl. Phys. Lett. 74, 3254 (1999).
[CrossRef]

Wang, J.

Williams, D. J.

P. N. Prasad and D. J. Williams, Introduction to Nonlinear Optical Effects in Molecules and Polymers (Wiley, New York, 1991).

Xia, T.

Yushmanov, V. E.

V. E. Yushmanov, H. Imasato, T. T. Tominaga, and M. Tabak, Inorg. Biochem. 61, 233 (1996).
[CrossRef]

Appl. Phys. Lett.

W. Sun, C. C. Byeon, C. M. Lawson, G. M. Gray, and D. Wang, Appl. Phys. Lett. 74, 3254 (1999).
[CrossRef]

H. Ma, A. S. L. Gomes, and C. B. de Araújo, Appl. Phys. Lett. 59, 2666 (1991).
[CrossRef]

D. V. Petrov, A. S. L. Gomes, and C. B. de Araújo, Appl. Phys. Lett. 65, 1067 (1994).
[CrossRef]

Cancer Treat. Rep.

N. J. Patronas, J. S. Cohen, R. H. Knop, A. J. Dwyer, D. Colcher, J. Lundy, F. Mornex, P. Hambright, M. Sohn, and C. E. Myers, Cancer Treat. Rep. 70, 391 (1986).
[PubMed]

Chem. Phys. Lett.

Z. Gryczynski, R. Paolesse, K. M. Smith, and E. Bucci, Chem. Phys. Lett. 69, 71 (1997).

Inorg. Biochem.

V. E. Yushmanov, H. Imasato, T. T. Tominaga, and M. Tabak, Inorg. Biochem. 61, 233 (1996).
[CrossRef]

Inorg. Chem.

P. K. Shantha and A. L. Verma, Inorg. Chem. 35, 2723 (1996).
[CrossRef]

J. Am. Chem. Soc.

Ö. Almarsson and T. C. Bruice, J. Am. Chem. Soc. 117, 4533 (1995).
[CrossRef]

J. Nonlin. Opt. Phys. Mater.

K. Kandasamy, P. N. Puntambekar, B. P. Singh, S. J. Shetty, and T. S. Srivastava, J. Nonlin. Opt. Phys. Mater. 6, 361 (1997).
[CrossRef]

J. Opt. Soc. Am. B

Opt. Commun.

S. R. Mishra, H. S. Rawat, and M. Laghat, Opt. Commun. 147, 328 (1998).
[CrossRef]

Opt. Lett.

Other

P. N. Prasad and D. J. Williams, Introduction to Nonlinear Optical Effects in Molecules and Polymers (Wiley, New York, 1991).

D. Dolphin, ed., The Porphyrins (Academic, New York, 1978), Vol. I.

N. Bloembergen, Nonlinear Optics (Benjamin, Reading, Mass., 1965).

Y. R. Shen, The Principles of Nonlinear Optics (Wiley, New York, 1984).

A. G. Bezerra, I. E. Borissevitch, R. E. de Araujo, A. S. L. Gomes, and C. B. de Araújo, “Investigation of picosecond optical nonlinearity in porphyrin metal complexes derivatives,” Chem. Phys. Lett. (to be published).

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Figures (4)

Fig. 1
Fig. 1

Molecular structure of Fe(III)TMPyP.

Fig. 2
Fig. 2

(a) Linear absorption spectra of Fe(III)TMPyP for three pH values. (b) Ratio between the areas of the band centered at 400 nm to those centered at 422 nm from pH 2.0 to pH 10.0 and of peaks centered at 422 and 441 nm for pH from 7.6 to 12.2.

Fig. 3
Fig. 3

Integral of the EPR spectrum at 4 K of Fe(III)TMPyP for pH values from 2.0 to 12.2 and nonlinear transmittance ΔT from Z-scan measurements at room temperature for the same material.

Fig. 4
Fig. 4

Typical small-aperture Z-scan nonlinear transmittance curve for Fe(III)TMPyP.

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