Abstract

We quantify and ascertain the nature of the second-harmonic generation (SHG) response of amphiphilic push–pull chromophores to a transmembrane electric field. Our technique is based on the application of an alternating field across labeled giant unilamelar vesicles. For chromophore responses that are purely electro-optic, our technique provides an estimate of photoinduced charge shifts based on the observed dispersion of the field response, in accord with a two-level perturbation theory. These results are applicable to the optimization of membrane potential sensors for SHG microscopy.

© 2003 Optical Society of America

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  1. L. Moreaux, O. Sandre, and J. Mertz, J. Opt. Soc. Am. B 17, 1685 (2000).
    [CrossRef]
  2. L. Moreaux, O. Sandre, S. Charpak, M. Blanchard-Desce, and J. Mertz, Biophys. J. 80, 1568 (2001).
    [CrossRef] [PubMed]
  3. O. Bouevitch, A. Lewis, I. Pinevsky, J. P. Wuskell, and L. Loew, Biophys. J. 65, 672 (1993).
    [CrossRef] [PubMed]
  4. P. J. Campagnola, M. D. Wei, A. Lewis, and L. M. Loew, Biophys. J. 77, 3341 (1999).
    [CrossRef] [PubMed]
  5. G. Peleg, A. Lewis, M. Linial, and L. M. Loew, Proc. Natl. Acad. Sci. USA 96, 6700 (1999).
    [CrossRef]
  6. A. Grinvald, R. D. Frostig, E. Lieke, and R. Hildesheim, Physiol. Rev. 68, 1285 (1988).
    [PubMed]
  7. L. M. Loew, G. W. Bonneville, and J. Surow, Biochemistry 17, 4065 (1978).
    [CrossRef] [PubMed]
  8. D. S. Chemla and J. Zyss, Nonlinear Optical Properties of Organic Molecules and Crystals (Academic, New York, 1984).
  9. V. Alain, M. Blanchard-Desce, I. Ledoux-Rak, and J. Zyss, Chem. Commun. 2000, 353.
  10. A. K. Kakkar, S. Yitzchaik, S. B. Roscoe, F. Kubota, D. S. Allan, T. J. Marks, W. Lei, and G. K. Wong, Langmuir 9, 388 (1993).
    [CrossRef]
  11. T. Wimmer, C. Fuchs, C. Kryschi, H.-D. Martin, and D. Schmid, J. Mol. Struct. 563–564, 457 (2001).
    [CrossRef]
  12. M. I. Angelova, S. Soleau, P. Meleard, J. F. Faucon, and P. Bothorel, Prog. Colloid. Polym. Sci. 89, 127 (1992).
    [CrossRef]
  13. D. Gross, L. M. Loew, and W. W. Webb, Biophys. J. 50, 339 (1986).
    [CrossRef] [PubMed]
  14. J. L. Oudar, J. Chem. Phys. 67, 446 (1977).
  15. B. J. Orr and J. F. Ward, Mol. Phys. 20, 513 (1971).
    [CrossRef]
  16. P. N. Butcher and D. Cotter, The Elements of Nonlinear Optics (Cambridge U. Press, Cambridge, 1990).

2001 (2)

L. Moreaux, O. Sandre, S. Charpak, M. Blanchard-Desce, and J. Mertz, Biophys. J. 80, 1568 (2001).
[CrossRef] [PubMed]

T. Wimmer, C. Fuchs, C. Kryschi, H.-D. Martin, and D. Schmid, J. Mol. Struct. 563–564, 457 (2001).
[CrossRef]

2000 (1)

1999 (2)

P. J. Campagnola, M. D. Wei, A. Lewis, and L. M. Loew, Biophys. J. 77, 3341 (1999).
[CrossRef] [PubMed]

G. Peleg, A. Lewis, M. Linial, and L. M. Loew, Proc. Natl. Acad. Sci. USA 96, 6700 (1999).
[CrossRef]

1993 (2)

A. K. Kakkar, S. Yitzchaik, S. B. Roscoe, F. Kubota, D. S. Allan, T. J. Marks, W. Lei, and G. K. Wong, Langmuir 9, 388 (1993).
[CrossRef]

O. Bouevitch, A. Lewis, I. Pinevsky, J. P. Wuskell, and L. Loew, Biophys. J. 65, 672 (1993).
[CrossRef] [PubMed]

1992 (1)

M. I. Angelova, S. Soleau, P. Meleard, J. F. Faucon, and P. Bothorel, Prog. Colloid. Polym. Sci. 89, 127 (1992).
[CrossRef]

1988 (1)

A. Grinvald, R. D. Frostig, E. Lieke, and R. Hildesheim, Physiol. Rev. 68, 1285 (1988).
[PubMed]

1986 (1)

D. Gross, L. M. Loew, and W. W. Webb, Biophys. J. 50, 339 (1986).
[CrossRef] [PubMed]

1978 (1)

L. M. Loew, G. W. Bonneville, and J. Surow, Biochemistry 17, 4065 (1978).
[CrossRef] [PubMed]

1977 (1)

J. L. Oudar, J. Chem. Phys. 67, 446 (1977).

1971 (1)

B. J. Orr and J. F. Ward, Mol. Phys. 20, 513 (1971).
[CrossRef]

Alain, V.

V. Alain, M. Blanchard-Desce, I. Ledoux-Rak, and J. Zyss, Chem. Commun. 2000, 353.

Allan, D. S.

A. K. Kakkar, S. Yitzchaik, S. B. Roscoe, F. Kubota, D. S. Allan, T. J. Marks, W. Lei, and G. K. Wong, Langmuir 9, 388 (1993).
[CrossRef]

Angelova, M. I.

M. I. Angelova, S. Soleau, P. Meleard, J. F. Faucon, and P. Bothorel, Prog. Colloid. Polym. Sci. 89, 127 (1992).
[CrossRef]

Blanchard-Desce, M.

L. Moreaux, O. Sandre, S. Charpak, M. Blanchard-Desce, and J. Mertz, Biophys. J. 80, 1568 (2001).
[CrossRef] [PubMed]

V. Alain, M. Blanchard-Desce, I. Ledoux-Rak, and J. Zyss, Chem. Commun. 2000, 353.

Bonneville, G. W.

L. M. Loew, G. W. Bonneville, and J. Surow, Biochemistry 17, 4065 (1978).
[CrossRef] [PubMed]

Bothorel, P.

M. I. Angelova, S. Soleau, P. Meleard, J. F. Faucon, and P. Bothorel, Prog. Colloid. Polym. Sci. 89, 127 (1992).
[CrossRef]

Bouevitch, O.

O. Bouevitch, A. Lewis, I. Pinevsky, J. P. Wuskell, and L. Loew, Biophys. J. 65, 672 (1993).
[CrossRef] [PubMed]

Butcher, P. N.

P. N. Butcher and D. Cotter, The Elements of Nonlinear Optics (Cambridge U. Press, Cambridge, 1990).

Campagnola, P. J.

P. J. Campagnola, M. D. Wei, A. Lewis, and L. M. Loew, Biophys. J. 77, 3341 (1999).
[CrossRef] [PubMed]

Charpak, S.

L. Moreaux, O. Sandre, S. Charpak, M. Blanchard-Desce, and J. Mertz, Biophys. J. 80, 1568 (2001).
[CrossRef] [PubMed]

Chemla, D. S.

D. S. Chemla and J. Zyss, Nonlinear Optical Properties of Organic Molecules and Crystals (Academic, New York, 1984).

Cotter, D.

P. N. Butcher and D. Cotter, The Elements of Nonlinear Optics (Cambridge U. Press, Cambridge, 1990).

Faucon, J. F.

M. I. Angelova, S. Soleau, P. Meleard, J. F. Faucon, and P. Bothorel, Prog. Colloid. Polym. Sci. 89, 127 (1992).
[CrossRef]

Frostig, R. D.

A. Grinvald, R. D. Frostig, E. Lieke, and R. Hildesheim, Physiol. Rev. 68, 1285 (1988).
[PubMed]

Fuchs, C.

T. Wimmer, C. Fuchs, C. Kryschi, H.-D. Martin, and D. Schmid, J. Mol. Struct. 563–564, 457 (2001).
[CrossRef]

Grinvald, A.

A. Grinvald, R. D. Frostig, E. Lieke, and R. Hildesheim, Physiol. Rev. 68, 1285 (1988).
[PubMed]

Gross, D.

D. Gross, L. M. Loew, and W. W. Webb, Biophys. J. 50, 339 (1986).
[CrossRef] [PubMed]

Hildesheim, R.

A. Grinvald, R. D. Frostig, E. Lieke, and R. Hildesheim, Physiol. Rev. 68, 1285 (1988).
[PubMed]

Kakkar, A. K.

A. K. Kakkar, S. Yitzchaik, S. B. Roscoe, F. Kubota, D. S. Allan, T. J. Marks, W. Lei, and G. K. Wong, Langmuir 9, 388 (1993).
[CrossRef]

Kryschi, C.

T. Wimmer, C. Fuchs, C. Kryschi, H.-D. Martin, and D. Schmid, J. Mol. Struct. 563–564, 457 (2001).
[CrossRef]

Kubota, F.

A. K. Kakkar, S. Yitzchaik, S. B. Roscoe, F. Kubota, D. S. Allan, T. J. Marks, W. Lei, and G. K. Wong, Langmuir 9, 388 (1993).
[CrossRef]

Ledoux-Rak, I.

V. Alain, M. Blanchard-Desce, I. Ledoux-Rak, and J. Zyss, Chem. Commun. 2000, 353.

Lei, W.

A. K. Kakkar, S. Yitzchaik, S. B. Roscoe, F. Kubota, D. S. Allan, T. J. Marks, W. Lei, and G. K. Wong, Langmuir 9, 388 (1993).
[CrossRef]

Lewis, A.

G. Peleg, A. Lewis, M. Linial, and L. M. Loew, Proc. Natl. Acad. Sci. USA 96, 6700 (1999).
[CrossRef]

P. J. Campagnola, M. D. Wei, A. Lewis, and L. M. Loew, Biophys. J. 77, 3341 (1999).
[CrossRef] [PubMed]

O. Bouevitch, A. Lewis, I. Pinevsky, J. P. Wuskell, and L. Loew, Biophys. J. 65, 672 (1993).
[CrossRef] [PubMed]

Lieke, E.

A. Grinvald, R. D. Frostig, E. Lieke, and R. Hildesheim, Physiol. Rev. 68, 1285 (1988).
[PubMed]

Linial, M.

G. Peleg, A. Lewis, M. Linial, and L. M. Loew, Proc. Natl. Acad. Sci. USA 96, 6700 (1999).
[CrossRef]

Loew, L.

O. Bouevitch, A. Lewis, I. Pinevsky, J. P. Wuskell, and L. Loew, Biophys. J. 65, 672 (1993).
[CrossRef] [PubMed]

Loew, L. M.

P. J. Campagnola, M. D. Wei, A. Lewis, and L. M. Loew, Biophys. J. 77, 3341 (1999).
[CrossRef] [PubMed]

G. Peleg, A. Lewis, M. Linial, and L. M. Loew, Proc. Natl. Acad. Sci. USA 96, 6700 (1999).
[CrossRef]

D. Gross, L. M. Loew, and W. W. Webb, Biophys. J. 50, 339 (1986).
[CrossRef] [PubMed]

L. M. Loew, G. W. Bonneville, and J. Surow, Biochemistry 17, 4065 (1978).
[CrossRef] [PubMed]

Marks, T. J.

A. K. Kakkar, S. Yitzchaik, S. B. Roscoe, F. Kubota, D. S. Allan, T. J. Marks, W. Lei, and G. K. Wong, Langmuir 9, 388 (1993).
[CrossRef]

Martin, H.-D.

T. Wimmer, C. Fuchs, C. Kryschi, H.-D. Martin, and D. Schmid, J. Mol. Struct. 563–564, 457 (2001).
[CrossRef]

Meleard, P.

M. I. Angelova, S. Soleau, P. Meleard, J. F. Faucon, and P. Bothorel, Prog. Colloid. Polym. Sci. 89, 127 (1992).
[CrossRef]

Mertz, J.

L. Moreaux, O. Sandre, S. Charpak, M. Blanchard-Desce, and J. Mertz, Biophys. J. 80, 1568 (2001).
[CrossRef] [PubMed]

L. Moreaux, O. Sandre, and J. Mertz, J. Opt. Soc. Am. B 17, 1685 (2000).
[CrossRef]

Moreaux, L.

L. Moreaux, O. Sandre, S. Charpak, M. Blanchard-Desce, and J. Mertz, Biophys. J. 80, 1568 (2001).
[CrossRef] [PubMed]

L. Moreaux, O. Sandre, and J. Mertz, J. Opt. Soc. Am. B 17, 1685 (2000).
[CrossRef]

Orr, B. J.

B. J. Orr and J. F. Ward, Mol. Phys. 20, 513 (1971).
[CrossRef]

Oudar, J. L.

J. L. Oudar, J. Chem. Phys. 67, 446 (1977).

Peleg, G.

G. Peleg, A. Lewis, M. Linial, and L. M. Loew, Proc. Natl. Acad. Sci. USA 96, 6700 (1999).
[CrossRef]

Pinevsky, I.

O. Bouevitch, A. Lewis, I. Pinevsky, J. P. Wuskell, and L. Loew, Biophys. J. 65, 672 (1993).
[CrossRef] [PubMed]

Roscoe, S. B.

A. K. Kakkar, S. Yitzchaik, S. B. Roscoe, F. Kubota, D. S. Allan, T. J. Marks, W. Lei, and G. K. Wong, Langmuir 9, 388 (1993).
[CrossRef]

Sandre, O.

L. Moreaux, O. Sandre, S. Charpak, M. Blanchard-Desce, and J. Mertz, Biophys. J. 80, 1568 (2001).
[CrossRef] [PubMed]

L. Moreaux, O. Sandre, and J. Mertz, J. Opt. Soc. Am. B 17, 1685 (2000).
[CrossRef]

Schmid, D.

T. Wimmer, C. Fuchs, C. Kryschi, H.-D. Martin, and D. Schmid, J. Mol. Struct. 563–564, 457 (2001).
[CrossRef]

Soleau, S.

M. I. Angelova, S. Soleau, P. Meleard, J. F. Faucon, and P. Bothorel, Prog. Colloid. Polym. Sci. 89, 127 (1992).
[CrossRef]

Surow, J.

L. M. Loew, G. W. Bonneville, and J. Surow, Biochemistry 17, 4065 (1978).
[CrossRef] [PubMed]

Ward, J. F.

B. J. Orr and J. F. Ward, Mol. Phys. 20, 513 (1971).
[CrossRef]

Webb, W. W.

D. Gross, L. M. Loew, and W. W. Webb, Biophys. J. 50, 339 (1986).
[CrossRef] [PubMed]

Wei, M. D.

P. J. Campagnola, M. D. Wei, A. Lewis, and L. M. Loew, Biophys. J. 77, 3341 (1999).
[CrossRef] [PubMed]

Wimmer, T.

T. Wimmer, C. Fuchs, C. Kryschi, H.-D. Martin, and D. Schmid, J. Mol. Struct. 563–564, 457 (2001).
[CrossRef]

Wong, G. K.

A. K. Kakkar, S. Yitzchaik, S. B. Roscoe, F. Kubota, D. S. Allan, T. J. Marks, W. Lei, and G. K. Wong, Langmuir 9, 388 (1993).
[CrossRef]

Wuskell, J. P.

O. Bouevitch, A. Lewis, I. Pinevsky, J. P. Wuskell, and L. Loew, Biophys. J. 65, 672 (1993).
[CrossRef] [PubMed]

Yitzchaik, S.

A. K. Kakkar, S. Yitzchaik, S. B. Roscoe, F. Kubota, D. S. Allan, T. J. Marks, W. Lei, and G. K. Wong, Langmuir 9, 388 (1993).
[CrossRef]

Zyss, J.

D. S. Chemla and J. Zyss, Nonlinear Optical Properties of Organic Molecules and Crystals (Academic, New York, 1984).

V. Alain, M. Blanchard-Desce, I. Ledoux-Rak, and J. Zyss, Chem. Commun. 2000, 353.

Biochemistry (1)

L. M. Loew, G. W. Bonneville, and J. Surow, Biochemistry 17, 4065 (1978).
[CrossRef] [PubMed]

Biophys. J. (4)

L. Moreaux, O. Sandre, S. Charpak, M. Blanchard-Desce, and J. Mertz, Biophys. J. 80, 1568 (2001).
[CrossRef] [PubMed]

O. Bouevitch, A. Lewis, I. Pinevsky, J. P. Wuskell, and L. Loew, Biophys. J. 65, 672 (1993).
[CrossRef] [PubMed]

P. J. Campagnola, M. D. Wei, A. Lewis, and L. M. Loew, Biophys. J. 77, 3341 (1999).
[CrossRef] [PubMed]

D. Gross, L. M. Loew, and W. W. Webb, Biophys. J. 50, 339 (1986).
[CrossRef] [PubMed]

Chem. Commun. (1)

V. Alain, M. Blanchard-Desce, I. Ledoux-Rak, and J. Zyss, Chem. Commun. 2000, 353.

J. Chem. Phys. (1)

J. L. Oudar, J. Chem. Phys. 67, 446 (1977).

J. Mol. Struct. (1)

T. Wimmer, C. Fuchs, C. Kryschi, H.-D. Martin, and D. Schmid, J. Mol. Struct. 563–564, 457 (2001).
[CrossRef]

J. Opt. Soc. Am. B (1)

Langmuir (1)

A. K. Kakkar, S. Yitzchaik, S. B. Roscoe, F. Kubota, D. S. Allan, T. J. Marks, W. Lei, and G. K. Wong, Langmuir 9, 388 (1993).
[CrossRef]

Mol. Phys. (1)

B. J. Orr and J. F. Ward, Mol. Phys. 20, 513 (1971).
[CrossRef]

Physiol. Rev. (1)

A. Grinvald, R. D. Frostig, E. Lieke, and R. Hildesheim, Physiol. Rev. 68, 1285 (1988).
[PubMed]

Proc. Natl. Acad. Sci. USA (1)

G. Peleg, A. Lewis, M. Linial, and L. M. Loew, Proc. Natl. Acad. Sci. USA 96, 6700 (1999).
[CrossRef]

Prog. Colloid. Polym. Sci. (1)

M. I. Angelova, S. Soleau, P. Meleard, J. F. Faucon, and P. Bothorel, Prog. Colloid. Polym. Sci. 89, 127 (1992).
[CrossRef]

Other (2)

P. N. Butcher and D. Cotter, The Elements of Nonlinear Optics (Cambridge U. Press, Cambridge, 1990).

D. S. Chemla and J. Zyss, Nonlinear Optical Properties of Organic Molecules and Crystals (Academic, New York, 1984).

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Figures (2)

Fig. 1
Fig. 1

(a) SHG image of a GUV labeled with molecule A when an excitation laser is polarized along the horizontal axis (laser power, 1 mW at the sample). A section of a GUV membrane labeled with molecule B (b) without and (c) with the application of a 250-mV transmembrane potential that alternates in sign every other image line (excitation, 945 nm) is shown. The laser polarization is horizontal, and the pixel acquisition time is 7 µs. The SHG signal intensity along the entire GUV equator is taken from a de-interlaced image where the transmembrane field is directed out of the vesicle for 0<ϕ<180° and into the vesicle for 180°<ϕ<360°. The resultant electro-optic modulation in SHG is 22%.

Fig. 2
Fig. 2

Measured relative electro-optic SHG sensitivity (points) of molecules A and B as a function of excitation laser wavelength for a 100-mV transmembrane potential and (solid curves) corresponding fits based on expression (4). The wavelength range spans minimum sensitivity for A and maximum sensitivity for B, which are expected to occur near 2λeg±Δλeg, respectively, where Δλeg is the full width of the two-level transition.

Equations (4)

Equations on this page are rendered with MathJax. Learn more.

SHGϕ=SHGmaxsin3 ϕ+3ϑ cos2 ϕ sin ϕ2.
β2μeg2ΔμDω,
γ2μeg2DωΔμ2ω˜eg-2ω-4Δμ2-μeg2ω˜eg,
κ2ΔμRe1ω˜eg-2ω+4ωeg1-μeg2Δμ2.

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