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Issue 7, 2016
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Plasmon-enhanced two-photon-induced isomerization for highly-localized light-based actuation of inorganic/organic interfaces

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Abstract

Two-photon initiated photo-isomerization of an azobenzene moiety adsorbed on silver nanoparticles (Ag NPs) is demonstrated. The azobenzene is linked to a materials-binding peptide that brings it into intimate contact with the Ag NP surface, producing a dramatic enhancement of its two-photon absorbance. An integrated modeling approach, combining advanced conformational sampling with Quantum Mechanics/Capacitance Molecular Mechanics and response theory, shows that charge transfer and image charges in the Ag NP generate local fields that enhance two-photon absorption of the cis isomer, but not the trans isomer, of adsorbed molecules. Moreover, dramatic local field enhancement is expected near the localized surface plasmon resonance (LSPR) wavelength, and the LSPR band of the Ag NPs overlaps the azobenzene absorbance that triggers cis to trans switching. As a result, the Ag NPs enable two-photon initiated cis to trans isomerization, but not trans to cis isomerization. Confocal anti-Stokes fluorescence imaging shows that this effect is not due to local heating, while the quadratic dependence of switching rate on laser intensity is consistent with a two-photon process. Highly localized two-photon initiated switching could allow local manipulation near the focal point of a laser within a 3D nanoparticle assembly, which cannot be achieved using linear optical processes.

Graphical abstract: Plasmon-enhanced two-photon-induced isomerization for highly-localized light-based actuation of inorganic/organic interfaces

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Publication details

The article was received on 11 Nov 2015, accepted on 18 Jan 2016 and first published on 19 Jan 2016


Article type: Paper
DOI: 10.1039/C5NR07973J
Author version available: Download Author version (PDF)
Citation: Nanoscale, 2016,8, 4194-4202
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    Plasmon-enhanced two-photon-induced isomerization for highly-localized light-based actuation of inorganic/organic interfaces

    C. Lim, X. Li, Y. Li, K. L. M. Drew, J. P. Palafox-Hernandez, Z. Tang, A. Baev, A. N. Kuzmin, M. R. Knecht, T. R. Walsh, M. T. Swihart, H. Ågren and P. N. Prasad, Nanoscale, 2016, 8, 4194
    DOI: 10.1039/C5NR07973J

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