Tuning two-photon photoluminescence of gold nanoparticle aggregates with DNA and its application as turn-on photoluminescence probe for DNA sequence detection.

Abstract

Plasmon coupling between noble metal nanoparticles has been known to dramatically enhance linear and nonlinear optical properties of nearby chromophores and metal nanoparticles themselves. The interparticle distance is expected to have significant influence on the coupling strength. Here we have prepared DNA tuned Au nanoparticle assemblies with well controlled separation distances from 2.0 to 12.2 nm to investigate plasmon coupling strength and particle size effects on two-photon photoluminescence (TPPL) enhancement. TPPL intensities of these DNA coupled nanoassemblies were found to increase rapidly as the separation distance decreases. The largest TPPL enhancement factors of 115 and 265 were achieved at the shortest available separation distance of 2.0 nm for 21 and 41 nm Au NPs-dsDNA assemblies, respectively. We have further utilized DNA induced coupling of Au NPs and TPPL enhancement to develop a two-photon sensing scheme for detection of DNA sequences. This TPPL based method displayed high sensitivity with a limit of detection of 2.9 pM and excellent selectivity against ssDNA with mismatched bases. A single mismatch can be easily differentiated at room temperature. Taking the unique advantages of two-photon excitation, this method could be potentially further extended to DNA detection inside cells or even in vivo. These findings can provide important insight for fundamental understanding of plasmon-coupling enhanced TPPL and development of various two-photon excitation based applications.