Unmodified "GNP-oligonucleotide" nanobiohybrids: a simple route for emission enhancement of DNA intercalators

Abstract

We present herein a simple method for enhancing the emission of DNA intercalators in homogeneous nanobiohybrids of unlabeled oligonucleotides and unmodified gold nanoparticles (GNPs). Pristine single-stranded DNA (ss-DNA) has been wrapped around unmodified GNPs to induce metal-enhanced fluorescence (MEF) of DNA intercalators, such as ethidium bromide and propidium iodide. The thickness of the ss-DNA layer on the gold nanosurface determines the extent of MEF, since this depends on the position of the intercalator in relation to the metal surface. Presumably, at a suitable thickness of this DNA layer, more of the intercalator is localized at the optimum distance from the nanoparticle to give rise to MEF. Importantly, no external spacer or coating agent was needed to induce the MEF effect of the GNPs. The concentration ratios of Au to DNA in the nanohybrids, as well as the capping agents applied to the GNPs, play key roles in enhancing the emission of the intercalators. The dimensions of both components of the nanobiohybrids, that is, the size of the GNPs and the length of the oligonucleotide, have considerable influences on the emission enhancement of the intercalators. Emission intensity increased with increasing size of the GNPs and length of the oligonucleotide only when the DNA efficiently wrapped the nanoparticles. An almost 100 % increment in the quantum yield of ethidium bromide was achieved with the GNP–DNA nanobiohybrid compared with that with DNA alone (in the absence of GNP), and the fluorescence emission was enhanced by 50 % even at an oligonucleotide concentration of 2 nM. The plasmonic effect of the GNPs in the emission enhancement was also established by the use of similar nanobioconjugates of ss-DNA with nonmetallic carbon nanoparticles and TiO₂ nanoparticles, with which no increase in the fluorescence emission of ethidium bromide was observed.