In this work, we report the interaction
of a fluorescent ZnO–Au
nanocomposite with deoxyribonucleic acid (DNA), leading to AT-specific
DNA interaction, which is hitherto not known. For this study, three
natural double-stranded (ds) DNAs having different AT:GC compositions
were chosen and a ZnO–Au nanocomposite has been synthesized
by anchoring a glutathione-protected gold nanocluster on the surface
of egg-shell-membrane (ESM)-based ZnO nanoparticles. The ESM-based
bare ZnO nanoparticles did not show any selective interaction toward
DNA, whereas intrinsic fluorescence of the ZnO–Au nanocomposite
shows an appreciable blue shift (Δλmax = 18
nm) in the luminescence wavelength of 520 nm in the presence of ds
calf thymus (CT) DNA over other studied DNAs. In addition, the interaction
of the nanocomposite through fluorescence studies with single-stranded
(ss) CT DNA, synthetic polynucleotides, and nucleobases/nucleotides
(adenine, thymine, deoxythymidine monophosphate, deoxyadenosine monophosphate)
was also undertaken to delineate the specificity in interaction. A
minor blue shift (Δλmax = 5 nm) in the emission
wavelength at 520 nm was observed for single-stranded CT DNA, suggesting
the proficiency of the nanocomposite for discriminating ss and ds
CT DNA. More importantly, fluorescence signals from the nano-bio-interaction
could be measured directly without any modification of the target,
which is the foremost advantage emanated from this study compared
with other previous reports. The AT base-pair-induced enhancement
was also found to be highest for the melting temperature of CT DNA
(ΔTmCT = 6.7 °C). Furthermore,
spectropolarimetric experiments followed by calorimetric analysis
provided evidence for specificity in AT-rich DNA interaction. This
study would lead to establish the fluorescent ZnO–Au nanocomposite
as a probe for nanomaterial-based DNA-binding study, featuring its
specific interaction toward AT-rich DNA.