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Nicco Corduri

Publications and source records attributed to Nicco Corduri.

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Sel-assembled Rhodium Nanoantennas for Single-Protein UV SERS

Surface-enhanced Raman scattering (SERS) provides critical insights into analyte structure, dynamic processes, and intermolecular interactions at the single-molecule level. By exploiting the hotspot formation in the vicinity of plasmonic structures, SERS constitutes an established tool for fundamental biological research, particularly for early-stage disease diagnostics. In this context, the DNA Origami technique, with its high addressability, enables both the assembly of plasmonic nanostructures with nanometric accuracy, and the deterministic placement of a single analyte molecule precisely at the generated hotspot within them. To date, most DNA Origami based nanoantennas rely on gold or silver nanoparticles (NPs), whose plasmonic resonances are confined to the visible spectrum, severely limiting their use in other spectral ranges. To extend the operating range, we have recently established a robust strategy for self-assembling programmable ultraviolet (UV)-plasmonic dimer antennas using rhodium nanocubes. Herein, we leverage this tailored architecture to systematically investigate its performance for single-molecule UV-SERS. We demonstrated how biofabricated Rh-dimers can be used to detect the characteristic SERS signal of a single streptavidin molecule linked at the dimer s gap. Our results are validated through polarization dependent measurements that yield the expected signal modulation depending on the the dimer orientation only for the DNA origami with a protein at the hotspot. This work establishes a highly sensitive and polarization-tunable UV-SERS platform, laying a solid foundation for label-free optical investigation and bio-spectroscopy of individual biomolecules in the UV spectral range.

physics.app-ph

DNA-Origami-Assembled Rhodium Nanoantennas for Deep-UV Label-Free Single-Protein Detection

Nanoparticles of plasmonic metals have significantly to the development of spectroscopic techniques, enabling strong confinement of electromagnetic fields at the nanoscale and corresponding signal amplification. However, to date, plasmonic applications have been limited mainly to the visible and near-infrared range, as materials supporting ultraviolet resonances typically exhibit poor chemical stability and lack robust surface functionalisation methods. In this work, we address these limitations by introducing a fully programmable approach to UV plasmonics based on rhodium nanocube dimers assembled using DNA origami templates. We have developed a reliable ligand exchange strategy that allows the functionalisation of rhodium nanocubes with DNA while maintaining their colloidal stability. These DNA-modified nanocubes act as modular building blocks that can be assembled into dimers with 69% efficiency and an average gap size of 10 nm. The DNA origami design also allows for the deterministic placement of a single streptavidin protein in the plasmonic gap, unlike previous methods based on stochastic diffusion. Experiments with single-molecule autofluorescence in UV, supported by numerical simulations, show an increase in brightness of up to 22, a reduction in fluorescence lifetime, and a more than tenfold increase in the total number of detected photons. By creating a robust and versatile platform for the production of UV-resonant plasmonic nanoantennas, this work extends the functionality of plasmonics to the deep UV spectrum and opens up new possibilities for labelling-free single-protein spectroscopy.

physics.optics

UV-SERS monitoring of plasmons photodegradation of biomolecules on Aluminum platforms decorated with Rhodium nanoparticles

In the search for novel nanostructured materials for UV plasmonics a limited number of choices can be done. Materials such as aluminum, rhodium, gallium and few others can be used. One of the most interesting application for UV plasmonics is Surface Enhanced Raman Spectroscopy. It can be extended to this spectral range to explore spectral properties of biomolecules that have only a small cross section in the visible spectral range. We have recently reported on a functional substrates based on nanoporous aluminum decorated with rhodium nanoparticles. This system showed an interesting behavior for UV excitation at 266 nm, with an unexpected decreasing Raman intensity for increasing rhodium nanoparticles concentrations. We proposed that this effect can be due to the difficult access to the hot spots for the molecules deposited via thermal evaporation. Here we extend this study exploring the performance of the system at another UV excitation wavelengths (325 nm) reporting on experimental results obtained using a deposition process that can bring the molecules at the hot-spots in a more efficient way. Extensive spectroscopic acquisitions, combined with 3D maps, allow to shade a more clear view on the performance of this plasmonic platform. In particular, the photodegration and the potential oxidation of biomolecules driven by the hot-electron/hot-holes produced by the rhodium nanoparticles will be reported.

physics.app-ph