4.8 Article

High-Density Plasmonic Nanopores for DNA Sensing at Ultra-Low Concentrations by Plasmon-Enhanced Raman Spectroscopy

Journal

ADVANCED FUNCTIONAL MATERIALS
Volume -, Issue -, Pages -

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/adfm.202301934

Keywords

DNA translocations; free-standing nanoassemblies; plasmonic hotspots; sensing at the single-molecule level; SERS in flow-through; solid-state nanopores

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Solid-state nanopores can sense biomolecules at the single-molecule level, but limitations and challenges exist in current electrical and optical sensing strategies. In contrast, plasmonic nanoassemblies that support high-density nanopores have shown promising results in capturing analytes and discriminating DNA sequences using surface-enhanced Raman scattering.
Solid-state nanopores are implemented in new and promising platforms that are capable of sensing fundamental biomolecular constituents at the single-molecule level. However, several limitations and drawbacks remain. For example, the current strategies based on both electrical and optical sensing suffer from low analyte capture rates and challenging nanofabrication procedures. In addition, their limited discrimination power hinders their application in the detection of complex molecular constructs. In contrast, Raman spectroscopy has recently demonstrated the ability to discriminate both nucleotides and amino acids. Herein, a plasmonic nanoassembly is proposed supporting nanopores at high density, in the order of 100 pores per mu m(2). These findings demonstrate that the device has a high capture rate in the range of a few fm. The pore size is approximate to 10 nm in diameter and provides an amplification of the electromagnetic field exceeding 10(3) in intensity at 785 nm. Owing to these features, single-molecule detection is achieved by means of surface-enhanced Raman scattering from a solution containing 50 fm DNA molecules (approximate to 4.4 kilobase pairs). Notably, the reported spectra show an average number of 2.5 Raman counts per nucleotide. From this perspective, this number is not far from what is necessary to discriminate the DNA sequence.

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