Surface-enhanced Raman scattering (SERS) systems utilizing the interparticle nanogaps as hot spots have demonstrated ultrasensitive single-molecule detection with excellent selectivity yet the electric fields are too confined in the small nanogaps to enable reproducible biomolecule detections. Here, guided by finite-difference-time-domain simulation, we report hexagonal-packed silver-coated silicon nanowire (Ag/SiNW) arrays as a nanogap-free SERS system with wide-range electric fields and controlled interwire separation. Significantly, the system achieves a SERS detection of long double-strand DNA of 25-50 nm in length with a relative standard deviation (RSD) of 14% for measurements of above 4000 spots over an area of 200 × 200 μm(2). The high reproducibility in the SERS detection is attributed to (1) the large interwire spacing of 150 nm that allows access and excitation of large biomolecules; and (2) 600 nm wide-range electric field generated by propagating surface plasmons along the surface of continuous Ag coating on a SiNW. Moreover, a reproducible multiplex SERS measurement is also demonstrated with RSDs of 7-16% with an enhancement factor of ~10(6). The above results show that the ordered Ag/SiNW array system may serve as an excellent SERS platform for practical chemical and biological detection.
Surface-enhanced Raman spectroscopy (SERS) sensing of DNA bases by plasmonic nanopores could pave a way to novel methods for DNA analyses and new generation single-molecule sequencing platforms. The SERS discrimination of single DNA bases depends critically on the time that a DNA strand resides within the plasmonic hot spot. In fact, DNA molecules flow through the nanopores so rapidly that the SERS signals collected are not sufficient for single-molecule analysis. Here, we report an approach to control the residence time of molecules in the hot spot by an electro-plasmonic trapping effect. By directly adsorbing molecules onto a gold nanoparticle and then trapping the single nanoparticle in a plasmonic nanohole up to several minutes, we demonstrate single-molecule SERS detection of all four DNA bases as well as discrimination of single nucleobases in a single oligonucleotide. Our method can be extended easily to label-free sensing of single-molecule amino acids and proteins.
Near infrared light photodiodes have been attracting increasing research interest due to their wide application in various fields. In this study, the fabrication of a new n‐type GaAs nanocone (GaAsNCs) array/monolayer graphene (MLG) Schottky junction is reported for NIR light detection. The NIR photodetector (NIRPD) shows obvious rectifying behavior with a turn‐on voltage of 0.6 V. Further device analysis reveals that the photovoltaic NIRPDs are highly sensitive to 850 nm light illumination, with a fast response speed and good spectral selectivity at zero bias voltage. It is also revealed that the NIRPD is capable of monitoring high‐switching frequency optical signals (∼2000 Hz) with a high relative balance. Theoretical simulations based on finite difference time domain (FDTD) analysis finds that the high device performance is partially associated with the optical property, which can trap most incident photons in an efficient way. It is expected that such a self‐driven NIRPD will have potential application in future optoelectronic devices.
The SERS‐based detection of protein sequences with single‐residue sensitivity suffers from signal dominance of aromatic amino acid residues and backbones, impeding detection of non‐aromatic amino acid residues. Herein, we trap a gold nanoparticle in a plasmonic nanohole to generate a single SERS hot spot for single‐molecule detection of 2 similar polypeptides (vasopressin and oxytocin) and 10 distinct amino acids that constitute the 2 polypeptides. Significantly, both aromatic and non‐aromatic amino acids are detected and discriminated at the single‐molecule level either at individual amino acid molecules or within the polypeptide chains. Correlated with molecular dynamics simulations, our results suggest that the signal dominance due to large spatial occupancy of aromatic rings of the polypeptide sidechains on gold surfaces can be overcome by the high localization of the single hot spot. The superior spectral and spatial discriminative power of our approach can be applied to single‐protein analysis, fingerprinting, and sequencing.
Electroporation of in-vitro cultured cells is widely used in biological and medical areas to deliver molecules of interest inside cells. Since very high electric fields are required to electroporate the plasma membrane, depending on the geometry of the electrodes the required voltages can be very high and often critical to cell viability. Furthermore, in traditional electroporation configuration based on planar electrodes there is no a priori certain feedback about which cell has been targeted and delivered and the addition of fluorophores may be needed to gain this information. In this study we present a nanofabricated platform able to perform intracellular delivery of membrane-impermeable molecules by opening transient nanopores into the lipid membrane of adherent cells with high spatial precision and with the application of low voltages (1.5–2 V). This result is obtained by exploiting the tight seal that the cells present with 3D fluidic hollow gold-coated nanostructures that act as nanochannels and nanoelectrodes at the same time. The final soft-electroporation platform provides an accessible approach for controlled and selective drug delivery on ordered arrangements of cells.
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