Plasmonic coupling-based electromagnetic field localization and enhancement are becoming increasingly important in chemistry, nanoscience, materials science, physics, and engineering over the past decade, generating a number of new concepts and applications. Among the plasmonically coupled nanostructures, metal nanostructures with nanogaps have been of special interest due to their ultrastrong electromagnetic fields and controllable optical properties that can be useful for a variety of signal enhancements such as surface-enhanced Raman scattering (SERS). The Raman scattering process is highly inefficient, with a very small cross-section, and Raman signals are often poorly reproducible, meaning that very strong, controllable SERS is needed to obtain reliable Raman signals with metallic nanostructures and thus open up new avenues for a variety of Raman-based applications. More specifically, plasmonically coupled metallic nanostructures with ultrasmall (∼1 nm or smaller) nanogaps can generate very strong and tunable electromagnetic fields that can generate strong SERS signals from Raman dyes in the gap, and plasmonic nanogap-enhanced Raman scattering can be defined as Raman signal enhancement from plasmonic nanogap particles with ∼1 nm gaps. However, these promising nanostructures with extraordinarily strong optical signals have shown limited use for practical applications, largely due to the lack of design principles, high-yield synthetic strategies with nanometer-level structural control and reproducibility, and systematic, reliable single-molecule/single-particle-level studies on their optical properties. All these are extremely important challenges because even small changes (<1 nm) in the structure of the coupled plasmonic nanogaps can significantly affect the plasmon mode and signal intensity. In this Account, we examine and summarize recent breakthroughs and advances in plasmonic nanogap-enhanced Raman scattering with metal nanogap particles with respect to the design and synthesis of plasmonic nanogap structures, as well as ultrasensitive and quantitative Raman signal detection using these structures. The applications and prospects of plasmonic nanogap particle-based SERS are also discussed. In particular, reliable synthetic and measurement strategies for plasmonically coupled nanostructures with ∼1 nm gap, in which both the nanogap size and the position of a Raman-active molecule in the gap can be controlled with nanometer/sub-nanometer-level precision, can address important issues regarding the synthesis and optical properties of plasmonic nanostructures, including structural and signal reproducibility. Further, single-molecule/single-particle-level studies on the plasmonic properties of these nanogap structures revealed that these particles can generate ultrastrong, quantifiable Raman signals in a highly reproducible manner.
The design, synthesis and control of plasmonic nanostructures, especially with ultrasmall plasmonically coupled nanogap (∼1 nm or smaller), are of significant interest and importance in chemistry, nanoscience, materials science, optics and nanobiotechnology. Here, we studied and established the thiolated DNA-based synthetic principles and methods in forming and controlling Au core-nanogap-Au shell structures [Au-nanobridged nanogap particles (Au-NNPs)] with various interior nanogap and Au shell structures. We found that differences in the binding affinities and modes among four different bases to Au core, DNA sequence, DNA grafting density and chemical reagents alter Au shell growth mechanism and interior nanogap-forming process on thiolated DNA-modified Au core. Importantly, poly A or poly C sequence creates a wider interior nanogap with a smoother Au shell, while poly T sequence results in a narrower interstitial interior gap with rougher Au shell, and on the basis of the electromagnetic field calculation and experimental results, we unraveled the relationships between the width of the interior plasmonic nanogap, Au shell structure, electromagnetic field and surface-enhanced Raman scattering. These principles and findings shown in this paper offer the fundamental basis for the thiolated DNA-based chemistry in forming and controlling metal nanostructures with ∼1 nm plasmonic gap and insight in the optical properties of the plasmonic NNPs, and these plasmonic nanogap structures are useful as strong and controllable optical signal-generating nanoprobes.
The enantioselective recognition of 3,4-dihydroxyphenylalanine using penicillamine-modified gold nanoparticles has been investigated. Smaller gold nanoparticles with one enantiomeric ligand facilitate the redox reaction of only one enantiomer of 3,4-dihydroxyphenylalanine, with cross inversion for the gold nanoparticles with the other enantiomeric ligand.
Observation of individual single-nanoparticle reactions provides direct information and insight for many complex chemical, physical, and biological processes, but this is utterly challenging with conventional high-resolution imaging techniques on conventional platforms. Here, we developed a photostable plasmonic nanoparticle-modified supported lipid bilayer (PNP-SLB) platform that allows for massively parallel in situ analysis of the interactions between nanoparticles with single-particle resolution on a two-dimensional (2D) fluidic surface. Each particle-by-particle PNP clustering process was monitored in real time and quantified via analysis of individual particle diffusion trajectories and single-particle-level plasmonic coupling. Importantly, the PNP-SLB-based nanoparticle cluster growth kinetics result was fitted well. As an application example, we performed a DNA detection assay, and the result suggests that our approach has very promising sensitivity and dynamic range (high attomolar to high femtomolar) without optimization, as well as remarkable single-base mismatch discrimination capability. The method shown herein can be readily applied for many different types of intermolecular and interparticle interactions and provide convenient tools and new insights for studying dynamic interactions on a highly controllable and analytical platform.
We have developed a selective, sensitive, and re-usable electrochemical sensor for Hg2+ ion detection. This sensor is based on the Hg2+-induced conformational change of a single-stranded DNA (ssDNA) which involves an electroactive, ferrocene-labeled DNA hairpin structure and provides strategically the selective binding of a thymine-thymine mismatch for the Hg2+ ion. The ferrocene-labeled DNA is self-assembled through S-Au bonding on a polycrystalline gold electrode surface and the surface blocked with 3-mercapto-1-propanol to form a mixed monolayer. The modified electrode showed a voltammetric signal due to a one-step redox reaction of the surface-confined ferrocenyl moiety. The 'signal-on' upon mercury binding could be attributed to a change in the conformation of ferrocene-labeled DNA from an open structure to a restricted hairpin structure. The differential pulse voltammetry (DPV) of the modified electrode showed a linear response of the ferrocene oxidation signal with increase of Hg2+ concentration in the range between 0.1 and 2 microM with a detection limit of 0.1 microM. The molecular beacon mercury(II) ion sensor was amenable to regeneration by simply unfolding the ferrocene-labeled DNA in 10 microM cysteine, and could be regenerated with no loss in signal gain upon subsequent mercury(II) ion binding.
Plasmonic nanostructures are widely studied and used because of their useful size, shape, composition and assembled structure-based plasmonic properties. It is, however, highly challenging to precisely design, reproducibly synthesize and reliably utilize plasmonic nanostructures with enhanced optical properties. Here, we devise a facile synthetic method to generate Au surface roughness-controlled nanobridged nanogap particles (Au-RNNPs) with ultrasmall (≈1 nm) interior gap and tunable surface roughness in a highly controllable manner. Importantly, we found that particle surface roughness can be associated with and enhance the electromagnetic field inside the interior gap, and stronger nanogap-enhanced Raman scattering (NERS) signals can be generated from particles by increasing particle surface roughness. The finite-element method-based calculation results support and are matched well with the experimental results and suggest one needs to consider particle shape, nanogap and nanobridges simultaneously to understand and control the optical properties of this type of nanostructures. Finally, the potential of multiplexed Raman detection and imaging with RNNPs and the high-speed, high-resolution Raman bio-imaging of Au-RNNPs inside cells with a wide-field Raman imaging setup with liquid crystal tunable filter are demonstrated. Our results provide strategies and principles in designing and synthesizing plasmonically enhanced nanostructures and show potential for detecting and imaging Raman nanoprobes in a highly specific, sensitive and multiplexed manner.
We present a library of high-resolution (R ≡ λ/∆λ ∼ 45,000) and high signal-to-noise ratio (S/N ≥ 200) near-infrared spectra for stars of a wide range of spectral types and luminosity classes. The spectra were obtained with the Immersion GRating INfrared Spectrograph (IGRINS) covering the full range of the H (1.496-1.780 µm) and K (2.080-2.460 µm) atmospheric windows. The targets were primarily selected for being MK standard stars covering a wide range of effective temperatures and surface gravities with metallicities close to the Solar value. Currently, the library includes flux-calibrated and telluric-absorption-corrected spectra of 84 stars, with prospects for expansion to provide denser coverage of the parametric space. Throughout the H and K atmospheric windows, we 2 Park et al.identified spectral lines that are sensitive to T eff or log g and defined corresponding spectral indices.We also provide their equivalent widths. For those indices, we derive empirical relations between the measured equivalent widths and the stellar atmospheric parameters. Therefore, the derived empirical equations can be used to calculate T eff and log g of a star without requiring stellar atmospheric models.
We report a robust one-dimensional (1D) nanoparticle-assembly strategy that uses the self-assembly of nanoparticles with ligand and thermal controls, polyethylene glycol (PEG) with thiol and carboxyl groups, and nanoparticle oligomer and polymer codewetting process to form ultralong and continuous 1D nanochains. The 1D nanochains were assembled with closely packed 1D nanoparticle oligomer building blocks, elongated and buttressed by dynamic 1D PEG templates formed on a hydrophobic surface via anisotropic spinodal dewetting. Using this strategy, nanoparticle-packed 1D nanochains (∼1 nm interparticle spacing) were fabricated with ∼60 nm-width and a few to >10 μm-length (nearly 20 μm in some cases) from 20 nm gold nanoparticles. Our findings offer insights and open revenues for particle assembly processes and, as given by 'universality in colloid aggregation', should be readily applicable to various nanoparticles.
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