Plasmonic nanogap-enhanced Raman scattering using a resonant nanodome array

The optical properties and surface-enhanced Raman scattering (SERS) of plasmonic nanodome array (PNA) substrates in air and aqueous solution are investigated. PNA substrates are inexpensively and uniformly fabricated with a hot spot density of 6.25 × 10(6) mm(-2) using a large-area nanoreplica moulding technique on a flexible plastic substrate. Both experimental measurement and numerical simulation results show that PNAs exhibit a radiative localized surface plasmon resonance (LSPR) due to dipolar coupling between neighboring nanodomes and a non-radiative surface plasmon resonance (SPR) resulting from the periodic array structure. The high spatial localization of electromagnetic field within the ～10 nm nanogap together with the spectral alignment between the LSPR and excited and scattered light results in a reliable and reproducible spatially averaged SERS enhancement factor (EF) of 8.51 × 10(7) for Au-coated PNAs. The SERS enhancement is sufficient for a wide variety of biological and chemical sensing applications, including detection of common metabolites at physiologically relevant concentrations.     

Tailoring plasmonic nanostructures for optimal SERS sensing of small molecules and large microorganisms

Local electric fields can be tuned dramatically by varying the diameter of quasi-3D gold plasmonic nanostructure arrays, as indicated by 3D finite-difference time-domain calculations. Utilizing quasi-3D arrays that exhibit a maximum electric field intensity (i.e., a "hot" spot) either at the bottom (gold nanodisks) or on the top (gold film patterned with nanoholes), the optimal surface-enhanced Raman scattering (SERS) sensitivity for the detection of small molecules or large microorganisms can be achieved. The precisely fabricated and optimized SERS-active quasi-3D nanostructure arrays make it possible to quantitatively and reproducibly detect chemical and biological species using SERS, leading to a new sensing platform with molecular specificity based on SERS for many important applications.     

Surface-enhanced Raman scattering of crystal violets from periodic array of gold nanocylinders

The periodic arrays of gold nanocylinder with 121?nm in diameter, 6.3?nm in gap, and 34?nm in thickness are fabricated on glass by electron-beam lithography and lift-off techniques. Some crystal violet molecules are coated on the array by using the dipping and drawing method. In addition, the surface-enhanced Raman scattering (SERS) spectra of these samples with and without gold nanocylinder arrays are characterized specifically. The largest enhancement factor is obtained when the excitation wavelength corresponds to the peak wavelength of localized surface plasmon resonance (LSPR). The density functional theory and the finite-difference time-domain method are used for the calculations of the extinction spectrum of the arrays and Raman spectra of the crystal violet, respectively. These results unambiguously demonstrate that the periodic arrays of gold nanocylinder have good and effective surface-enhanced properties for Raman scattering of crystal violets, and they also show that the excitation wavelength corresponding to the peak one of the LSPR is one of the major reasons causing SERS.     

SERS detection of biomolecules using lithographed nanoparticles towards a reproducible SERS biosensor

In this paper we highlight the accurate spectral detection of bovine serum albumin and ribonuclease-A using a surface-enhanced Raman scattering (SERS) substrate based on gold nanocylinders obtained by electron-beam lithography (EBL). The nanocylinders have diameters from 100 to 180 nm with a gap of 200 nm. We demonstrate that optimizing the size and the shape of the lithographed gold nanocylinders, we can obtain SERS spectra of proteins at low concentration. This SERS study enabled us to estimate high enhancement factors (10(5) for BSA and 10(7) for RNase-A) of important bands in the protein Raman spectrum measured for 1 mM concentration. We demonstrate that, to reach the highest enhancement, it is necessary to optimize the SERS signal and that the main parameter of optimization is the LSPR position. The LSPR have to be suitably located between the laser excitation wavelength, which is 632.8 nm, and the position of the considered Raman band. Our study underlines the efficiency of gold nanocylinder arrays in the spectral detection of proteins.     

Composite‐Scattering Plasmonic Nanoprobes for Label‐Free,Quantitative Biomolecular Sensing

Biosensing based on localized surface plasmon resonance (LSPR) relies on concentrating light to a nanometeric spot and leads to a highly enhanced electromagnetic field near the metal nanostructure. Here, a design of plasmonic nanostructures based on rationally structured metal–dielectric combinations is presented, called composite scattering probes (CSPs), to generate an integrated multimodal biosensing platform featuring LSPR and surface‐enhanced Raman spectroscopy (SERS). Specifically, CSP configurations are proposed, which have several prominent resonance peaks enabling higher tunability and sensitivity for self‐referenced multiplexed analyte sensing. Using electron‐beam evaporation and thermal dewetting, large‐area, uniform, and tunable CSPs are fabricated, which are suitable for label‐free LSPR and SERS measurements. The CSP prototypes are used to demonstrate refractive index sensing and molecular analysis using albumin as a model analyte. By using partial least squares on recorded absorption profiles, differentiation of subtle changes in refractive index (as low as 0.001) in the CSP milieu is demonstrated. Additionally, CSPs facilitate complementary untargeted plasmon‐enhanced Raman measurements from the sample's compositional contributors. With further refinement, it is envisioned that the method may lead to a sensitive, versatile, and tunable platform for quantitative concentration determination and molecular fingerprinting, particularly where limited a priori information of the sample is available.     

Surface-enhanced Raman scattering on single-wall carbon nanotubes

Exploiting the effect of surface-enhanced Raman scattering (SERS), the Raman signal of single-wall carbon nanotubes (SWNTs) can be enhanced by up to 14 orders of magnitude when the tubes are in contact with silver or gold nanostructures and Raman scattering takes place predominantly in the enhanced local optical fields of the nanostructures. Such a level of enhancement offers exciting opportunities for ultrasensitive Raman studies on SWNTs and allows resonant and non-resonant Raman experiments to be done on single SWNTs at relatively high signal levels. Since the optical fields are highly localized within so-called "hot spots" on fractal silver colloidal clusters, lateral confinement of the Raman scattering can be as small as 5 nm, allowing spectroscopic selection of a single nanotube from a larger population. Moreover, since SWNTs are very stable "artificial molecules" with a high aspect ratio and a strong electron-phonon coupling, they are unique "test molecules" for investigating the SERS effect itself and for probing the "electromagnetic field contribution" and "charge transfer contribution" to the effect. SERS is also a powerful tool for monitoring the "chemical" interaction between the nanotube and the metal nanostructure.     

Active coherent control of nanoscale light confinement: Modulation of plasmonic modes and position of hotspots for surface-enhanced Raman scattering detection

Multistep plasmonic nanostructures can induce the deep modulation of electromagnetic-field interactions on the nanoscale for positioning hotspots, and this generation of enhanced fields is important in many optical applications. In this article, a new strategy is proposed for fabricating a plasmonic doublestacked nanocone (DSC) nanostructure. In the DSC structure, a tunable plasmonic hybrid mode proceeds from the strong coupling of the plasmonic resonance of a fundamental cavity mode with a localized surface plasmon gap mode. In the nanostructure, the far-field response is deeply modulated and the hottest spots can be effectively positioned on the top surface of the DSC nanostructure. A controllable and cost-effective mask-reconfiguration technique for manufacturing the multiscale nanostructure is developed, which guarantees the generation of the introduced crucial stage on the DSC nanostructure. To evaluate the features of the plasmonic resonance, the DSC nanostructure is used as a surface-enhanced Raman scattering (SERS) substrate for detecting 4-mercaptopyridine molecules under specific excitation conditions. Its good performance, with an average measured SERS enhancement factor as high as 10⁸, demonstrates its strong plasmonic-mode hybridization and extreme field enhancement.

Open image in new window

     

Multilayer enhanced gold film over nanostructure surface-enhanced Raman substrates

We have developed a novel class of gold multilayer, surface-enhanced Raman scattering (SERS) substrates that are capable of enhancing SERS signals by 15.3-fold over conventional gold film over nanostructure (GFON) SERS substrates, making them comparable in sensitivity to optimized silver film over nanostructure (SFON) substrates, while providing the long-term stability obtained from gold. They are fabricated by depositing 10 A thick silver oxide islands on conventional GFON substrates, followed by deposition of a second continuous gold layer. The silver oxide layer acts as a dielectric spacer between the two continuous gold films and produces significantly enhanced SERS signals, as compared to optimized single layer substrates of the same geometry or comparable substrates prepared by deposition of silver islands that are not oxidized. In addition to the enhanced sensitivity of these multilayer substrates, they also exhibit long SERS active shelf-lives (i.e., months), with no measurable degradation in SERS enhancement, and relative standard deviations in SERS enhancement of less than 5.2% across the substrate's surface.     

Diverse bio-sensing and therapeutic applications of plasmon enhanced nanostructures

Substantial advancements have been observed over the years in the research and development of Localized Surface Plasmon Resonance (LSPR). A variety of current and future applications involving anisotropic plasmonic nanoparticles include biosensors, photothermal therapies, photocatalysis, and various other fields. Amongst various other applications, plasmonic enhancements are deployed in Surface Enhanced Raman Spectroscopy (SERS) mediated bio-sensing, absorption spectroscopy based analyte quantification, and fluorescence spectroscopy-based biomolecular detection up to femtomolar level and even on the level of single molecules. LSPR based healthcare diagnostics and therapeutics have grown much faster than expected, with an increased number of published original research articles and reviews. Despite the extensive literature available, a comprehensive review with a focused emphasis on recent advances in the field of plasmonic particle anisotropy, plasmonic nanostructure, plasmonic coupling mediated enhanced LSPR intensity and their diverse applications in biosensing is needed. This article focuses on LSPR properties of anisotropic nanostructures like spherical gold nanoparticles (AuNP), gold nanorod (AuNR), gold nanostar (AuNs), gold nanorattles (AuNRT), gold nanoholes (AuNH), dimeric nanostructures and their role in plasmonic enhancements for targeted biosensing and therapeutic research. The contemporary state of the art biosensing development around SERS has also been discussed. A detailed literature analysis of recent development in micro-surgery, photothermal tumor killing, biosensor development for detection up to single molecule level, high-efficiency drug delivery are covered in this article. Furthermore, recent and advanced technologies including Spatially Offset Raman Spectroscopy (SORS), Surface Enhanced Resonance Raman Spectroscopy (SERRS), and Surface Enhanced Spatially Offset Raman Spectroscopy (SESORS) are presented citing their importance in biosensing. We complement this review article with relevant theoretical frameworks to understand finer nuances within the literature that is discussed.     

In situ growth of silver nanoparticles in porous membranes for surface-enhanced raman scattering

We demonstrate the in situ growth of silver nanoparticles in porous alumina membranes (PAMs) for use as a surface-enhanced Raman scattering (SERS) detection substrate. This fabrication method is simple, cost-effective, and fast, while providing control over the size of silver nanoparticles through the entire length of the cylindrical nanopores with uniform particle density inside the pores unachievable by the traditional infiltration technique. The in situ growth of silver nanoparticles was conducted from electroless-deposited nanoscale seeds on the interior of the PAM and resulted in the formation of numerous hot spots, which facilitated significantly higher SERS enhancement for these substrates compared with previously reported porous substrates.     

Precision Synthesis: Designing Hot Spots over Hot Spots via Selective Gold Deposition on Silver Octahedra Edges

A major challenge in plasmonic hot spot fabrication is to efficiently increase the hot spot volumes on single metal nanoparticles to generate stronger signals in plasmon‐enhanced applications. Here, the synthesis of designer nanoparticles, where plasmonic‐active Au nanodots are selectively deposited onto the edge/tip hot spot regions of Ag nanoparticles, is demonstrated using a two‐step seed‐mediated precision synthesis approach. Such a “hot spots over hot spots” strategy leads to an efficient enhancement of the plasmonic hot spot volumes on single Ag nanoparticles. Through cathodoluminescence hyperspectral imaging of these selective edge gold‐deposited Ag octahedron (SEGSO), the increase in the areas and emission intensities of hot spots on Ag octahedra are directly visualized after Au deposition. Single‐particle surface‐enhanced Raman scattering (SERS) measurements demonstrate 10‐fold and 3‐fold larger SERS enhancement factors of the SEGSO as compared to pure Ag octahedra and non‐selective gold‐deposited Ag octahedra (NSEGSO), respectively. The experimental results corroborate well with theoretical simulations, where the local electromagnetic field enhancement of our SEGSO particles is 15‐fold and 1.3‐fold stronger than pure Ag octahedra and facet‐deposited particles, respectively. The growth mechanisms of such designer nanoparticles are also discussed together with a demonstration of the versatility of this synthetic protocol.     

Robust SERS enhancement factor statistics using rotational correlation spectroscopy

We characterize the distribution of surface-enhanced Raman spectroscopy (SERS) enhancement factors observed in individual hot spots of single Ag "nanocapsules", encapsulated Ag nanoparticle dimers formed via controlled nanoparticle linking, polymer encapsulation, and small molecule infusion. The enhancement factors are calculated for over 1000 individual nanocapsules by comparing Raman scattering intensities of 4-mercaptobenzoic acid (MBA) measured from single SERS hot spots to intensities measured from high-concentration solutions of MBA. Correlation spectroscopy measurements of the rotational diffusion identify nanocapsules with signals dominated by single hot spots via their strong polarization response. Averaging over the entire surface of the nanocapsules, the distribution of enhancement factors is found to range from 10(6) to 10(8), with a mean of 6 × 10(6). Averaging only over nanoparticle junctions (where most SERS signals are expected) increases this average value to 10(8), with a range from 2 × 10(7) to 2 × 10(9). This significant statistical sampling shows that very high SERS enhancement factors can be obtained on a consistent basis using nanoparticle linking.     

Biological applications of localised surface plasmonic phenomenae

Researchers and industrialists have taken advantage of the unusual optical, magnetic, electronic, catalytic, and mechanical properties of nanomaterials. Nanoparticles and nanoscale materials have proven to be useful for biological uses. Nanoscale materials hold a particular interest to those in the biological sciences because they are on the same size scale as biological macromolecules, proteins and nucleic acids. The interactions between biomolecules and nanomaterials have formed the basis for a number of applications including detection, biosensing, cellular and in situ hybridisation labelling, cell tagging and sorting, point-of-care diagnostics, kinetic and binding studies, imaging enhancers, and even as potential therapeutic agents. Noble metal nanoparticles are especially interesting because of their unusual optical properties which arise from their ability to support surface plasmons. In this review the authors focus on biological applications and technologies that utilise two types of related plasmonic phenomonae: localised surface plasmon resonance (LSPR) spectroscopy and surface-enhanced Raman spectroscopy (SERS). The background necessary to understand the application of LSPR and SERS to biological problems is presented and illustrative examples of resonant Rayleigh scattering, refractive index sensing, and SERS-based detection and labelling are discussed.     

Distinct Rayleigh Scattering from Hot Spot Mutant p53 Proteins Reveals Cancer Cells

The scattering of light redirects and resonances when an electromagnetic wave interacts with electrons orbits in the hot spot core protein and oscillated electron of the gold nanoparticles (AuNP). This report demonstrates convincingly that resonant Rayleigh scattering generated from hot spot mutant p53 proteins is correspondence to cancer cells. Hot spot mutants have unique local electron density changes that affect specificity of DNA binding affinity compared with wild types. Rayleigh scattering changes introduced by hot‐spot mutations were monitored by localized surface plasmon resonance (LSPR) shift changes. The LSPR λ_max shift for hot‐spot mutants ranged from 1.7 to 4.2 nm for mouse samples and from 0.64 nm to 2.66 nm for human samples, compared to 9.6 nm and 15 nm for wild type and mouse and human proteins, respectively with a detection sensitivity of p53 concentration at 17.9 nM. It is interesting that hot‐spot mutants, which affect only interaction with DNA, launches affinitive changes as considerable as wild types. These changes propose that hot‐spot mutants p53 proteins can be easily detected by local electron density alterations that disturbs the specificity of DNA binding of p53 core domain on the surface of the DNA probed‐nanoplasmonic sensor.     

Correct Spectral Conversion between Surface‐Enhanced Raman and Plasmon Resonance Scattering from Nanoparticle Dimers for Single‐Molecule Detection

Simultaneous measurement of surface‐enhanced Raman scattering (SERS) and localized surface plasmon resonance (LSPR) in nanoparticle dimers presents outstanding opportunities in molecular identification and in the elucidation of physical properties, such as the size, distance, and deformation of target species. SERS–LSPR instrumentation exists and has been used under limited conditions, but the extraction of SERS and LSPR readouts from a single measurement is still a challenge. Herein, the extraction of LSPR spectra from SERS signals is reported and a tool for measuring the interparticle distance from Raman enhancement data by the standardization of the SERS signal is proposed. The SERS nanoruler mechanism incorporates two important aspects (the LSPR scattering peak shift and the Raman shift for measuring interparticle distance), and signifies their exact one‐to‐one correspondence after spectral correction. The developed methodology is applied to calculate the interparticle distance between nanoparticle dimers from SERS signals, to detect and quantify DNA at the single‐molecule level in a base‐pair‐specific manner. It is also shown that the SERS nanoruler concept can be used in structural analysis for the specific detection of the interaction of immunoglobulin G (IgG) with its target from bianalyte Raman signals with identical shaping at single‐molecule resolution. The SERS profile shaping approach not only offers a new detection mechanism for single molecules, but also has excellent potential for studying protein interactions and the intracellular detection of mRNA.     

自组装金纳米粒子及其SERS应用

利用柠檬酸钠还原法制备了粒径均匀的AuNPs,并成功实现了其在APTMS修饰的玻璃表面的自组装,得到表面增强拉曼(SERS)基底。以R6G为探针分子检验了SERS基底的活性,其具有较强的增强性能。探讨了不同粒径AuNPs对SERS基底性能的影响,结果表明SERS基底的增强因子随着粒径的增大而增强。这种自组装策略为低浓度有机污染物的探测提供了一种有效的方法。     

High tunability of the surface-enhanced Raman scattering response with a metal-multiferroic composite

We demonstrate active control of the plasmonic response from Au nanostructures by the use of a novel multiferroic substrate-LuFe(2)O(4) (LFO)-to tune the surface-enhanced Raman scattering (SERS) response in real time. From both experiments and numerical simulations based on the finite-difference time-domain method, a threshold field is observed, above which the optical response of the metal nanostructure can be strongly altered through changes in the dielectric properties of LFO. This offers the potential of optimizing the SERS detection sensitivity in real time as well as the unique functionality of detecting multiple species of Raman active molecules with the same template.     

Identification and characterization of artists' red dyes and their mixtures by surface-enhanced Raman spectroscopy

Silver film over nanospheres (AgFONs) were successfully employed as surface-enhanced Raman spectroscopy (SERS) substrates to characterize several artists' red dyes including: alizarin, purpurin, carminic acid, cochineal, and lac dye. Spectra were collected on sample volumes (1 x 10(-6) M or 15 ng/microL) similar to those that would be found in a museum setting and were found to be higher in resolution and consistency than those collected on silver island films (AgIFs). In fact, to the best of the authors' knowledge, this work presents the highest resolution spectrum of the artists' material cochineal to date. In order to determine an optimized SERS system for dye identification, experiments were conducted in which laser excitation wavelengths were matched with correlating AgFON localized surface plasmon resonance (LSPR) maxima. Enhancements of approximately two orders of magnitude were seen when resonance SERS conditions were met in comparison to non-resonance SERS conditions. Finally, because most samples collected in a museum contain multiple dyestuffs, AgFONs were employed to simultaneously identify individual dyes within several dye mixtures. These results indicate that AgFONs have great potential to be used to identify not only real artwork samples containing a single dye but also samples containing dyes mixtures.     

Multiple surface plasmon resonances and near-infrared field enhancement of gold nanowells

Arrays of Au nanowells (NWs) were fabricated by electron-beam lithography (EBL) and characterized by surface plasmon resonance (SPR) and surface-enhanced Raman scattering (SERS). It is revealed that these Au NW arrays exhibit multiple SP resonances that can be tuned by adjusting the geometrical characteristics of the NWs. SERS activity of Au NWs was confirmed for a range of excitation wavelengths and a number of model compounds including rhodamine 6G (R6G), phthalazine, and single-stranded oligonucleotides. According to numerical simulations based on the discrete dipole approximation (DDA), SERS enhancement originates from high electromagnetic fields (hot spots) localized both inside and outside individual NWs. In addition, far-field intercoupling effects between NWs have been observed experimentally in arrays with subwavelength pitch sizes. We show that the SERS enhancement factors can also be tuned and optimized by adjusting the geometry of NWs.     

Hierarchical silver nanodendrites: One-step preparation and application for SERS

Without using any other reducing reagents or templates, a one-step approach for synthesizing dendritic Ag nanostructure by the treatment of sliver ions only in the presence of silk fibroin biomacromolecule is described. The morphology and structure of as-prepared silver nanodendrite are characterized, and its application for surface-enhanced Raman scattering (SERS) is also investigated. It has been found that the morphology of as-prepared Ag dendrite is dependent on the reaction duration, but not the concentration of sliver ions in the reaction process. SERS study shows that the silver nanodendrites give an intensive and enhanced Raman scattering when pyridine is used as a probing molecule. It is suggested that silk fibroin provides dual reductant and structure-directing roles to promote sliver ions forming shape-controlled nanostructures in high yield.