Molecularly-mediated assemblies of plasmonic nanoparticles for Surface-Enhanced Raman Spectroscopy applications (original) (raw)
Related papers
Journal of the American Chemical Society, 2009
Small particles on the nanometer scale are of considerable current interest in chemistry, biology, and medicine due to their size-dependent electronic and optical properties and also their dimensional similarities with biomacromolecules (e.g., proteins and nucleic acids). 1 Colloidal gold nanocrystals are considered to be "plasmonic nanoruler" because they contain free electrons that can be collectively and resonantly excited at optical frequencies, leading to large enhancement of the electromagnetic field near the particle surface. 2 Recent work has shown that nanoscale junctions or nanogaps between two or more particles are associated with plasmonic "hot spots", 3-5 and that surface-enhanced Raman scattering (SERS) increases by two orders of magnitude when the gap distance is reduced from 35 nm to 10 nm. 6 Plasmonic nanoparticles have also find uses in super-resolution optical imaging 7,8 and tip-enhanced Raman scattering (TERS), 9 and sequence-specific DNA detection. 10,11
Controlled assembly of plasmonic colloidal nanoparticle clusters
Nanoscale, 2011
Coupling of localized surface plasmon resonances results in singular effects at the void space between noble metal nanoparticles. However, implementation of practical applications based on plasmon coupling calls for the high yield production of metal nanoparticle clusters (dimers, trimers, tetramers,.) with small gaps. Therefore, controlled assembly using colloid chemistry methods is an emerging and promising field. We present a brief overview over the controlled assembly of plasmonic nanoparticle clusters by colloid chemistry methods, together with a description of their plasmonic properties and some applications, with an emphasis in sensing through surface-enhanced Raman scattering spectroscopy for bio-detection purposes. We point out the important role of separation methods to obtain colloidal clusters in high yield. A special encouragement to explore assembly of anisotropic building blocks is pursued.
RSC Advances, 2019
This report describes the systematic combination of structurally diverse plasmonic metal nanoparticles (AgNPs, AuNPs, Ag core-Au shell NPs, and anisotropic AuNPs) on flexible paper-based materials to induce signal-enhancing environments for surface enhanced Raman spectroscopy (SERS) applications. The anisotropic AuNP-modified paper exhibits the highest SERS response due to the surface area and the nature of the broad surface plasmon resonance (SPR) neighboring the Raman excitation wavelength. The subsequent addition of a second layer with these four NPs (e.g., sandwich arrangement) leads to the notable increase of the SERS signals by inducing a high probability of electromagnetic field environments associated with the interparticle SPR coupling and hot spots. After examining sixteen total combinations, the highest SERS response is obtained from the second layer with AgNPs on the anisotropic AuNP paper substrate, which allows for a higher calibration sensitivity and wider dynamic range than those of typical AuNP-AuNP arrangement. The variation of the SERS signals is also found to be below 20% based on multiple measurements (both intra-sample and inter-sample). Furthermore, the degree of SERS signal reductions for the sandwiched analytes is notably slow, indicating their increased long-term stability. The optimized combination is then employed in the detection of let-7f microRNA to demonstrate their practicability as SERS substrates. Precisely introducing interparticle coupling and hot spots with readily available plasmonic NPs still allows for the design of inexpensive and practical signal enhancing substrates that are capable of increasing the calibration sensitivity, extending the dynamic range, and lowering the detection limit of various organic and biological molecules.
2012
The understanding of the relationship between plasmonic and surface-enhanced Raman scattering (SERS) properties of dynamic nanoparticle assemblies is of paramount importance for the optimal design of related plasmonic nanostructures, especially for SERS applications. In this regard, recent studies have provided new important insights for well-ordered nanoparticle assemblies but little is known about the relationship between the physical and optical properties for large ensembles of randomly aggregated metal nanoparticles in suspension, which still represents the simplest and most common route to obtain highly effective SERS substrates. Here we exploit the triplex-assembling ability of DNA-conjugated silver nanoparticles to engineer interparticle junctions with controlled interparticle distance and tune the aggregation rate to allow accurate investigation into the correlation between the averaged time-dependent plasmonic and SERS responses within a complex ensemble of nanoparticles in suspension. Solution-based single particle tracking was used to characterize the heterogeneity of the nanoparticle assembly with statistical reliability, acting as a key tool to unravel the connection between these two bulk responses. To achieve this, we report the first example of the parallel hybridization of dye-labeled locked nucleic acid (LNA) silver nanoparticle probes to double stranded DNA bridges of different lengths to form a triplex assembly, that provides SERS enhancements directly related to the interparticle distance imposed by the high structural rigidity of the double stranded linker. This is also a crucial step towards utilising SERS for the study of DNA in its natural double stranded state and, ultimately, to obtain nanoscale distance-dependent information in challenging biological environments using specially designed nanoparticles. 141 552 0876; Tel: +44 141 548 4701 † Electronic supplementary information (ESI) available: Triplex-to-duplex melting transitions of oligo-modified NPs for target dsDNA of different lengths and duplex-to-single stranded transition of dsDNA. Detailed description of the subtraction procedure for triplex-assembled NP extinction spectra. Scanning electron microscope (SEM) study of the NP assembly. See
Nanostructure-based plasmon-enhanced Raman spectroscopy for surface analysis of materials
Since 2000, there has been an explosion of activity in the field of plasmon-enhanced Raman spectroscopy (PERS), including surface-enhanced Raman spectroscopy (SERS), tip-enhanced Raman spectroscopy (TERS) and shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). In this Review, we explore the mechanism of PERS and discuss PERS hotspots — nanoscale regions with a strongly enhanced local electromagnetic field — that allow trace-molecule detection, biomolecule analysis and surface characterization of various materials. In particular, we discuss a new generation of hotspots that are generated from hybrid structures combining PERS-active nanostructures and probe materials, which feature a strong local electromagnetic field on the surface of the probe material. Enhancement of surface Raman signals up to five orders of magnitude can be obtained from materials that are weakly SERS active or SERS inactive. We provide a detailed overview of future research directions in the field of PERS, focusing on new PERS-active nanomaterials and nanostructures and the broad application prospect for materials science and technology.
Applied Spectroscopy, 2019
Plasmonic nanoassemblies with amplified optical responses are attractive as chemo/bio sensors and diagnostic tracking agents. For real-life implementation, such nanostructures require a well-designed and controlled formation for maximizing the optical amplification. Forming these nanoassemblies typically requires numerous steps; however, the importance of the sequence of the steps is typically not discussed. Thus, here we have investigated the role of the sequence of tagging (or labeling, barcoding) of such plasmonic nanoassemblies with Raman active molecules in a quest to maximize the surface-enhanced Raman scattering (SERS) enhancement that could be achieved from the nanoassemblies. We have chosen the core-satellite nanoassembly arrangement to study the role of tagging sequence because it allows us to keep structural parameters constant that would otherwise influence the SERS amplification. We demonstrate that incorporating the tag molecule at an assembly point before formation of...