Nanogap-engineerable Raman-active nanodumbbells for single-molecule detection
TL;DR: Atomic-force-microscope-correlated nano-Raman measurements of individual dumbbell structures demonstrate that Raman signals can be repeatedly detected from single-DNA-tethered nanodumbbells and open avenues for the high-yield synthesis of optically active smart nanoparticles and structurally reproducible nanostructure-based single-molecule detection and bioassays.
Abstract: Surface-enhanced Raman scattering (SERS)-based signal amplification and detection methods using plasmonic nanostructures have been widely investigated for imaging and sensing applications. However, SERS-based molecule detection strategies have not been practically useful because there is no straightforward method to synthesize and characterize highly sensitive SERS-active nanostructures with sufficiently high yield and efficiency, which results in an extremely low cross-section area in Raman sensing. Here, we report a high-yield synthetic method for SERS-active gold-silver core-shell nanodumbbells, where the gap between two nanoparticles and the Raman-dye position and environment can be engineered on the nanoscale. Atomic-force-microscope-correlated nano-Raman measurements of individual dumbbell structures demonstrate that Raman signals can be repeatedly detected from single-DNA-tethered nanodumbbells. These programmed nanostructure fabrication and single-DNA detection strategies open avenues for the high-yield synthesis of optically active smart nanoparticles and structurally reproducible nanostructure-based single-molecule detection and bioassays.
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TL;DR: The use of nanosphere lithography for the fabrication of highly reproducible and robust SERS substrates is described and progress in applying SERS to the detection of chemical warfare agents and several biological molecules is described.
Abstract: The ability to control the size, shape, and material of a surface has reinvigorated the field of surface-enhanced Raman spectroscopy (SERS). Because excitation of the localized surface plasmon resonance of a nanostructured surface or nanoparticle lies at the heart of SERS, the ability to reliably control the surface characteristics has taken SERS from an interesting surface phenomenon to a rapidly developing analytical tool. This article first explains many fundamental features of SERS and then describes the use of nanosphere lithography for the fabrication of highly reproducible and robust SERS substrates. In particular, we review metal film over nanosphere surfaces as excellent candidates for several experiments that were once impossible with more primitive SERS substrates (e.g., metal island films). The article also describes progress in applying SERS to the detection of chemical warfare agents and several biological molecules.
2,986 citations
TL;DR: Chemical applications of SERS cover a broad range of topics such as catalysis and spectroelectrochemistry, single-molecule detection, and (bio)analytical chemistry.
Abstract: Surface-enhanced Raman scattering (SERS) has become a mature vibrational spectroscopic technique during the last decades and the number of applications in the chemical, material, and in particular life sciences is rapidly increasing. This Review explains the basic theory of SERS in a brief tutorial and-based on original results from recent research-summarizes fundamental aspects necessary for understanding SERS and provides examples for the preparation of plasmonic nanostructures for SERS. Chemical applications of SERS are the centerpiece of this Review. They cover a broad range of topics such as catalysis and spectroelectrochemistry, single-molecule detection, and (bio)analytical chemistry.
1,817 citations
Donostia International Physics Center1, Rovira i Virgili University2, MacDiarmid Institute for Advanced Materials and Nanotechnology3, Victoria University of Wellington4, University of Cambridge5, University of California, Santa Barbara6, Queen's University Belfast7, Technical University of Denmark8, University of Victoria9, Chung-Ang University10, University of Jena11, Leibniz Institute of Photonic Technology12, Rutgers University13, University of Strathclyde14, University of Liverpool15, University of Iowa16, University of Minnesota17, Heidelberg University18, National Institute of Advanced Industrial Science and Technology19, Chalmers University of Technology20, Humboldt University of Berlin21, University of Michigan22, Jiangnan University23, Stanford University24, Xiamen University25, Ludwig Maximilian University of Munich26, Hokkaido University27, Seoul National University28, University of Illinois at Urbana–Champaign29, Kwansei Gakuin University30, University of Vigo31, Free University of Berlin32, Northwestern University33, University of Duisburg-Essen34, National Research Council35, Indian Institute of Science Education and Research, Thiruvananthapuram36, Duke University37, Northeastern University (China)38, Temple University39, Wuhan University40, Japan Advanced Institute of Science and Technology41, Jilin University42, Ikerbasque43
TL;DR: Prominent authors from all over the world joined efforts to summarize the current state-of-the-art in understanding and using SERS, as well as to propose what can be expected in the near future, in terms of research, applications, and technological development.
Abstract: The discovery of the enhancement of Raman scattering by molecules adsorbed on nanostructured metal surfaces is a landmark in the history of spectroscopic and analytical techniques. Significant experimental and theoretical effort has been directed toward understanding the surface-enhanced Raman scattering (SERS) effect and demonstrating its potential in various types of ultrasensitive sensing applications in a wide variety of fields. In the 45 years since its discovery, SERS has blossomed into a rich area of research and technology, but additional efforts are still needed before it can be routinely used analytically and in commercial products. In this Review, prominent authors from around the world joined together to summarize the state of the art in understanding and using SERS and to predict what can be expected in the near future in terms of research, applications, and technological development. This Review is dedicated to SERS pioneer and our coauthor, the late Prof. Richard Van Duyne, whom we lost during the preparation of this article.
1,768 citations
1,477 citations
TL;DR: The nanocomposite nature of the extracellular matrix is reviewed, the design considerations for different tissues are described, and the impact of nanostructures on the properties of scaffolds and their uses in monitoring the behaviour of engineered tissues are discussed.
Abstract: Tissue engineering aims at developing functional substitutes for damaged tissues and organs. Before transplantation, cells are generally seeded on biomaterial scaffolds that recapitulate the extracellular matrix and provide cells with information that is important for tissue development. Here we review the nanocomposite nature of the extracellular matrix, describe the design considerations for different tissues and discuss the impact of nanostructures on the properties of scaffolds and their uses in monitoring the behaviour of engineered tissues. We also examine the different nanodevices used to trigger certain processes for tissue development, and offer our view on the principal challenges and prospects of applying nanotechnology in tissue engineering.
1,272 citations
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TL;DR: In this article, surface-enhanced Raman scattering was used to detect single molecules and single nanoparticles at room temperature with the use of surface enhanced Raman, and the intrinsic Raman enhancement factors were on the order of 10 14 to 10 15, much larger than the ensemble-averaged values derived from conventional measurements.
Abstract: Optical detection and spectroscopy of single molecules and single nanoparticles have been achieved at room temperature with the use of surface-enhanced Raman scattering. Individual silver colloidal nanoparticles were screened from a large heterogeneous population for special size-dependent properties and were then used to amplify the spectroscopic signatures of adsorbed molecules. For single rhodamine 6G molecules adsorbed on the selected nanoparticles, the intrinsic Raman enhancement factors were on the order of 10 14 to 10 15 , much larger than the ensemble-averaged values derived from conventional measurements. This enormous enhancement leads to vibrational Raman signals that are more intense and more stable than single-molecule fluorescence.
9,609 citations
TL;DR: In this article, the first observation of single molecule Raman scattering was made using a single crystal violet molecule in aqueous colloidal silver solution using one second collection time and about $2.
Abstract: By exploiting the extremely large effective cross sections ( ${10}^{\ensuremath{-}17}--{10}^{\ensuremath{-}16}{\mathrm{cm}}^{2}/\mathrm{molecule}$) available from surface-enhanced Raman scattering (SERS), we achieved the first observation of single molecule Raman scattering. Measured spectra of a single crystal violet molecule in aqueous colloidal silver solution using one second collection time and about $2\ifmmode\times\else\texttimes\fi{}{10}^{5}\mathrm{W}/{\mathrm{cm}}^{2}$ nonresonant near-infrared excitation show a clear ``fingerprint'' of its Raman features between 700 and $1700{\mathrm{cm}}^{\ensuremath{-}1}$. Spectra observed in a time sequence for an average of 0.6 dye molecule in the probed volume exhibited the expected Poisson distribution for actually measuring 0, 1, 2, or 3 molecules.
6,454 citations
TL;DR: A method for assembling colloidal gold nanoparticles rationally and reversibly into macroscopic aggregates by using the specificity of DNA interactions to direct the interactions between particles of different size and composition is described.
Abstract: COLLOIDAL particles of metals and semiconductors have potentially useful optical, optoelectronic and material properties1–4 that derive from their small (nanoscopic) size. These properties might lead to applications including chemical sensors, spectro-scopic enhancers, quantum dot and nanostructure fabrication, and microimaging methods2–4. A great deal of control can now be exercised over the chemical composition, size and polydis-persity1,2 of colloidal particles, and many methods have been developed for assembling them into useful aggregates and materials. Here we describe a method for assembling colloidal gold nanoparticles rationally and reversibly into macroscopic aggregates. The method involves attaching to the surfaces of two batches of 13-nm gold particles non-complementary DNA oligo-nucleotides capped with thiol groups, which bind to gold. When we add to the solution an oligonucleotide duplex with 'sticky ends' that are complementary to the two grafted sequences, the nanoparticles self-assemble into aggregates. This assembly process can be reversed by thermal denaturation. This strategy should now make it possible to tailor the optical, electronic and structural properties of the colloidal aggregates by using the specificity of DNA interactions to direct the interactions between particles of different size and composition.
6,188 citations
TL;DR: A strategy for the synthesis of 'nanocrystal molecules', in which discrete numbers of gold nanocrystals are organized into spatially defined structures based on Watson-Crick base-pairing interactions is described.
Abstract: PATTERNING matter on the nanometre scale is an important objective of current materials chemistry and physics. It is driven by both the need to further miniaturize electronic components and the fact that at the nanometre scale, materials properties are strongly size-dependent and thus can be tuned sensitively1. In nanoscale crystals, quantum size effects and the large number of surface atoms influence the, chemical, electronic, magnetic and optical behaviour2—4. 'Top-down' (for example, lithographic) methods for nanoscale manipulation reach only to the upper end of the nanometre regime5; but whereas 'bottom-up' wet chemical techniques allow for the preparation of mono-disperse, defect-free crystallites just 1–10 nm in size6–10, ways to control the structure of nanocrystal assemblies are scarce. Here we describe a strategy for the synthesis of'nanocrystal molecules', in which discrete numbers of gold nanocrystals are organized into spatially defined structures based on Watson-Crick base-pairing interactions. We attach single-stranded DNA oligonucleotides of defined length and sequence to individual nanocrystals, and these assemble into dimers and trimers on addition of a complementary single-stranded DNA template. We anticipate that this approach should allow the construction of more complex two-and three-dimensional assemblies.
2,864 citations
TL;DR: In this article, the authors present an in-depth study of surface enhanced Raman scattering (SERS) enhancement factors and cross-sections, including several issues often overlooked, and demonstrate that SERS EFs as low as 107, as opposed to the figure of 1014 often claimed in the literature, are sufficient for SERS applications.
Abstract: This paper presents an in-depth study of Surface Enhanced Raman Scattering (SERS) enhancement factors (EFs) and cross-sections, including several issues often overlooked. In particular, various possible rigorous definitions of the SERS EFs are introduced and discussed in the context of SERS applications, such as analytical chemistry and single molecule SERS. These definitions highlight the importance of a careful characterization of the non-SERS cross-sections of the probes under consideration. This aspect is illustrated by experimental results for the non-SERS cross-sections of representative SERS probes along with average SERS EFs for the same probes. In addition, the accurate experimental determination of single molecule enhancement factors is tackled with two recently developed techniques, namely: bi-analyte SERS (BiASERS) and temperature-dependent SERS vibrational pumping. We demonstrate that SERS EFs as low as 107, as opposed to the figure of 1014 often claimed in the literature, are sufficient for...
2,298 citations