Plasmons in strongly coupled metallic nanostructures.

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.

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Present and Future of Surface-Enhanced Raman Scattering

Surface-enhanced Raman spectroscopy (SERS) inherits the rich chemical fingerprint information on Raman spectroscopy and gains sensitivity by plasmon-enhanced excitation and scattering. In particular, most Raman peaks have a narrow width suitable for multiplex analysis, and the measurements can be conveniently made under ambient and aqueous conditions. These merits make SERS a very promising technique for studying complex biological systems, and SERS has attracted increasing interest in biorelated analysis. However, there are still great challenges that need to be addressed until it can be widely accepted by the biorelated communities, answer interesting biological questions, and solve fatal clinical problems. SERS applications in bioanalysis involve the complex interactions of plasmonic nanomaterials with biological systems and their environments. The reliability becomes the key issue of bioanalytical SERS in order to extract meaningful information from SERS data. This review provides a comprehensive over...

Surface-Enhanced Raman Spectroscopy for Bioanalysis: Reliability and Challenges

https://web.uvic.ca/~agbrolo/ACA_GFS_MF_2011.pdf

A review on the fabrication of substrates for surface enhanced Raman spectroscopy and their applications in analytical chemistry.

Surface-enhanced Raman spectroscopy (SERS) combines molecular fingerprint specificity with potential single-molecule sensitivity. Therefore, the SERS technique is an attractive tool for sensing molecules in trace amounts within the field of chemical and biochemical analytics. Since SERS is an ongoing topic, which can be illustrated by the increased annual number of publications within the last few years, this review reflects the progress and trends in SERS research in approximately the last three years. The main reason why the SERS technique has not been established as a routine analytic technique, despite its high specificity and sensitivity, is due to the low reproducibility of the SERS signal. Thus, this review is dominated by the discussion of the various concepts for generating powerful, reproducible, SERS-active surfaces. Furthermore, the limit of sensitivity in SERS is introduced in the context of single-molecule spectroscopy and the calculation of the 'real' enhancement factor. In order to shed more light onto the underlying molecular processes of SERS, the theoretical description of SERS spectra is also a growing research field and will be summarized here. In addition, the recording of SERS spectra is affected by a number of parameters, such as laser power, integration time, and analyte concentration. To benefit from synergies, SERS is combined with other methods, such as scanning probe microscopy and microfluidics, which illustrates the broad applications of this powerful technique.

Surface-enhanced Raman spectroscopy (SERS): progress and trends

Defined nanoparticle cluster arrays (NCAs) with total lateral dimensions of up to 25.4 microm x 25.4 microm have been fabricated on top of a 10 nm thin gold film using template-guided self-assembly. This approach provides precise control of the structural parameters in the arrays, allowing a systematic variation of the average number of nanoparticles in the clusters (n) and the edge-to-edge separation (Lambda) between 1 < n < 20 and 50 nm < or = Lambda < or = 1000 nm, respectively. Investigations of the Rayleigh scattering spectra and surface-enhanced Raman scattering (SERS) signal intensities as a function of n and Lambda reveal direct near-field coupling between the particles within individual clusters, whose strength increases with the cluster size (n) until it saturates at around n = 4. Our analysis shows that strong near-field interactions between individual clusters significantly affect the SERS signal enhancement for edge-to-edge separations Lambda < 200 nm. The observed dependencies of the Raman signals on n and Lambda indicate that NCAs support a multiscale signal enhancement which originates from simultaneous inter- and intracluster coupling and |E|-field enhancement. The NCAs provide strong and reproducible SERS signals not only from small molecules but also from whole bacterial cells, which enabled a rapid spectral discrimination between three tested bacteria species: Escherichia coli, Bacillus cereus, and Staphylococcus aureus.

Engineered SERS substrates with multiscale signal enhancement: nanoparticle cluster arrays.

The accurate and reproducible control of intense electromagnetic fields localized on the nanoscale is essential for the engineering of optical sensors based on the surface-enhanced Raman scattering (SERS) effect. In this paper, using rigorous generalized Mie theory (GMT) calculations and a combined top-down/bottom-up nanofabrication approach, we design and experimentally demonstrate ∼10 8 spatially averaged, reproducible SERS enhancement in deterministic aperiodic arrays of Au nanoparticles with different length scales. Deterministic aperiodic arrays of 200 nm diameter nanocylinders are first fabricated using electron-beam lithography on quartz substrates, and smaller size (30 nm diameter) Au nanoparticles are subsequently positioned by in situ Au reduction at regions of maximum field enhancement. These multiscale structures, which we call “plasmonic nanogalaxies”, feature a cascade enhancement effect due to the strong electromagnetic interactions of small satellite nanoparticles with localized fields in aperiodic arrays of nanocylinders. The development of SERS substrates based on aperiodic arrays with different length scales provides a novel strategy to engineer plasmon-enhanced biosensors with chemical fingerprinting capability.

https://www.bio-page.org/boriskina/Boriskina_NanoLett2009.pdf

Plasmonic Nanogalaxies: Multiscale Aperiodic Arrays for Surface-Enhanced Raman Sensing

The dominant molecular species contributing to the surface-enhanced Raman spectroscopy (SERS) spectra of bacteria excited at 785 nm are the metabolites of purine degradation: adenine, hypoxanthine, xanthine, guanine, uric acid, and adenosine monophosphate. These molecules result from the starvation response of the bacterial cells in pure water washes following enrichment from nutrient-rich environments. Vibrational shifts due to isotopic labeling, bacterial SERS spectral fitting, SERS and mass spectrometry analysis of bacterial supernatant, SERS spectra of defined bacterial mutants, and the enzymatic substrate dependence of SERS spectra are used to identify these molecular components. The absence or presence of different degradation/salvage enzymes in the known purine metabolism pathways of these organisms plays a central role in determining the bacterial specificity of these purine-base SERS signatures. These results provide the biochemical basis for the development of SERS as a rapid bacterial diagnostic and illustrate how SERS can be applied more generally for metabolic profiling as a probe of cellular activity.

https://link.springer.com/content/pdf/10.1007%2Fs00216-016-9540-x.pdf

The biochemical origins of the surface-enhanced Raman spectra of bacteria: a metabolomics profiling by SERS

Background and Objective: We examine the use of Raman spectroscopy to analyze components in human urine. Study Design/Methods and Meterials: Targeted urine components include urea, uric acid, and creatinine. Results: Urea concentration in urine is sufficiently high that normal Raman spectroscopy may be used for its analysis. All other components are in low concentrations requiring the use of surface-enhanced Raman spectroscopic methods (SERS). Conclusion: Both normal Raman and SERS approaches have been investigated for total urine-nitrogen determination, urine urea-nitrogen determination, and for the urea/ creatinine excretion ratio.

Urine analysis by laser Raman spectroscopy

Noble metal nanoparticle cluster arrays (NCAs) are a novel class of engineered substrates for surface enhanced Raman spectroscopy (SERS), in which the noble metal nanoparticles interact on multiple length scales to create a multiscale E-field cascade enhancement. In this work the role of the building block for the NCA performance is quantified. Periodic NCAs with constant cluster diameter (D = 200 nm) but variable nanoparticle diameter (d) and intercluster separation (A) were assembled on glass and their optical response and SERS enhancement were systematically characterized as a function of D, A, and d. An increase of d from 40 to 80 nm and simultaneous decrease of A from 200 to 50 nm led to an improvement of the ensemble averaged SERS enhancement factor by a factor of up to ∼8. The coefficient of variation (c v ) ofthe enhancement factors (G) is significantly lower for the d = 80 nm NCAs than for the d = 40 nm and d = 60 nm NCAs. Optimized (D = 200 nm, A = 50 nm, d = 80 nm) NCAs show the overall highest signal reproducibility of all investigated NCAs and random nanoparticle substrates and achieve effective single cell detection sensitivity.

W. Ranjith Premasiri

Papers

Engineered SERS substrates with multiscale signal enhancement: nanoparticle cluster arrays.

Plasmonic Nanogalaxies: Multiscale Aperiodic Arrays for Surface-Enhanced Raman Sensing

The biochemical origins of the surface-enhanced Raman spectra of bacteria: a metabolomics profiling by SERS

Urine analysis by laser Raman spectroscopy

Engineering Nanoparticle Cluster Arrays for Bacterial Biosensing: The Role of the Building Block in Multiscale SERS Substrates