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.

Surface-enhanced Raman spectroscopy: concepts and chemical applications.

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

Droplet microfluidics generates and manipulates discrete droplets through immiscible multiphase flows inside microchannels Due to its remarkable advantages, droplet microfluidics bears significant value in an extremely wide range of area In this review, we provide a comprehensive and in-depth insight into droplet microfluidics, covering fundamental research from microfluidic chip fabrication and droplet generation to the applications of droplets in bio(chemical) analysis and materials generation The purpose of this review is to convey the fundamentals of droplet microfluidics, a critical analysis on its current status and challenges, and opinions on its future development We believe this review will promote communications among biology, chemistry, physics, and materials science

Emerging Droplet Microfluidics

Microdroplets in microfluidics offer a great number of opportunities in chemical and biological research. They provide a compartment in which species or reactions can be isolated, they are monodisperse and therefore suitable for quantitative studies, they offer the possibility to work with extremely small volumes, single cells, or single molecules, and are suitable for high-throughput experiments. The aim of this Review is to show the importance of these features in enabling new experiments in biology and chemistry. The recent advances in device fabrication are highlighted as are the remaining technological challenges. Examples are presented to show how compartmentalization, monodispersity, single-molecule sensitivity, and high throughput have been exploited in experiments that would have been extremely difficult outside the microfluidics platform.

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Microdroplets in microfluidics: an evolving platform for discoveries in chemistry and biology

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

Raman spectroscopy is a valuable tool in various research fields. The technique yields structural information from all kind of samples often without the need for extensive sample preparation. Since the Raman signals are inherently weak and therefore do not allow one to investigate substances in low concentrations, one possible approach is surface-enhanced (resonance) Raman spectroscopy. Here, rough coin metal surfaces enhance the Raman signal by a factor of 10(4)-10(15), depending on the applied method. In this review we discuss recent developments in SERS spectroscopy and their impact on different research fields.

SERS: a versatile tool in chemical and biochemical diagnostics

The application of a liquid/liquid microsegmented flow for serial high-throughput microanalytical systems shows promising prospects for applications in clinical chemistry, pharmaceutical research, process diagnostics, and analytical chemistry. Microscopy and microspectral analytics offer powerful approaches for the analytical readout of droplet based assays. Within the generated segments, individuality and integrity are retained during the complete diagnostic process making the approach favored for analysis of individual microscaled objects like cells and microorganisms embedded in droplets. Here we report on the online application of surface-enhanced micro-Raman spectroscopy for the detection and quantization of analytes in a liquid/liquid segmented microfluidic system. Data acquisition was performed in microsegments down to a volume of 180 nl. With this approach, we overcome the well-known problem of adhesion of colloid/analyte conjugates to the optical windows of detection cuvettes, which causes the so-called "memory effect". The combination of the segmented microfluidic system with the highly sensitive SERS technique reaches in a reproducible quantification of analytes with the SERS technique.

A reproducible surface-enhanced raman spectroscopy approach. Online SERS measurements in a segmented microfluidic system.

The development of fast identification techniques of viruses is an ongoing important research topic. Conventional virus detection and identification is generally based on various different microbiological methods. However, these techniques are not suitable for the analysis of single virus particles. Therefore, our goal is to establish tip-enhanced Raman scattering (TERS), providing vibrational spectroscopic information with a spatial resolution less than 50 nm, to characterize single viruses at a molecular level. Here we report, to the best of our knowledge for the first time, about TERS spectra of a tobacco mosaic virus, showing the great capability of this technique. However, the application of the TERS technique for a rapid and direct detection of different species of single viruses is under development, which is useful for a wide range of analytical fields. Copyright © 2008 John Wiley & Sons, Ltd.

Raman to the limit: tip‐enhanced Raman spectroscopic investigations of a single tobacco mosaic virus

In order to detect biomolecules, different approaches using for instance biological, spectroscopic or imaging techniques are established. Due to the broad variety of these methods, this review is focused on surface enhanced Raman spectroscopy (SERS) as an analytical tool in biomolecule detection. Here, the molecular speci- ficity of Raman spectroscopy is combined with metallic nanoparticles as sensor platform, which enhances the sig- nal intensity by several orders of magnitude. Within this article, the characterization of diverse biomolecules by means of SERS is explained and moreover current applica- tion fields are presented. The SERS intensity and as a con- sequence thereof the reliable detection of the biomolecule of interest is effected by distance, orientation and affinity of the molecule towards the metal surface. Furthermore, the great capability of the SERS technique for cutting-edge applications like pathogen detection and cancer diagnosis is highlighted. We wish to motivate by this comprehensive and critical summary researchers from various scientific background to create their own ideas and schemes for a SERS-based detection and analysis of biomolecules.

Dana Cialla

Papers

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

SERS: a versatile tool in chemical and biochemical diagnostics

A reproducible surface-enhanced raman spectroscopy approach. Online SERS measurements in a segmented microfluidic system.

Raman to the limit: tip‐enhanced Raman spectroscopic investigations of a single tobacco mosaic virus

SERS-based detection of biomolecules