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

Optical chemical sensors have been the focus of much research attention in recent years because of their importance in industrial, environmental and biomedical applications [1]. This class of sensors combines chemical and biological recognition with advances in optoelectronic technologies. The application of solgel materials to these sensors, especially in the form of thin films, has attracted considerable interest due to the ease of fabrication and design flexibility of the process. The nature of the sol-gel process lends itself very well to the deposition of thin films using a variety of techniques such as dip-coating, spin-coating and spraying. In many sensor applications, the sol-gel film is used to provide a micro-porous support matrix in which analyte-sensitive molecules are entrapped and into which smaller analyte species may diffuse and interact [2,3]. Sol-gel films have many advantages as support matrices over polymer supports, including, for example, strong adhesion, good mechanical strength as well as excellent optical transparency. The versatility of the process facilitates tailoring of the physico-chemical film properties to optimize sensor performance. For example, films can be designed which have optimum porosity while minimizing leaching of the indicator molecules. In this chapter, the versatility of the sol-gel process with regard to the design of films for specific optical chemical sensor applications is highlighted.

Optical chemical sensors.

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.

Robotic systems are increasingly being utilized as fundamental data-gathering tools by scientists, allowing new perspectives and a greater understanding of the planet and its environmental processes. Today's robots are already exploring our deep oceans, tracking harmful algal blooms and pollution spread, monitoring climate variables, and even studying remote volcanoes. This article collates and discusses the significant advancements and applications of marine, terrestrial, and airborne robotic systems developed for environmental monitoring during the last two decades. Emerging research trends for achieving large-scale environmental monitoring are also reviewed, including cooperative robotic teams, robot and wireless sensor network (WSN) interaction, adaptive sampling and model-aided path planning. These trends offer efficient and precise measurement of environmental processes at unprecedented scales that will push the frontiers of robotic and natural sciences.

Robots for Environmental Monitoring: Significant Advancements and Applications

This review describes advances made toward the application of surface-enhanced Raman scattering (SERS) in sensitive analysis and diagnostics. In the early sections of this review we briefly introduce the fundamentals of SERS including a discussion of SERS at the single-molecule level. Applications relevant to trace analysis, environmental monitoring, and homeland security and defense, for example high explosives and contaminant detection, are emphasized. Because the key to wider application of SERS analysis lies in the development of highly enhancing substrates, in the second half of the review we focus our attention on the extensive progress made in designing innovative soluble, supported, and ordered SERS-active nano-architectures to harness the potential of this technique toward solving current and emerging analytical tasks. No attempt or claim is made to review the field exhaustively in its entirety nor to cover all applications, but only to describe several significant milestones and progress made in these important areas and to provide some perspective on where the field is quickly moving.

Progress in plasmonic engineering of surface-enhanced Raman-scattering substrates toward ultra-trace analysis.

. Marine environments are influenced by a wide diversity of anthropogenic and natural substances and organisms that may have adverse effects on human health and ecosystems. Real-time measurements of pollutants, toxins, and pathogens across a range of spatial scales are required to adequately monitor these hazards, manage the consequences, and to understand the processes governing their magnitude and distribution. Significant technological advancements have been made in recent years for the detection and analysis of such marine hazards. In particular, sensors deployed on a variety of mobile and fixed-point observing platforms provide a valuable means to assess hazards. In this review, we present state-of-the-art of sensor technology for the detection of harmful substances and organisms in the ocean. Sensors are classified by their adaptability to various platforms, addressing large, intermediate, or small areal scales. Current gaps and future demands are identified with an indication of the urgent need for new sensors to detect marine hazards at all scales in autonomous real-time mode. Progress in sensor technology is expected to depend on the development of small-scale sensor technologies with a high sensitivity and specificity towards target analytes or organisms. However, deployable systems must comply with platform requirements as these interconnect the three areal scales. Future developments will include the integration of existing methods into complex and operational sensing systems for a comprehensive strategy for long-term monitoring. The combination of sensor techniques on all scales will remain crucial for the demand of large spatial and temporal coverage.

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Detecting marine hazardous substances and organisms: sensors for pollutants, toxins, and pathogens

Detection of PAHs in seawater using surface-enhanced Raman scattering (SERS)

Preliminary investigation on the relationship of Raman spectra of sheep meat with shear force and cooking loss.

As a tool for the in situ characterization of meat quality, a hand-held Raman sensor head using an excitation wavelength of 671 nm was developed. A microsystem-based external cavity diode laser module was integrated into the sensor head and attached to a Raman probe, which is equipped with lens optics for excitation and signal collection as well as a Raman filter stage for Rayleigh rejection. The Raman signal was guided by an optical fiber to the detection unit, which was in the initial phase a laboratory spectrometer with a charge-coupled device (CCD) detector. The laser and the sensor head were characterized in terms of stability and performance for in situ Raman investigations. Raman spectra of meat were obtained with 35 mW within 5 seconds or less, ensuring short measuring times for the hand-held device. In a series of measurements with raw and packaged pork meat, the Raman sensor head was shown to detect microbial spoilage on the meat surface, even through the packaging foil.

A prototype hand-held Raman sensor for the in situ characterization of meat quality.

The development of surface-enhanced Raman scattering substrates suitable for in situ environmental analysis in sea-water is presented. Substrates consist of metal colloids encapsulated in a sol-gel-derived xerogel layer. Control of the gel parameters, such as porosity, pore size, and polarity, enables tailoring of sensitivity to different analyte groups. Gold and silver colloids were used along with tetraethoxysilane (TEOS) and methyltriethoxysilane (MTEOS) precursors. Substrates are characterised by measurement of optical spectra and use of scanning electron microscopy (SEM). Activity is discussed in terms of the choice of precursor and choice of metal colloid. Spectra were obtained for a range of substituted benzene derivatives with limits of detection (LODs) of 100 ppb and 10 ppb for chlorobenzene and phenylacetylene, respectively. Substrate selectivity is shown by the contrasting response of a single substrate type to similar molecules, in particular phenylacetylene and benzonitrile. Details of mechanical and chemical stability tests on the substrates are also included.

Use of sol-gel techniques in the development of surface-enhanced Raman scattering (SERS) substrates suitable for in situ detection of chemicals in sea-water

Heinar Schmidt

Papers

Detecting marine hazardous substances and organisms: sensors for pollutants, toxins, and pathogens

Detection of PAHs in seawater using surface-enhanced Raman scattering (SERS)

Preliminary investigation on the relationship of Raman spectra of sheep meat with shear force and cooking loss.

A prototype hand-held Raman sensor for the in situ characterization of meat quality.

Use of sol-gel techniques in the development of surface-enhanced Raman scattering (SERS) substrates suitable for in situ detection of chemicals in sea-water