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With the continuous development in nanoscience and nanotechnology, analytical techniques like surface-enhanced Raman spectroscopy (SERS) render structural and chemical information of a variety of analyte molecules in ultra-low concentration. Although this technique is making significant progress in various fields, the reproducibility of SERS measurements and sensitivity towards small molecules are still daunting challenges. In this regard, microfluidic surface-enhanced Raman spectroscopy (MF-SERS) is well on its way to join the toolbox of analytical chemists. This review article explains how MF-SERS is becoming a powerful tool in analytical chemistry. We critically present the developments in SERS substrates for microfluidic devices and how these substrates in microfluidic channels can improve the SERS sensitivity, reproducibility, and detection limit. We then introduce the building materials for microfluidic platforms and their types such as droplet, centrifugal, and digital microfluidics. Finally, we enumerate some challenges and future directions in microfluidic SERS. Overall, this article showcases the potential and versatility of microfluidic SERS in overcoming the inherent issues in the SERS technique and also discusses the advantage of adding SERS to the arsenal of microfluidics. [ABSTRACT FROM AUTHOR]

In this feature article, we discuss in detail developmental bottleneck issues in Raman spectroscopy in its early stages and surface-enhanced Raman spectroscopy (SERS) in the past four decades. We divide SERS research into two different directions with different targets. Fundamental research is extending the limits of SERS to single-molecule, sub-nanometer resolution and femtosecond processes. In contrast, practical research is expanding the range of applications with the aim of providing versatile analytical tools for surface, materials, life, environmental, forensic and food sciences and also commercial instruments for use in daily life. In the second direction there have continually been many complex bottlenecks to be overcome. We attempt to enumerate the key issues in detail and also describe the achievements made to overcome the bottlenecks. In the last, but not least important part, we discuss the remaining bottlenecks and possible strategies for overcoming them to enable SERS to be an even more powerful and versatile technique. [ABSTRACT FROM AUTHOR]

Surface-enhanced Raman spectroscopy (SERS) can provide a fingerprint of molecules with ultrahigh sensitivity, down to the single-molecule level. However, accurate quantitative detection in practical samples using SERS is still a great challenge. Herein, a highly uniform shell-isolated Ag@SiO2 nanoparticle (Ag SHIN) monolayer film was prepared and employed as a substrate for the quantitative determination of melamine in milk samples through shell-isolated nanoparticle-enhanced Raman spectroscopy. The Ag SHIN film exhibits excellent reproducibility, high stability, as well as ultrahigh sensitivity with a limit of detection of 0.03 ppm. A linear relationship between the Raman intensity and the melamine concentration in a wide range (1 ppb to 5 ppm) was obtained. These results demonstrate that the Ag SHIN monolayer film is a promising and reliable substrate for the quantitative SERS analysis of practical samples. Copyright © 2017 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Electrochemical surface-enhanced Raman spectroscopy has been used to characterize adsorbed species widely but rarely to reaction intermediates on electrodes. In previous studies, the observed surface-enhanced Raman spectroscopy signals were proposed from benzyl species due to the electrochemical reduction of benzyl chloride on silver electrode surfaces. In this work, we reinvestigated the vibrational assignments of benzyl chloride and benzyl radical as the reaction intermediate. On the basis of density functional theory calculations and normal mode analysis, our systematic results provide more reasonable new assignments for both surface species. Further, we investigated adsorption configurations, binding energies, and vibrational frequency shifts of benzyl radical interacting with silver. Our calculated results show that the wagging vibration displays significant vibrational frequency shift, strong coupling with some intramolecular modes in the phenyl ring, and significant changes in intensity of Raman signals. The study also provides absolute Raman intensity in benzyl halides and discusses the enhancement effect mainly due to the binding interaction with respect to free benzyl radical. Copyright © 2016 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

By simply spinning Au nanoparticles on the surface of graphene/GaAs heterojunction, a stable solar cell with a power conversion efficiency (PCE) of 16.2% is achieved. The surface plasmon resonance of Au nanoparticles enhances the electromagnetic field near the graphene/GaAs junction area, which significantly improves the short current value and PCE. [ABSTRACT FROM AUTHOR]

Potential dependent adsorption of target molecules on electrode surface has long been analyzed by several analytical techniques at the electrochemical interfaces. Here, the adsorption of thiocyanate (SCN−) on gold electrodes [Au (111) and Au (poly)] is investigated by electrochemical shell isolated nanoparticle-enhanced Raman spectroscopy (EC-SHINERS) and surface-enhanced Raman spectroscopy. Based on the experimental observation, C − N stretching mode of N-bound SCN− can be observed around 2080 cm−1 throughout the whole potential range. The band corresponding to νC−N of S-bound SCN− appears as a shoulder at more negative potentials, and as a well-defined band are more positive potentials. However, the overlapped bands provoke a negative shift in the frequency of S-bound thiocyanate. Therefore, a change in the calculated Stark slope is observed. Interestingly, SHINERS has been employed to demonstrate the thiocyanate orientation and its effect on Raman spectra. Our results widen the opportunities of SHINERS to unravel the potential-dependent adsorption behavior of target molecules on single-crystal electrode surfaces. Copyright © 2016 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

For the first time, we used the electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy (EC-SHINERS) technique to in situ characterize the adsorption behaviour of four DNA bases (adenine, guanine, thymine, and cytosine) on atomically flat Au(111) electrode surfaces. The spectroscopic results of the various molecules reveal similar features, such as the adsorption-induced reconstruction of the Au(111) surface and the drastic Raman intensity reduction of the ring breathing modes after the lifting reconstruction. As a preliminary study of the photo-induced charge transfer (PICT) mechanism, the in situ spectroscopic results obtained on single crystal surfaces are excellently illustrated with electrochemical data. [ABSTRACT FROM AUTHOR]

Silver nanoparticles (Ag NPs) enjoy a reputation as an ultrasensitive substrate for surface-enhanced Raman spectroscopy (SERS). However, large-scale synthesis of Ag NPs in a controlled manner is a challenging task for a long period of time. Here, we reported a simple seed-mediated method to synthesize Ag NPs with controllable sizes from 50 to 300 nm, which were characterized by scanning electron microscopy (SEM) and UV-Vis spectroscopy. SERS spectra of Rhodamine 6G (R6G) from the as-prepared Ag NPs substrates indicate that the enhancement capability of Ag NPs varies with different excitation wavelengths. The Ag NPs with average sizes of ~150, ~175, and ~225 nm show the highest SERS activities for 532, 633, and 785-nm excitation, respectively. Significantly, 150-nm Ag NPs exhibit an enhancement factor exceeding 108 for pyridine (Py) molecules in electrochemical SERS (EC-SERS) measurements. Furthermore, finite-difference time-domain (FDTD) calculation is employed to explain the size-dependent SERS activity. Finally, the potential of the as-prepared SERS substrates is demonstrated with the detection of malachite green. Copyright © 2016 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) as a new member of Raman technique garnered great atten- tion among scientific community. In this work, we used an improved experimental setup to float the bare silver nanoparticles in air with the help of extraneous airflow, and used atomic layer deposition (ALD) method to coat ultra-thin inert shell without pinholes. Under optimal conditions, we successfully prepared three kinds of SHINERS NPs (Ag@Al2O3, Ag@SiO2 and Ag@TiO2) in large quantity without pinholes. The ultra-thin inert shell maintains the SERS activity of silver nanoparticles for long period of time. Transmission electron microscopy (TEM) images confirm the uniform coating of shell material on silver nanoparticles. Finally, the as-prepared SHINs have been applied to detect various samples to demonstrate the applications. The presented ALD method offers a unique way to coat ultrathin shell (1-10 nm) on metal nanoparticles in large quantity (1-10 g) for practical applications. [ABSTRACT FROM AUTHOR]

Fast and efficient water quality monitoring is essential in the pursuit of reducing the impact of human activities on the environment. We address this issue by presenting a sensing system and method based on Raman spectroscopy in liquid-filled capillaries, that enables quantitative measurement of polyatomic anions in solution. We demonstrate quantitative measurement of nitrate concentrations in water via multivariate analysis with partial least squares regression. We achieve a limit of detection of 0.13 millimolar for a measurement time of 30 s. Our Raman method is compared with gravimetrically measured concentration with good agreement and reproducibility. The Raman monitoring method can be performed in a continuous manner, thus suitable for fast continuous monitoring of water and wastewater quality. [ABSTRACT FROM AUTHOR]

Correction for ‘Shell-isolated nanoparticle-enhanced Raman spectroscopy study of the adsorption behaviour of DNA bases on Au(111) electrode surfaces’ by Bao-Ying Wen et al., Analyst, 2016, DOI: 10.1039/c6an00180g. [ABSTRACT FROM AUTHOR]

Surface-enhanced Raman spectroscopy (SERS) has evolved significantly over fifty years into a powerful analytical technique. This review aims to achieve five main goals. (1) Providing a comprehensive history of SERS's discovery, its experimental and theoretical foundations, its connections to advances in nanoscience and plasmonics, and highlighting collective contributions of key pioneers. (2) Classifying four pivotal phases from the view of innovative methodologies in the fifty-year progression: initial development (mid-1970s to mid-1980s), downturn (mid-1980s to mid-1990s), nano-driven transformation (mid-1990s to mid-2010s), and recent boom (mid-2010s onwards). (3) Illuminating the entire journey and framework of SERS and its family members such as tip-enhanced Raman spectroscopy (TERS) and shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) and highlighting the trajectory. (4) Emphasizing the importance of innovative methods to overcome developmental bottlenecks, thereby expanding the material, morphology, and molecule generalities to leverage SERS as a versatile technique for broad applications. (5) Extracting the invaluable spirit of groundbreaking discovery and perseverant innovations from the pioneers and trailblazers. These key inspirations include proactively embracing and leveraging emerging scientific technologies, fostering interdisciplinary cooperation to transform the impossible into reality, and persistently searching to break bottlenecks even during low-tide periods, as luck is what happens when preparation meets opportunity.

In this feature article, we discuss in detail developmental bottleneck issues in Raman spectroscopy in its early stages and surface-enhanced Raman spectroscopy (SERS) in the past four decades. We divide SERS research into two different directions with different targets. Fundamental research is extending the limits of SERS to single-molecule, sub-nanometer resolution and femtosecond processes. In contrast, practical research is expanding the range of applications with the aim of providing versatile analytical tools for surface, materials, life, environmental, forensic and food sciences and also commercial instruments for use in daily life. In the second direction there have continually been many complex bottlenecks to be overcome. We attempt to enumerate the key issues in detail and also describe the achievements made to overcome the bottlenecks. In the last, but not least important part, we discuss the remaining bottlenecks and possible strategies for overcoming them to enable SERS to be an even more powerful and versatile technique.

Core-shell nanoparticles are at the leading edge of the hot research topics and offer a wide range of applications in optics, biomedicine, environmental science, materials, catalysis, energy, and so forth, due to their excellent properties such as versatility, tunability, and stability. They have attracted enormous interest attributed to their dramatically tunable physicochemical features. Plasmonic core-shell nanomaterials are extensively used in surface-enhanced vibrational spectroscopies, in particular, surface-enhanced Raman spectroscopy (SERS), due to the unique localized surface plasmon resonance (LSPR) property. This review provides a comprehensive overview of core-shell nanoparticles in the context of fundamental and application aspects of SERS and discusses numerous classes of core-shell nanoparticles with their unique strategies and functions. Further, herein we also introduce the concept of shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) in detail because it overcomes the long-standing limitations of material and morphology generality encountered in traditional SERS. We then explain the SERS-enhancement mechanism with core-shell nanoparticles, as well as three generations of SERS hotspots for surface analysis of materials. To provide a clear view for readers, we summarize various approaches for the synthesis of core-shell nanoparticles and their applications in SERS, such as electrochemistry, bioanalysis, food safety, environmental safety, cultural heritage, materials, catalysis, and energy storage and conversion. Finally, we exemplify about the future developments in new core-shell nanomaterials with different functionalities for SERS and other surface-enhanced spectroscopies.

A well-dispersed PtCu alloy nanoparticles (NPs) on three-dimensional nitrogen-doped graphene (PtCu/3D N-G) electrocatalyst has been successfully synthesized by a conventional hydrothermal method combined with a high-efficiency microwave-assisted polyol process. The morphology, composition, and structures are well-characterized by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, X-ray powder diffraction, and X-ray photoelectron spectroscopy. Cyclic voltammograms illustrate that the as-prepared PtCu/3D N-G electrocatalyst possesses the larger electrochemical active surface area, lower onset potential, higher current density, and better tolerance to CO poisoning than PtCu NPs on reduced graphene oxide and XC-72 carbon black in acid solution. In addition, long-time chronoamperometry reveals that the PtCu/3D N-G catalyst exhibits excellent stability even longer than 60 min toward acid methanol electrooxidation. The remarkably enhanced performance is related to the combined effects of uniformly interconnected three-dimensional porous graphene networks, nitrogen doping, modified Pt alloy NPs, and strong binding force between Pt alloy NPs and 3D N-G structures.

Silver is an ideal candidate for surface plasmon resonance (SPR)-based applications because of its great optical cross-section in the visible region. However, the uses of Ag in plasmon-enhanced spectroscopies have been limited due to their interference via direct contact with analytes, the poor chemical stability, and the Ag(+) release phenomenon. Herein, we report a facile chemical method to prepare shell-isolated Ag nanoparticle/tip. The as-prepared nanostructures exhibit an excellent chemical stability and plasmonic property in plasmon-enhanced spectroscopies for more than one year. It also features an alternative plasmon-mediated photocatalysis pathway by smartly blocking "hot" electrons. Astonishingly, the shell-isolated Ag nanoparticles (Ag SHINs), as "smart plasmonic dusts", reveal a ∼1000-fold ensemble enhancement of rhodamine isothiocyanate (RITC) on a quartz substrate in surface-enhanced fluorescence. The presented "smart" Ag nanostructures offer a unique way for the promotion of ultrahigh sensitivity and reliability in plasmon-enhanced spectroscopies.

Identifying the intermediate species in an electrocatalytic reaction can provide a great opportunity to understand the reaction mechanism and fabricate a better catalyst. However, the direct observation of intermediate species at a single crystal surface is a daunting challenge for spectroscopic techniques. In this work, electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy (EC-SHINERS) is utilized to in situ monitor the electrooxidation processes at atomically flat Au(hkl) single crystal electrode surfaces. We systematically explored the effects of crystallographic orientation, pH value, and anion on electrochemical behavior of intermediate (AuOH/AuO) species. The experimental results are well correlated with our periodic density functional theory calculations and corroborate the long-standing speculation based on theoretical calculations in previous electrochemical studies. The presented in situ electrochemical SHINERS technique offers a unique way for a real-time investigation of an electrocatalytic reaction pathway at various well-defined noble metal surfaces.