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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]

A three-dimensional microfluidic chip that combines sample manipulation and SERS detection on-chip was developed. This was successfully achieved by chip integration of a nanoporous polycarbonate track-etched (PCTE) membrane which connects microfluidic channels on two different levels with each other. The membrane fulfills two functions at the same time. On the one hand, it enables sample enrichment by selective electrokinetic transport processes through the membrane. On the other hand, the silver nanoparticle–coated backside of the same membrane enables SERS detection of the enriched analytes. The SERS substrate performance and the electrokinetic transport phenomena were studied using Rhodamine B (RhB) by Raman microscopy and fluorescence video microscopy. After system validation, the approach was attested by on-chip processing of a complex food sample. In a proof-of-concept study, the microfluidic device with the SERS substrate membrane was used to detect a concentration of 1 ppm melamine (705 cm−1) in whole milk. Electrokinetic transport across the nanoporous SERS substrate facilitates the extraction of analyte molecules from a sample channel into a detection channel via a potential gradient, thus easily removing obscuring compounds present in the sample matrix. The SERS signal of the analyte could be significantly increased by on-target sample drying. This was achieved by guiding an additional gas flow over the membrane which further extends the microfluidic functionality of the chip device. The proposed method possesses the advantages of combining a rapid (within 15 min) sample clean-up using electrokinetic transport in a three-dimensional microfluidic device which is highly suitable for sensitive and selective SERS detection of chemical and biological analytes. [ABSTRACT FROM AUTHOR]

Graphical abstract Abstract Colloidal silver (Ag) nanoparticles (AgNP) have been widely used for surface-enhanced Raman spectroscopy (SERS) applications. We report a simple, rapid and effective method to prepare AgNP colloids for SERS using the classic organic chemistry Ag mirror reaction with Tollens’ reagent. The AgNP colloid prepared with this process was characterized using SEM, and the reaction conditions further optimized using SERS measurements. It was found that Ag mirror reaction conditions that included 20 mM AgNO 3 , 5 min reaction time, and 0.5 M glucose produced AgNP colloids with an average size of 319.1 nm (s.d ± 128.1). These AgNP colloids exhibited a significant SERS response when adenine was used as the reporter molecule. The usefulness of these new AgNP colloids was demonstrated by detecting the nucleotides adenosine 5′-mono-phosphate (AMP), guanosine 5′-monophosphate (GMP), cytidine 5′-monophosphate (CMP), and uridine 5′-monophosphate (UMP). A detection limit of 500 nM for AMP was achieved with the as-prepared AgNP colloid. The bacterium Mycoplasma pneumoniae was also easily detected in laboratory culture with these SERS substrates. These findings attest to the applicability of this AgNP colloid for the sensitive and specific detection of both small biomolecules and microorganisms. [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]

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]

The synthesis of three-dimensional silver nanopopcorns (Ag NPCs) onto a flexible polycarbonate membrane (PCM) for the detection of nitrofurazone (NFZ) on the fish surface by surface-enhanced Raman spectroscopy (SERS) is presented. The proposed flexible Ag-NPCs/PCM SERS substrate exhibits significant Raman signal intensity enhancement with the measured enhancement factor of 2.36 × 106. This is primarily attributed to the hotspots created on Ag NPCs, including numerous nanoscale protrusions and internal crevices distributed across the surface of Ag NPCs. The detection of NFZ by this flexible SERS substrate demonstrates a low limit of detection (LOD) of 3.7 × 10−9 M and uniform and reproducible Raman signal intensities with a relative standard deviation below 8.34%. It also exhibits excellent stability, retaining 70% of its efficacy even after 10 days of storage. Notably, the practical detection of NFZ in tap water, honey water, and fish surfaces achieves LOD values of 1.35 × 10−8 M, 5.76 × 10−7 M, and 3.61 × 10−8 M, respectively, which highlights its effectiveness across different sample types. The developed Ag-NPCs/PCM SERS substrate presents promising potential for sensitive SERS detection of toxic substances in real-world samples. [ABSTRACT FROM AUTHOR]

Cardiovascular diseases cause enormous morbidity and mortality worldwide. Excessive blood total homocysteine (tHcy) is an independent risk factor for cardiovascular diseases. Therefore, it is imperative to measure the content of tHcy in human blood. However, the currently available analytical methods have the disadvantages such as being time-consuming and expensive. Herein, we propose a rapid clinical quantification of tHcy in human serum using high-performance Ag Nanopolyhedra (Ag NPOLY) as surface-enhanced Raman spectroscopy (SERS) substrates. Generally, 80% of homocysteine (Hcy) in serum is oxidized, and only 20% of Hcy is free. To understand this behavior, we explored the reduction effect of tris(2-carboxyethyl) phosphine (TCEP) on serum Hcy at different pH. The results confirmed that our method can detect 2 µM of Hcy in human serum. As a proof-of-concept, the developed method was applied to the actual clinical detection of human serum tHcy, and the serum of 5 hyperhomocysteinemia (HHcy) patients was verified. Moreover, the obtained, results were consistent with high-performance liquid chromatography (HPLC) results. The linear correlation coefficient of the two methods was 0.9766. Importantly, our analysis can be completed within 15 min, while HCLP requires more than 1 h. Overall, we have successfully developed a rapid SERS-based quantitative method for human serum tHcy, which can provide a new solution for the clinical diagnosis of cardiovascular diseases in the future. [Display omitted] • Constructed a high-performance Ag NPOLY for the detection of tHcy in human serum. • The detection limit for Hcy is 1 µM. • Discussed the optimal condition of TCEP for Hcy reduction. • This method allows the clinical quantification of tHcy. [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]

[Display omitted] • A flexible and cost-effective SERS sensor is created utilizing fish scales as a template. • The resulting SERS substrate exhibits notable porosity and wettability, promoting the formation of densely packed hotspots. • An impressive SERS enhancement factor of 1.3 × 106 is achieved, with a relative standard deviation of 6.4 %. • Demonstrations of fish scale substrates in detecting harmful environmental pollutant perfluorooctane sulfonamide in lake water, soil, and human urine samples are presented. Biological materials with unique surface properties provide a new avenue for fabricating green and sensitive SERS-active substrates. Herein, we present a simple but efficient method to prepare surface-enhanced Raman scattering (SERS) substrates by depositing silver nanoparticles (AgNPs) on fish scale substrates using an evaporation-induced self-assembly method (EISA). Characterization of the formed flexible Ag-impregnated substrate proved outstanding SERS sensitivity, uniformity, and reproducibility properties, with a Raman enhancement factor of 1.3 × 106 and a relative standard deviation of 6.4 %. Using this powerful fish scale substrate, a toxic environmental pollutant perfluorooctane sulfonamide (PFOSA) was indirectly detected in lake water, soil, and human urine samples. Due to its chemical structure, it is difficult to detect low concentrations of PFOSA in real samples. Interestingly, malachite green (MG) was smartly used as the Raman label for PFOSA detection in real samples. One of the main appeals is that the concentration of PFOSA can be correlated with a decrease in the SERS signal of MG in real samples. In conclusion, the strategy employed and reproducible SERS substrates may have diverse applications in clinical and environmental analyses. [ABSTRACT FROM AUTHOR]

The impact of the carbon nanomaterials (CNMs) wave in agro-application has been growing in recent years. The carbon nanomaterials family includes graphene oxide (GO), carbon nanotube (CNT), carbon nanofiber (CNF), carbon nanohorns (CNH), carbon nanodots (CND), carbon nano-onions (CNO), fullerene, and nano-diamond. The former seven belong to the sp2 carbon and the later belong to sp3 carbon. Based on the selection of the forms of allotropes, morphology, size, and the potential combination to form hybrids; the CNMs have shown different performance in the agro activities. Hence, in this review, all these studies along with our contributions are detailed briefly with the information about material synthesis, characterization, and application efficiency; the application includes the role in pesticide, fertilizer, and preservative sector. The review is finally concluded with the highlights about advantages, gaps/risks identified for the industry application, quality assurance status, and future perspectives. [Display omitted] [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]

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. [ABSTRACT FROM AUTHOR]

Dioxin is a highly toxic and carcinogenic pollutant created during industrial production and waste incineration. Pollutant monitoring has made extensive use of surface-enhanced Raman spectroscopy (SERS) as a quick, non-destructive, sensitive, and affordable analytical method. However, the fabrication of a SERS substrate with ultrahigh sensitivity is a challenging task, the detection cost is expensive. Currently, these are the challenges faced by SERS technique for the detection of dioxin pollutants. In this paper, we present Au nanocakes (Au NCs) as an easy-to-build SERS substrate for sensitive SERS detection of dioxins in real samples. Based on three-dimensional finite-difference time-domain (3D-FDTD) calculations, the enhancement factor of the substrate following aggregation is approximately 1010. Using a portable Raman spectrometer, the limit of detection for dioxins such as 1-chloro-dibenzo-p-dioxin (1-CDD), 2,8-dichloro-dibenzo-p-dioxin (2,8-DCDD), and 2,3,7-trichloro-dibenzo-p-dioxin (2,3,7-TrCDD) in clean water reached as low as 5, 5, and 10 ng/mL, respectively. As a real-world application, the same toxic pollutants were detected in sewage water samples. Our findings could lead to the development of novel SERS-based sensors for the rapid detection of dioxins in real-world scenarios. Moreover, a portable Raman spectrometer is used to detect the pollutants, which is easy to use and inexpensive. [Display omitted] • Ultra-sensitive Au nanocake was constructed for detection of dioxins in water. • This facile approach provides a stable platform for field-based analysis. • All experimental data were measured by a portable Raman spectrometer with a detection limit of 5 ppb. [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]

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) is employed to investigate the electrochemical behavior of adenine molecules on smooth Ag electrodes. To attain this goal, pinhole-free shell-isolated Ag nanoparticles (Ag SHINs) have been synthesized and then used as signal “amplifiers” in the gap-mode configuration (Ag SHINs are coupled with a Ag electrode surface). The as-prepared Ag SHINs exhibit remarkable plasmonic performance under 488, 532, and 633 nm excitations as revealed by finite-difference time-domain (FDTD) simulations and SHINERS experiments. Furthermore, wavelength-dependent SHINERS investigation of adenine on Ag electrodes is excellently combined with the electrochemical technique. With outstanding chemical stability and plasmonic property, the Ag SHINs are extraordinarily suitable for fundamental studies at various electrochemical interfaces. [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]

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 spectros-copies 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 spectros-copies. [ABSTRACT FROM AUTHOR]

The article presents a study on the in situ monitoring of the electrooxidation processes of the gold single crystal electrode surfaces using electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy (EC-SHINERS). Topics include the exploration of the effects of anion, potential of hydrogen (pH) value, and crystallographic orientation on the behavior of intermediate species gold hydroxide (AuOH) and gold oxide (AuO), spectrosopic techniques, and the result of EC- SHINERS technique.

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]