Improved surface-enhanced Raman scattering on optimum electrochemically roughened silver substrates

In this work, the effects of preparation conditions used in roughening silver substrates by electrochemical triangular-wave oxidation-reduction cycles (ORC) on surface-enhanced Raman scattering (SERS) were first investigated. The optimum roughening conditions for obtaining strongest SERS of Rhodamine 6G (R6G) are as follows. Ag electrodes were cycled in deoxygenated aqueous solutions containing 0.1 M NaCl from −0.3 to +0.2 V versus Ag/AgCl at 25 mV s⁻¹ for five scans. The SERS of R6G adsorbed on this optimum procedure-prepared roughened Ag substrate exhibits a higher intensity by one order of magnitude, as compared with that of R6G adsorbed on a normally roughened Ag substrate.     

In-situ surface-enhanced Raman scattering and FT-Raman spectroscopy of black prints

The black inkjet and laser prints were analysed with regard to application in forensic analysis of questioned documents. The purpose of this work was to study spectral properties and compare the suitability of surface-enhanced Raman scattering (SERS) with Fourier transform Raman spectra of prints. This work aimed to find optimal surface-enhanced Raman spectroscopic approach for the future analysis of documents using statistical methods. In this work, we analysed eight prints of four laser and four inkjet devices. The samples were measured using two dispersive Raman devices; (DXR Raman microscope with excitation line 532 nm, Foram 685-2 spectrometer − 685 nm) and FT-Raman device (Bruker Spectrometer MultiRAM with excitation line 1064 nm). The silver nanoparticles (AgNPs) colloid for SERS experiment were synthesised and checked by UV–vis spectroscopy and scanning electron microscopy (SEM). The remarkable differences caused by centrifugation of silver colloid were observed just in the SEM images. The main contribution of this paper is to propose the novel approach achieving sufficient SERS signal intensity of black prints using the both, laser and inkjet printers. Moreover, this method is based on just a single metal colloid, and the analysis can be performed in-situ, i.e. directly on the printed sample surface. We consider the SERS could by highly promising and universal for applications in the forensic analysis of printed documents with the combination of statistical method when conventional methods are not effective.     

Improved surface-enhanced Raman scattering on electrochemically roughened silver substrates prepared in bielectrolyte solutions

In this work, the effect of supplemental LiClO₄ electrolytes in KCl solutions used in roughening silver substrates by electrochemical triangular-wave oxidation-reduction cycles (ORC) on surface-enhanced Raman scattering (SERS) was first investigated. To prepare SERS-active substrates by ORC procedures, electrolytes of KCl were generally employed. In contrast, LiClO₄ ones were unsuitable for producing SERS-active substrates. Encouragingly, SERS of Rhodamine 6G (R6G) adsorbed on the roughened Ag substrate prepared in an aqueous solution containing KCl and LiClO₄ electrolytes exhibits a higher intensity by one order of magnitude, as compared with that of R6G adsorbed on a roughened Ag substrate prepared in a solution only containing KCl. Further investigations indicate that the oxidation state of Cl on the roughened Ag substrate demonstrates decided effects on this improved SERS.     

Silver-particle-based surface-enhanced resonance Raman scattering spectroscopy for biomolecular sensing and recognition

We demonstrate in this work that 2-μm-sized Ag (μAg) powders can be used as a core material for constructing biomolecular sensing/recognition units operating via surface-enhanced resonance Raman scattering (SERRS). This is possible because μAg powders are very efficient substrates for both the diffuse reflectance IR and the surface-enhanced Raman scattering–SERRS spectroscopic characterization of molecular adsorbates prepared in a similar manner on silver surfaces. Besides, the agglomeration of μAg particles in a buffer solution can be prevented by the layer-by-layer deposition of cationic and anionic polyelectrolytes such as poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA). In this particular study, we used rhodamine B isothiocyanate (RhBITC) as a SERRS marker molecule, and μAg powders adsorbed consecutively with RhBITC and PAH–PAA bilayers were finally derivatized with biotinylated poly(l-lysine). On the basis of the nature of the SERRS peaks of RhBITC, those μAg powders were confirmed to selectively recognize streptavidin molecules down to concentrations of 10⁻¹⁰ g mL⁻¹. Since a number of different molecules can be used as SERS–SERRS marker molecules, the present method proves to be an invaluable tool for multiplex biomolecular sensing/recognition via SERS and SERRS.     

Low-frequency surface-enhanced Raman scattering spectroscopy at metal electrode surfaces

Low-frequency surface-enhanced Raman scattering (SERS) spectroscopy is a versatile tool for studying surface phenomena under electrochemical conditions. This spectroscopy enables us to obtain rich information on extramolecular vibrations between substrate and adsorbates, which are sensitive to atomistic surface features of the substrate. Owing to recent advancements in optical filter technology, low-frequency SERS signals are now becoming easily detectable using conventional Raman systems equipped with holographic notch filters. In addition, SERS background signals, which have been simply ignored, can provide electronic information on the metal substrate. This allows us to observe both sides of electrode–electrolyte interfaces in situ and simultaneously, which is never expected in far-infrared or terahertz absorption spectroscopy. This advanced SERS spectroscopy can help our understanding of electrochemical and electrocatalytic reactions at the molecular scale.     

Explosive and chemical threat detection by surface-enhanced Raman scattering: A review

Acts of terror and warfare threats are challenging tasks for defense agencies around the world and of growing importance to security conscious policy makers and the general public. Explosives and chemical warfare agents are two of the major concerns in this context, as illustrated by the recent Boston Marathon bombing and nerve gas attacks on civilians in the Middle East. To prevent such tragic disasters, security personnel must be able to find, identify and deactivate the threats at multiple locations and levels. This involves major technical and practical challenges, such as detection of ultra-low quantities of hazardous compounds at remote locations for anti-terror purposes and monitoring of environmental sanitation of dumped or left behind toxic substances and explosives. Surface-enhanced Raman scattering (SERS) is one of todays most interesting and rapidly developing methods for label-free ultrasensitive vibrational “fingerprinting” of a variety of molecular compounds. Performance highlights include attomolar detection of TNT and DNT explosives, a sensitivity that few, if any, other technique can compete with. Moreover, instrumentation needed for SERS analysis are becoming progressively better, smaller and cheaper, and can today be acquired for a retail price close to 10,000 US$. This contribution aims to give a comprehensive overview of SERS as a technique for detection of explosives and chemical threats. We discuss the prospects of SERS becoming a major tool for convenient in-situ threat identification and we summarize existing SERS detection methods and substrates with particular focus on ultra-sensitive real-time detection. General concepts, detection capabilities and perspectives are discussed in order to guide potential users of the technique for homeland security and anti-warfare purposes.     

Strategy for obtaining improved surface-enhanced Raman scattering by combining electrochemical and plasmas technologies

In this work, surface-enhanced Raman scattering (SERS)-active gold substrates were first developed by combining the technologies of oxidation–reduction cycles (ORCs) and plasmas treatments in roughening metal substrates. First, a gold substrate was treated by argon plasmas. Then the treated gold substrate was further roughened by triangular-wave ORCs in an aqueous solution containing 0.1 M HCl. Encouragingly, the SERS of Rhodamine 6G (R6G) adsorbed on this roughened gold substrate modified by argon plasmas pretreatment exhibits a higher intensity by 10-fold of magnitude and a better resolution, as compared with the SERS of R6G adsorbed on an unmodified roughened gold substrate. Meanwhile, the probing concentration of R6G adsorbed on the modified substrate can be reduced by one order. It was also found that the pretreatment of argon plasmas demonstrates a positive effect on the (2 2 0) face of Au partly changing into the (1 1 1) face with the lowest surface energy after the ORCs roughening, which is contributive to the improved SERS observed.     

Highly reproducible surface-enhanced Raman scattering-active Au nanostructures prepared by simple electrodeposition: Origin of surface-enhanced Raman scattering activity and applications as electrochemical substrates

The fabrication of effective surface-enhanced Raman scattering (SERS) substrates has been the subject of intensive research because of their useful applications. In this paper, dendritic gold (Au) rod (DAR) structures prepared by simple one-step electrodeposition in a short time were examined as an effective SERS-active substrate. The SERS activity of the DAR surfaces was compared to that of other nanostructured Au surfaces with different morphologies, and its dependence on the structural variation of DAR structures was examined. These comparisonal investigations revealed that highly faceted sharp edge sites present on the DAR surfaces play a critical role in inducing a high SERS activity. The SERS enhancement factor was estimated to be greater than 10⁵, and the detection limit of rhodamine 6G at DAR surfaces was 10⁻⁸ M. The DAR surfaces exhibit excellent spot-to-spot and substrate-to-substrate SERS enhancement reproducibility, and their long-term stability is very good. It was also demonstrated that the DAR surfaces can be effectively utilized in electrochemical SERS systems, wherein a reversible SERS behavior was obtained during the cycling to cathodic potential regions. Considering the straightforward preparation of DAR substrates and the clean nature of SERS-active Au surfaces prepared in the absence of additives, we expect that DAR surfaces can be used as cost-effective SERS substrates in analytical and electrochemical applications.     

Temporal evolution of Raman intensities on surface-enhanced Raman scattering active copper and gold electrodes at negative potentials

The effect of a roughening procedure on surface-enhanced Raman scattering (SERS) intensity of pyridine at copper and gold electrodes subjected to negative potential has been investigated. Among four procedures tested for a copper electrode the one consisting of electrochemical activation in a solution of LiCl and CuCl₂ resulted in the most stable and effective surface. It was proved that the presence of pyridine during the pretreatment procedure caused a very fast, irreversible decay of SERS intensity for both copper and gold electrodes. Quite stable, at least at room temperatures, gold surfaces were obtained by oxidation-reduction cycles activation in KCl solution.     

Direct evidence of chemical effect of surface-enhanced Raman scattering observed on electrochemically prepared rough gold substrates

In this study, polypyrrole (PPy) films were electrochemically deposited on gold substrates roughened by an electrochemical triangular-wave oxidation-reduction cycles (ORC) in an aqueous solution containing 0.1N KCl. Then the substrates were heated from 25 to 50 °C and the corresponding SERS performances of PPy were observed in situ. The results indicate that the SERS enhancement capabilities of substrates are gradually raised from 25 °C to a maximum at 40 °C and monotonically decreased from 40 to 50 °C. These SERS enhancement capabilities ascribed to the charge transfers from PPy to Au, which are responsible for the chemical effects of SERS mechanisms, are successfully observed via SERS and high resolution X-ray photoelectron spectroscopy (HRXPS) analyses. The variation in content of the oxidized PPy peak of the double peaks in the range of 1000-1150 cm⁻¹ in SERS spectrum obtained on an Au substrate at different temperatures is consistent with its corresponding variation in the SERS intensity of PPy. The variation in content of the oxidized nitrogen of PPy deposited on an Au substrate at different temperatures revealed from an HRXPS analysis also confirms this consistence.     

Interaction of soil humic acids with herbicide paraquat analyzed by surface-enhanced Raman scattering and fluorescence spectroscopy on silver plasmonic nanoparticles

A study of the interaction between paraquat (methyl viologen) and humic acids, extracted from a soil amended over 30 years with crop residues, cow slurries and cattle manure, was carried out by two emission spectroscopies based on plasmonic effects: surface-enhanced Raman scattering (SERS) and surface-enhanced fluorescence (SEF). To carry out this study Ag nanoparticles were used. The complex formation was tested by analyzing the effect of the herbicide on humic acids, and by varying experimental parameters such as the pH and the laser excitation wavelength. The study of the vibrational bands led to infer information about the interaction mechanism of paraquat with humic acids and to find a correlation between this interaction and the humic acids structural modification induced by the different amendments added to soil.     

Fast and sensitive trace analysis of malachite green using a surface-enhanced Raman microfluidic sensor

A rapid and highly sensitive trace analysis technique for determining malachite green (MG) in a polydimethylsiloxane (PDMS) microfluidic sensor was investigated using surface-enhanced Raman spectroscopy (SERS). A zigzag-shaped PDMS microfluidic channel was fabricated for efficient mixing between MG analytes and aggregated silver colloids. Under the optimal condition of flow velocity, MG molecules were effectively adsorbed onto silver nanoparticles while flowing along the upper and lower zigzag-shaped PDMS channel. A quantitative analysis of MG was performed based on the measured peak height at 1615 cm⁻¹ in its SERS spectrum. The limit of detection, using the SERS microfluidic sensor, was found to be below the 1–2 ppb level and this low detection limit is comparable to the result of the LC-Mass detection method. In the present study, we introduce a new conceptual detection technology, using a SERS microfluidic sensor, for the highly sensitive trace analysis of MG in water.     

Characteristics of the ring stretching of oxidized polypyrrole on the surface-enhanced Raman spectrum

In this study, polypyrrole (PPy) films were electropolymerized under different preparation conditions on rough gold substrates. The peak shown at the higher frequency of the double peaks at about 1329 and 1386 cm^–1 in surface-enhanced Raman scattering of PPy was initially assigned to the ring stretching of oxidized PPy. A systematic study was carried out to confirm this assignment. It was found that the conductivity of PPy was strongly related to and increased with this Raman peak intensity of oxidized PPy. Meanwhile, the normalized relative intensities of this Raman peak for various PPy films are consistent with their corresponding doping levels. Electronic Publication     

A dual-functional membrane for bisphenol A enrichment and resonance amplification by surface-enhanced Raman scattering

A dual-functional membrane with enrichment and resonance amplification property, combined with an automatic sampler was designed for bisphenol A detection by surface-enhanced Raman scattering.     

Partition layer-modified substrates for reversible surface-enhanced Raman scattering detection of polycyclic aromatic hydrocarbons

Herein, we present progress towards an analytical sensor for polycyclic aromatic hydrocarbons (PAHs) using surface-enhanced Raman scattering (SERS) on partition layer-modified nanostructured substrates. Specifically, a 1-decanethiol monolayer has been assembled on a silver film over nanospheres substrate to concentrate PAHs within the zone of SERS detection. Both anthracene and pyrene were detected with limits of detection at 300 and 700 pM, respectively. The measured SERS spectra allowed for easy distinction of the two PAH compounds, due to varying peak locations, and insight into the partitioning mechanism. Additionally, exposure to a common environmental interferant, Suwannee River fulvic acid, did not impede the measurement of the PAHs, and the sensor is reusable after a short exposure to 1-octanol. Finally, the utility of this sensing platform for PAH detection was compared to that achievable for other classes of organic pollutants such as polychlorinated biphenyls and polybrominated diphenyl ethers. Figure SERS detection of polycyclic aromatic hydrocarbons facilitated via partition layer modified substrates.

Effects of electrolytes used in roughening gold substrates by oxidation–reduction cycles on surface-enhanced Raman scattering

In this work, the effects of electrolytes used in roughening gold substrates by electrochemical methods on surface-enhanced Raman scattering (SERS) were first investigated. First, gold substrates were roughened by triangular-wave oxidation–reduction cycles (ORC) in aqueous solutions containing different kinds of 0.1 M electrolytes. Then Rhodamine 6G (R6G) was used as Raman probe to examine this effect of electrolytes used on the SERS observed. The result indicates that the highest intensity of SERS of R6G was obtained on the roughened Au substrate prepared in 0.1 M NaCl, which was less used in the literature. Meanwhile, it was also found that the rougher surface morphology observed, which is contributive to the higher SERS obtained, is corresponding to the smaller cathodic peak area shown in the cyclic voltammograms for roughening the Au substrate.     

Surface-enhanced Raman scattering detection of lysophosphatidic acid

Surface-enhanced Raman scattering using silver nanoparticles was applied to detect various forms of lysophosphatidic acid (LPA) to examine its potential application as an alternative to current detection methods of LPA as biomarkers of ovarian cancer. Enhancement of the Raman modes of the molecule, especially those related to the acyl chain within the 800–1300 cm⁻¹ region, was observed. In particular, the C–C vibration mode of the gauche-bonded chain around 1100 cm⁻¹ was enhanced to allow the discrimination of two similar LPA molecules. Given the molecular selectivity of this technique, the detection of LPA using SERS may eliminate the need for partial purification of samples prior to analysis in cancer screening.     

Photochemical decoration of silver nanoparticles on magnetic microspheres as substrates for the detection of adenine by surface-enhanced Raman scattering

In this work, silver nanoparticles (AgNPs) decorated magnetic microspheres (MMs) are prepared as surface-enhanced Raman scattering (SERS) substrate for the analysis of adenine in aqueous solutions. To prepare these substrates, magnetic particles were first synthesized by coprecipitation of Fe(II) and Fe(III) with ammonium hydroxide. A thin layer of cross-linked polymer was formed on these magnetic particles by polymerization through suspension of magnetic particles into a solution of divinyl benzene/methyl methacrylate. The resulted polymer protected magnetic particles are round in shape with a size of 80 μm in diameter. To form AgNPs on these MMs, photochemical reduction method was employed and the factors in photochemical reduction method were studied and optimized for the preparation of highly sensitive and stable AgNPs on MMs substrates (abbreviated as AgMMs substrates). By dispersing the AgMMs in aqueous samples, cylindrical magnet was used to attract the AgMMs for SERS detections. The observed enhancement factor of AgMMs reached 7 orders in magnitude for detection of adenine with a detection limit approaching to few hundreds of nanomolar.     

等离激元激励表面增强拉曼光谱检测技术与仪器

本文总结了近年来基于传播型表面等离激元（Propagafingsurfaceplasmons,PSPs）参与的表面增强拉曼（Surface—enhancedRamanscattering,SERS）技术和仪器方面的研究进展．内容主要包括3部分：（1）基于PSPs激励拉曼散射的装置和技术,包括在消逝场下激发PSPs共振增强拉曼的原理与装置、与表面等离子体共振（Surfaceplasmonresonance,SPR）传感技术的联用及新型结构的长程等离激元激励拉曼技术的研究进展;（2）通过引入局域型表面等离激元（Localizedsurfaceplasmons,LSPs）进一步增强SERS,进而实现PSPs-LSPs共同增强拉曼的超灵敏检测技术,包括在消逝场激发的PSPs基础上,增加纳米粒子实现的PSPs与LSPs共同增强拉曼的原理、装置,以及用该方法进行生物体系的免疫识别检测,此外,还在微纳周期结构上实现了PSPs与LSPs共同激励拉曼;（3）基于PSPs耦合的定向SERS技术,包括在消逝场结构和周期结构上实现SERS定向耦合发射以达到高激发和高收集效率的新技术．     

A simple approach for ultrasensitive detection of bisphenols by multiplexed surface-enhanced Raman scattering

Bisphenol A (BPA) is well known for its use in plastic manufacture and thermal paper production despite its risk of health toxicity as an endocrine disruptor in humans. Since the publication of new legislation regarding the use of BPA, manufacturers have begun to replace BPA with other phenolic molecules such as bisphenol F (BPF) and bisphenol B (BPB), but there are no guarantees regarding the health safety of these compounds at this time. In this context, a very simple, cheap and fast surface-enhanced Raman scattering (SERS) method was developed for the sensitive detection of these molecules in spiked tap water solutions. Silver nanoparticles were used as SERS substrates. An original strategy was employed to circumvent the issue of the affinity of bisphenols for metallic surfaces and the silver nanoparticles surface was functionalized using pyridine in order to improve again the sensitivity of the detection. Semi-quantitative detections were performed in tap water solutions at a concentrations range from 0.25 to 20 μg L⁻¹ for BPA and BPB and from 5 to 100 μg L⁻¹ for BPF. Moreover, a feasibility study for performing a multiplex-SERS detection of these molecules was also performed before successfully implementing the developed SERS method on real samples.