Surface-enhanced Raman scattering: a new optical probe in molecular biophysics and biomedicine

Sensitive and detailed molecular structural information plays an increasing role in molecular biophysics and molecular medicine. Therefore, vibrational spectroscopic techniques, such as Raman scattering, which provide high structural information content are of growing interest in biophysical and biomedical research. Raman spectroscopy can be revolutionized when the inelastic scattering process takes place in the very close vicinity of metal nanostructures. Under these conditions, strongly increased Raman signals can be obtained due to resonances between optical fields and the collective oscillations of the free electrons in the metal. This effect of surface-enhanced Raman scattering (SERS) allows us to push vibrational spectroscopy to new limits in detection sensitivity, lateral resolution, and molecular structural selectivity. This opens up exciting perspectives also in molecular biospectroscopy. This article highlights three directions where SERS can offer interesting new capabilities. This includes SERS as a technique for detecting and tracking a single molecule, a SERS-based nanosensor for probing the chemical composition and the pH value in a live cell, and the effect of so-called surface-enhanced Raman optical activity, which provides information on the chiral organization of molecules on surfaces.     

表面增强拉曼光谱:应用和发展

表面增强拉曼光谱技术(Surface-enhanced Raman spectroscopy,SERS)是一种具有超高灵敏度的指纹光谱技术,目前已广泛应用于表面科学、材料科学、生物医学、药物分析、食品安全、环境检测等领域,是一种极具潜力的痕量分析技术。 本文对SERS技术及相关的针尖增强拉曼光谱(Tip-enhanced Raman spectroscopy,TERS),壳层隔绝纳米粒子增强拉曼光谱(Shell-isolated nanoparticle-enhanced Raman spectroscopy,SHINERS)技术的发展及应用进行了综合评述,并探讨了其未来的研究热点及发展方向。     

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.     

静电纺纳米复合纤维柔性表面增强拉曼散射传感基底的研究进展

表面增强拉曼散射(Surface enhanced Raman scattering,SERS)是一种分子检测光谱技术,借助SERS基底,可对生物、化学等复杂体系中的痕量分子进行分析。 其中静电纺纳米纤维SERS基底由于具有高比表面积、可透气透水、柔韧可折叠弯曲等特点,在复杂体系中提取、过滤、浓缩痕量分子等应用场景中,其表面结构具有其他刚性SERS基底不可比拟的优势。然而,静电纺纳米纤维SERS基底的发展却受到制备方法的限制,存在检测灵敏度较低、制备过程复杂等问题。 因此,目前的研究工作主要集中在新型制备方法及工艺的开发。 本文综述了静电纺纳米金银复合纤维SERS基底的几种常用制备方法,包括直接混合纺丝法、化学吸附法、静电吸附法、物理沉积法和原位化学还原法,并总结了静电纺纳米纤维SERS基底在复杂体系中提取、过滤、浓缩待测分子的应用,最后对静电纺纳米复合纤维SERS基底的发展进行了展望。     

Diterpenoic Acids Analysis Using a Coupled TLC-Surface-Enhanced Raman Spectroscopy System

Hyphenation of thin layer chromatography (TLC) with surface-based spectral methods requires a homogeneous surface for direct and quantitative analysis on the chromatographic plate after separation. Since most chromatographic materials do not produce strong background signals in Raman spectroscopy (RS) or surface-enhanced RS (SERS), we tested the suitability of two different chromatographic substrates and one interface for coupling SERS with TLC. This was carried out by using a chromatographic thin layer, specially produced for RS measurements, and a monolithic silica thin layer. A typical TLC plate with a modified aluminium backplate foil on one side was used as an interface. Three biologically active diterpenes, namely gibberellic acid (GA), abietic acid (AA) and kaurenoic acid (KA), were used as test analytes. Stock solutions were applied directly onto the surface, followed by the addition of silver colloid and measurements were taken by SERS. The strongest signal (excitation at 514.5 nm) was obtained for GA using a Raman treated thin layer where the enhancement factor value was determined to be 10². Several fundamental Raman bands for GA were found at 1622, 1593, 1570, 1542, 1366 and 1236 cm⁻¹. When the monolithic silica layer was used, no useful SERS signals were observed. The SERS spectra on modified aluminium backplate for AA and GA were quite similar and no SERS spectrum was obtained for KA. Future research will be concerned towards the use of nanostructured surfaces for SERS analysis. An erratum to this article can be found at     

Rapid monitoring of antibiotics using Raman and surface enhanced Raman spectroscopy

Comparatively few studies have explored the ability of Raman spectroscopy for the quantitative analysis of microbial secondary metabolites in fermentation broths. In this study we investigated the ability of Raman spectroscopy to differentiate between different penicillins and to quantify the level of penicillin in fermentation broths. However, the Raman signal is rather weak, therefore the Raman signal was enhanced using surface enhanced Raman spectroscopy (SERS) employing silver colloids. It was difficult by eye to differentiate between the five different penicillin molecules studied using Raman and SERS spectra, therefore the spectra were analysed by multivariate cluster analysis. Principal components analysis (PCA) clearly showed that SERS rather than the Raman spectra produced reproducible enough spectra to allow for the recovery of each of the different penicillins into their respective five groups. To highlight this further the first five principal components were used to construct a dendrogram using agglomerative clustering, and this again clearly showed that SERS can be used to identify which penicillin molecule was being analysed, despite their molecular similarities. With respect to the quantification of penicillin G it was shown that Raman spectroscopy could be used to quantify the amount of penicillin present in solution when relatively high levels of penicillin were analysed (>50 mM). By contrast, the SERS spectra showed reduced fluorescence, and improved signal to noise ratios from considerably lower concentrations of the antibiotic. This could prove to be advantageous in industry for monitoring low levels of penicillin in the early stages of antibiotic production. In addition, SERS may have advantages for quantifying low levels of high value, low yield, secondary metabolites in microbial processes.     

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

In this study, we demonstrate that 2-microm-sized Ag (microAg) powders can be used as a core material for constructing molecular sensing/recognition units operating via surface-enhanced Raman scattering (SERS). This is possible because microAg powders are very efficient substrates for both the infrared and Raman-spectroscopic characterization of molecular adsorbates prepared in a similar manner on silver surfaces; we can obtain an infrared spectrum of organic molecules adsorbed on microAg particles with a very high signal-to-noise ratio by diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), and the Raman spectrum of organic monolayers on powdered silver is an SERS spectrum. The agglomeration of microAg particles in a highly concentrated buffer solution could 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 fact, prior to depositing PAA and PAH, 4-aminobenzenethiol (4-ABT) was assembled on the surfaces of the microAg particles as SERS markers. Because of the presence of amine groups of 4-ABT, PAA could be readily deposited on the microAg particles. On the other hand, the outermost PAA layer could also be derivatized with biotin-derivatized poly(L-lysine). The nonspecific interaction of poly(L-lysine) with proteins could be suppressed by grafting poly(ethylene glycol) into the biotin-derivatized poly(L-lysine) molecules. On the basis of the nature of the SERS peaks of 4-ABT, it was confirmed that these biotinylated microAg powders were effective in selectively recognizing the streptavidin arrays. Because a number of different molecules can be used as SERS-marker molecules, such as probable 4-ABT, commercially available microAg powders must be a prospective material in molecular sensing/recognition, particularly via SERS.     

New Tools for Investigating Electromagnetic Hot Spots in Single‐Molecule Surface‐Enhanced Raman Scattering

Surface‐enhanced Raman scattering (SERS) is quickly growing as an analytical technique, because it offers both molecular specificity and excellent sensitivity. For select substrates, SERS can even be observed from single molecules, which is the ultimate limit of detection. This review describes recent developments in the field of single‐molecule SERS (SM‐SERS) with a focus on new tools for characterizing SM‐SERS‐active substrates and how they interact with single molecules on their surface. In particular, techniques that combine optical spectroscopy and microscopy with electron microscopy are described, including correlated optical and transmission electron microscopy, correlated super‐resolution imaging and scanning electron microscopy, and correlated optical microscopy and electron energy loss spectroscopy.     

Potential-Averaged Raman Spectroscopy for the Time-Resolved Study

Raman spectroscopy, especially surface enhanced Raman spectroscopy (SERS) has long been used to study the interfacial phenomena, it provides a possible method to characterize a variety of surface and interfacial processes at molecular levels in detail.     

Surface-enhanced Raman spectroscopy: benefits,trade-offs and future developments

Surface-enhanced Raman spectroscopy (SERS) is a vibrational spectroscopy technique with sensitivity down to the single molecule level that provides fine molecular fingerprints, allowing for direct identification of target analytes. Extensive theoretical and experimental research, together with continuous development of nanotechnology, has significantly broadened the scope of SERS and made it a hot research field in chemistry, physics, materials, biomedicine, and so on. However, SERS has not been developed into a routine analytical technique, and continuous efforts have been made to address the problems preventing its real-world application. The present minireview focuses on analyzing current and potential strategies to tackle problems and realize the SERS performance necessary for translation to practical applications.

Surface-enhanced Raman spectroscopy (SERS) is a vibrational spectroscopy technique with sensitivity down to the single molecule level that provides fine molecular fingerprints, allowing for direct identification of target analytes.     

Raman and surface Raman spectroscopy with ultraviolet excitation

We record the accurate and reliable Raman spectra of benzoic acid (BA), p-nitrobenzoic acid (PNBA) and o-nitrobenzoic (ONBA) in aqueous solution with ultraviolet excitation. And we find that the ultraviolet (UV) Raman spectrum of aqueous BA solution has one-to-one correspondence to that of BA solid whereas the others are less resemble to the solid counterparts. We also report surface Raman spectroscopy of them in silver colloid without any enhancement in UV region and call it surface-unenhanced Raman spectroscopy (SUERS) while the surface-enhanced Raman scattering (SERS) effects are perfect in near infrared or visible regions. It demonstrates the SERS effects are strongly dependent on the excitation wavelength. On the basis of the experiments, we discuss the mechanism of SERS excited in different regions.     

Raman and Surface-enhanced Raman Scattering of Chlorophenols

Raman spectrum is a powerful analytical tool for determining the chemical information of compounds. In this study, we obtained analytical results of chlorophenols(CPs) molecules including 4-chlorophenol(4-CP), 2,6-dich- lorophenol(2,6-DCP) and 2,4,6-trichlorophenol(2,4,6-TCP) on the surface of Ag dendrites by surface-enhanced Raman scattering(SERS) spectra. SEM images indicate that the SERS substrate of Ag dendrites is composed of a large number of polygonal nanocrystallites, which self-assembled into a 3D hierarchical structure. It was found that there were distinct differences for those three molecules from Raman and SERS spectra. This indicates that SERS could be a new tool of detection technique regarding trace amounts of CPs.     

Surface enhanced Raman spectroscopy on copper hydrosols

Surface enhanced Raman spectroscopy (SERS) allows the detection of trace quantities of molecular species adsorbed onto a surface. The potential use of silver colloids as substrates for analytical SERS measurements is demonstrated. Detection limits and other analytical figures of merit for pyridine, p-aminobenzoic acid and p-nitrobenzoic acid are presented.     

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．     

用于电化学界面研究的共焦显微拉曼光谱技术(英文)

系统地介绍了将共焦显微拉曼光谱系统用于电化学界面研究的方法 ,包括铂电极的粗糙和电化学拉曼电解池的设计 .进行了铂上氢、氧和氯共吸附的拉曼光谱研究 .通过对甲醇氧化过程的现场跟踪 ,提出检测界面区溶液浓度变化和计算溶液 pH值的方法 .实验表明拉曼光谱技术可作为研究实际应用体系的重要工具 .     

Electromagnetic and chemical interaction between Ag nanoparticles and adsorbed rhodamine molecules in surface-enhanced Raman scattering

The critical importance of the junction between touching or closely adjacent Ag nanoparticles associated with single-molecule sensitivity (SMS) in surface-enhanced Raman scattering (SERS) was confirmed via the following observations: (1) an additional peak is observed in elastic scattering only for the SERS-active state, which originated from absorption of adsorbates, (2) local- and far-field evaluation using a finite difference time domain method could reproduce this extra peak and anticipate the significantly enhanced field even inside the adsorbates sitting at the junction through an increased coupling of the localized surface plasmons, and (3) in addition to enhanced fluorescence of adsorbed dye, an inelastic scattering peak was observed and attributed to the metal surface electron. Concerning the chemical enhancement in SERS, Cl⁻ anions activate the Ag-Cl-R6G (rhodamine) samples by inducing intrinsic electronic interaction between Ag and R6G molecules. This electronic interaction is irreversibly quenched by the addition of thiosulfate anions which dissolve Ag⁺ cations while the electromagnetic (EM) effect remains intact.     

New developments in Raman spectroscopy

Summary A short review is given on some new instrumental and methodical developments in Raman spectroscopy. In linear Raman spectroscopy a microsampling technique, which is based on the optical levitation by radiation pressure, and the surface enhanced Raman effect (SERS) are discussed. In non-linear Raman spectroscopy new developments in coherent anti-Stokes Raman spectroscopy (CARS) and ionization detected stimulated Raman spectroscopy (IDSRS) as well as their applications in high resolution molecular spectroscopy and in combustion research are described.

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Neuere Entwicklungen in der Raman-Spektroskopie

Zusammenfassung Es wird ein kurzer Überblick über einige neuere instrumentelle und methodische Entwicklungen in der Raman-Spektroskopie gegeben. In der linearen Raman-Spektroskopie wird eine Mikroprobentechnik, die auf der optischen Levitation durch Strahlungsdruck beruht, sowie der oberflächenverstärkte Ramaneffekt (SERS) diskutiert. Weiterhin werden neuere Entwicklungen nichtlinearer Ramanmethoden, wie CARS (Coherent anti-Stokes Raman Spectroscopy) and IDSRS (Ionization Detected Stimulated Raman Spectroscopy) sowie deren Anwendungen in der hochauflösenden Molekülspektroskopie und in der Erforschung von Verbrennungsvorgängen besprochen.

     

Expanding generality of surface-enhanced Raman spectroscopy with borrowing SERS activity strategy

Surface-enhanced Raman scattering (SERS) was discovered three decades ago and has gone through a tortuous pathway to develop into a powerful diagnostic technique. Recently, the lack of substrate, surface and molecular generalities of SERS has been circumvented to a large extent by devising and utilizing various nanostructures by many groups including ours. This article aims to present our recent approaches of utilizing the borrowing SERS activity strategy mainly through constructing two types of nanostructures. The first nanostructure is chemically synthesized Au nanoparticles coated with ultra-thin shells (ca. one to ten atomic layers) of various transition metals, e.g., Pt, Pd, Ni and Co, respectively. Boosted by the long-range effect of the enhanced electromagnetic (EM) field generated by the highly SERS-active Au core, the originally low surface enhancement of the transition metal can be substantially improved giving total enhancement factors up to 10(4)-10(5). It allows us to obtain the Raman spectra of surface water, having small Raman cross-section, on several transition metals for the first time. To expand the surface generality of SERS, tip-enhanced Raman spectroscopy (TERS) has been employed. With TERS, a nanogap can be formed controllably between an atomically flat metal surface and the tip with an optimized shape, within which the enhanced EM field from the tip can be coupled (borrowed) effectively. Therefore, one can obtain surface Raman signals (TERS signals) from adsorbed species at Au(110), Au(111) and, more importantly, Pt(l10) surfaces. The enhancement factor achieved on these single crystal surfaces can be up to 106, especially with a very high spatial resolution down to about 14 nm. To fully accomplish the borrowing strategy from different nanostructures and to explain the experimental observations, a three-dimensional finite-difference time-domain method was used to calculate and evaluate the local EM field on the core-shell nanoparticle surfaces and the TERS tips. Finally, prospects and further developments of this valuable strategy are briefly discussed with emphasis on the emerging experimental methodologies.     

In situ surface-enhanced Raman spectroscopic studies of nafion adsorption on Au and Pt electrodes

Understanding interactions between Nafion (perfluorosulfonic acid) and Pt catalysts is important for the development and deployment of proton exchange membrane fuel cells. However, study of such interactions is challenging and Nafion/Pt interfacial structure remains elusive. In this study, adsorption of Nafion ionomer on Au and Pt surfaces was investigated for the first time by in situ surface-enhanced Raman spectroscopy. The study is made possible by the use of uniform SiO(2)@Au core-shell particle arrays which provides very strong enhancement of Raman scattering. The high surface sensitivity offered by this approach yields insightful information on interfacial Nafion structure. Through spectral comparison of several model compounds, vibration assignments of SERS bands were made. The SER spectra suggest the direct interaction of sulfonate group with the metal surfaces, in accord with cyclic voltammetric results. Comparison of present SERS results with previous IR spectra was briefly made.