An improved self‐assembly gold colloid film as surface‐enhanced Raman substrate for detection of trace‐level polycyclic aromatic hydrocarbons in aqueous solution

To detect trace‐level polycyclic aromatic hydrocarbons, some investigations of an improved self‐assembly method are carried out using gold colloid films for the preparation of the surface‐enhanced Raman scattering (SERS)‐active substrate. Extinction spectra and scanning electron microscopy images reveal that controllable surface plasmonic metal substrates can be obtained by increasing the temperature of (3‐aminopropyl)trimethoxysilane solution up to 64.5 °C. The SERS‐active substrates have a high enhancement factor, and they can be both easily prepared and reproducible. With the use of these substrates, different concentrations of pyrene and anthracene in aqueous solutions were detected by SERS. A further enhancement can be supported by shifted excitation Raman difference spectroscopy. Raman signals of pyrene and anthracene adsorbed on gold colloid substrates up to limits of detection at 5 and 1 nmol/l, respectively, can be obtained. The quantitative analysis shows the possibility of in situ detection of polycyclic aromatic hydrocarbons while such gold colloid film serves as a SERS‐active substrate. Copyright © 2012 John Wiley & Sons, Ltd.     

Application of calixarene to high active surface‐enhanced Raman scattering (SERS) substrates suitable for in situ detection of polycyclic aromatic hydrocarbons (PAHs) in seawater

The characteristics of the sol–gel matrix embedding Ag nanoparticles functionalized with 25,27‐dimercaptoacetic acid‐26,28‐dihydroxy‐4‐tert‐butylcalix[4]arene (DMCX) suitable for the in situ detection of polycyclic aromatic hydrocarbons (PAHs) in seawater is presented. The DMCX‐functionalized silver nanoparticles were produced by the thermal reduction method in xerogel film. The silver colloid blocks were formed in the sol–gel matrix, with a diameter ranging from 50 to 120 nm. DMCX forming the monolayer on the silver nanoparticle surface contributes to the surface‐enhanced Raman scattering (SERS) activity due to the aggregation of silver nanoparticles and the preconcentration of PAH molecules within the zone of electromagnetic enhancement. When selected, PAH molecules e.g. pyrene and naphthalene were adsorbed onto the SERS substrate; Raman band positions of PAH were slightly shifted. A calibration procedure reveals that this type of SERS substrate has a limit of detection of 3 × 10⁻¹⁰ mol/l for pyrene and 13 × 10⁻⁹ mol/l for naphthalene in artificial seawater. The Raman signal response on a pyrene concentration change in artificial seawater was evaluated using a 671‐nm Raman setup with a flow‐through cell. This type of SERS substrate will be suitable for the in situ trace detection of pollutant chemicals in seawater. Copyright © 2012 John Wiley & Sons, Ltd.     

应用球形和海胆状金混合SERS基底检测高环多环芳烃

合成了海胆状金银复合纳米材料,并与球形金纳米材料混合作为表面增强拉曼活性基底实现了对水中高环多环芳烃的痕量检测。对海胆状材料进行表征,粒径大小约为300～400 nm,表面有40～100 nm明显的刺状凸起。与球形金溶胶混合后并优化pH值及混合比例等参数,产生了优于球形金溶胶2～3倍的增强效果。利用此增强基底检测了危害严重的高环多环芳烃污染物——芘(四环)、苯并蒽(四环)、苯并芘(五环),得到的光谱数据反映出混合SERS基底有良好的重复性和稳定性,对测得光谱进行特征峰归属分析,固体拉曼光谱与水溶液SERS光谱有确定的对应关系,并且在低浓度范围多环芳烃特征峰峰强与其水溶液浓度有良好的线性关系。经计算,芘(四环)、苯并蒽(四环)、苯并芘(五环)的检测限分别为0.44,2.92和1.64 nmol·L-1。该研究的创新点为合成了海胆金纳米颗粒,与球形金溶胶混合后制成新型高效SERS检测基底;选用自制高效SERS基底,实现了高环PAHs痕量检测。结果表明,利用该方法制备的活性基底,可实现对水中高环多环芳烃的痕量检测,为检测水中高环多环芳烃提供了实验室依据。     

Multiscale electromagnetic SERS enhancement on self‐assembled micropatterned gold nanoparticle films

In this work, we demonstrate a cascaded, multiplicative electromagnetic enhancement effect in surface‐enhanced Raman scattering (SERS) on periodically micropatterned films made of colloidal gold nanoparticles, prepared by a self‐assembly approach, without implying lithography procedures. The multiplicative enhancement effect is obtained by combining surface plasmon near‐field enhancement due to nanoscale features with far‐field photonic coupling by periodic microscale features. The effect is observed for both internal Raman reporters (molecules attached to the Au colloids before their assembly) and external Raman probes (molecules adsorbed on the samples after film assembly). The ability of the patterned films for far‐field light coupling is supported by reflectivity spectra, which present minima/maxima in the visible spectral range. Finite‐difference time‐domain computer simulations of the electric field distribution also support this interpretation. The fabricated dual‐scale SERS substrates exhibit a good spot‐to‐spot reproducibility and time stability, as proved by the SERS response over a time scale longer than 1 month. The experimental demonstration of this cascaded electromagnetic enhancement effect contributes to a better understanding of SERS and can affect future design of SERS substrates. Moreover, such dual‐scale colloidal films prepared by convective self‐assembly can be of general interest for the broader field of nanoparticle‐based devices. Copyright © 2014 John Wiley & Sons, Ltd.     

Portable smart films for ultrasensitive detection and chemical analysis using SERS and SERRS

Metallic nanostructures, much smaller than the wavelength of visible light, which support localized surface plasmon resonances, are central to the giant signal enhancement achieved in surface‐enhanced Raman scattering (SERS) and surface‐enhanced resonance Raman scattering (SERRS). Plasmonic driven SERS and SERRS is a powerful analytical tool for ultrasensitive detection down to single molecule detection. For all practical SERS applications a key issue is the development of reproducible and portable SERS‐active substrates, where the most widely used metals for nanostructure fabrication are silver and gold. Here, we report the fabrication of a ‘smart film’, containing gold nanoparticles (AuNPs), produced by in situ reduction of gold chloride III (Au⁺³) in natural rubber (NR) membranes for SERS and SERRS applications. The composite films (NR/AuNP membranes) show characteristic plasmon absorption of Au nanostructures, which notably do not influence the mechanical properties of the NR membranes. The term ‘smart film’ has to do with the fact that the SERS substrate (smart film) is flexible and standalone, which allows one to take it anywhere and to dip it into solutions containing the analyte to be characterized by SERS or SERRS technique. Besides, the synthesis of the AuNPs at the surface of NR films is much simpler than making an Au colloid and cast it onto a substrate surface or preparing an Au evaporated film. Copyright © 2012 John Wiley & Sons, Ltd.     

On‐line surface enhanced Raman spectroscopic detection in a recyclable Au@SiO2 modified glass capillary

A facile method was developed to fabricate a high sensitive, reproducible and recyclable surface enhanced Raman spectroscopy (SERS) active glass capillary. The Au nanoparticles were synthesized through a seed‐mediated growth approach and then self‐assembled onto the inner wall of glass capillaries. The attached Au nanoparticles were homogeneously coated with thin silica shell by using the silane coupling agent to functionalize the Au surface. By using thiophenol (TP) as SERS probe molecules, the substrate exhibited robust SERS effects. The adsorbed SERS probe molecules could be rapidly and completely removed away by flowing sodium borohydride solution and thus to obtain a refresh Au@SiO₂ film‐coated substrate for the cyclic detection on different species. The on‐line detection of TP and malachite green (MG) with different concentrations was performed in the flowing system. The intensities of SERS signals were dependent on concentrations of the detected molecules. The results indicated that the SERS‐active substrate has potential applications on the on‐line qualitative and quasi‐quantitative analysis. Copyright © 2014 John Wiley & Sons, Ltd.     

金纳米-Nylon柔性膜基底的制备及其SERS性能研究

表面增强拉曼光谱（SERS）是目前最灵敏的分析技术之一,广泛应用于生命科学、材料科学、环境科学及分析化学等领域。SERS基底的特性决定了该技术的实际应用范围,是推动该技术发展的关键,高活性SERS基底的制备已经逐渐成为SERS研究领域的热点。为了获得最佳的拉曼信号,对具有特殊特性的SERS活性基底的需求一直很大。柔性SERS基底因具有良好的柔韧性,3D支架结构和表面可控的孔径大小等独特优势,在检测化合物和细菌等方面有很好的应用价值。Nylon(尼龙)柔性膜表面具有分级及多孔交错排列3D结构的特点,将固相萃取装置与特殊材料Nylon柔性膜相结合,通过改变金纳米颗粒的附着量以及金纳米颗粒与膜结合次数,制备了高SERS活性的金纳米-Nylon（Au-Nylon）柔性膜基底。研究表明,金纳米颗粒能很好地附着在Nylon纤维上,纳米颗粒与Nylon柔性膜表面等离子共振耦合作用,形成金纳米颗粒与Nylon纤维的复合体,Au-Nylon柔性膜基底的等离子共振吸收峰发生蓝移。首次处理后的Nylon纤维与其所附着的金纳米颗粒形成新的活性截留层,有助于使再次处理时金颗粒更好地附着在柔性膜表面,产生SERS“热点”效应,提高其SERS性能。利用结晶紫（CV）作为SERS探针分子,对Au-Nylon柔性膜基底SERS性能进行分析,发现CV探针分子在Au-Nylon柔性膜基底上的SERS强度随金纳米颗粒的附着量以及金纳米颗粒与膜结合次数而变化。对于面积为1 cm2的Au-Nylon柔性膜基底,当单次过滤金溶胶1 mL,与膜结合2次,总结合量2 mL时,CV探针分子的SERS信号最强,SERS活性最强。采用Au-Nylon柔性膜基底对浓度为2.5×10-5,1×10-5,1×10-6,5×10-7及1×10-7 mol·L-1的CV溶液进行的SERS检测,发现Au-Nylon柔性膜基底对CV探针分子检测极限达1×10-6 mol·L-1,增强因子达到1.0×104。此外,Au-Nylon柔性膜基底均匀性较好,相对平均偏差为11.8%。Au-Nylon柔性膜基底在微生物检测中,仍具有良好SERS活性,对金黄色葡萄球菌的SERS增强效果优于金溶胶。由此可见,研究中制备的Au-Nylon柔性具有良好的均一性,并具有较好的SERS活性,该方法简单且易批量制备,无论在化合物检测还是微生物检测中都具有良好的实际应用价值。     

Surface Enhanced Raman Scattering on Self-assembled Nano Silver Film Prepared by Electrolysis Method

用一种廉价的电解方法制备了纳米银膜,并详细研究了在这种银膜上的表面增强拉曼散射效果．结晶紫为本实验的检测性分子．通过实验发现,这种银膜用便携式拉曼光谱仪测试并计算出的表面增强拉曼散射的增强因子为603,并对结晶紫的最小检出限为0.1 nmol/L     

多环芳烃的表面增强拉曼光谱探测与分析

首次实现了以参数优化的金溶胶为表面增强拉曼散射(SERS)活性基底探测水中痕量的多环芳烃。采用化学还原法制备不同颗粒大小的金溶胶,实验确定了632.8 nm激发光下的最优金纳米颗粒的平均粒径为(32±3) nm,并以此金溶胶为基底,探索pH值对多环芳烃增强效果的影响,发现pH=13效果最佳,与pH=6相比谱线绝对强度提高约20倍。以粒径为(32±3) nm,pH=13的金溶胶为活性基底对不同浓度萘、菲、芘溶液进行了SERS光谱探测,探测到的最低浓度分别为20,4和4 nmol·L-1,特征峰强与浓度呈线性关系,线性拟合相关系数均在0.985以上,三者混合溶液的SERS光谱可清晰分辨出各自的特征峰。结果表明,该实验所采用的SERS活性基底灵敏度较高,具有广阔的应用前景。     

应用银溶胶膜探测水中抗生素的表面增强拉曼光谱研究

以自组装法制备的银溶胶膜为表面增强拉曼散射活性基底实现了对水中抗生素的痕量检测。采用微波加热法制备银溶胶,自组装法制备银溶胶膜。通过改变银溶胶的pH值及镀膜的次数,研究其对抗生素增强效果的影响。实验发现,采用不同pH值的银溶胶镀膜所获得的银溶胶膜的增强效果有很大差异,当银溶胶pH=4,且镀膜次数为五次时,增强效果最佳。以此银溶胶膜为基底对三种抗生素(氯霉素、环丙沙星、恩诺沙星)进行了SERS检测,可以检测到的最低浓度分别为120,15,120 nmol·L-1。结果表明,利用改进方法制备的银溶胶膜,可以对水中抗生素进行痕量检测,为实现养殖水中残留抗生素的检测提供了方法。     

Fabrication of uniform substrate based on silver nanoparticles decorated glycidyl methacrylate‐ethylene dimethacrylate porous material for ultrasensitive surface‐enhanced Raman scattering detection

Surface‐enhanced Raman scattering (SERS) in practical application and theoretical research mostly depends on the performance of the SERS substrate. In this study, a new SERS substrate which is based on inverted self‐assembly of Ag nanoparticles (AgNPs) on glycidyl methacrylate‐ethylene dimethacrylate (GMA‐EDMA) porous material is developed. The characterization results show the GMA‐EDMA material with intertwined pores may contribute to the distribution of the AgNPs to fabricate an ideal substrate for SERS detection. In view of the characteristics of porous material, an inverted assembly method is proposed and used in operation to avoid the adverse gravity effect which may make the AgNPs plug up the pore channel and distribute on the surface unevenly. By the inverted self‐assembly method, the AgNPs could uniformly distribute on the surface of the material stably. The prepared substrate presents ultrasensitivity and good reproducibility for SERS detection. The enhancement factor of rhodamine 6G (R6G) detection is approximately 10¹⁴ and the relative standard deviation of each characteristic peak is about 15% when the substrate is used. The substrate also shows a good performance in detecting paraquat and thymine. The ultrasensitive SERS substrate can be readily integrated into pesticide detection systems and biological sample analysis. Copyright © 2013 John Wiley & Sons, Ltd.     

聚甲基丙烯酸甲酯间隔的金纳米立方体与金膜复合结构的表面增强拉曼散射研究

金属纳米颗粒与金属薄膜的复合结构由于其局域表面等离子体和传播表面等离子体间的强共振耦合作用,可作为表面增强拉曼散射(SERS)基底,显著增强吸附分子的拉曼信号.本文提出了一种聚甲基丙烯酸甲酯(PMMA)间隔的90 nm金纳米立方体与50 nm金膜复合结构的SERS基底,通过有限元方法数值模拟,得到PMMA的最优化厚度为15 nm.实验制备了PMMA间隔层厚度为14 nm的复合结构,利用罗丹明6G (R6G)为拉曼探针分子, 633 nm的氦氖激光器作为激发光源,研究了复合结构和单一金纳米立方体的SERS效应,发现复合结构可以使探针分子产生比单一结构更强的拉曼信号.在此基础上,研究了不同浓度金纳米立方体水溶液条件下复合结构中R6G的拉曼光谱.结果表明,当金纳米立方体水溶液浓度为5.625μg/mL的条件下复合结构中R6G的拉曼信号最强,且可测量R6G的最低浓度达10~(–11) mol/L.     

Adjustment and control of SERS activity of metal substrates by pressure

Metal pellets of silver and copper for surface‐enhanced Raman scattering (SERS) spectroscopy were prepared by compression with different pressures. It was found that the SERS activity of the pellet could be controlled by pressure. Enhanced Raman scattering properties of the metal pellets in the presence of adsorbed 4‐mercaptobenzoic acid (4‐MBA) with excitation at 632.8 or 514 nm could be obtained by choosing proper pressure of pellatization. The SERS peak intensity of the band at ∼1584 cm⁻¹ of 4‐MBA adsorbed on the metal pellets varies as a function of applied pressure, and which is about 1.2–32 times greater than when it is adsorbed on silver and copper particles. The calculated results of three‐dimensional finite‐difference time‐domain method (3D‐FDTD) are in good agreement with the experimental data. Moreover, no spurious peaks appear in the SERS spectra of the samples because no other chemicals are involved in the simple preparation process of the metal pellets, which will facilitate its use as an SERS‐active substrate for analytical purposes. In summary, SERS‐active metal pellets can be produced simply and cost effectively by the method reported here, and this method is expected to be utilized in the development of SERS‐based analytical devices. Copyright © 2009 John Wiley & Sons, Ltd.     

Improved performance of surface‐enhanced Raman scattering on silver substrates prepared in nitric acid solutions

In this work, we propose a new electrochemical method to prepare surface‐enhanced Raman scattering (SERS)‐active silver substrates in nitric acid solutions. Experimental results indicate that the SERS intensity of adsorbed Rhodamine 6G (R6G) can be significantly increased, as compared with that of R6G adsorbed on a SERS‐active Ag substrate prepared by an electrochemical method in a chloride‐containing solution, which was generally employed in the literature. Moreover, the SERS of R6G on the newly developed substrate (prepared in a nitric acid solution) still performs well at a high temperature of 250 °C. However, the enhancement capability of the SERS‐active substrate prepared in a chloride‐containing solution is seriously destroyed at temperatures higher than 150 °C. Further investigations indicate that the oxidation states of roughened Ag substrates prepared in nitric acid solutions under different experiment conditions have less influence on the corresponding SERS performances. Instead, different surface morphologies of roughened Ag substrates and different contents of nitrogen‐containing dopping ions on the roughened Ag substrates demonstrate significant effects on the corresponding SERS performances. Copyright © 2011 John Wiley & Sons, Ltd.     

硫化钠表面增强拉曼光谱及其在味精检测中的应用研究

采用表面增强拉曼光谱(SERS)表征了硫化钠分子的振动模式,获得了硫化钠较为全面的分子结构振动信息,确定以472 cm-1的特征峰为研究对象。以金溶胶为表面增强活性基底,研究了金纳米粒子粒径对增强效果的影响,确定粒径为97 nm的金溶胶增强效果最佳。以硝酸作为促凝剂,测得不同浓度硫化钠溶液的SERS。结果表明,当硫化钠浓度低至10-6 g·mL-1时,依然可以得到明显的拉曼光谱信号,光谱强度与金溶胶和硫化钠溶液的配比有关。将这种硫化钠的检测方法应用于味精样品的检测之中。分别在不同浓度的10 mL硫化钠溶液中溶入1 g味精,检测所得溶液的SERS。结果表明,当每千克味精中硫化钠的含量为10 mg时仍可检测出SERS信号,此种方法无需样品的预处理,操作简便快捷,在味精中硫化钠的定性检测方面具有特有的优势。     

Surface‐enhanced Raman scattering study of human serum on PVA?Ag nanofilm prepared by using electrostatic self‐assembly

Polyvinyl alcohol (PVA)‐protected silver nanoarchitecture (PVA Ag nanofilm) on the surface of the glass substrate was prepared by using electrostatic self‐assembly at a proper voltage. The two‐dimensional morphology of the PVA Ag nanofilm has been examined by scanning electron microscopy (SEM). The surface‐enhanced Raman scattering (SERS) spectra of human serum (HS) on PVA Ag nanofilms were recorded. The results show that the Raman scattering of HS can be enhanced efficiently based on these PVA Ag nanofilms. However, it also can be seen that the effect of sodium citrate (SC) acting as anticoagulant on the SERS spectrum of HS is unnegligible, which has not been discussed adequately in the previous reports. To discuss the effect of SC on the SERS spectrum of HS, we have studied the normal Raman spectra of solid SC and the SERS spectra of 1.0 × 10⁻³ mol/l aqueous solution of SC adsorbed on the PVA–Ag nanofilms. Meanwhile, Raman wavenumbers of the SC molecule were calculated by using the method of DFT‐B3LYP/6‐31G*, and the dominant assignations of the calculated wavenumbers were performed. It was found that the density functional theory (DFT) calculation of SC Raman spectrum matches well with the experimental results. With the perfect reproducibility and high SERS activity, this method will be useful in the development of HS detection methods. Copyright © 2010 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman spectroscopy for trace‐level detection of explosives

The detection of explosives and their associated compounds for security screening is an active area of research and a wide variety of detection methods are involved in this very challenging area. Surface‐enhanced Raman scattering (SERS) spectroscopy is one of the most sensitive tools for the detection of molecules adsorbed on nano‐scale roughened metal surface. Moreover, SERS combines high sensitivity with the observation of vibrational spectra of species, giving complete information on the molecular structure of material under study. In this paper, SERS was applied to the detection of very small quantities of explosives adsorbed on industrially made substrates. The spectra were acquired with a compact Raman spectrometer. Usually, a high signal‐to‐noise (S/N) spectrum, suitable for identification of explosive molecules down to few hundreds of picograms, was achieved within 30 s. Our measurements suggest that it is possible to exploit SERS using a practical detection instrument for routine analysis. Copyright © 2010 John Wiley & Sons, Ltd.     

激光拉曼光谱研究苏丹红Ⅲ分子的吸附方式

用近红外傅里叶拉曼光谱研究了苏丹红Ⅲ分子在覆银纳米颗粒的抛光铝片表面上的吸附行为,得到了一系列高质量的增强拉曼散射（SERS）谱图。对苏丹红Ⅲ分子在银胶溶液、覆银滤纸、覆银粗糙铝片上的SERS谱进行比较,结果表明苏丹红Ⅲ分子在各基底上与银纳米颗粒表现出不同的吸附行为。在银胶溶液中,苏丹红Ⅲ分子主要是通过N=N双键吸附在银纳米颗粒上的;在沉积了银纳米颗粒的滤纸表面,同样地,主要是由N=N双键吸附;而在沉积了银纳米颗粒的抛光铝片表面,不仅N=N双键参与了吸附,苏丹红Ⅲ分子中的羟基与银颗粒有相互作用,并且铝片上的氧化铝颗粒也可能吸附了苏丹红Ⅲ分子。     

Enhancements in intensity and thermal stability of Raman spectra based on roughened gold substrates modified by underpotential deposition of silver

In this study, electrochemically roughened gold is modified with underpotential deposition (UPD) silver to investigate the effects on enhancements in the intensity and the thermal stability of surface‐enhanced Raman scattering (SERS). The SERS of Rhodamine 6G (R6G) adsorbed on the UPD Ag‐modified Au substrate exhibits a higher intensity by six‐fold of magnitude, as compared with that of R6G adsorbedon the unmodified Au substrate. Moreover, the SERS enhancement capabilities of UPD Ag‐modified Au and unmodified Au substrates are seriously depressed at temperatures higher than 200 and 150 °C, respectively. It indicates that the modification of UPD Ag can significantly depress the thermal destruction of SERS‐active substrates. Copyright © 2009 John Wiley & Sons, Ltd.     

Improved performances on surface‐enhanced Raman scattering based on electrochemically roughened gold substrates modified with SiO2 nanoparticles

In this work, we use electrochemical oxidation–reduction cycles (ORC) methods to prepare surface‐enhanced Raman scattering (SERS)‐active gold substrates modified with SiO₂ nanoparticles to improve the corresponding SERS performances. Based on the modified substrates, the SERS of Rhodamine 6G (R6G) exhibits a higher intensity by 3‐fold of magnitude, as compared with that of R6G adsorbed on a SERS‐active Au substrate without the modification of SiO₂ nanoparticles. Moreover, the SERS enhancement capabilities of the modified and the unmodified Au substrates are seriously destroyed at temperatures higher than 250 and 200 °C, respectively. These results indicate that the modification of SiO₂ nanoparticles can improve the thermal stability of SERS‐active substrates. The aging in SERS intensity is also depressed on this modified Au substrate due to the contribution of SiO₂ nanoparticles to SERS effects. Copyright © 2009 John Wiley & Sons, Ltd.