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1.
    
Melamine, a nitrogen‐rich chemical, has recently caused enormous economic losses to the food industry due to the cases of milk products adulterated by melamine. This has led to an urgent need of rapid and reliable methods for detection of melamine in food. In this study, surface‐enhanced Raman scattering (SERS) spectroscopy was used to detect melamine in liquid milk. The sample preparation with liquid milk is very easy; it has to be only diluted with double‐distilled water followed by centrifugation. By using a silver colloid, at least a 105‐fold enhancement of the Raman signal was achieved for the measurement of melamine. The limit of detection by this method was 0.01 µg ml−1 for melamine standard samples. Based on the intensity of the Raman vibrational bands normalised to that of the band at 928 cm−1 (CH2), an external standard method was employed for quantitative analysis. The linear regression square (R2) of the curve was 0.9998; the limit of quantitation using this approach was 0.5 µg ml−1 of melamine in liquid milk; the relative standard deviation was ≤10%; and recoveries were from 93 to 109%. The test results for SERS were very precise and as good as those obtained by liquid chromatography/tandem mass spectrometry. The method was simple, fast(only needs about 3 min), cost effective, and sensitive for the detection of melamine in liquid milk samples. Therefore, it is more suitable for the field detection of melamine in liquid milk. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

2.
宿健  张谷令  彭洪尚 《发光学报》2018,39(9):1323-1329
提出一种新型的荧光及表面增强拉曼散射（SERS）双模式光学纳米探针。首先,通过再沉淀-包覆法合成二氧化硅包覆香豆素6的纳米颗粒,再在二氧化硅表面静电吸附多聚赖氨酸分子形成包覆层,随后通过原位还原的方法在多聚赖氨酸壳层复合银纳米颗粒,最后在银纳米颗粒表面吸附拉曼分子即形成双模式纳米探针。该探针通过二氧化硅包覆的荧光分子产生荧光信号,以多聚赖氨酸表面的银纳米颗粒作为SERS增强基底,利用拉曼分子获得SERS信号,实现了荧光及SERS双模式成像。荧光与表面增强拉曼散射相结合的双模式分析技术可同时发挥二者的优点,提高成像的分辨率和灵敏度,在生物医学领域具有重要的应用价值。

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3.
    
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.  相似文献   

4.
    
The Ag–Au compound nanostructure films with controllable patterns of Ag nanoparticle (NP) aggregates were fabricated. A strategy of two‐step synthesis was employed toward the target products. Firstly, the precursor Au NP (17 nm) films were synthesized as templates. Secondly, the Ag NPs (45 nm) were deposited on the precursor films. Three types of Ag NP aggregates were obtained including discrete Ag NPs (discrete type), necklace‐like Ag NP aggregates (necklace type), and huddle‐like Ag NP aggregates (huddle type). The surface‐enhanced Raman scattering (SERS) property was studied on these nanostructures by using the probing molecule of rhodamine 6G under the excitation laser of 514.5 nm. Interestingly, the different types of samples showed different enhancement abilities. A statistical method was employed to assess the enhancement. The relative enhancement factor for each Ag NP was estimated quantitatively under the ratio of 1 : 25 : 18 for the discrete‐type, necklace‐type, and huddle‐type samples at the given concentration of 10−8 mol/l. This research shows that the enhancement ability of each Ag NP is dependent on the aggregate morphology. Moreover, the different enhancement abilities displayed different limit detection concentrations up to 10−8, 10−11, and 10−9 mol/l, separately. The understanding of the relationship between the defined nanostructures and the SERS enhancement is very meaningful for the design of new SERS substrates with better performance. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

5.
    
Silver thiolate is a layered compound with a Raman spectrum that is known to change with time, becoming the same as the surface‐enhanced Raman scattering (SERS) spectrum of the parent thiol molecule adsorbed on Ag nanoparticles. On this basis, the Raman scattering characteristics of silver 4‐aminobenzenethiolate (Ag‐4ABT) compounds were investigated to determine whether certain peaks that are identifiable in the SERS spectrum of 4‐aminobenzenethiol (4‐ABT) but absent in its normal Raman spectrum were also apparent in the Ag salt spectrum. For comparative purposes, the Raman scattering characteristics of silver 4‐dimethylaminobenzenethiolate (Ag‐4MABT) were also examined. Raman spectra acquired while spinning the sample were typified by only a1‐type vibrational bands of Ag‐4ABT and Ag‐4MABT, whereas in the static condition, several non‐a1‐type bands were identified. The spectral patterns acquired in the static condition were similar to the intrinsic SERS spectra of 4‐ABT or 4‐dimethylaminobenzenethiol (4‐MABT) adsorbed on pure Ag nanoparticles. Notably, the CH3 group vibrational bands were observable for Ag‐4MABT irrespective of the sample rotation. In addition, no decrease in intensity during irradiation with a visible laser was observed for any of the bands, suggesting that no chemical conversion actually took place in either 4‐ABT or 4‐MABT. The preponderance of evidence led to the conclusion that the non‐a1‐type bands observable in the SERS spectra must be associated with the chemical enhancement mechanism acting on the Ag nanoparticles. The chemical enhancement effect was more profound at 514.5 nm than at 632.8 nm, and was more favorable for 4‐ABT than 4‐MABT at both wavelengths. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

6.
    
Carbendazim (MBC) is a fungicide widely used in agriculture, and there are serious concerns regarding the health risks that could be caused by this fungicide. Here, we explore its ultrasensitive detection by surface‐enhanced Raman scattering (SERS). First, to obtain maximum SERS signal, the adsorption of the target molecule onto metallic surface is essential. Therefore, we study the adsorption of the MBC onto the nanoparticle surface by SERS under different experimental conditions, such as different synthesis methods of nanoparticle, variable excitation wavelength, and fungicide concentration with the aim to detect MBC at low concentrations. Experiments are carried out with three kinds of colloidal nanoparticles: Ag and Au reduced by citrate and Ag reduced by hydroxylamine. However, mainly Ag colloids are highly efficient in the SERS detection of MBC. In addition, theoretical calculations of MBC Raman spectrum and that of the surface complex are used to help with the understanding the mechanisms responsible for the interaction between MBC and Ag. Ultraviolet–visible absorption spectroscopy showed displacement to the red of the plasmon resonance of Ag colloid in the presence of MBC. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

7.
    
Surface plasmon resonance (SPR) in noble metal nanoparticles and nanostructures offers an efficient means to transport and localize the energy of light into some nanoscale space regions called hot spots, where the electromagnetic field is enhanced by many orders of magnitude upon the incident light. This local field enhancement can induce very huge enhancement of Raman signal for a molecule embedded within the hot spot, which has tremendous applications in surface‐enhanced Raman spectroscopy (SERS) and tip‐enhanced Raman spectroscopy (TERS). Here, a discussion is presented on how to engineer this SPR‐enhanced Raman scattering from both the mesoscopic and microscopic levels. The mesoscopic level focuses on engineering and optimizing the geometric and physical configurations of plasmonic nanoparticles in order to have as large as possible electromagnetic field enhancement factor in the hot spot. The microscopic level focuses on investigating the light–molecule interaction (both chemical and physical) in the microscopic level, either classical or quantum, in order to have deep and complete understanding of the key microscopic issues influencing the Raman scattering and then exploring microscopic means to further enhance the Raman scattering as large as possible. Although in many situations these two scopes can be considered separately, there are also many situations where these two scopes need to be considered together. A prominent example, discussed here, is the critical role of molecule Rayleigh scattering in a plasmonic nanogap. Furthermore, several important issues are pointed out that need attention and caution in exploring and evaluating the quantitative SPR‐based Raman enhancement, including the quantum plasmonics correction, surface and interface electron scattering correction, and the validity of classical electromagnetics and electrodynamics approaches used in single and few atom scale plasmonics.  相似文献   

8.
    
This work aims to explore the application of silver nanoparticle‐based surface‐enhanced Raman scattering (SERS) for nasopharyngeal carcinoma cell line CNE2's DNA analysis after X‐ray radiation. The cells are separated into control group and radiated groups with different dose of 6, 10, 15 and 20 Gy. The results show that after radiation (6, 10, 15 and 20 Gy), the DNA of radiated CNE2 have changed after 72 h of cell incubation. Principal components analysis is employed for significant differences and the DNA extracted after 72 h of incubation show significant divisions from control group. Moreover, a classifier based on support vector machines shows high classification accuracy between DNA extracted after 72 h of incubation and control group. In conclusion, this study first reveals SERS characteristics of CNE2's DNA under different dose of X‐ray radiation, and the final results may do favor to make known the mechanism of X‐ray radiation interacting with tumor. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

9.
    
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.  相似文献   

10.
曾甜  陈钱  江茜  周吉  叶勇 《光散射学报》2016,(3):209-213
本文报道了一种利用聚偏二氟乙烯(Polyviny Lidene Fluoride,PVDF)微孔滤膜为载体的三聚氰胺(Melamine,MAM)的简便快速痕量分析技术。通过柠檬酸钠还原法制得平均粒径为30nm的纳米金溶胶,加入不同浓度的三聚氰胺后金纳米粒子快速聚集,这种纳米金聚集体可以通过简便快捷的过滤技术截留在PVDF微孔滤膜表面,进而用于SERS检测,在水溶液中最低检测浓度为0.05mg/L。我们进一步在牛奶样品中进行检测,在牛奶中检测限可以达到1mg/L,满足大部分国家规定的婴儿配方食品中三聚氰胺的限量值为1mg/kg的参考标准。该分析方法制备过程简单、成本低廉、总分析时间短,易于实现现场快速灵敏检测,应用前景广阔。  相似文献   

11.
    
Surface‐enhanced Raman scattering (SERS) spectroscopy has been used to characterize multilayers of three isomeric aromatic compounds adsorbed on silver nanoclusters. The three structural isomers, all of which adsorb in the carboxylate form onto the silver nanoclusters, bind in two different geometries to the silver surface. Different molecular configurations correlate to differences in bonding strength of these molecules to the silver surface, which can be probed by SERS. For ortho‐hydroxybenzoic acid (salicylic acid), we observed red shifts of major SERS peaks in comparison to the normal Raman vibrations of nonadsorbed crystalline material. For this molecule the steric hindrance between the adjacent carboxylate and hydroxyl groups causes the carboxylate group to rotate from the common flat geometry of benzene substituents on surfaces and bond directly through one of the oxygen atoms to the surface. In this case, strong coordinative bonding between the carboxylate group and the metal surface causes the red shifts in the SERS peaks. For para‐, and meta‐hydroxybenzoic acid, the steric hindrance is less likely since the two functional groups are not at adjacent positions, and therefore these molecules adsorb on the silver surface in a totally flat geometry. For these molecules, in contrast to the ortho isomer, the CO2 interacts with the surface through an extended π bond, and these molecules are physically adsorbed in the common flat position. Therefore, for the meta and para substituents, we do not observe significant red shifts in the SERS spectrum. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

12.
    
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13.
    
Uric acid concentration in human bodily fluids is an important marker for disorders such as gout, pre‐eclamsia or cardiovascular disease. However, currently used methods for its detection either lack sensitivity or require sophisticated, bulky and expensive equipment. In this work, we show that by using surface‐enhanced Raman scattering spectroscopy (SERS) on dried Ag colloidal drops and with 1064 nm excitation, concentrations of uric acid in aqueous solutions down to 10−6 M can be detected. Such sensitivity is sufficient for medical applications as concentration of uric acid in various bodily fluids are in the range of 10−3–10−4 M. Drying of the colloidal drops is known to result in the formation of ‘coffee‐ring’ structures that allow obtaining high enhancements but poor reproducibility. Here, the formation of the structures was avoided by choosing aluminum oxide as a base substrate and by controlling environment conditions. Despite the fact that variations of signal enhancement from sample to sample prevent quantitative analysis from being performed, the results of this work imply that strict control of sample preparation conditions could lead to obtaining reproducible SERS enhancements. Results of density functional theory calculations of uric acid tautomer – five‐atom silver cluster complexes performed for the first time show that the differences between Raman and SERS spectra of uric acid can be mainly explained by tautomerization of the molecule and its bonding to the silver surface. Assignment of spectral bands is important for correct SERS signal interpretation and detection of uric acid in biological fluids in the future studies. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

14.
    
Surface‐enhanced Raman spectroscopy (SERS) has potential for unique clinical, environmental, and military applications, among many others, but it is limited by a rapid decrease in signal with distance from the sensing surface. For this reason, much study of SERS‐based biosensing involves chemical or physical adsorption of analytes to an active surface. Adsorption, however, limits the types of analytes that can be detected and detection sensitivity. The three‐dimensional closely packed architecture of zinc oxide (ZnO) nanowires decorated with silver nanoparticles increases SERS intensity, allowing for adsorption‐free biosensing. This approach greatly expands the potential applications of Raman spectroscopy as a biosensing technique. This work demonstrates a significant SERS enhancement from silver nanoparticle‐decorated ZnO nanoprobes to the Raman spectra of crystal violet, melamine, and adenine solutions. These enhancements were quantified by comparing the intensity of Raman peaks from each of the three solutions through ZnO nanowires decorated with silver nanoparticles with that through bare ZnO nanowires. Estimated enhancement of the Raman signal accounted for the volume difference between solution affected by SERS and solution sensed by the Raman system. More importantly, the detected SERS signal is from molecules in solution and unadsorbed to the sensing surfaces. This lack of adsorption was confirmed by tracking the SERS enhancement of a crystal violet Raman peak over time. This greatly enhances the value and flexibility of Raman spectroscopy as a detection technique for a wide variety of applications. Copyright © 2017 John Wiley & Sons, Ltd.  相似文献   

15.
    
We show in this paper how zinc oxide (ZnO)/silver (Ag) composite microspheres can be prepared by the reduction of Ag(NH3)2+ with the reducing agent formaldehyde in aqueous solution on the surface of ZnO microspheres. During the preparation, Sn2+ was absorbed on the surface of ZnO microspheres for sensitization and activation, and then Ag(NH3)2+ was reduced to Ag nanoparticles by the reducing agent to obtain ZnO/Ag composite microspheres. SEM and TEM images revealed silver nanoparticles with a diameter ranging from tens to 100 nm. X‐Ray photoelectron spectra (XPS), X‐ray diffraction (XRD) patterns and UV‐vis spectra were used to characterize the structure of the ZnO/Ag composite microspheres. The origin of the surface‐enhanced Raman scattering properties was traced to the surface of the ZnO/Ag composite microspheres. The enhancement factor was estimated in detail, and the enhancement mechanism for the SERS effect was also investigated. Copyright © 2007 John Wiley & Sons, Ltd.  相似文献   

16.
    
The NC stretching frequency in the potential‐dependent surface‐enhanced Raman scattering spectrum of 1,4‐phenylenediisocyanide (1,4‐PDI) is very sensitive to the electrode potential, and much the same peak shift is observed when an Au nanoparticle with mean diameter from 16 to 90 nm attached to 1,4‐PDI‐adsorbed gold nanogap system is exposed solely to organic vapors. This leads us to conclude that the surface potential of Au nanoparticles should change by as much as +0.57 and −0.34 V, respectively, in the presence of CCl4 and NH3 because of their respective electron‐withdrawing and electron‐donating properties, regardless of the size of Au nanoparticles in the gold nanogap system. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

17.
    
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18.
    
One of the greatest challenges in developing protein chips is the detection of trace amounts of proteins on their surfaces. Traditionally employed techniques, such as optical microscopy and fluorescence, are effective and widely used, but it is sometimes hard to obtain fingerprint signals of biomolecules. In this paper, we use surface‐enhanced Raman scattering (SERS) spectroscopy as a platform for protein detection. Micropatterned protein‐mediated Au/Ag sandwich structures were employed as the detecting objects. Two types of proteins, pure hemoprotein and immunocomplex, were used as the media. Au/Ag layers were used as the SERS substrates. The resulting spectra showed good sensitivity and resolution. It indicates that SERS is a powerful tool in protein detection and has great potential for application in protein chips. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

19.
    
Rapid and accurate diagnosis of cancers at early stage is clearly desirable, because it provides possibilities to cure the cancers in next treatments. Cancers at early stage usually occur and develop at a molecule level; however, it remains challenging for traditional methods to screen them timely. Here, the capability of using human blood serum surface‐enhanced Raman scattering (BS‐SERS) spectroscopy for label‐free, non‐invasive detection of liver cancer at the molecule level is presented. By using the solid device of silver nanofilms, we performed human BS‐SERS measurements of 40 liver cancer patients and 40 healthy controls and demonstrated a promising diagnostic algorithm for liver cancer detection based on the method of multivariate statistical analysis. The principal components analysis combined with independent sample t test were performed on these BS‐SERS spectral data, separating the cancerous samples from the normal ones with high‐diagnostic sensitivity of ~95.0% and diagnostic specificity of ~97.6%, respectively. This study demonstrates great potential in applications of label‐free, non‐invasive, and rapid human BS‐SERS detection for liver cancer at the molecule level.  相似文献   

20.
    
A controllable heterostructure consisting of ZnO nanorod arrays with attached Ag nanoparticles at only one end has been synthesized via a facile and convenient galvanic reduction method. Scanning electron microscopic images of these nanostructures showed good selectivity of Ag deposition on the tip of ZnO nanorod arrays. The formation of these regular Ag ZnO heterogeneous nanorod arrays can be explained by a localization of the electrons at the ends of the ZnO nanorods after the electron transfer step. By tuning the reaction time and the concentration of silver nitrate, the density of Ag nanoparticles on the tip of ZnO nanorods can be well controlled. Owing to the introduction of Ag nanoparticles with different densities, the resulting Ag ZnO heterogeneous nanorod arrays have been proved to be a versatile substrate for surface‐enhanced Raman scattering not only for common organic molecules but also for label‐free protein detection. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

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