Surface-enhanced Raman spectroscopy coupled with gold nanoparticles for rapid detection of amoxicillin residues in duck meat

Antibiotic residues in meat pose serious threats to human beings and animals, and are one of the main food safety concerns all around the world. A novel method based upon surface-enhanced Raman spectroscopy (SERS) coupled with gold nanoparticles was developed in this study for rapid detection of amoxicillin residues in duck meat, one widely used in duck farming. Three different particle sizes of gold nanoparticles were synthesized using 0.3, 0.7, and 1.1?mL 1% trisodium citrate, while 0.7?mL was found to be the optimal volume as Raman enhancement substrate for the detection of amoxicillin residues in duck meat. The amounts of gold nanoparticles (0.5?mL), duck meat extract containing amoxicillin (50?μL), and sodium chloride solution (100?μL), as well as adsorption time (5?min) were optimized by single factor experiments. A calibration curve with the determination coefficient of 0.9661 was established for quantitative analysis of unknown amoxicillin samples. The average recoveries of amoxicillin residues in duck meat extract were 96–139%. This study provided a rapid and simple approach to analyze amoxicillin residues in duck meat in excess of 0.2?mg?L^?1 using SERS coupled with gold nanoparticles, which has the potential for wide applications in the detection of the antibiotic residues in meat.     

Quantitative analysis of chromate (CrVI) by normal Raman spectroscopy and surface-enhanced Raman spectroscopy using poly(diallyldimethylammonium) chloride-capped gold nanoparticles

Chromate (Cr^VI) has emerged as a widespread environmental contaminant found in groundwater and surface water, and there is a great need for rapid detection and monitoring of this contaminant. Normal Raman scattering (NRS) spectroscopy with a detection limit of Cr^VI at concentrations of 0.2 g/L was attached. And surface-enhanced Raman scattering (SERS) spectroscopy technique was found to be capable of detecting Cr^VI at concentrations as low as 2.5 mg/L using poly(diallyldimethylammonium) chloride modified gold nanoparticles (PDDA-AuNPs) as a substrate. The SERS substrate was successfully fabricated by combining the selfassembly technique with a heat-treatment-based strategy using poly(diallyldimethylammonium) chloride (PDDA) as the reducing and stabilizing agents. With the 520 cm^?1 band of silicon as internal standard, band intensity ratios of Cr^VI to silicon, that is I ₉₀₂/I ₅₂₀, were found to have a quantitative relationship with a large concentration range of Cr^VI from 0.2 to 20.0 g/L for NRS (R ² = 0.994) and from 2.5 to 25.0 mg/L for SERS (R ² = 0.980), respectively. Besides, the SERS methodology was reproducible, and susceptible to the interference of pH value. The optimum pH for Cr^VI detection by SERS was 3.38. The application of NRS and SERS showed high practical potential for rapid screening and routine analysis of Cr^VI in environmental samples.     

Raman spectroscopy of combinatory anticancer drug release from gold nanoparticles inside a single leukemia cell

Combinatory anticancer drug release from gold nanoparticles (AuNPs) in K562 human myeloid leukemia cells was performed using Raman spectroscopy. We fabricated the anticancer drug of imatinib as a BCR‐ABL tyrosine kinase inhibitor on AuNP surfaces along with a transferrin (Tf)‐targeting moiety to treat the leukemia cells. DNA topoisomerase I inhibitor topotecan was also assembled to monitor its fluorescence onto AuNPs. The linker group of 4‐carboxylic benzoic acid was used to conjugate to targeting the Tf protein. Our Raman data indicated that the drug molecules were not detached in the cell culture media but released after treatment with glutathione (2 mM). Intracellular distribution and release of the anticancer drug–AuNP conjugates in K562 cells were examined by both fluorescence microscopy and dark‐field microscopy with surface‐enhanced Raman scattering. Copyright © 2013 John Wiley & Sons, Ltd.     

Raman spectroscopy investigation of magnetite nanoparticles in ferrofluids

Raman spectroscopy is used to investigate magnetite nanoparticles dispersed in two types of β-cyclodextrin suspensions. An approach is presented for characterization of the magnetic core in liquid surrounding at room temperature and atmospheric pressure. The effect of elevating laser power on the structural stability and chemical composition of magnetite in the ferrofluids is discussed. The data are compared with data from dry by-products from the fluids. Powder samples undergo total phase transition from magnetite to hematite at laser power of 1.95 mW. The same nanoparticles in the fluid undergo transformation at 9 mW, but no hematite positions appear throughout that investigation. The Raman spectra revealed that the main phase of the magnetic core in the fluids is magnetite. That is indicated by a strong and non-diminishing in intensity peak at 670 cm⁻¹. A second phase is present at the nanoparticle’s surface with Raman spectroscopy unveiling maghemite-like and small fractions of goethite-like structures. The Fourier transform infrared spectroscopy investigations confirm deviations in the surface structure and also point to the fact that the oxidation process starts at an early stage after formation of the nanoparticles. The analyses of the infrared data also show that β-cyclodextrin molecules retain their cyclic character and the coating does not affect the oxidation process once the particles are evicted from the fluids. A Mössbauer spectroscopy measurement on a ferrofluidic sample is also presented.     

Cavity ring-down spectroscopy of metallic gold nanoparticles

The optical properties of supported gold nanoparticles with sizes of 1.3 nm, 1.6 nm, 2.5 nm, and 2.9 nm have been studies by using cavity ring-down spectroscopy in the photon energy range between 1.8 eV and 3.0 eV. The obtained results show the possibility to obtain optical information of nanoassembled materials with high sensitivity. The experimental findings are compared to calculations using Mie-Drude theory. Whereas the broadening of the surface plasmon resonance with decreasing size is well described by this model, the observed blue-shift of the surface plasmon resonance contradicts the predictions of the Mie-Drude theory. The latter effect can be explained by the presence of a skin region with decreased polarizability typical for coinage metal particles. Furthermore, it is found that the supported gold nanoparticles are robust under ambient conditions, an important issue when using these materials for optical applications.     

Study of polycrystalline boron-doped diamond films by Raman spectroscopy and optical absorption spectroscopy

The effect of the degree of doping polycrystalline diamond films by boron on their Raman and absorption spectra has been studied in the visible region (from 200 to 1000 nm). As the boron concentration increases in a polycrystalline diamond film, its Raman spectrum exhibits a number of new specific features caused by the effect of boron atoms on the diamond lattice. The dependences that relate these features to the boron concentration in the films are given. Moreover, the absorption spectra of the films have revealed a peak whose maximum corresponds to photons with an energy near 2 eV.     

纳米级润滑膜分子排列取向的拉曼光谱表征技术

利用激光拉曼散射技术,对剪切作用下受限于钢球与石英盘之间的纳米级液晶5 CB的分子排列取向进行研究. 结果表明,在特定的实验条件下,可以得到高信噪比的纳米级润滑膜的拉曼散射信号(20∶1). 同时发现,当激光偏振方向与剪切运动方向平行(垂直)时,所得拉曼信号强度达到最大(小)值,表明纳米级液晶5 CB分子在剪切诱导作用下,沿剪切运动方向趋于定向排列. 另外,当钢球与石英盘之间的剪切速度逐渐增大时,受限的纳米级液晶5 CB的拉曼信号强度也逐渐增大. 最后,利用根据相对光强干涉原理研制的纳米膜厚测量仪对纳米级 关键词： 薄膜润滑 分子排列取向 拉曼散射     

Near-field spectroscopy of surface plasmons in flat gold nanoparticles

We use near-field interference spectroscopy with a broadband femtosecond, white-light probe to study local surface plasmon resonances in flat gold nanoparticles (FGNPs). Depending on nanoparticle dimensions, local near-field extinction spectra exhibit none, one, or two resonances in the range of visible wavelengths (1.6-2.6 eV). The measured spectra can be accurately described in terms of interference between the field emitted by the probe aperture and the field reradiated by driven FGNP surface plasmon oscillations. The measured resonances are in good agreement with those predicted by calculations using discrete dipole approximation. We observe that the amplitudes of these resonances are dependent upon the spatial position of the near-field probe, which indicates the possibility of spatially selective excitation of specific plasmon modes.     

Optically addressable selective nanovolume Raman spectroscopy of nanoparticles

We present recent experimental and theoretical advances in the selective nanovolume Raman spectroscopy of nanoparticles. Our setup is based on previously available microspectrometry imaging systems for working in the near-field domain combined with a stigmatic solid immersion lens. By spectrally selecting nanoparticles, we registered the spatial distribution of the emitted photons in x, y, z vectors to determine the position in the near-field domain. This near-field capability is applied to resolve local variations unambiguously in the Raman spectra for nanoparticles with unity throughput.     

Plasma desorption mass spectroscopy of thiol-passivated gold nanoparticles

Plasma desorption mass spectrometry has been applied to characterization of dodecanthiol-passivated gold nanoparticles. An overview of the experimental set-up and mass analyses for the nanoparticles prepared in different conditions are shown. Mass distributions were found to shift to higher mass regions with increasing reaction temperature and reaction period. The results are consistent with those of transmission electron microscopy observations, UV-visible absorption spectra and also with a reported laser desorption mass spectrometry.     

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.     

新型冠状病毒S蛋白在金纳米粒子中的表面增强拉曼效应

表面增强拉曼光谱技术因其高灵敏度、操作简单、快速检测等优点,被广泛用于病毒检测方面。国内外的病毒拉曼检测研究主要集中在检测病毒核酸以及组成核酸的各种碱基的表面增强拉曼光谱(SERS),但少见对病毒蛋白的SERS检测。以新型冠状病毒（SARS-CoV-2）的S蛋白为检测对象,采用无标记SERS检测方法,对比SARS-CoV-2固态、饱和液态S蛋白的普通拉曼光谱和选用40 nm金纳米粒子为基底的SARS-CoV-2低浓度S蛋白SERS光谱。结果表明,以40 nm金纳米粒子为基底,采用SERS技术检测SARS-CoV-2的S蛋白是完全可行的。SARS-CoV-2的S蛋白分子中的羧基与金纳米粒子发生了分子增强,氨基与金纳米粒子发生了电磁增强,从而使得SARS-CoV-2的S蛋白拉曼效应得到了增强,并使得峰位发生一定移动。实验获得了较好的SARS-CoV-2低浓度S蛋白SERS光谱,为建立敏感、特异、快速的SARS-CoV-2检测新技术提供了一种方法。     

Near-infrared surface-enhanced Raman spectroscopy of chemisorbed compounds on gold colloids

Near-infrared surface-enhanced Raman scattering (SERS) spectra have been measured for strongly chemisorbed compounds, such as 4-mercaptopyridine and thiophenol, on gold colloids in mixed solvents of ethanol and water using a diode laser as an excitation source. From UV-vis spectroscopy, the aggregated gold colloids show a broad absorbance band through the visible to the near-infrared after adding chemisorbing compounds. The absorption maximum is located in the range 750–850 nm, permitting the use of a near-IR source (826 nm) for the first time in SERS of gold colloid systems. The estimated enhancement is on the order of 10⁵. Transmission electron microscopy of aggregated gold particles revealed a cluster morphology. The aggregated mixed-solvent colloids were more stable than those prepared in water, and were useful in dissolving compounds with poor water solubility.     

Preparation of gold electrodes for surface enhanced Raman spectroscopy SERS

An electrochemical method for preparation of electrodes for SERS involving repetitive dissolution-deposition potential cycling of a polycrystalline, smooth gold electrode is described, which can be applied in both halide-free and halide containing solutions. The SERS-active electrodes obtained this way can be cleaned effectively and subsequently exposed to electrolyte solutions containing adsorbable molecules. No trapping of molecules or ions present during the activation is found in SER spectra, the signal-to-noise ratio obtained with these electrodes even allows detection of weakly adsorbed species.     

Thin film substrates from the Raman spectroscopy point of view

We have investigated ten standard single crystal substrates of complex oxides on the account of their applicability in the Raman spectroscopy‐based thin film research. In this study, we suggest a spectra normalization procedure that utilizes a comparison of the substrate's Raman spectra to those of well‐established Raman reference materials. We demonstrate that MgO, LaGaO₃, (LaAlO₃)_0.3(Sr₂AlTaO₆)_0.7 (LSAT), DyScO₃, YAlO₃, and LaAlO₃ can be of potential use for Raman‐based thin film research. At the same time TiO₂ (rutile), NdGaO₃, SrLaAlO₄, and SrTiO₃ single crystals exhibit multiple phonon modes accompanied by strong Raman background that substantially hinder Raman‐based thin film experiments. Copyright © 2014 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman scattering spectroscopy via gold nanostars

Anisotropic metallic nanoparticles (NPs) have unique optical properties, which lend them to applications such as surface‐enhanced Raman scattering (SERS) spectroscopy. Star‐shaped gold (Au) NPs were prepared in aqueous solutions by the seed‐mediated growth method and tested for Raman enhancement using 2‐mercaptopyridine (2‐MPy) and crystal violet (CV) probing molecules. For both molecules, the SERS activity of the nanostars was notably stronger than that of the spherical Au NPs of similar size. The Raman enhancement factors (EFs) for 2‐MPy on Au nanostars and nanorods are comparable and estimated as greater than 5 orders of magnitude. However, the enhancement for CV on nanostars was significantly higher than for nanorods, in particular at CV concentrations of 100 nM or lower. This article is a US Government work and is in the public domain in the USA. Published in 2008 by John Wiley & Sons, Ltd.     

Negative pressure effects in SrTiO3 nanoparticles investigated by Raman spectroscopy

The size effects on SrTiO₃ nanoparticles have been investigated by means of Raman spectroscopy with changing the grain size in the range 10–80 nm. The intensities of the first-order polar TO₂ and TO₄ modes increase as the grain size reduces, suggesting the enhanced interaction of the surface-defect dipoles on the grain boundary. By contrast, the intensities for the first-order nonpolar TO₃ mode decrease with reducing the grain size. Further we have found that the Raman frequencies of the vibration modes are very sensitive to the variation of the grain size. The softening of the TO₂ and TO₃ modes with decreasing the grain size indicates the increase of the Ti–O bond length, which is consistent with the lattice expansion investigated by XRD. We have ascribed the size effects to the negative pressure effects due to the enhanced interaction of the surface-defect dipoles.     

Low-frequency Raman scattering in a polycrystalline C60 film: The role of orientational disorder

Low-frequency Raman scattering in the orientationally disordered phase of a polycrystalline C₆₀ film is investigated. By analogy with disordered media (glasses), the low-frequency Raman spectra are interpreted in terms of light scattering by localized vibrational states.     

Self-assembly 2D plasmonic nanorice film for surface-enhanced Raman spectroscopy

As an ultrasensitive sensing technology, the application of surface enhanced Raman spectroscopy (SERS) is one interesting topic of nano-optics, which has huge application prospectives in plenty of research fields. In recent years, the bottleneck in SERS application could be the fabrication of SERS substrate with excellent enhancement. In this work, a two-dimensional (2D) Ag nanorice film is fabricated by self-assembly method as a SERS substrate. The collected SERS spectra of various molecules on this 2D plasmonic film demonstrate quantitative detection could be performed on this SERS substrate. The experiment data also demonstrate this 2D plasmonic film consisted of anisotropic nanostructures has no obvious SERS polarization dependence. The simulated electric field distribution points out the SERS enhancement comes from the surface plasmon coupling between nanorices. And the SERS signals is dominated by molecules adsorbed at different regions of nanorice surface at various wavelengths, which could be a good near IR SERS substrate for bioanalysis. Our work not only enlarges the surface plasmon properties of metal nanostructure, but also exhibits the good application prospect in SERS related fields.