Ag‐nanoparticle‐modified single Ag nanowire for detection of melamine by surface‐enhanced Raman spectroscopy

Silver nanowires synthesized by a solvothermal method were used as templates for fabricating silver‐nanoparticle‐decorated silver (AgNP/Ag) nanowires. The number density and particle size of Ag nanoparticles can be controlled by varying the concentration of Ag precursor. Single AgNP/Ag nanowire exhibited strong surface‐enhanced Raman scattering effect. Detection of melamine molecules at concentrations as low as 1.0 × 10⁻⁸ M was used as an example to show the possible applications of such AgNP/Ag nanowires. Their application in rapid detection of melamine in milk solution was further demonstrated. It was shown that melamine in milk solution at a low concentration of 5.0 × 10⁻⁸ M can be easily detected with little sample pretreatment. The results demonstrate the potential of single AgNP/Ag nanowire as a surface‐enhanced Raman scattering substrate for convenient and sensitive detection of trace amounts of melamine in a complex mixture. Copyright © 2012 John Wiley & Sons, Ltd.     

Photodissociation effects on pulsed laser deposited silver oxide thin films: surface‐enhanced resonance Raman scattering

Temporal Raman scattering measurements with 488, 532 and 632 nm excitation wavelengths and normal Raman studies by varying the power (from 30 W/cm² to 2 MW/cm²) at 488 nm were performed on silver oxide thin films prepared by pulsed‐laser deposition. Initially, silver oxide Raman spectra were observed with all three excitation wavelengths. With further increase in time and power, silver oxide photodissociated into silver nanostructures. High‐intensity spectral lines were observed at 1336 ± 25 and 1596 ± 10 cm⁻¹ with 488 nm excitation. No spectral features were observed with 633 nm excitation. Surface‐enhanced resonance Raman scattering theory is used to explain the complex behavior in the intensity of the 1336/1596 cm⁻¹ lines with varying power of 488 nm excitation. Copyright © 2011 John Wiley & Sons, Ltd.     

Raman spectra of benzoic acid enhanced by the silver nanoparticles of various sizes

Using sodium borohydride as the reducing agent and polyvinyl pyrrolidone (PVP, MW = 10 000) as the stabilizer, we obtained silver nanoparticles of various diameters (8–78 nm) from silver nitrate aqueous solutions in the concentration range from 0.001 to 0.1 M. The surface‐enhanced Raman scattering (SERS) from benzoic acid's ring‐breathing mode at 1003 cm⁻¹ was detected from its dilute solutions (∼10⁻² M) doped with these silver nanoparticles under 488‐nm laser excitation. The observed size dependences of SERS intensities fit quite well with those calculated by Schatz's theoretical model for spherical silver nanoparticles. The only exception occurred with the smallest particles (8 nm), possibly due to the failure of Maxwell's electromagnetic theory used in this model. Copyright © 2009 John Wiley & Sons, Ltd.     

Stilbazolium merocyanine dye determination in different solutions,concentrations and colloids using SERS

Surface‐enhanced Raman scattering (SERS) measurements were carried out on stilbazolium merocyanine dye in methanol and pyridine solvents. Both solutions were measured in a series of concentrations covering a range of 5 × 10⁻⁵ M to 5 × 10⁻⁸ M . In these measurements, Ag and Au colloids were used, and the results have shown that Ag colloids yield better enhancement in the Raman spectra of this dye. Moreover, the effect of adding NaCl solution to the SERS samples was also studied. All measurements were carried out using the state‐of‐the‐art ChiralRaman instrument, which utilizes a 532 nm laser source. We report here on the success of using SERS to obtain Raman spectra of merocyanine dye at very low concentrations in an attempt to find a new approach that can be used for further investigations of the dye. The SERS spectra are reported here, and the results from different solutions, colloids, concentrations and pH values are compared. Copyright © 2006 John Wiley & Sons, Ltd.     

Fabrication and characterization of SERS‐active silver clusters on glassy carbon

In this article, a novel technique for the fabrication of surface enhanced Raman scattering (SERS) active silver clusters on glassy carbon (GC) has been proposed. It was found that silver clusters could be formed on a layer of positively charged poly(diallyldimethylammonium) (PDDA) anchored to a carbon surface by 4‐aminobenzoic acid when a drop containing silver nanoparticles was deposited on it. The characteristics of the obtained silver clusters have been investigated by atomic force microscopy (AFM), SERS and an SERS‐based Raman mapping technique in the form of line scanning. The AFM image shows that the silver clusters consist of several silver nanoparticles and the size of the clusters is in the range 80–100 nm. The SERS spectra of different concentrations of rhodamine 6G (R6G) on the silver clusters were obtained and compared with those from a silver colloid. The apparent enhancement factor (AEF) was estimated to be as large as 3.1 × 10⁴ relative to silver colloid, which might have resulted from the presence of ‘hot‐spots’ at the silver clusters, providing a highly localized electromagnetic field for the large enhancement of the SERS spectra of R6G. The minimum electromagnetic enhancement factor (EEF) is estimated to be 5.4 × 10⁷ by comparison with the SERS spectra of R6G on the silver clusters and on the bare GC surface. SERS‐based Raman mapping technique in the form of line scanning further illustrates the good SERS activity and reproducibility on the silver clusters. Finally, 4‐mercaptopyridine (4‐Mpy) was chosen as an analyte and the lowest detected concentration was investigated by the SERS‐active silver clusters. A concentration of 1.6 × 10⁻¹⁰ M 4‐Mpy could be detected with the SERS‐active silver clusters, showing the great potential of the technique in practical applications of microanalysis with high sensitivity. Copyright © 2006 John Wiley & Sons, Ltd.     

Spectroscopic analysis of a dye–mineral composite–a Raman and FT‐IR study

In this investigation, we address the question of how organic thioindigo binds to inorganic palygorskite to form a pigment similar to Maya Blue. We also address how such binding, if it occurs, might be affected by varying the proportion of dye relative to that of the mineral, and by varying the length of heating time used in preparation of the pigment. In addition to samples of palygorskite and thioindigo both alone, four synthetic pigment samples were prepared; two samples of 8 wt.% dye, one heated at 170 °C for 3 h and one at 170 °C for 9 h, and two samples of 16 wt.% dye, one heated at 170 °C for 3 h and one at 170 °C for 9 h. All samples were examined using Fourier transform‐infrared (FT‐IR) and FT‐Raman spectroscopy. For the pigment samples, FT‐IR peaks at 1627 cm⁻¹ are attributed to a downshifted CO stretching mode of thioindigo due to dye–clay interaction. This interpretation is corroborated by FT‐Raman CO peaks with 14 cm⁻¹ shifts to lower wavenumber for the pigment relative to thioindigo alone. Additional Raman scattering between 550 cm⁻¹ and 650 cm⁻¹ also suggests dye–clay interaction through metal–oxygen bonding. We are thus led to the possibility of mostly hydrogen bonding between silanol and carbonyl at lower dye concentration, with a predominance of metal–oxygen bonding at higher dye concentration. Copyright © 2008 John Wiley & Sons, Ltd.     

Au@SiO2 core/shell nanoparticle assemblage used for highly sensitive SERS‐based determination of glucose and uric acid

The use of Au@SiO₂ core/shell nanoparticle (NP) assemblage with highly sensitive surface‐enhanced Raman scattering (SERS) was investigated for the determination of glucose and uric acid in this study. Rhodamine 6G dye molecules were used to evaluate the SERS enhancement factor for the synthesized Au@SiO₂ core/shell NPs with various silica shell thicknesses. The enhancement of SERS signal from Rhodamine 6G was found to increase with a decrease in the shell thickness. The core/shell assemblage with silica layer of 1–2 nm over a Au NP of ~36 nm showed the highest SERS signal. Our results show that the SERS technique is able to detect glucose and uric acid within wide concentration ranges, i.e. 20 ng/dL to 20 mg/dL (10⁻¹²–10⁻³ M) and 16.8 ng/dL to 2.9 mg/dL (10⁻¹¹–1.72 × 10⁻⁴ M), respectively, with associated lower detection limits of ~20 ng/dL (~1.0 × 10⁻¹² M) and ~16.8 ng/dL (~1.0 × 10⁻¹¹ M). Our work offers a low‐cost route to the fabrication of agile sensing devices applicable to the monitoring of disease progression. Copyright © 2013 John Wiley & Sons, Ltd.     

Rapid and simple detection of sodium thiocyanate in milk using surface‐enhanced Raman spectroscopy based on silver aggregates

Surface‐enhanced Raman spectroscopy (SERS) was used for rapid detection of sodium thiocyanate in milk employing silver aggregates as active substrate. Silver nanoparticles were induced to silver aggregates by trichloroacetic acid (TCA). The limit of detection (LOD) for sodium thiocyanate was 10⁻² µg ml⁻¹ in water with an analytical enhancement factor of 5.4 × 10⁶. The silver aggregates represent good reproducibility and stability. Good linear relationship was obtained for sodium thiocyanate in milk at concentration ranges from 0.1 to 10 µg ml⁻¹ (R² = 0.995). Using TCA as protein precipitator, silver colloid would aggregate spontaneously when mixing with samples during SERS measurement without the need of additional aggregating agent. The simple pretreatment procedures and analytical methods are less time consuming (<10 min) and environmentally friendly, making the proposed method much practical for in situ detection of sodium thiocyanate in market milk. Copyright © 2014 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.     

SERS activity of pulsed laser ablated silver thin films with controlled nanostructure

The surface‐enhanced Raman scattering (SERS) activity of silver thin films deposited by the pulsed laser ablation technique was investigated. The samples were grown in a controlled Ar atmosphere at pressures ranging between 10 and 70 Pa, and changing the number of laser pulses. Different surface morphologies, from isolated nearly spherical nanoparticles (NPs) to larger islands with smooth edges, were observed by means of scanning and transmission electron microscopies, as a function of the different deposition conditions adopted. SERS measurements were performed by soaking the samples in rhodamine 6G aqueous solutions over the concentration range between 1.0 × 10⁻⁴ and 5.0 × 10⁻⁸ M . Raman spectra were acquired using both the 632.8 and 514.5 nm excitation sources. The dependence of the SERS activity of the samples on the observed surface morphology is presented and discussed. The presence of the so called hot spots is envisaged. Copyright © 2011 John Wiley & Sons, Ltd.     

Measurement of the absolute Raman scattering cross section of the 1584‐cm−1 band of benzenethiol and the surface‐enhanced Raman scattering cross section enhancement factor for femtosecond laser‐nanostructured substrates

The absolute Raman scattering cross section (σ_RS) for the 1584‐cm⁻¹ band of benzenethiol at 897 nm (1.383 eV) has been measured to be 8.9 ± 1.8 × 10⁻³⁰ cm² using a 785‐nm pump laser. A temperature‐controlled, small‐cavity blackbody source was used to calibrate the signal output of the Raman spectrometer. We also measured the absolute surface‐enhanced Raman scattering cross section (σ_SERS) of benzenethiol adsorbed onto a silver‐coated, femtosecond laser‐nanostructured substrate. Using the measured values of 8.9 ± 1.8 × 10⁻³⁰ and 6.6 ± 1.3 × 10⁻²⁴ cm² for σ_RS and σ_SERS respectively, we calculate an average cross‐section enhancement factor (EF) of 0.8 ± 0.3 × 10⁶. Copyright © 2009 John Wiley & Sons, Ltd.     

DFT study and quantitative detection by surface‐enhanced Raman scattering (SERS) of ethyl carbamate

Ethyl carbamate (EC), a potentially toxic compound, is found in alcoholic beverages and fermented foodstuff. A combined experimental and theoretical study of Raman on EC is reported in this work for the first time. The Raman bands observed for EC in solid phase are characteristic for the carbonyl group, C―C, C―H and N―H stretching and deformation vibrations. These spectral features coupled with a pKa study allowed establishing the neutral species of EC present in the aqueous solutions experimentally tested at different concentrations. In addition, by performing a density functional theory study in the gas phase, the calculated geometry, the harmonic vibrational modes, and the Raman scattering activities of EC were found to be in good agreement with our experimental data and helped establish the surface‐enhanced Raman scattering (SERS) behavior and EC adsorption geometry on the silver surfaces. The Raman peak at 1006 cm⁻¹, assigned to the υ_s(CC) + ω(CH) modes, the strongest and best reproducible peak in the SERS spectra, was used for a quantitative evaluation of EC. The limit of detection, which corresponds to a signal‐to‐noise ratio equal to 3, was found to be 2 × 10⁻⁷ M (17.8 µg l⁻¹). SERS spectra obtained by using hydroxylamine hydrochloride‐reduced silver nanoparticles provide a fast and reproducible qualitative and quantitative determination of EC in aqueous solution. Copyright © 2013 John Wiley & Sons, Ltd.     

Effect of the structural order of all‐trans‐β‐carotene on the Raman scattering cross section at low concentrations

Using the technique of liquid‐core optical fiber (LCOF), we measured the Raman scattering cross sections (RSCSs) of the carbon–carbon (C C) stretching vibrational modes of all‐trans‐β‐carotene in carbon disulfide (CS₂) at concentrations ranging from 10⁻⁶ to 10⁻¹¹ M . It was found that the RSCSs of all‐trans‐β‐carotene were extremely high with decreasing concentration, and the absolute RSCS of C stretching modes of all‐trans‐β‐carotene reached the value of 2.6 × 10⁻²⁰ cm² molecule⁻¹ Sr⁻¹ at 8 × 10⁻¹¹ M , which is larger than at 8 × 10⁻⁶ Mby 4 orders of magnitude. A theoretical interpretation of the anomalous experimental results is given, which introduces a qualitative nonlinear model of coherent weakly damped electron‐lattice vibrations in structural order of all‐trans‐β‐carotene. Copyright © 2010 John Wiley & Sons, Ltd.     

Single‐molecule detection of thionine on aggregated gold nanoparticles by surface enhanced Raman scattering

We report observations of single‐molecule detection of thionine and its dynamic interactions on aggregated gold nanoparticle clusters using surface enhanced Raman scattering (SERS). Spectral intensities were found to be independent of the size of Au nanoparticles studied (from 17 to 80 nm) at thionine concentration below 10⁻¹² M or at single‐molecule concentration levels. Raman line separations and, in particular, spectral fluctuations and blinking were also observed, suggesting temporal changes in single molecular motion and/or arrangements of thionine on Au nanoparticle surfaces. In contrast, by using dispersed Au nanoparticles, only ensemble SERS spectra could be observed at relatively high concentrations (> 10⁻⁸ M thionine), and spectral intensities varied with the size of Au nanoparticles. Copyright © 2007 John Wiley & Sons, Ltd.     

Pump power dependence in resonance femtosecond stimulated Raman spectroscopy

Femtosecond stimulated Raman spectroscopy (FSRS) has emerged as a powerful new technique that is capable of obtaining resonance Raman spectra of fluorescent species and transient photochemical intermediates. Unlike related transient infrared absorption techniques, the FSRS signal is quite sensitive to the laser power utilized in the vibrational probing event. In particular, FSRS spectra are highly sensitive to the intensity of the picosecond Raman‐pump pulse. We have measured the power dependence of the FSRS signal using pulse energies from ~10⁻⁹ to ~10⁻⁵ J and molecules with a range of molar absorptivities at the Raman‐pump wavelength of 400 nm, including β‐carotene (ε₄₀₀ = 58 300 M⁻¹ cm⁻¹), para‐nitroaniline (17 800 M⁻¹ cm⁻¹), nitronaphthalene (247 M⁻¹ cm⁻¹) and ferrocene (57 M⁻¹ cm⁻¹). We show that for strongly absorbing molecular systems, such as β‐carotene and para‐nitroaniline, the ground‐state (GS) FSRS signal actually decreases with increasing pump power at pump fluences above ~10⁻² J cm⁻², due to depletion of the GS population. However, for weakly absorbing species like nitronaphthalene and ferrocene, the signal increases linearly with increasing pump fluence until ~0.5 J cm⁻², at which point two‐photon absorption by the solute induces nonlinear absorption of the pump pulse and attenuation of the FSRS signal. The data are quantitatively simulated with a photophysical kinetic model, and the results are analyzed to provide simple guidelines for acceptable Raman‐pump powers in resonance FSRS experiments. The acceptable Raman‐pump power is proportional to the focused beam area and depends inversely on the sample's molar absorptivity. Copyright © 2013 John Wiley & Sons, Ltd.     

Rapid atto‐molar level detection of surface‐enhanced Raman spectroscopy technique based on glycidyl methacrylate–ethylene dimethacrylate (GMA–EDMA) porous material

A novel miniature device for rapid ultra‐sensitive surface‐enhanced Raman scattering (SERS) detection was developed in the present study. The device was made of a syringe, a piece of filter, and a Teflon tube. Therefore, it was with advantages of simplicity, miniaturization, and easy operability. The tube was filled in advance with the glycidyl methacrylate‐ethylene dimethacrylate powder porous material which has been proved to increase the sensitivity of normal SERS dramatically, then the mixture solution containing the analyte, silver colloid, and NaCl solution passed through the porous material by the action of the syringe. SERS signals were collected from the surface of the material. Rhodamine 6G (R6G), p‐aminothiophenol (PATP), and thiabendazole (TBZ) were employed as the probe molecules in the present work. R6G at microlitre‐scale can be detected at an extremely low concentration of 10^–18 mol/l, and the relative standard deviation of spot to spot is 14.16% at the intensity of the band at 609 cm⁻¹. The concentrations of PATP and TBZ that can be detected with the method are 10⁻¹¹ mol/l and 1.3 × 10⁻⁶ mol/l, respectively. This method not only has achieved the ultra‐sensitive detection of dye and pesticide but also realized the simple, rapid, and small sample quantity requirement detection, and it is of great potential use for lots of analytes. Copyright © 2013 John Wiley & Sons, Ltd.     

Uric acid detection by means of SERS spectroscopy on dried Ag colloidal drops

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.     

Measurement of the absolute Raman scattering cross sections of sulfur and the standoff Raman detection of a 6‐mm‐thick sulfur specimen at 1500 m

The absolute Raman scattering cross sections (σ_RS) for the 471, 217, and 153 cm⁻¹ modes of sulfur were measured as 6.0 ± 1.2 × 10⁻²⁷, 7.7 ± 1.6 × 10⁻²⁷, and 1.2 ± 0.24 × 10⁻²⁶ cm² at 815, 799, and 794 nm, respectively, using a 785‐nm pump laser. The corresponding values of σ_RS at 1120, 1089, and 1081 nm were determined to be 1.5 ± 0.3 × 10⁻²⁷, 1.2 ± 0.24 × 10⁻²⁷, and 1.2 ± 0.24 × 10⁻²⁷ cm² using a 1064‐nm laser. A temperature‐controlled, small‐cavity (2.125 mm diameter) blackbody source was used to calibrate the signal output of the Raman spectrometers for these measurements. Standoff Raman detection of a 6‐mm‐thick sulfur specimen located at 1500 m from the pump laser and the Raman spectrometer was made using a 1.4‐W, CW, 785‐nm pump laser. Copyright © 2010 John Wiley & Sons, Ltd.     

Identification of chemical modification in single human keratinocyte cells exposed to low doses of chlorpyriphos by Raman micro‐spectroscopy

Raman micro‐spectroscopy can be used to investigate biological single cells exposed to different chemicals. Since chronic exposure at low doses of pesticides can promote several diseases, the investigation of cellular changes induced by exposure to non‐cytotoxic doses of pesticides is of increasing interest. The efficiency of Raman micro‐spectroscopy to detect chemical modification in normal human keratinocytes induced by exposure to non‐cytotoxic doses of chlorpyriphos, an organophosphate pesticide present in many plant‐protection products, was investigated. Such modification affects mainly proteineous components (both single amino acids and amide linkages between amino acids) of the nucleus, cellular membranes and cytoplasm as well as the nucleic acid component of the nucleus. Chemical modifications are already detectable after 24 h exposure of keratinocytes at a chlorpyriphos concentration of 10⁻⁶ M , which is three orders of magnitude lower than the cytotoxic concentration (10⁻³ M ). Heavy damage to the lipid component occurs after exposure to the nearly cytotoxic concentration (10⁻⁴ M ). Atomic force microscopy images of keratinocyte cells exposed for 24 h to various chlorpyriphos concentrations show a progressive deterioration of the morphology of cellular membrane as the chlorpyriphos concentration increases. The results of this work may have wide applications in the monitoring of molecular changes in single human cells exposed to toxic agents. Copyright © 2010 John Wiley & Sons, Ltd.     

Experimental and ab initio DFT calculated Raman spectrum of Sudan I,a red dye

The red dye Sudan I was investigated by Raman spectroscopy using different excitation wavelengths (1064, 532 and 244 nm). A calculation of the Raman spectrum based on quantum mechanical ab initio density functional theory (DFT) was made using the RB3LYP method with the 3‐21G and 6‐311 + G(d,p) basis sets. The vibrations in the region 1600–1000 cm⁻¹ were found to comprise various mixed modes including in‐plane stretching and bending of various C C, N N, C N and C O bonds and angles in the molecule. Below ∼900 cm⁻¹, the out‐of‐plane bending modes were dominant. The central hydrazo chromophore of the Sudan I molecule was involved in the majority of the vibrations through NN and C N stretching and various bending modes. Low‐intensity bands in the lower wavenumber range (at about 721, 616, 463 and 218 cm⁻¹) were selectively enhanced by the resonance Raman effect when using the 532 nm excitation line. Comparison was made with other azo dyes in the literature on natural, abundant plant pigments. The results show that there is a possibility in foodstuff analysis to distinguish Sudan I from other dyes by using Raman spectroscopy with more than one laser wavelength for resonance enhancement of the different bands Copyright © 2011 John Wiley & Sons, Ltd.