Time-dependent micro-Raman scattering studies of polyvinyl alcohol and silver nitrate thin films

In-situ monitoring of silver nanoparticle formation was studied in thin films of polyvinyl alcohol and silver nitrate. We proposed the observation of surface-enhanced Raman spectroscopy (SERS) as a novel and simple technique to record the growth of silver nanoparticles in polyvinyl alcohol thin films. Observed enhancement in the Raman bands of polyvinyl alcohol is explained through the localized surface plasmon resonance of silver nanoparticles. Influence of temperature generated by silver nanoparticles on the formation of nanoparticles is also discussed.     

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.     

Size‐dependent SERS enhancement of colloidal silver nanoplates: the case of 2‐amino‐5‐nitropyridine

Surface‐enhanced Raman scattering (SERS) spectra of 2‐amino‐5‐nitropyridine (ANP) adsorbed on colloidal silver triangular nanoplates were obtained using samples with different mean sizes and surface plasmon frequencies. The relative SERS enhancement factor for each sample was determined by the analysis of the normalized SERS excitation profiles of ANP vibrational modes for nanoplates in suspension, without aggregation. The SERS profiles are blue‐shifted in relation to the localized surface plasmon peak. The detailed characterization of both morphology and concentration of the samples in addition to a rigorous normalization of the SERS spectra allowed a quantitative correlation between the SERS profiles and the mean size of the nanoplates. This correlation indicated the existence of an optimum size of the nanoplates for maximum Raman enhancement. Copyright © 2008 John Wiley & Sons, Ltd.     

Adsorption of 4,4′‐thiobisbenzenethiol on silver surfaces: surface‐enhanced Raman scattering study

Adsorption of 4,4′‐thiobisbenzenethiol (4,4′‐TBBT) on a colloidal silver surface and a roughened silver electrode surface was investigated by means of surface‐enhanced Raman scattering (SERS) for the first time, which indicates that 4,4′‐TBBT is chemisorbed on the colloidal silver surface as dithiolates by losing two H‐atoms of the S H bond, while as monothiolates on the roughened silver electrode. The different orientations of the molecules on both silver surfaces indicate the different adsorption behaviors of 4,4′‐TBBT in the two systems. It is inferred from the SERS signal that the two aromatic rings in 4,4′‐TBBT molecule are parallel to the colloidal silver surface as seen from the disappearance of ν_{C H} band (3054 cm⁻¹), which is a vibrational mode to be used to determine the orientation of a molecule on metals according to the surface selection rule, while on the roughened silver electrode surface they are tilted to the surface as seen from the enhanced signal of ν_{C H}. The orientation of the C‐S bond is tilted with respect to the silver surface in both cases as inferred from the strong enhancement of the ν_{C S}. SERS spectra of 4,4′‐TBBT on the roughened silver electrode with different applied potentials reveal that the enhancement of 4,4′‐TBBT on the roughened silver electrode surface may be related to the chemical mechanism (CM). More importantly, the adsorption of 4,4′‐TBBT on the silver electrode is expected to be useful to covalently adsorb metal nanoparticles through the free S H bond to form two‐ or three‐ dimensional nanostructures. Copyright © 2007 John Wiley & Sons, Ltd.     

Enhancement of Raman scattering of light by ultramarine microcrystals in presence of silver nanoparticles

Approximately 10²‐fold enhancement of Raman scattering by ultramarine microcrystals is reported by means of interaction with silver nanoparticles in films and powders. Theoretical modeling predicts the maximal 10¹⁰‐fold enhancement in close vicinity of a silver spherical nanoparticle (0.24 nm) with rapid decay of enhancement factor to 1 in the range of approximately 50 nm. Experimental enhancement factor is treated as overall effect within the small portion of every microcrystal in the close vicinity of silver nanoparticle(s). The results are considered as an important extension of traditional surface enhanced molecular Raman spectroscopy towards bigger inorganic probes. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis of graphene oxide sheets decorated by silver nanoparticles in organic phase and their catalytic activity

The graphene oxide(GO) sheets decorated by Ag nanoparticles were prepared using a liquid–liquid two-phase method at the room temperature. The synthesized samples existed in the organic phase and were characterized by X-ray diffraction, transmission electron microscopy, UV–vis spectroscopy and Raman spectra. The results demonstrate that these silver-nanoparticles with diameter of about 10 nm assembled on graphene oxide sheets are flexible and can form stable suspensions in organic phase. Raman signals of graphene oxide sheets are increased by the attached silver nanoparticles, displaying higher surface-enhanced Raman scattering activity. Furthermore, Ag/GO are found to serve as effective catalysts to activate the reduction of 4-nitrophenol (4NP) in the presence of NaBH₄.     

Influence of surface plasmon resonance wavelength on SERS activity of naturally grown silver nanoparticle ensemble

We present experimental results to quantify and optimize the surface‐enhanced Raman scattering (SERS) activity of naturally grown silver nanoparticles. Ag nanoparticle ensembles with mean equivalent radii ranging from 10.6 to 20.3 nm were prepared under ultrahigh vacuum conditions by Volmer–Weber growth on quartz plates. A tuning of the localized surface plasmon polariton resonance wavelength from 453 to 548 nm was performed by varying the morphology of the silver nanoparticles. The dependence of the SERS activity on the plasmon resonance wavelength was investigated with a Raman set‐up containing a microsystem light source with an emission line at 488 nm. Shifted excitation Raman difference spectroscopy was applied to remove the fluorescence‐based background from the SERS spectra of pyrene in water using two slightly different emission wavelengths (487.61 and 487.91 nm) of the microsystem light source. We demonstrate that the Raman activities for all SERS substrates are available in the nanomolar range in a water sample. However, the Raman activity crucially depends on the plasmon resonance wavelength of the nanoparticle ensembles. Although for an on‐resonance ensemble the limit of detection for pyrene in water is very low and was estimated to be 2 nmol/L, it increases rapidly to several tens of nanomol for slightly off‐resonance ensembles. Hence, the highest SERS activity was obtained with a nanoparticle ensemble exhibiting a plasmon resonance wavelength at 491 nm, which almost coincides with the excitation wavelengths. Copyright © 2012 John Wiley & Sons, Ltd.     

Comparison of SERS effectiveness of copper substrates prepared by different methods: what are the values of enhancement factors?

Surface‐enhanced Raman scattering (SERS) spectroscopy is an analytical method for the detection of low amounts of analytes adsorbed on an appropriate coinage metal (Au, Ag, Cu) surface. Generally, the values of the enhancement factor are the highest on silver, lower on gold and relatively very low on copper. In this study, we have focused on the estimation of the enhancement factors of copper surface/substrates formed by different preparation procedures. The SERS activity of large electrochemically prepared substrates and colloidal systems is compared. The surface morphology of the large substrates was studied using scanning electron microscopy and atomic force microscopy. The size distribution of colloidal nanoparticles was monitored by dynamic light scattering. The values of enhancement factor are in both cases more than 10⁵ for the FT‐SERS spectra, demonstrating the fundamental role of nanostructured copper as a substrate material at the excitation wavelength (1064 nm) used. Copyright © 2011 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman scattering and fluorescence emission of gold nanoparticle–multiwalled carbon nanotube hybrids

Multiwalled carbon nanotubes (MWCNTs) are grafted with gold (Au) nanoparticles of different sizes (1–12 and 1–20 nm) to form Au–MWCNT hybrids. The Au nanoparticles pile up at defect sites on the edges of MWCNTs in the form of chains. The micro‐Raman scattering studies of these hybrids were carried using visible to infrared wavelengths (514.5 and 1064 nm). Enhanced Raman scattering and fluorescence is observed at an excitation wavelength of 514.5 nm. It is found that the graphitic (G) mode intensity enhances by 10 times and down shifts by approximately 3 cm⁻¹ for Au–MWCNT hybrids in comparison with pristine carbon nanotubes. This enhancement in G mode due to surface‐enhanced Raman scattering effect is related to the interaction of MWCNTs with Au nanoparticles. The enhancement in Raman scattering and fluorescence for large size nanoparticles for Au–MWCNTs hybrids is corroborated with localized surface plasmon polaritons. The peak position of localized surface plasmons of Au nanoparticles shifts with the change in environment. Further, no enhancement in G mode was observed at an excitation wavelength of 1064 nm. However, the defect mode (D) mode intensity enhances, and peak position is shifted by approximately 40 cm⁻¹ to lower side at the same wavelength. The enhanced intensity of D mode at 1064 nm excitation wavelength is related to the double resonance phenomenon and shift in the particular mode occurs due to more electron phonon interactions near Fermi level. Copyright © 2012 John Wiley & Sons, Ltd.     

Adsorbed states of substituted α‐aminophosphinic acids on a silver electrode surface: comparison with a colloidal silver substrate

We investigated the interfacial structures of various aromatic (each compound contains one or two phenyls) di‐α‐amino ( L¹ – L³ ) and α‐amino‐α‐hydroxyphosphinic ( L⁴ – L⁶ ) acids immobilized onto an electrochemically roughened silver electrode surface in an aqueous solution using surface‐enhanced Raman scattering (SERS). These structures were compared to those on a colloidal silver surface to determine the relationship between adsorption strength and geometry. The presence of an enhanced ν_19a ring band in the SERS spectra of L⁶ , L² , and L³ on the electrode indicated that the benzene rings of those molecules interact with the electrode surface through localized CC bond(s). We observed significant band broadening of the benzene ring modes for all α‐hydroxyphosphinic acids on both substrates, except for L¹ deposited onto the electrode surface. This suggests the possibility of direct interaction between the ring and Ag, although the benzene ring–surface π overlap is weaker for the colloidal silver than for the Ag electrode. The downward shift in wavenumber and alternations in the enhancement of a ν₁₂ ring band indicate a general increase of tilt angle on both silver substrates in the order L³ < L⁴ < L⁵ < L⁶ . The altered enhancement of the bands due to the vibrations of the  NH₂ and O PO fragments, a finding observed on both silver substrates, strongly suggests that the groups interact with different strength and geometry with these substrates. Copyright © 2009 John Wiley & Sons, Ltd.     

Optimizing surface-enhanced Raman scattering by template guided assembling of closely spaced silver nanocluster arrays

We present an easy approach to synthesize closely spaced regular arrays of silver nanoclusters, which are self-assembled by depositing gas-phase synthesized metal nanoclusters onto pre-patterned triblock copolymer templates. The array has a high particle density of about 2 ×10³ particles per μm², and an average interparticle space of about 20 nm. The surface plasmon resonance wavelength of the array is tuned due to the interparticle plasmon coupling. High SERS sensitivity for less than one layer trans-1,2-bi-(4-pyridyl) ethylene (BPE) molecule detection, with an enhancement factor of 2.6 ×10⁶, has been demonstrated for a substrate with this array. The enhanced Raman signal was found to be 5 times higher than that measured from the substrate with randomly distributed silver nanoparticles.     

The influence of pH and anions on the adsorption mechanism of rifampicin on silver colloids

The influence of pH and anions on the adsorption mechanism of rifampicin on colloidal silver nanoparticles has been analysed by electronic absorption, resonance Raman (RR) and surface‐enhanced resonance Raman spectroscopy (SERRS). Rifampicin is a widely used antibiotic with a zwitterionic nature. SERRS spectra of rifampicin adsorbed on silver sols, prepared using hydroxylamine hydrochloride as reducing agent, undergo dramatic changes upon lowering the pH. The spectral form changes progressively from that characteristic of chemisorbed rifampicin (at pH > 7) to one very similar to the rifampicin RR spectrum (at lower pH), indicative of a modification of the adsorption mechanism on the surface of the Ag nanoparticles. The RR‐type SERRS spectrum is proposed to result from formation of an ion pair between rifampicin and Cl⁻ anions, which, deriving from the colloid preparation, are adsorbed on the Ag surface. The addition of anions to the hydroxylamine hydrochloride sol facilitates conversion from the chemisorbed to ion pair form and leads to an order of magnitude increase in the SERRS signal. Copyright © 2007 John Wiley & Sons, Ltd.     

Direct visual evidence for the chemical mechanism of surface‐enhanced resonance Raman scattering via charge transfer: (II) Binding‐site and quantum‐size effects

We describe quantum‐size and binding‐site effects on the chemical and local field enhancement mechanisms of surface‐enhanced resonance Raman scattering (SERRS), in which the pyridine molecule is adsorbed on one of the vertices of the Ag₂₀ tetrahedron. We first investigated the influence of the binding site on normal Raman scattering (NRS) and excited state properties of optical absorption spectroscopy. Second, we investigated the quantum‐size effect on the electromagnetic (EM) and chemical mechanism from 300 to 1000 nm with charge difference density. It is found that the strong absorption at around 350 nm is mainly the charge transfer (CT) excitation (CT between the molecule and the silver cluster) for large clusters, which is the direct evidence for the chemical enhancement mechanism for SERRS; for a small cluster the strong absorption around 350 nm is mainly intracluster excitation, which is the direct evidence for the EM enhancement mechanism. This conclusion is further confirmed with the general Mie theory. The plasmon peak in EM enhancement will be red‐shifted with the increase of cluster size. The influence of the binding site and quantum‐size effects on NRS, as well as chemical and EM enhancement mechanisms on SERRS, is significant. Copyright © 2009 John Wiley & Sons, Ltd.     

Structure and conformation of Arg8 vasopressin modified analogs

Fourier‐transform Raman and infrared spectra were acquired for four arginine vasopressin (AVP) analogs containing L ‐diphenylalanine (Dpa): [Dpa²]AVP, [Cpa¹,Dpa²]AVP, [Dpa³]AVP, and [Cpa¹,Dpa³]AVP (where Cpa denotes 1‐mercaptocyclohexaneacetic acid). We compared and analyzed these spectra. In addition, the Raman spectra were compared to the corresponding surface‐enhanced Raman scattering spectra recorded in an aqueous silver colloidal dispersion. Silver colloidal dispersions prepared by the simple borohydride reduction of silver nitrate were used as substrates. The geometry of these molecules etched on the silver surface was deduced from the observed changes in the intensity enhancement, breadth, and shift in wavenumber of the Raman bands in the spectra of the bound versus free species. Based on the obtained data, adsorption mechanisms were proposed for each case, and the suggested adsorbate structures were compared. All the molecules were thought to adsorb onto a silver surface via a phenyl ring, free electron pairs on the sulfur atom, and CO and  CONH‐bonds. However, the orientation of these fragments on the colloidal silver surface and the strength of the interactions with this surface are different. For [Dpa³]AVP and [Cpa¹,Dpa³]AVP, a strong interaction among the—CCN‐peptide fragment and the colloidal silver surface occurs. Copyright © 2011 John Wiley & Sons, Ltd.     

界面自组装的金/氧化石墨烯复合材料的表面增强拉曼散射行为研究

采用Frens法制备金纳米粒子溶胶,通过界面自组装技术在掺磷的非晶碳衬底表面构筑三维的金/氧化石墨烯/金复合结构.以罗丹明B为探针分子,考察金/氧化石墨烯/金复合材料的表面增强拉曼散射活性.结果表明,由于氧化石墨烯的化学增强和金纳米粒子的电磁场增强的协同作用,在该三维复合材料上获得了很强的罗丹明B拉曼信号.所设计的三维金/氧化石墨烯/金复合材料在生物分析、环境监测、疾病防控、食品安全等领域具有潜在的应用价值.     

Piperidine adsorption on two different silver electrodes: A combined surface enhanced Raman spectroscopy and density functional theory study

The surface enhanced Raman scattering (SERS) spectra of piperidine in silver colloid solution, on roughened silver electrode and on roughened silver electrode modified with silver nanoparticles were studied, and the high-quality SERS spectra of piperidine on roughened silver electrode modified with silver nanoparticles were obtained for the first time. Surface selection rules derived from the EM enhancement model were employed to deduce piperidine orientations on the different surfaces. On the basis of this, two models of piperidine adsorbed on the surface of the silver nanoparticles were built, and DFT-B3PW91/LanL2dz was applied to calculate the Raman frequencies. It proves that, at higher potential values, the piperidine is perpendicularly standing on the roughened silver electrode surface though its lone-electron pair, but in silver colloid solution and on the silver nanoparticles modified silver electrode the piperidine molecular lies flat on the silver surface. In the meantime, the potential dependent SERS of piperidine on the modified electrode were studied.     

Experimental and theoretical Raman and surface‐enhanced Raman scattering study of cysteine

Raman spectra in solid and 1 M solution of L ‐cysteine and surface‐enhanced Raman scattering (SERS) spectra of this molecule in the zwitterionic form, by using colloidal silver nanoparticles, have been recorded. Density functional theory with the B3LYP functional was used for the optimizations of the ground state geometries and simulation of the vibrational spectrum of this amino acid. The SERS spectrum with a large silver cluster as a model metallic surface was simulated for the first time. Taking into account the experimental and calculated Raman and SERS vibrations and the corresponding assignments, as well as a comparison of force constants and geometrical parameters between the free zwitterion cysteine and the one in the presence of the colloidal silver nanoparticles, we can confirm the presence of gauche (P_H) and trans (P_N) rotamers in the solid state, the formation of a S S bond in the solution state, the dissociation of the peptide bond and mixing of rotamers because of the SERS effect, and the relative importance of the interaction of sulphyldryl, NH₃⁺, and carboxylate groups with the metallic surface. Copyright © 2009 John Wiley & Sons, Ltd.     

银纳米颗粒对四苯基卟啉Q带荧光寿命的延长

文章报道了吸附在银纳米颗粒表面的四苯基卟啉(TPP)的Q带荧光寿命的变化.实验发现将银纳米颗粒的表面等离激元共振吸收峰调至与TPP的Q吸收带共振时,会使TPP的Q带荧光寿命得到延长.这是由于银纳米颗粒对表面的光电场有较大的表面等离激元共振增强效应,而处于激发态的TPP分子有较高的极性,这种增强的光电场会对有较高极性的TPP分子有稳定作用,所以延长了其Q带寿命.这对于以卟啉为光敏剂的光动力治疗有重要的意义.     

Poly(vinylpyrrolidone)‐stabilized silver nanoparticles for strained‐silicon surface enhanced Raman spectroscopy

Poly(vinylpyrrolidone)‐stabilized silver nanoparticles deposited onto strained‐silicon layers grown on graded Si_1−xGe_x virtual substrates are utilized for selective amplification of the Si–Si vibration mode of strained silicon via surface‐enhanced Raman scattering spectroscopy. This solution‐based technique allows rapid, highly sensitive and accurate characterization of strained silicon whose Raman signal would usually be overshadowed by the underlying bulk SiGe Raman spectra. The analysis was performed on strained silicon samples of thickness 9, 17.5 and 42 nm using a 488 nm Ar⁺ micro‐Raman excitation source. The quantitative determination of strained‐silicon enhancement factors was also made. Copyright © 2011 John Wiley & Sons, Ltd.     

The Effect of L-Cysteine on Surface-Enhanced Raman Scattering of Malachite Green in Silver Colloids

ABSTRACT

Colloidal silver nanoparticles were prepared by a simple chemical reduction method. The effect of L-cysteine on the surface-enhanced Raman scattering activity of colloidal silver nanoparticles was investigated by using malachite green as a probe molecule. It was found that the surface-enhanced Raman scattering activity of colloidal silver nanoparticles was improved tremendously with the help of L-cysteine. The possible reasons for this enhancement effect were given. Specifically, in silver colloidal solution, no surface-enhanced Raman scattering spectrum of malachite green was observed at a relatively low concentration (≤2.5 × 10^?5 mol/L). However, well-resolved and high-quality surface-enhanced Raman scattering spectra of malachite green were successfully obtained after the addition of L-cysteine to silver colloids, and the minimum detection limit for malachite green was down to 10^?8 mol/L.