SERS Intensity Research Articles

Nanoembossed gold nanoshell with a fluorescence-like strong SERS signal

We present a nanoembossed nanoshell with a new internal location for the formation of strong electromagnetic fields. The internally nanoembossed gold nanoshell (AuNS) is fabricated by electrostatically assembling smaller silica nanoparticles (∼15.7 nm) around the silica core (∼123.6 nm) followed by growing gold nanoseeds on the core in a wet process. FDTD calculations reveal the creation of a strong electromagnetic field (|E/Ein|max = 55 at 633 nm) at sharp edges formed by the contact between the nanoembosses and the silica core. The field formation is supported by measuring the SERS signal of Ru(bpy) encapsulated in the nanoembossing silica nanoparticles. SERS signals as strong as the corresponding fluorescence are obtained. The Raman enhancement factor (EF) is estimated to be up to 1010 at 633 nm excitation, in addition to a comparable EF at 785 nm laser excitation. The SERS intensity of the nanoembossed nanoshell layer is sufficiently high compared to the outer or the core of the nanoshell. Finally, we fabricate all-in-one nanoparticles with all the three places where the reporter dyes are loaded and acquire the highest SERS intensity to potentially enable bio-medical applications of the nanoembossed AuNS as a sensitive and reliable labeling particle.

Surface enhanced Raman scattering improvement of gold triangular nanoprisms by a gold reflective underlayer for chemical sensing

We report on an improvement way of the SERS signal of Au triangular nanoprisms for a highly sensitive detection of chemical molecules. This improvement is obtained by a simple addition of a gold reflective layer under Au nanoprisms. Using the same Au triangular nanoprisms obtained by nanosphere lithography, we studied experimentally the thickness effect of this gold underlayer on the SERS intensity of the triangular nanoprisms. We demonstrated that this SERS intensity increased with the thickness of the gold reflective underlayer, and this is due to the increment of the Au underlayer reflectivity. Thus, we showed that the metallic reflective underlayer has an important key for SERS enhancement. Indeed, enhancement factors of 108 were found for the most important thickness of the gold underlayer.

Dynamics of a plasmon-activated p-mercaptobenzoic acid layer deposited over Au nanoparticles using time-resolved SERS.

Time-dependent SERS intensity recorded over a drop-coated coffee-ring pattern of p-MBA with gold colloids was investigated as a function of the specific laser power applied. Pure electromagnetic enhancement produced stochastic intensity variations of the whole SER spectra, which were mainly correlated with evolutions of the background intensity. Besides long-term, non-reversible spectral changes caused by plasmon-induced decarboxylation of p-MBA, transient original spectral profiles showing additional lines were also observed as the specific power reached 5.5 × 10(4) W cm(-2). An unprecedented qualitative and quantitative study of SERS intensity variations based on the complementary use of both extreme deviation and cross-correlation statistics is provided, which resulted in an improved understanding of SERS mechanisms. More precisely, cross-correlation analysis made it possible to follow the evolution of groups of modes assigned to one species or sharing the same symmetry while so-called individual events denote particular resonance structures, whose occurrence was tentatively related to a photo-thermally activated motion of the gold nanostructures.

One-step fabrication of hollow-channel gold nanoflowers with excellent catalytic performance and large single-particle SERS activity.

Hollow metallic nanostructures have shown potential in various applications including catalysis, drug delivery and phototherapy, owing to their large surface areas, reduced net density, and unique optical properties. In this study, novel hollow gold nanoflowers (HAuNFs) consisting of an open hollow channel in the center and multiple branches/tips on the outer surface are fabricated for the first time, via a facile one-step synthesis using an auto-degradable nanofiber as a bifunctional template. The one-dimensional (1D) nanofiber acts as both a threading template as well as a promoter of the anisotropic growth of the gold crystal, the combination of which leads to the formation of HAuNFs with a hollow channel and nanospikes. The synergy of favorable structural/surface features, including sharp edges, open cavity and high-index facets, provides our HAuNFs with excellent catalytic performance (activity and cycling stability) coupled with large single-particle SERS activity (including ∼30 times of activity in ethanol electro-oxidation and ∼40 times of single-particle SERS intensity, benchmarked against similar-sized solid gold nanospheres with smooth surfaces, as well as retaining 86.7% of the initial catalytic activity after 500 cycles in ethanol electro-oxidation). This innovative synthesis gives a nanostructure of the geometry distinct from the template and is extendable to fabricating other systems for example, hollow-channel silver nanoflowers (HAgNFs). It thus provides an insight into the design of hollow nanostructures via template methods, and offers a versatile synthetic strategy for diverse metal nanomaterials suited for a broad range of applications.

Mixed-monolayer glyconanoparticles for the detection of cholera toxin by surface enhanced Raman spectroscopy.

We have produced silver glyconanoparticles for the sensitive (56 ng mL -1), low volume and rapid detection of cholera toxin B-subunit (CTB) in synthetic freshwater (simulating the ion compositions of natural waters in which CTB could be found). This is achieved by monitoring the changes in surface enhanced Raman scattering (SERS) intensity of a Raman reporter bound to the glyconanoparticle surface. The particles selectively aggregate upon interaction with CTB, causing an increase in the measured SERS signal. The particles are designed to mimic the interactions involving the cell surface GM1 ganglioside and CTB. This is achieved by using a combination of polyethylene glycol linkers terminated with either galactose or sialic acid.

In situ analysis of dynamic laminar flow extraction using surface-enhanced Raman spectroscopy.

In this study, we performed micro-scale dynamic laminar flow extraction and site-specific in situ chloride concentration measurements. Surface-enhanced Raman spectroscopy was utilized to investigate the diffusion process of chloride ions from an oil phase to a water phase under laminar flow. In contrast to common logic, we used SERS intensity gradients of Rhodamine 6G to quantitatively calculate the concentration of chloride ions at specific positions on a microfluidic chip. By varying the fluid flow rates, we achieved different extraction times and therefore different chloride concentrations at specific positions along the microchannel. SERS spectra from the water phase were recorded at these different positions, and the spatial distribution of the SERS signals was used to map the degree of nanoparticle aggregation. The concentration of chloride ions in the channel could therefore be obtained. We conclude that this method can be used to explore the extraction behaviour and efficiency of some ions or molecules that enhance the SERS intensity in water or oil by inducing nanoparticle aggregation.

Preparation of sensitive and recyclable porous Ag/TiO2 composite films for SERS detection

Porous Ag/TiO2 composite films were prepared by spin coating of titania on normal glass slides and subsequent photochemical deposition of silver nanoparticles (AgNPs). The films were characterized by XRD and FESEM to reveal micro structural and morphological differences between films obtained under varied conditions. The SERS properties of these films were investigated using aqueous crystal violet (CV) as probe molecules. The results indicate that the content of polyethylene glycol (PEG) and photo-reduction time had significant influences on both the microstructure and SERS performance of Ag/TiO2 films. The highest SERS sensitivity that allowed as low as 10−10M aqueous CV to be detected, was achieved with the PEG/(C4H9O)4Ti molar ratio being 0.08% and with 30min of UV irradiation. With this film a linear relationship was established through experiment between SERS intensity and CV concentration from 10−10 to 10−5M, which could be used as a calibration curve for CV concentration measurement. In addition, the film could be reused as a SERS substrate for up to four times without significantly losing SERS sensitivity if a simple regeneration was followed. It is visualized that the Ag/TiO2 film on glass has potentials for being developed into a practical SERS substrate with high sensitivity and good reusability.

Gold nanoparticles enhanced SERS aptasensor for the simultaneous detection of Salmonella typhimurium and Staphylococcus aureus.

Salmonella typhimurium and Staphylococcus aureus are most common causes of food-associated disease. A Raman based biosensor was developed for S. typhimurium and S. aureus detection simultaneously. The biosensor was based on nanoparticles enhanced Raman intensity and the specific recognition of aptamer. The Raman signal probe and the capture probe are built. Gold nanoparticles (GNPs) modified with Raman molecules (Mercaptobenzoic acid and 5,5'-Dithiobis(2-nitrobenzoic acid)) and aptamer are used as the signal probe for S. typhimurium and S. aureus, respectively. Fe3O4 magnetic gold nanoparticles (MGNPs) immobilized with both aptamer of S. typhimurium and S. aureus are used as the capture probe. When S. typhimurium and S. aureus are added in the reaction system, the capture probe will capture the target bacteria through the specific binding effect of aptamer. And then the signal probe will be connected to the bacteria also by the effect of aptamer to form the sandwich like detection structure. The Raman intensified spectrum was measured to quantify S. typhimurium and S. aureus. Under optimal conditions, the SERS intensity of MBA at 1582 cm(-1) are used to measure S. typhimurium (y=186.4762+704.8571x, R(2)=0.9921) and the SERS intensity of DNTB at 1333 cm(-1) are used to measure S. aureus (y=135.2381+211.4286x, R(2)=0.9946) in the range of 10(2)-10(7) cfu mL(-1). The LOD is 35 cfu mL(-1) for S. aureus and 15 cfu mL(-1) for S. typhimurium. This method is simple and rapid, results in high sensitivity and specificity, and can be used to detect actual samples.

Plasmonic Ag Core-Satellite Nanostructures with a Tunable Silica-Spaced Nanogap for Surface-Enhanced Raman Scattering.

Plasmonic Ag core-satellite nanostructures were synthesized by utilizing the ultrathin silica shell as a spacer to generate a tunable nanogap between the Ag core and satellites. To synthesize the nanoparticles, Ag nanoparticles (Ag NPs) with a diameter of ∼60 nm were synthesized as cores, on which Raman dyes were adsorbed and then tunable ultrathin silica shells from 2.0 to 6.5 nm were coated, followed by the deposition of Ag NPs as satellites onto the silica surface. The relationships between the SERS signal and the important parameters, including the satellite diameter and the nanogap distance, were studied by experimental methods and theoretical calculations. The maximum SERS intensity of the core-satellite nanoparticles was over 14.6 times stronger than that of the isolated Raman-encoded Ag/PATP@SiO2 NP. The theoretical calculations indicated that the local maximum calculated enhancement factor (EF) of the hot spots with a 2.0 nm nanogap was 9.5 × 10(5). The well-defined Ag core-satellite nanostructures have a high structural uniformity and an anomalously strong electromagnetic enhancement for highly quantitative SERS, leading to a better understanding of hot spot formation and providing new insights into the optimal design and synthesis of the hot SERS nanostructures in a controlled manner.

A facile surface-enhanced Raman scattering (SERS) detection of rhodamine 6G and crystal violet using Au nanoparticle substrates

In this study, Au nanoparticle (5nm) colloid was employed for a facile preparation of SERS substrates from three approaches: (1) original Au nanoparticles, (b) Au colloid coated 200nm polystyrene (PS) beads, and (3) Au colloid annealed at 200–500°C. Rhodamine 6G (R6G) and crystal violet were employed as the Raman active probes. The Au colloid deposited PS beads (PS@Au) exhibit intensive SERS signal for R6G detection, which is promising for crystal violet detection after being annealed at 400°C. The 200°C annealed Au nanoparticles demonstrate excellent combined SERS sensitivity for both R6G and crystal violet. For the original Au colloid, elevated annealing temperature from 200°C to 500°C decreases the SERS intensity as Au particles were coarsened gradually.

Single Molecules under High Pressure

Single-molecule Raman spectra were studied at high pressure (1–4 GPa) in a diamond-anvil cell (DAC) with an Ar hydrostatic pressure medium, with the intent of resolving the different pressure-induced vibrational blueshifts of individual molecules. The molecules were two isotopologues of the dye rhodamine 6G (R6G and d4-R6G), adsorbed on colloidal Ag particles immobilized in poly(vinyl alcohol) (PVA). Surface-enhanced Raman (SERS) ensemble measurements were compared to single-molecule surface-enhanced Raman (SMSERS) measurements made in a confocal Raman microscope. Spectra of mixed isotopologues in the 610 cm–1 region (the “isotope-sensitive” transition) allowed us to identify when the majority of spectra came from single-isotope sites, and were thereby statistically likely to arise from single molecules. There was a dramatic drop in SERS intensity when samples were pressurized in the DAC. SMSERS measurements revealed the intensity drop was caused by a pressure-induced destruction of SMSERS-active hot spots. A hot spot is a site with ultrahigh Raman enhancement containing at least one R6G molecule. The hot spots that were not destroyed had large enhancement factors. The disappearance of hot spots was attributed to deoptimization of the gap junctions between Ag nanoparticles due to pressure-induced strain. Because the isotope-sensitive transition had little pressure-induced blueshift (<5 cm–1 between 0 and 6 GPa), we also studied a transition near 1650 cm–1 (the “pressure-sensitive” transition), which had a >30 cm–1 blueshift and an approximate doubling of line width in the 0–6 GPa pressure range. The single-molecule spectra of this transition did not broaden as pressure was increased to 4.1 GPa. However, there was a variation in the blueshift of different molecules. The fwhm of the blueshift variation was able to account for most or all of the observed pressure-induced spectral broadening. The pressure-induced broadening of this R6G vibrational transition is due to the different blueshifts of different molecules.

Onset of Intense Surface Enhanced Raman Scattering and Aggregation in the Au@Ag System

Gold core/silver shell (Au@Ag) nanoparticles of ~37 ± 5 nm diameter generate intense SERS (λEX=785 nm) responses in solution when they interact with the SERS labels rhodamine 6G (R6G), 4-mercaptopyridine (MPY), and 4-mercaptobenzoic acid (MBA). Herein the relationship between SERS intensity, aggregation, and adsorption phenomenon isobserved by titrating Au@Ag with the above labels. As the labels adsorb to the Au@Ag, they drive aggregation as evidenced by the creation of NIR extinction peaks, and the magnitude of this NIR extinction (measured at 830 nm) correlates very closely to magnitude of the intense SERS signals. The label MBA is an exception since it does not trigger aggregation nor does it result in intense SERS; rather intense SERS is recovered only after MBA coated Au@Ag is aggregated with KCl. An “inner filter” model is introduced and applied to compensate for solution extinction when the exciting laser radiation is significantly attenuated. This model permits a summary of the SERS responses in the form of plots of SERS intensity versus the aggregate absorption at 830 nm, which shows the excellent correlation between intense SERS and LSPR bands extinction.

Detection of low concentrations of ampicillin in milk.

Ampicillin, a common antibiotic, is detected at trace concentrations in milk using surface enhanced Raman spectroscopy in a microfluidic device, using less than 20 μL of sample, in 10 minutes, with minimal off-chip preparation. The device is configured so as to favor the interaction of the analyte with colloidal silver, and the optimization of the aggregation of the silver nanoparticles so as to increase the SERS intensity and the consequential sensitivity of analyte detection.

Plasmonic properties of regiospecific core-satellite assemblies of gold nanostars and nanospheres.

Solution-based molecularly-mediated bottom-up assembly of gold nanostars and nanospheres in regiospecific core-satellite nanoarchitectures is reported. The controlled assembly is driven by coupling reactions in solution between small, rigid, Raman-active organic molecules bound to the surface of the nanoparticles, and leads to much narrower interparticle gaps than achievable with DNA-based assembly methods. In the described system, gold nanostars with multiple sharp spikes, ideal for electromagnetic field enhancement, are used as the core particle onto which spherical satellites are assembled. Transmission electron micrographs show that the core-satellite structures assemble with <2 nm interparticle gaps and regiospecific binding of only one sphere per spike, and the process can be followed by monitoring changes in the surface enhanced Raman scattering (SERS) spectra of the Raman active linkers. The assembled structures give rise on average to two orders of magnitude SERS signal enhancement per nanoparticle in comparison to their constituents, which can be attributed to the creation of SERS "hot spots" between the nanostar tip and the satellite sphere. Two dimensional finite element electromagnetic models show strongly confined electromagnetic field intensity in the narrow interparticle gaps of core-satellite assemblies, which is significantly enhanced in comparison to the constituent nanoparticles, thus corroborating the experimental findings. Thus, the assemblies reported here can be envisioned as SERS-tags for imaging purposes as well as a model system for SERS-based chemical sensing with improved sensitivity.

Calculating average surface enhancement factors of randomly nanostructured electrodes by a combination of SERS and impedance spectroscopy.

Polyhedron Ag nanostructures were created on top of a polished Au electrode via step-wise electrodeposition and tested as substrates for SERS spectroscopy. Average Raman enhancement factors were derived by combining SERS measurements with electrochemical impedance spectroscopy (EIS), which is able to determine the electroactive surface area of a randomly nanostructured surface. Depending on the deposition step an alternating increase and decrease of surface area was observed while the SERS intensity showed a clear maximum for the first deposition cycle. SEM pictures reveal the formation of Ag polyhedrons that are randomly dispersed on the Au surface. Furthermore the presence of a sub nanostructure on top of the polyhedron after the first deposition cycle is observed which becomes smoother after subsequent deposition cycles. Correlating the SEM pictures with SERS and EIS measurements it is concluded that the coral-like sub nanostructure is dominating the enhancement factor while the polyhedron structure itself only plays a minor role for electromagnetic field enhancement.

Release of Cyanopyridine from a Ruthenium Complex Adsorbed on Gold: Surface-Enhanced Raman Scattering, Electrochemistry, and Density Functional Theory Analyses

The results presented in this work definitely show that the stability of the SAM formed with [Ru(NH3)4(CNpy)(pyS)]2+ on gold, where CNpy = 4-cyanopyridine and pyS = 4-mercaptopyridine, is dependent on the applied potential and on the chemical properties of the solution in the solid/liquid interface. By means of SERS spectroscopy, it was found that CNpy ligand is released from the coordination sphere if no reducing condition is imposed to the system, i.e., citrate solution or applied potential lower than the formal potential of the complex. Theoretical Raman spectra obtained from DFT presented reasonable correlation with the experimental spectra and gave support for the assignments. The relative intensities of the bands in the SERS spectra showed to be dependent on the applied potential as well as on the wavelength of the exciting radiation, indicating the contribution of a charge transfer process to the SERS intensification. In fact, the shift of the potential of maximum SERS intensity (Emax) to negative ...

Dependence of Raman intensity on the surface coverage of silver nanocubes in SERS active monolayers

Control over surface coverage while fabricating efficient silver nanocube (AgNC) based SERS substrates is crucial to develop an enhanced electromagnetic field. These substrates with tunable surface coverages made it possible to demonstrate the dependence of the SERS enhancement on the surface coverage and to quantify the enhancement factors (EFs) in the SERS enhancement obtained in various surface coverages of AgNC monolayers. It was found that the EFs apparently increased with the increase of nanocube surface coverage. These results indicate that electromagnetic filed (EM) enhancement is the main factor for SERS activity. In addition to the effects of surface coverage of AgNCs on the SERS enhancement, the effects of surface plasmon resonance (SPR) on SERS enhancement reveal an interesting dependence of SERS intensity on the close degree between surface plasmon resonance (SPR) and laser wavelength.

Dispersion Stability, Ligand Structure and Conformation, and SERS Activities of 1-Alkanethiol Functionalized Gold and Silver Nanoparticles

Dispersion stability, ligand structure and conformation, and SERS activities of 1-alkanethiol (CnH2n+1SH, n = 2–14) functionalized gold and silver nanoparticles (AuNPs and AgNPs) were studied as a function of alkanethiol carbon chain length and nanoparticle (NP) type and size. The dispersion stability of alkanethiol functionalized NPs in water increases with increasing alkanethiol chain length and NP size, and the stabilities of the alkanethiol-containing AuNPs are higher than their AgNP counterparts. C3H7SH and longer alkanethiols are highly ordered on AgNPs but disordered on AuNPs. The SERS intensity of the C–S stretch band for the model alkanethiols on AgNPs and AuNPs decays exponentially (I = I0 exp(−Nc/N0)) with increasing number of carbon atoms (Nc). The empirical decay length N0, in terms of the number of the carbon atoms, is 1.29, 0.53, and 0.10 for AgNPs with diameters of 50, 30, and 10 nm, respectively. This decay length is less than 1 for AuNPs of difference sizes. These results show that changing the NP gap size by a distance equivalent to a single chemical bond can have a significant impact on the NP integrated SERS activities.

Ultrasensitive detection of carcino-embryonic antigen by using novel flower-like gold nanoparticle SERS tags and SERS-active magnetic nanoparticles

In this work, an ultrasensitive detection of cancer marker CEA has been developed by using novel gold nanoflowers as SERS tags and SERS-active magnetic nanoparticles as supporting substrates. A good linear relationship between concentration and SERS intensity is found in the range between 0.01 fg mL−1 and 1 ng mL−1, and the LOD is 0.01 fg mL−1.

Statistically quantified measurement of an Alzheimer's marker by surface-enhanced Raman scattering.

Fibrillar forms of the Amyloid-β (Aβ) protein have been implicated in the early stages of Alzheimer's disease (AD), however there are no standardised assays for soluble Aβ oligomer biomarkers that provide the best indication of the disease progression [1,2]. As a step towards a fast and label-free method for testing different AD biomarkers, we have combined laser nano-textured substrates with a SERS mapping technique and validated it using soluble Aβ-40 oligomers [3-5]. The nano-textured SERS substrates provide fast (&5 min), label-free spectra associated with soluble Aβ-40 oligomers down to a concentration of 10 nM. Statistical analysis of the spectral intensities mapped over the substrate surface shows a quantitative correlation with the oligomer concentration. Schematics of experiments: SERS mapping of Aβ-40 (left figure: measured SERS intensity overlayed with an SEM image of ripples) was carried out on the laser nano-textured (ripple) surface of sapphire and statistical analysis of the SERS intensity was carried out for qualitative (a high SERS intensity at low probability) and quantitative (a moderate SERS intenisty at the highest probability) measures. Quantitative statistical analysis of SERS mapping data can be performed off line for cross correlations with other known SERS signatures.