Signal Enhancement In Spectroscopy Research Articles

Recyclable Au@R–Fe3O4/g-C3N4 substrates for rapid SERS detection and degradation of multiple pollutants

Developing a Surface-enhanced Raman spectroscopy (SERS) method with excellent detecting ability, good recyclability and analyzing multiple pollutants rapidly are critical for evaluation of water quality in emergency pollution affairs. While constructing a multifunctional substrate with these characteristics to realize the application of SERS in water quality monitoring remains a challenge. In this work, a reusable Au@R–Fe3O4/g-C3N4 SERS substrate is prepared by loading Au nanoparticles (Au NPs) on Fe3O4 nanorings (R–Fe3O4) and the formed Au@R–Fe3O4 is further combined with g-C3N4 nanosheets through a simple electrostatic assembly method. The Au@R–Fe3O4/g-C3N4 nanocomposite presents multifunction of magnetic enrichment, SERS signal enhancement, multiple pollutants analyzing, and photocatalytic activity, which achieves quantitative detection of rhodamine B (RhB), tetracycline hydrochloride (TC), and 4-chlorophenol (4-CP), with detection limits of 5.30 × 10−9, 7.50 × 10−8, 7.69 × 10−8 mol/L, respectively. Furthermore, the recyclable detection capability of Au@R–Fe3O4/g-C3N4 for multi components is demonstrated by the strong SERS signal after 9 cycles of “detection-degradation” processes. Combined with good uniformity and stability, this SERS method based on Au@R–Fe3O4/g-C3N4 substrate provides a new strategy for the multi-pollutants detection and degradation in water environment.

Probing Hyperbolic Shear Polaritons in β-Ga2O3 Nanostructures Using STEM-EELS.

Phonon polaritons, quasiparticles arising from strong coupling between electromagnetic waves and optical phonons, have potential for applications in subdiffraction imaging, sensing, thermal conduction enhancement, and spectroscopy signal enhancement. A new class of phonon polaritons in low-symmetry monoclinic crystals, hyperbolic shear polaritons (HShPs), have been verified recently in β-Ga2O3 by free electron laser (FEL) measurements. However, detailed behaviors of HShPs in β-Ga2O3 nanostructures still remain unknown. Here, by using monochromatic electron energy loss spectroscopy in conjunction with scanning transmission electron microscopy, the experimental observation of multiple HShPs in β-Ga2O3 in the mid-infrared (MIR) and far-infrared (FIR) ranges is reported. HShPs in various β-Ga2O3 nanorods and a β-Ga2O3 nanodisk are excited. The frequency-dependent rotation and shear effect of HShPs reflect on the distribution of EELS signals. The propagation and reflection of HShPs in nanostructures are clarified by simulations of electric field distribution. These findings suggest that, with its tunable broad spectral HShPs, β-Ga2O3 is an excellent candidate for nanophotonic applications.

Effect of Au Nanoparticle Agglomeration on SERS Signal Amplification.

An analyzed substance's signal intensity and detection sensitivity in surface-enhanced Raman spectroscopy (SERS) significantly depend on the size and agglomeration degree of nanoparticles (NPs) forming the enhancing structure. Structures were manufactured by aerosol dry printing (ADP), where NPs' agglomeration depends on printing conditions and additional particle modification techniques. The influence of agglomeration degree on SERS signal enhancement was studied in three types of printed structures using the methylene blue model molecule as an analyte. We demonstrated that the ratio between individual NPs and agglomerates in a studied structure strongly affects SERS signal amplification, and structures formed mainly from non-agglomerated NPs enhance the signal better. In this sense, aerosol NPs modified by pulsed laser radiation provide better results than thermally modified NPs, since in laser modification a larger number of individual NPs is observed due to the absence of secondary agglomeration effects in the gas stream. However, increasing gas flow may minimize the secondary agglomeration, since the time allotted for the agglomeration processes is reduced. In this paper, we show how different NPs' agglomeration tendencies influence SERS enhancement to demonstrate the process of using ADP to form inexpensive and highly efficient SERS substrates with huge application potential.

Early warning of Diaporthe infection in kiwifruit soft rot by plasmonic dimer-enhanced Raman spectroscopy.

Diaporthe genus is the dominant pathogens of kiwifruit soft rot with long incubation period and rapid onset and very hard to detect in advance. It is of great significance to develop point-of-care tests for disease prevention and field management. Here we screen a pair of genus-level primers for constructing plasmonic dimer Rayleigh/Raman spectroscopy, which enables rapid, specific, and sensitive detection of Diaporthe genus in real kiwifruits. Dark-filed Rayleigh scattering clearly visualizes the target-induced dimer assembly of nanoprobes. Plasmonic dimer-enhanced Raman spectroscopy has high specificity for 12 common isolates of Diaporthe genus in one batch samples with highly accurate results and much higher sensitivity than polymerase chain reaction (PCR). It realizes the recognition of Diaporthe infection at an early stage of 24h when the kiwifruits do not have any noticeable symptoms. It demonstrates a bright prospect of point-of-care tests for early warning of kiwifruit soft rot infection and quality control.

Background-penalty-free waveguide enhancement of CARS signal in air-filled anti-resonance hollow-core fiber.

We study coherent anti-Stokes Raman spectroscopy in air-filled anti-resonance hollow-core photonic crystal fiber, otherwise known as "revolver" fiber. We compare the vibrational coherent anti-Stokes Raman signal of N2, at ∼2331 cm-1, generated in ambient air (no fiber present), with the one generated in a 2.96 cm of a revolver fiber. We show a ∼170 times enhancement for the signal produced in the fiber, due to an increased interaction path. Remarkably, the N2 signal obtained in the revolver fiber shows near-zero non-resonant background, due to near-zero overlap between the laser field and the fiber cladding. Through our study, we find that the revolver fiber properties make it an ideal candidate for the coherent Raman spectroscopy signal enhancement.

Laser-induced breakdown spectroscopy signal enhancement effect for argon caused by the presence of gold nanoparticles

The effect of the presence of nanoparticles (NPs) on the laser induced breakdown spectroscopy (LIBS) signal of argon gas was studied experimentally. 10–20 nm diameter gold NPs, produced by a spark discharge nanoparticle generator, were suspended in argon gas. The effect of particle size, number concentration and mass concentration, as well as laser pulse energy on the LIBS argon signal was systematically investigated. It was found that the breakdown threshold of the gas decreases considerably, facilitating the detection of Ar emission at such laser fluences, which do not allow plasma formation without the presence of the NPs. Our observations persist even at aerosol mass concentrations that are too low to allow the direct detection of nanoparticles. The effect, which is attributed to electron thermo- and field emission induced by the high intensity laser pulse, shows an asymptotically increasing magnitude with the aerosol mass concentration. The signal enhancement was found to be 102–104 and the effect is suggested to be useful in trace gas analysis or for the indirect detection of NPs. The achievable indirect aerosol mass concentration detection limit was estimated to be in the parts per trillion regime (as low as 50 ng·m−3), which is comparable to the best literature values reported for direct analysis.

Selective Enhancement of SERS Spectral Bands of Salicylic Acid Adsorbate on 2D Ti3C2Tx-Based MXene Film

In this research, we have demonstrated that 2D Ti3C2Xn-based MXene (MXene) films are suitable for the design of surface-enhanced Raman spectroscopy (SERS)-based sensors. The enhanced SERS signal was observed for a salicylic acid molecule on Ti3C2Tx-based MXene film. Confirmation of the adsorption of the salicylic acid molecule and the formation of a salicylic acid–MXene complex were determined by experimental SERS-based spectral observations such as greatly enhanced out-of-plane bending modes of salicylic acid at 896 cm−1 and a band doublet at 681 cm−1 and 654 cm−1. Additionally, some other spectral features indicate the adsorption of salicylic acid on the MXene surface, namely, a redshift of vibrational modes and the disappearance of the carboxyl deformation spectral band at 771 cm−1. The determined enhancement factor indicates the value that can be expected for the chemical enhancement mechanism in SERS of 220 for out-of-plane vibrational modes. Theoretical modeling based on density functional theory (DFT) calculations using B3LYP/6311G++ functional were performed to assess the formation of the salicylic acid/MXene complex. Based on the calculations, salicylic acid displays affinity of forming a chemical bond with titanium atom of Ti3C2(OH)2 crystal via oxygen atom in hydroxyl group of salicylic acid. The electron density redistribution of the salicylic acid–MXene complex leads to a charge transfer effect with 2.2 eV (428 nm) and 2.9 eV (564 nm) excitations. The experimentally evaluated enhancement factor can vary from 220 to 60 when different excitation wavelengths are applied.

Self-energized organic-inorganic hybrid composite for surface enhanced Raman spectroscopy

In this study, we integrate plasmonic metal nanomaterials with a piezoelectric polyvinylidene fluoride (PVDF) polymer and lithium niobate (LiNbO3) based composite to form an all-solid-state flexible self-energized sensor. We demonstrate that following the application of a load, the film enhances the surface-enhanced Raman spectroscopy (SERS) signal of an analyte molecule up to 14 times. The piezoelectric β-phase of PVDF in the film is optimized through the introduction of multi-walled carbon nanotubes and post-fabrication UV irradiation annealing. Additionally, the SERS signal enhancement can be further increased by the application of in situ UV light irradiation of the sample, resulting in the generation of photoexcited electrons from LiNbO3 microparticles introduced into the composite. Both the application of a mechanical displacement and the UV light-induced charge generation result in an improved charge transfer between the film and an analyte molecule. The piezoelectric PVDF/LiNbO3 film has been shown to be a suitable SERS platform for the detection of important biological molecules, demonstrating the potential of the substrate for fast on-site detection applications.

Filament-induced breakdown spectroscopy signal enhancement using optical wavefront control

Filament-induced breakdown spectroscopy (FIBS) is an analytical method that holds significant promise for remote sensing. In FIBS, it is desirable to maximize the intensity and improve the reproducibility of a selected spectroscopic feature. We demonstrate the use of wavefront control in conjunction with a genetic algorithm in FIBS of metallic copper and show that this approach can increase the efficacy of filament-induced breakdown signal production. Through wavefront optimization, we enhance the intensity of a chosen characteristic spectroscopic feature of copper by a factor of approximately 3 when performing filamentation over a 1-meter distance. The relative standard deviation of signal intensity is reduced from ∼17% to ∼12% after optimization. We find that modification of the wavefront by introduction of astigmatism and coma maximizes the signal intensity, and these aberrations appear in two distinct trials of the genetic algorithm. We compare these findings to previous work on multiple filament control and discuss the possible mechanisms that lead to signal enhancement associated with both the beam amplitude and phase profile. A broader use of wavefront control with feedback may improve the performance of FIBS in remote sensing applications.

Highly efficient sers performance from the silver nanoparticles/graphene nanoribbons/ cellulose paper

Introduction: Metal/graphene heterojunction structure has been one of the most crucial tools in the growth of high-performance Surface-enhanced Raman spectroscopy (SERS) platform, which is appropriate for sensing applications. In this research, we developed a SERS platform, graphene nanoribbons (GNRs) decorated silver nanoparticles (AgNPs) on cellulose paper substrate, in which GNRs was synthesized by wet chemical based on unzipping process of Multi-walled carbon nanotubes (MWCNTs), then GNRs hybridized with AgNPs through magnetron sputtering method.
 Methods: The morphology of graphene nanoribbons coated-Ag (AgNPs@GNRs) was analyzed by field emission scanning electronic microscopy (FESEM) and transmission electron microscopy (TEM). The quality and thermal stability of GNRs were characterized using thermogravimetric analysis. Besides, its structure and quality were also characterized by Raman spectroscope.
 Results: The results show that the unzipping process of MWCNTs to form GNRs was strongly affected by dispersing time and stirring temperature. The suitable condition creating the Graphene Nanoribbons using MWCNTs was the dispersing time of 10 mins in an acid environment, stirring in 30 mins at room temperature and in 45 min at 100°C. Moreover, SERS platform of AgNPs@GNRs exhibit the outstanding SERS signal enhancement with rhodamine 6G (R6G) low concentration of 10-5 M compared with pristine graphene and silver thin film. This could be attributed to the synergistic effect between AgNPs, GNRs and analyze molecules based on the enhancement of electromagnetic mechanism (EM) and chemical mechanism (CM), which plays a vital role in promoting the improvement SERS behavior.
 Conclusion: Ag NPs assembled onto graphene nanoribbons/ cellulose paper substrate could also serve as SERS active substrates for practical applications in various fields at trace levels.

Triple-pulse LIBS: laser-induced breakdown spectroscopy signal enhancement by combination of pre-ablation and re-heating laser pulses

The goal of this work is to examine the effect of a third additional laser pulse on orthogonal double-pulse laser-induced breakdown spectroscopy (DP LIBS).

Additional enhancement of SERS effect by a surface wave in photonic crystal

AbstractWe propose and demonstrate an enhancement of the Raman signal additional to that provided by the surface‐enhanced Raman spectroscopy (SERS) effect. Such an additional enhancement appears due to a resonance attributed to the existence of a surface wave at a photonic crystal (PC)/vacuum interface. Such a PC is realized as a system of alternating layers deposited on a prism, through which light enters the structure. The SERS‐active layer of aggregates of gold nanoparticles modified by dithionitrobenzoic acid is deposited on the PC/vacuum interface, where the resonant field is located. In the experiment, up to 170‐fold SERS signal enhancement is demonstrated with respect to the same SERS‐active layer deposited at a nonresonant substrate.

SERS Enhancement on the Basis of Temperature-Dependent Chemisorption: Microcalorimetric Evidence.

The mechanism of surface-enhanced Raman spectroscopy (SERS) is not very clear in view of the magnitude of the contribution of electromagnetic factor as well as the chemical mechanism. This report presents the extent of adsorption at different temperatures in terms of signal enhancements in SERS employing silver nanoparticles (AgNPs) of various shapes as substrate and dye molecules, crystal violet or Rhodamine 6G, as model Raman probes. Initially, the SERS signal increases with increasing temperature until a maximum intensity is reached, before it gradually decreases with increasing temperature. This trend is independent of the shape of the Raman substrates and probes. However, the temperature at which maximum intensity is obtained may depend upon the nature of the Raman probe. The energetics involved in the chemisorption process between dye molecules and AgNPs were determined through isothermal titration calorimetry and their implications for the observed SERS signals were assessed. The maximum heat change occurred at the temperature at which the maximum signal enhancement in SERS was obtained and the enhanced interaction at optimum temperature was confirmed by absorption spectroscopy.

Effect of laser pulse energies in laser induced breakdown spectroscopy in double-pulse configuration

In this paper, the effect of laser pulse energy on double-pulse laser induced breakdown spectroscopy signal is studied. In particular, the energy of the first pulse has been changed, while the second pulse energy is held fixed. A systematic study of the laser induced breakdown spectroscopy signal dependence on the interpulse delay is performed, and the results are compared with the ones obtained with a single laser pulse of energy corresponding to the sum of the two pulses. At the same time, the crater formed at the target surface is studied by video-confocal microscopy, and the variation in crater dimensions is correlated to the enhancement of the laser induced breakdown spectroscopy signal. The results obtained are consistent with the interpretation of the double-pulse laser induced breakdown spectroscopy signal enhancement in terms of the changes in ambient gas pressure produced by the shock wave induced by the first laser pulse.