Surface-enhanced resonance Raman scattering spectroscopy of single R6G molecules

Surface-enhanced resonance Raman scattering （SERRS） of Rhodamine 6G （R6G） adsorbed on colloidal silver clusters has been studied. Based on the great enhancement of the Raman signal and the quench of the fluorescence, the SERRS spectra of R6G were recorded for the samples of dye colloidal solution with different concentrations. Spectral inhomogeneity behaviours from single molecules in the dried sample films were observed with complementary evidences, such as spectral polarization, spectral diffusion, intensity fluctuation of vibrational lines and even ＂breathing＂ of the molecules. Sequential spectra observed from a liquid sample with an average of 0.3 dye molecules in the probed volume exhibited the expected Poisson distribution for actually measuring 0, 1 or 2 molecules. Difference between the SERRS spectra of R6G excited by linearly and circularly polarized light were experimentally measured.

Advancing Energy Systems with In-Situ and Operando Surface-Enhanced Raman Scattering Spectroscopy

Surface-enhanced Raman scattering spectroscopy(SERS)has emerged as a powerful analytical technique to enable nanoscale investigations of energy systems.This mini-review focuses on the applications of in-situ and operando SERS in energy-related research,highlighting its unique capabilities and significant contributions to understanding energy storage and conversion processes.We first introduce the fundamental principles of SERS,key SERS-derived techniques,and commonly employed platforms.Subsequently,we delve into the diverse applications of in-situ and operando SERS across various energy systems,encompassing photocatalytic and electrocatalytic systems,fuel cells,solar cells,and batteries.Finally,we conclude with our perspective on the current challenges and prospects in this area.We hope thismini-review serves as an essential overview to guide the design and implementation of in-situ and operando SERS studies of energy systems.

Ultrasensitive Detection of Polycyclic Aromatic Hydrocarbons(PAHs) in Water Using Three-Dimensional SERS Substrate Based on Porous Material and pH 13 Gold Nanoparticles

Sensitivity is crucially important for surface-enhanced Raman spectroscopy(SERS)application to detect trace-level polycyclic aromatic hydrocarbons(PAHs)in the seawater.In this study,a high sensitivity three-dimensional(3-D)SERS substrate composed with syringe filter,glycidyl methacrylate-ethylene dimethacrylate(GMA-EDMA)porous material and optimal parameters(57 nm,pH 13)gold nanoparticles(Au NPs)was developed for the detection of PAHs in water.The enhancement effect and repeatability of this 3-D substrate were also explored.The Raman intensity of pyrene using 3-D SERS substrate is about 8 times higher than that of substrate only using p H 13 gold colloid solution and about 12 times higher than that of substrate using natural Au NPs and GMA-EDMA porous material,which means both the pH 13 AuN Ps and the GMA-EDMA porous material are important factors for the sensitivity of this 3-D SERS substrate.Good repeatability of this optimal 3-D substrate was obtained.The relative standard deviation(RSD)is less than 8.66% on the same substrate and less than 3.69% on other different substrates.Four kinds of PAHs,i.e.,phenanthrene,pyrene,benzo(a)pyrene,benzo(k)fluoranthene and their mixture,were detected at the different concentrations.Their limits of detection(LODs)are 8.3×10^-10(phenanthrene),2.1×10^-10(pyrene),3.8×10^-10(benzo(a)pyrene)and 1.7×10^-10 mol L^-1(benzo(k)fluoranthene),respectively.In addition,these four PAHs were also detected by fluorescence spectroscopy to evaluate the sensitivity of SERS technology using this optimal 3-D SERS substrate.The results showed that the sensitivity of SERS based on the 3-D SERS substrate even using the portable Raman system was closed to that of fluorescence spectroscopy.Therefore,the SERS technology using this optimal 3-D substrate is expected to be an in-situ method for the detection of environmental PAHs.

SERS activity of carbon nanotubes modified by silver nanoparticles with different particle sizes

A two-dimensional(2D)surface-enhanced Raman scattering(SERS)substrate is fabricated by decorating carbon nanotube(CNT)films with Ag nanoparticles(Ag NPs)in different sizes,via simple and low-cost chemical reduction method and self-assembling method.The change of Raman and SERS activity of carbon nanotubes/Ag nanoparticles(CNTs/Ag NPs)composites with varying size of Ag NPs are investigated by using rhodamine 6G(R6G)as a probe molecule.Meanwhile,the scattering cross section of Ag NPs and the distribution of electric field of CNTs/Ag NPs composite are simulated through finite difference time domain(FDTD)method.Surface plasmon resonance(SPR)wavelength is redshifted as the size of Ag NPs increases,and the intensity of SERS and electric field increase with Ag NPs size increasing.The experiment and simulation results show a Raman scattering enhancement factor(EF)of 108for the hybrid substrate.

Optical responses of metallic plasmonic arrays under the localized excitation

The metallic plasmonic array that can support both propagating surface plasmon polaritons(PSPPs)and localized surface plasmon resonance(LSPR)possesses rich optical properties and remarkable optical performance,making it a powerful platform for applications in photonics,chemistry,and materials.For practical applications,the excitation spot is usually smaller than the area of metal arrays.It is thus imperative to address“how many array units are enough?”towards a rational design of plasmonic nanostructures.Herein,we employed focused ion beam(FIB)to precisely fabricate a series of plasmonic array structures with increased unit number.By utilizing photoluminescence(PL)and surface-enhanced Raman spectroscopy(SERS),we found that the array units outside the excitation spot still have a significant impact on the optical response within the spot.Combined with the numerical simulation,we found that the boundary of the finite array leads to the loss of PSPP outside the excitation point,which subsequently affects the coupling of PSPP and LSPR in the excitation spot,leading to variations in PL and SERS intensity.Based on the findings,we further tuned the LSPR mode of the metal arrays by electrodeposition to obtain strong near-field enhancement without any influence on the PSPP mode.This work advances the understanding of near-field and far-field optical behavior in finite-size array structures and provides guidance for designing highly-efficient photonic devices.

薄层色谱和表面增强拉曼散射光谱联用检测猪肉中二甲硝咪唑

采用薄层色谱和表面增强拉曼散射光谱(TLC-SERS)联用技术对猪肉中的二甲硝咪唑进行分离检测。硅藻土作为固定相制备薄层色谱板,将含有二甲硝咪唑的混合物直接滴在硅藻土板上,可实现对二甲硝咪唑的快速分离检测。经过薄层色谱分离后,确定比移值(R_(f)),在对应位置滴加浓缩40倍的纳米金溶胶,表面增强拉曼光谱检测二甲硝咪唑的灵敏度为10μmol/L,检出限为4.16 mmol/L,低于食品中二甲硝咪唑的最高残留限量。

Macroscopic Ag nanostructure array patterns with high-density hotspots for reliable and ultra-sensitive SERS substrates

Syn thesis of metal nano structures arrays with large amounts of small nano-gaps on a homoge nous macroscale is of significant in terest and importa nee in chemistry,biotech no logy,physics,and nan otech no logy because of their enhan ced properties.However,the fabricatio n of uncovered nano-gaps with high-density and uniformity is rather difficult due to the complex and multiple synthetic steps.In this research,a facile and low-cost approach is demonstraind for the synthesis of high-density small nano-gaps(about 3.4 nm)between silver nanostructure array patter ns(SNAPs)over a large area.Uniform nan o?hole patter ns were periodically gen erated over an entire substrate using nano-impri nt lithography.Electrochemical reacti on at the high over-potential produced multiple silver nano crystals inside the nano-hole patter ns,gen erati ng a high-de nsity of small and un covered nano-gaps.Finally,we fully dem on strate their applicati on in the rapid detectio n of rhodamine 6G(R6G)molecules by surface-enhaneed Raman scattering(SERS)spectroscopy with a very low detection limit(1 fM)as well as excellent signal uniformity(RSD<8.0%±2.5%),i ndicati ng an extra ordinary capability for single-molecule detecti on.