Facile electrochemical surface-alloying and etching of Au wires to enable high-performance substrates for surface enhanced Raman scattering

Surface-enhanced Raman Spectroscopy(SERS)is a nondestructive technique for rapid detection of analytes even at the single-molecule level.However,highly sensitive and reliable SERS substrates are mostly fabricated with complex nanofabrication techniques,greatly restricting their practical applications.A convenient electrochemical method for transforming the surface of commercial gold wires/foils into silver-alloyed nanostructures is demonstrated in this report.Au substrates are treated with repetitive anodic and cathodic bias in an electrolyte of thiourea,in a one-pot one-step manner.X-rays absorption fine structure(XAFS)spectroscopy confirms that the AuAg alloy is induced at the surface.The unique AuAg alloyed surface nanostructures are particularly advantageous when served as SERS substrates,enabling a remarkably sensitive detection of Rhodamine B(a detection limit of 10^(-14)M,and uniform strong response throughout the substrates at 10^(-12)M).

Application of Monodisperse Thermo-Responsive Composite Microgels with Core-Shell Structure Based on Au@Ag Bimetallic Nanorod as Core in Surface Enhanced Raman Spectroscopy Substrate

The monodisperse Au@Ag bimetallic nanorod is encapsulated by crosslinked poly( N-isopropylacrylamide)( PNIPAM) to produce thermo-responsive composite microgel with well-defined core-shell structure( Au@ Ag NR@ PNIPAM microgel)by seed-precipitation polymerization method using butenoic acid modified Au @ Ag NRs as seeds. When the temperature of the aqueous medium increases from 20℃ to 50℃,the localized surface plasmon resonance( LSPR) band of the entrapped Au @ Ag NR is pronouncedly red-shifted because of the decreased spatial distances between them as a result of shrinkage of the microgels,leading to their plasmonic coupling. The temperature tunable plasmonic coupling is demonstrated by temperature dependence of the surface enhanced Raman spectroscopy( SERS) signal of 1-naphthol in aqueous solution. Different from static plasmonic coupling modes from nanostructured assembly or array system of noble metals,the proposed plasmonic coupling can be dynamically controlled by environmental temperature. Therefore, the thermo responsive hybrid microgels have potential applications in mobile LSPR or SERS microsensors for living tissues or cells.

THE CHARACTERIZATION OF SILVER SUBCOLLOID USED IN SURFACE ENHANCED RAMAN SPECTROSCOPY

A clear light-yellow silver sol which has the visible spectral absorption at 390 nm, when adsorbed phenylmercaptotetrazole(PMT) or mercaptobenzothiazole(MBT), has a new absorption at 510-550 nm. It was found that the adsorption of halide ions competes with PMT and MBT. However, halide ions have a completely different influence from PMT and MBT on the spectral absorption of the silver sol. The differences may result from the change of the properties of the surface of the silver subcolloidal particles and from the bond forms combining adsorbates with the substrates.

Monitoring the penetration and accumulation of gold nanoparticles in rat skin ex vivo using surface-enhanced Raman scattering spectroscopy

Contamination by accidental cutaneous contact with the commercial products and the air pol-hutants raised a considerable health and safety issue.This study aimed to trace the dynamics of the 20 nm gold nanopartide(GNP)penetration and accumulation in rat skin tissues using a surface-enhanced Raman scattering(SERS)techmique.After the topical application of GNPs on rat skin surface,the SERS spectra were recorded for every 15 pum to an overall depth of 75 pum from skin surface for 150 min.The processes of GNP penetration in rat skin were accompanied by aggregation of GNPs,which affected SERS spectra.The results revealed that 20 nm GNPs can penetrate through stratum corneum layer,viable epidermis layer,and then into dermis layer.This study demonstrated for the first time the potential of SERS spectroscopy to monitor the penetration and accumulation of GNPs in rat skin.

Synthesis of magnetic polyphosphazene-Ag composite particles as surface enhanced Raman spectroscopy substrates for the detection of melamine

Magnetic polyphosphazene(MPZS) particles coated by Ag nanoparticles(MPZS-Ag) have been developed as surface enhanced Raman spectroscopy(SERS) substrates for sensitive detection of melamine in aqueous solutions and milk samples.5,5’-Dithiobis-(2-nitrobenzoic acid)(DTNB) was used as model analyte to test the SERS activity of the MPZS-Ag particles.The prepared MPZS-Ag particles possess both magnetic responsiveness and excellent SERS properties.SERS detection of different concentrations of melamine aqueous solutions and spiked milk samples were performed by the MPZS-Ag particles.The limit of detection(LOD) of the melamine in aqueous solutions was 10^-7 mol/L(0.0126 mg/L) and 0.6 mg/L in real milk samples using the MPZS-Ag particles as SERS substrates.The LOD of the melamine are much lower than the safety values of Food and Drug Administration and Codex Alimentarius Commission.These results indicate that the MPZS-Ag particles have promising application prospect for SERS analysis in food safety fields.

Detection of chlorpyrifos in apples using gold nanoparticles based on surface enhanced Raman spectroscopy

In this study,gold nanoparticles(AuNPs)were synthesized for rapid and sensitive characterization and quantification of chlorpyrifos in apples.Min-max signal adaptive zooming and second derivative transformation method were adopted to pre-process Raman spectral signal.The min-max signal adaptive zooming method showed a higher correlation coefficient than derivative transformation when developing linear calibration curve between chlorpyrifos pesticide and Raman spectral peak intensity.The present method had a high reproducibility with the relative standard deviation less than 15%.Regression models showed a good linear relationship(R=0.962)between intensity of characteristic spectral peaks(at 677 cm-1)and chlorpyrifos concentration on whole apples ranging from 0.13 mg/kg to 7.59 mg/kg.The application of surface enhancement Raman spectroscopy(SERS)detected chlorpyrifos pesticide to the detection limit of 0.13 mg/kg,which can be applied further for lower concentration in the future.The method presented in this study can provide a way-out for detection of pesticide residue in whole apple to trace amount.

Detection of pesticides on navel orange skin by surface-enhanced Raman spectroscopy coupled with Ag nanostructures

Residual pesticides such as phosmet and chlorpyrifos in fruit have become a public concern problem in recent years.In this study,surface-enhanced Raman spectroscopy(SERS)was used to detect and characterize pesticides extracted from navel orange surfaces.Silver colloid was prepared for getting the SERS of phosmet and chlorpyrifos.Enhanced Raman signals of phosmet over a concentration range of 5 mg/L to 30 mg/L and chlorpyrifos over a concentration range of 5 mg/L to 20 mg/L were acquired.Partial least squares(PLS)regression combined with different data preprocessing methods was used to develop quantitative models.With the second derivative data preprocessing,the best prediction model of phosmet pesticide was achieved with a correlation coefficient(r)of 0.852 and the root mean square error of prediction(RMSEP)of 5.177 mg/L.The best prediction model of chlorpyrifos pesticide was achieved with r of 0.843 and the RMSEP of 2.992 mg/L using the multiplicative scatter correction(MSC)and first derivative data preprocessing.This study indicated that SERS coupled with Ag nanostructures is a potential tool for analysis of phosmet and chlorpyrifos pesticide residues.

Structure of water at ionic liquid/Ag interface probed by surface enhanced Raman spectroscopy

The potential-dependent adsorption behavior of water and ionic liquid was probed by surface-enhanced Raman spectroscopy （SERS） at the Ag electrode surface in the ionic liquids containing water with different concentrations. The configuration of water at the ionic liquid/electrode interface and the relationship between the potential of zero charge （pzc） and the molar frac- tion of water were deduced through the changes in the vibrational frequency of OH stretching mode. A small Stark effect value was determined in the system with lower molar fraction of water. With the increase of the water concentration, the OH stretching vibrational frequency gradually shifted to the high wavenumber region, the pzc was also moved positively, and the Stark effect value of OH stretching vibrational mode increased. It reached about 76 cm-1 V-I in the 1 tool L-1 [BMIM]Br aqueous solution. These differences were mainly contributed by hydrogen bonding and the configuration of water in the ionic liquid solution. In the solution with lower water content, water molecules existed at the interface layer through hydrogen bond- ing with cations, while in the higher content solution, the intermolecular hydrogen bonding between water molecules was strengthened and the possibility of the direct interaction between the water molecule and electrode surface increased.

The Fabrication and SERS Performance of Multi-layer Hollow Au-Ag Alloy Nano Urchins Structure-based SERS Fiber Probe

Novel hollow Au Ag alloy nano urchins were synthesized via Ag seeds growth method,and self-assembly coated on the wall and end-tip of silica fiber for fiber probe fabrication.The nano urchins homogeneously distributed on fiber surface because of fiber silanization.The sizes and tip sharpness of the nano-urchins could be controlled by Ag seeds.The elements distribution analysis indicated there was high Ag content in tip-top for better surface enhance Raman scattering performance.The detectable concentration could be as low as 10-8 M using crystal violet molecules as analyte.Moreover,the fiber probes were stable in air,due to Au in the alloy.This fiber probe could be used for low content single molecular analysis.

Determine the position of nanoparticles in cells by using surfaceenhanced Raman three-dimensional imaging

The development of efficient three-dimensional cell imaging technology is a necessary means to study cell composition and structure,especially to track and monitor the phagocytosis process of nanoparticles by cells.Herein,we prepared a MoO_(2)hollow nanosphere with a strong surface plasmon resonance effect in the visible light region,which exhibited an excellent surface enhanced Raman scattering effect.When the 4-mercaptobenzoic acid(4-MBA)molecules are modified,it can be efficiently used as Raman probe molecules to perform clear three-dimensional cell imaging.No matter when the nanoparticles are located inside the cell,outside the cell or partly inside the cell,they all can be clearly presented by this enhanced Raman probe molecule.These results provide a rapid and accurate method for three-dimensional imaging of cells,especially for tracking the phagocytosis of nanoparticles.

Molecular-level investigation on electrochemical interfaces by Raman spectroscopy

The structure and dynamics of electrode/liquid interfaces play an increasingly important role in electrochemistry. Raman spectroscopy is capable of providing detailed structural information at molecular level and new insight into the interfacial structure, adsorption, reaction, electrocatalysis and corrosion. In this account we will summarize some progresses of surface Raman spectroscopy in the study of electrochemical interfaces, mainly based on our group's work, laying emphasis on the detection sensitivity, spectral resolution, time resolution and spatial resolution as well as the hyphenated technique.

SERS-tag techology in food safety and detection:sensing from the"fingerprint"region to the"biological-silent"region

Surface enhanced Raman spectroscopy(SERS)offers many advantages for the fast and sensitive detection of specific compounds,metal ions or pathogens in foods,motivating to its increasing utilization in food safety.SERS-tags,typically constructed using signal enhanced substrate,Raman reporter molecules,a biocompatible protective layer and a specific recognition element,provide a powerful tool for the analysis of food hazards.This article reviews recent progress in the development of SERS-tags for food safety assessment covering SERS-tags with characteristic peaks in the“fingerprint”region(800-1800 cm-1)and the“biological-silent”region(1800-2800 cm-1).Following a brief description of SERS substrates,the design,synthesis and applications of SERS-tag are explored in detail.The application of SERS-tags technology for the detection of microorganisms,pesticides and antibiotics are then investigated.Finally,the prospects of using SERS-tag in real-world food safety analysis are critically discussed.

Hybrid silver nanoparticles:Modes of synthesis and various biomedical applications

In the present day,there is a growing trend of employing new strategies to synthesize hybrid nanoparticles,which involve combining various functionalities into a single nanocomposite system.These modern methods differ significantly from the traditional classical approaches and have emerged at the forefront of materials science.The fabrication of hybrid nanomaterials presents an unparalleled opportunity for applica-tions in a wide range of areas,including therapy to diagnosis.The focus of this review article is to shed light on the different modalities of hybrid nanoparticles,providing a concise description of hybrid silver nano-particles,exploring various modes of synthesis and classification of hybrid silver nanoparticles,and highlighting their advantages.Addi-tionally,we discussed core-shell silver nanoparticles and various types of core and shell combinations based on the material category,such as dielectric,metal,or semiconductor.The two primary classes of hybrid silver nanoparticles were also reviewed.Furthermore,various hybrid nanoparticles and their methods of synthesis were discussed but we emphasize silica as a suitable candidate for hybridization alongside metal nanoparticles.This choice is due to its hydrophilic surface qualities and high surface charge,which provide the desired repulsive forces to minimize aggregation between the metal nanoparticles in the liquid solution.Silica shell encapsulation also provides chemical inertness,robustness and the adaptability to the desired hybrid nanoparticle.Therefore,among all the materials used to coat metal nanoparticles;silica is highly approved.

Simultaneous Raman and reflection UV/Vis absorption spectroelectrochemistry

In the present work,a new combination of Raman and ultraviolet and visible(UV/Vis)absorption spectroelectrochemistry in reflection mode is proposed.The new experimental setup allows obtaining the two kinds of spectroscopic data without interferences concomitantly with the electrochemical information.To the best of our knowledge,it is the first time to report the simultaneous obtention of electrochemical,electronic,and vibrational information in the same experiment.This new combination provides time-resolved information about the processes that are taking place on the electrode/solution interface which has significant implications in different fields of chemistry,such as modification of electrodes,studies of electrocatalytic reaction mechanisms,development of sensors,among others.Two different systems were used to demonstrate the advantages and capabilities of the brand-new technique,namely,the oxidation of potassium ferrocyanide,an out-sphere system that is usually employed in the validation of SEC techniques,and the electrochemical-surface enhanced Raman spectroscopy(EC-SERS)detection of crystal violet by in-situ formation of the silver SERS substrate,where the UV/Vis spectra were used to follow the formation of the SERS substrate,whereas the Raman response of a probe molecule was used to confirm either the formation of a nanostructured surface and to obtain the fingerprint of the molecule with a high time resolution.The brand-new experimental setup has shown to be useful,versatile,robust,compact,and easy to use for future applications.

An anisotropic propagation technique for synthesizing hyperbranched polyvillic gold nanoparticles

Of late, many synthesis processes have been studied to develop irregular nano-rnorphologies of gold nanostructures for biomedical applications in order to increase the efficacy of nanoparticle theranostics, tune the plasmonic absorbance spectra, and increase the sensitivity of biomolecule detection through surface enhanced Raman spectroscopy. Here we report, a novel, non-seed mediated versatile single pot synthesis method capable of producing hyperbranched gold ＂nano-polyvilli＂ with more than 50-90 branching nanowires propagating from a single origin within each structure. The technique was capable of achieving precise tuning of the branch propagation where the branching could be controlled by varying the duration of incubation, temperature, and hydrogen ion concentration.

The origin of potential rise during charging of Li-O2 batteries

When aprotic Li-O2 batteries recharge, the solid Li2O2 in the positive electrode is oxidized, which often exhibits a continuous or step increase in the charging potential as a function of the charging capacity, and its origin remains incompletely understood. Here, we report a model study of electro-oxidation of a Li2O2 film on an Au electrode using voltammetry coupled with in situ Raman spectroscopy. It was found that the charging reaction initializes at the positive electrodelLizO2 interface, instead of the previously presumed Li2O2 surface, and consists of two temporally and spatially separated Li2O2 oxidation processes, accounting for the potential rise during charging of Li-O2 batteries. Moreover, the electrode surface-initialized oxidation can disintegrate the Li2O2 film resulting in a loss of Li2O2 into electrolyte solution, which drastically decreases the charging efficiency and highlights the importance of using soluble electro-catalyst for the complete charging of Li-02 batteries.

Optical response and SERS properties of individual large scale supracrystals made of small silver nanocrystals

There is a considerable interest in producing and understanding the optical and spectroscopic properties of ordered nanoparticle assemblies. Herein, we describe and interpret the optical absorbance and Raman properties of 5.9 nm ± 0.3 nm diameter silver nanocrystals coated with dodecanethiol and organized in highly ordered 3D superlattices of different heights. Each superlattice was studied individually, which allowed to elaborate a model based on Maxwell-Garnett theory to reproduce qualitatively the height and wavelength dependence of the absorbance. Importantly, because of their small size compared to that of traditional nanoparticles used in Surface Enhanced Raman Spectroscopy （SERS）, the large 3D distribution of hot spots generated by the silver superlattices allowed to easily obtain SERS spectra of the surrounding ligands despite their intrinsic low Raman cross section. Accordingly, traces of thiophenol could be detected very easily.

2D profiling of tumor chemotactic and molecular phenotype at single cell resolution using a SERS-microfluidic chip

Emerging single-cell technologies create new opportunities for unraveling tumor heterogeneity.However,the development of high-content phenotyping platform is still at its infancy.Here,we develop a microfluidic chip for two-dimensional(2D)profiling of tumor chemotactic and molecular features at single cell resolution.Individual cells were captured by the triangular micropillar arrays in the cell-loading channel,facilitating downstream single-cell analysis.For 2D phenotyping,the chemotactic properties of tumor cells were visualized through cellular migratory behavior in microchannels,while their protein expression was profiled with multiplex surface enhanced Raman scattering(SERS)nanovectors,in which Raman reporter-embedded gold@silver core-shell nanoparticles(Au@Ag REPs)were modified with DNA aptamers targeting cellular surface proteins.As a proof of concept,breast cancer cells with diverse phenotypes were tested on the chip,demonstrating the capability of this platform for simultaneous chemotactic and molecular analysis.The chip is expected to provide a powerful tool for investigating tumor heterogeneity and promoting clinical precision medicine.

A New SERS Method Based on Shell-isolated Nanoparticles for Rapidly Quantitative Determination of Hydrogen Peroxide

Hydrogen peroxide(H_(2)O_(2))is an important chemical substance produced in the metabolic process of organisms.Excess or less production could lead to serious effects on the body.Therefore,the development of advanced technology to accurately detect the content of H_(2)O_(2) is of great significance.Herein,we developed a new ratiometric SERS nanoprobe based on shell-isolated nanoparticles(SHINs)for rapidly quantitative detection of H_(2)O_(2)-Because of the small Raman cross-section of H_(2)O_(2),the ratiometric nanoprobe is an effective method for indirect detection of H_(2)O_(2),which is designed based on the reaction of p-mercaptophenylboric acid(MPB)with H_(2)O_(2) to form p-mercaptophenol(MP).Meanwhile,the nanoprobe was used to achieve quantitative detection of H_(2)O_(2) and applied in quantitative detection of actual sample-glucose,whose linear correlation coefficient could reach 0.9947 and 0.9812,respectively.This method expands the application of SERS technology,especially provides a reference for the detection of molecules with small Raman cross-section.