Facile SERS screening of melamine in bovine milk with 2D printed AgNPs/glass fabric filter paper as the flexible substrate

Melamine is one of the most frequently detected adulterants in dairy products.The current study proposes a surface-enhanced Raman spectroscopy(SERS)-based analytical tool for fast and reliable screening of melamine in bovine milk.A hand-held Raman spectrometer was used in conjunction with a substrate composed of silver nanoparticles(AgNPs)that was 2D printed onto glass fiber(GF)filter paper.Under optimized conditions,a sensitive and fingerprint-like signal at 674 cm^(-1) was obtained.The AgNPs/GF substrate exhibited high sensitivity to melamine in milk down to 1.9498×10^(-5)mg/mL,which is well below the USA and EU safety limits(2.5×10^(-3)mg/mL).Remarkably,the proposed technology was also highly reproducible,showing spot-to-spot and block-to-block variations below 3.3%and 4.9%at 674 cm^(-1) in Raman intensity,respectively.The characteristic peak intensity and concentration of melamine showed an acceptable linear relationship(R^(2)=0.9909)within the range of 0.0001-1 mg/mL.Overall,the method established in this study can provide an efficient and effective method for the quantitative target screening and detection of melamine in dairy products.

Self-assembly 2D plasmonic nanorice film for surface-enhanced Raman spectroscopy

As an ultrasensitive sensing technology,the application of surface enhanced Raman spectroscopy(SERS)is one interesting topic of nano-optics,which has huge application prospectives in plenty of research fields.In recent years,the bottleneck in SERS application could be the fabrication of SERS substrate with excellent enhancement.In this work,a two-dimensional(2D)Ag nanorice film is fabricated by self-assembly method as a SERS substrate.The collected SERS spectra of various molecules on this 2D plasmonic film demonstrate quantitative detection could be performed on this SERS substrate.The experiment data also demonstrate this 2D plasmonic film consisted of anisotropic nanostructures has no obvious SERS polarization dependence.The simulated electric field distribution points out the SERS enhancement comes from the surface plasmon coupling between nanorices.And the SERS signals is dominated by molecules adsorbed at different regions of nanorice surface at various wavelengths,which could be a good near IR SERS substrate for bioanalysis.Our work not only enlarges the surface plasmon properties of metal nanostructure,but also exhibits the good application prospect in SERS related fields.

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.

Multivariate analysis of serum surface-enhanced Raman spectroscopy of liver cancer patients

Early diagnosis of liver cancer plays a significant role in reducing its high mortality.In this preliminary study,the feasibility of using serum surface-enhanced Raman spectroscopy(SERS)to identify liver cancer was studied.Serum samples were obtained from liver cancer patients and healthy controls.The differences between the SERS spectra of pre-operation and postoperation of liver cancer patients were also analyzed.The general shape and trend of SERS spectra of health control and liver cancer patients were similar.Multivariate analysis,e.g.,PLSSVM,might be useful for the discrimination of serum SERS spectra of pre-operation and post-operation.

Identification and Analysis of the Intermediates from Photodegradation of 3,3′-diamino-4,4′-azoxyfurazan(DAAF)by SERS and HPLC–MS/MS

Understanding the structural changes and degradation mechanisms of organic pollutants is critical in environmental research.In this work,a xenon lamp was used as an analog light source to simulate the effect of sunlight on 3,3′-diamino-4,4′-azoxyfurazan(DAAF)in aqueous solution.Combining high-performance liquid chromatography coupled with tandem mass spectrometry(HPLC–MS/MS),surface-enhanced Raman spectroscopy(SERS)with density functional theory(DFT),the degradation intermediates and mechanisms of DAAF were investigated.The sequential breakdown of the–NH2 and–O–N=bonds,followed by the removal of atomic O from–N=N(O)–,was emphasized and investigated using two-dimensional correlation spectroscopy(2D-COS)and SERS spectra.Three intermediates with mass-to-charge ratios(m/z)181,251 and 180 were identified and characterized by integrating experimental SERS data with DFT-calculated Raman spectra based on structures hypothesized from MS spectra.The findings from HPLC–MS and SERS not only corroborate each other but also provide a foundation for a detailed examination of the DAAF degradation process.

Selective deposition of a MOF at the spikes of Au nanostars for SERS detection

In the pursuit of advancing molecular sensing through surface-enhanced Raman spectroscopy(SERS),the combination of plasmonic nanoparticles and metal-organic frameworks(MOFs)has emerged as a highly effective approach to enhance the sensitivity and selectivity of SERS substrates.However,most prior investigations have predominantly focused on MOF-coated plasmonic nanoparticles in core@shell or layer-by-layer configurations,leaving a notable knowledge gap in exploring alternative configurations.Herein we present a facile method to construct a particle-on-mirror architecture by selectively coating a MOF,zeolitic imidazolate framework-8(ZIF-8),onto the tips of Au nanostars and subsequently depositing the resultant nanoparticles onto a Au film.This design integrates the electric field enhancement at the sharp tips and nanogaps,along with the molecular enrichment function within the porous MOF immobilized at the tips and nanogaps,leading to a substantial boost in the SERS signal intensity.Such a unique SERS platform enables consistent and outstanding SERS performance for analytes of different sizes.This work opens up a promising strategy for constructing multifunctional nanostructures for sensitive SERS detection in real-life scenarios.

Study on gastric cancer blood plasma based on surface-enhanced Raman spectroscopy combined with multivariate analysis

A surface-enhanced Raman spectroscopy (SERS) method combined with multivariate analysis was developed for non-invasive gastric cancer detection. SERS measurements were performed on two groups of blood plasma samples: one group from 32 gastric patients and the other group from 33 healthy volunteers. Tentative assignments of the Raman bands in the measured SERS spectra suggest interesting cancer-specific biomolecular changes, including an increase in the relative amounts of nucleic acid, collagen, phospholipids and phenylalanine and a decrease in the percentage of amino acids and saccharide in the blood plasma of gastric cancer patients as compared with those of healthy subjects. Principal components analysis (PCA) and linear discriminant analysis (LDA) were employed to develop effective diagnostic algorithms for classification of SERS spectra between normal and cancer plasma with high sensitivity (79.5%) and specificity (91%). A receiver operating characteristic (ROC) curve was employed to assess the accuracy of diagnostic algorithms based on PCA-LDA. The results from this exploratory study demonstrate that SERS plasma analysis combined with PCA-LDA has tremendous potential for the non-invasive detection of gastric cancers.

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.

Stable and unique graphitic Raman internal standard nanocapsules for surface-enhanced Raman spectroscopy quantitative analysis

Graphitic nanomaterials have unique, strong, and stable Raman vibrations that have been widely applied in chemistry and biomedicine. However, utilizing them as internal standards （ISs） to improve the accuracy of surface-enhanced Raman spectroscopy （SERS） analysis has not been attempted. Herein, we report the design of a unique IS nanostructure consisting of a large number of gold nanoparticles （AuNPs） decorated on multilayered graphitic magnetic nanocapsules （AGNs） to quantify the analyte and eliminate the problems associated with traditional ISs. The AGNs demonstrated a unique Raman band from the graphitic component, which was localized in the Raman silent region of the biomolecules, making them an ideal IS for quantitative Raman analysis without any background interference. The IS signal from the AGNs also indicated superior stability, even under harsh conditions. With the enhancement of the decorated AuNPs, the AGN nanostructures greatly improved the quantitative accuracy of SERS, in particular the exclusion of quantitative errors resulting from collection loss and non-uniform distribution of the analytes. The AGNs were further utilized for cell staining and Raman imaging, and they showed great promise for applications in biomedicine.

Fabrication of plasmonic nanopyramidal array as flexible SERS substrate for biosensing application

The proposed work aims to develop a sensitive surface-enhanced Raman spectroscopy(SERS)nano-biosensor.The inverted nano pyramid array on silicon substrate fabricated using electron beam lithography(EBL)was utilised as a master template and the mold was later replicated via nanoimprinting process to prepare gold-coated polymer nanopyramid three-dimensional(3D)SERS substrate.The fast and versatile replication process using nanoimprinting lithography(NIL)can produce polymer nanopyramids in a low-cost and reproducible fashion.Also,the proposed fabrication protocol can be easily upscale for large scale fabrication.The intense electric field confinement at nanotips and four edges of gold-coated polymer nanopyramid enhanced the Raman signal of probe molecules,i.e.,Rhodamine 6G with a limit of detection down to 3.277×10−9 M was achieved.This work also underlines the efficiency of gold-coated polymer nanopyramid arrays in the spectral detection of hemoglobin proteins at low concentrations.The Raman signal enhancement mechanism was further studied through the electromagnetic simulation using COMSOL Multiphysics.In addition,bending test experiments were performed to understand the effect of flexibility on SERS signal response.The fabricated gold-coated polymer nanopyramids arrays could pave the way for the development of low-cost SERS platforms for the detection of hazardous biological and chemical compounds at ultra-low concentrations in practical applications.

Toroidal dipole-modulated dipole-dipole double-resonance in colloidal gold rod-cup nanocrystals for improved SERS and secondharmonic generation

Colloidal metal nanocrystals(NCs)show great potential in plasmon-enhanced spectroscopy owing to their attractive and structure-depended plasmonic properties.Herein,unique Au rod-cup NCs,where Au nanocups are embedded on the one or two ends of Au nanorods(NRs),are successfully prepared for the first time via a controllable wet-chemistry strategy.The Au rod-cup NCs possess multiple plasmon modes including transverse and longitudinal electric dipole(TED and LED),magnetic dipole(MD),and toroidal dipole(TD)modulated LED resonances,producing large extinction cross-section and huge near-field enhancements for plasmon-enhanced spectroscopy.Particularly,Au rod-cup NCs with two embedded cups show excellent surface-enhanced Raman spectroscopy(SERS)performance than Au NRs(75.6-fold enhancement excited at 633 nm)on detecting crystal violet owing to the strong electromagnetic hotspots synergistically induced by MD,LED,and TED-based plasmon coupling between Au cup and rod.Moreover,the strong TD-modulated dipole-dipole double-resonance and MD modes in Au rod-cup NCs bring a 37.3-fold enhancement of second-harmonic generation intensity compared with bare Au NRs,because they can efficiently harvest photoenergy at fundamental frequency and generate large near-field enhancements at second-harmonic wavelength.These findings provide a strategy for designing optical nanoantennas for plasmon-enhanced applications based on multiple plasmon modes.

Rapid determination of histamine concentration in fish(Miichthys Miiuy)by surface-enhanced Raman spectroscopy and density functional theory

Histamine is a type of biogenic amine,which plays a major role in the health problems associated with seafood consumption.Legislative limits of histamine level in seafood have been set in many countries.This study focuses on investigating the feasibility and potentiality of determining histamine concentration in fish(Miichthys miiuy)by surface-enhanced Raman spectroscopy(SERS)combined with density functional theory(DFT).Both a gold colloid and a silver colloid were used to determine the enhancement effect for SERS detection of histamine standard solution,and the gold colloid exhibited more effective as compared to the silver colloid.The protocol on extraction of histamine with 12%trichloroacetic acid and adjustment of pH with NaOH solution(5 mol/L)could significantly shorten sample preparation(20 min)and provide clear SERS spectra of histamine.The peaks of histamine molecules were classified using the DFT and five spectra(953 cm^(-1),992 cm^(-1),1106 cm^(-1),1262 cm^(-1)and 1317 cm^(-1))were selected as the characteristic bands of histamine discrimination.Moreover,the intensity of the peak at 1262 cm^(-1)had a good linear relationship with histamine concentration at 5-400 mg/kg with R^(2)=0.9755.It is concluded that the SERS-DFT approach will be a potential method for rapidly and reliably detecting histamine at levels from 5 mg/kg to 400 mg/kg in fresh fish.

Diagnosis of breast cancer by analysis of sialic acid concentrations in human saliva by surface-enhanced Raman spectroscopy of silver nanoparticles

Breast cancer is the most common type of malignant tumor among women and their second leading cause of cancer-related deaths.The most common method for screening and diagnosis is mammography.Nonetheless,two main problems have been identified.First,the dose of radiation received during the test prevents the method from the use on women who are 〈 40 years old.Second,there can be mammogram failure owing to the lack of tumor contrast with the fibrous tissue.Therefore,there is a need for screening methods that will help to identify high-risk cases.We developed a biological marker test that can help to identify them.Increased levels of sialic acid （SA） in saliva are known to correlated with breast cancer.In this study,we evaluated the feasibility of Raman spectroscopy as a method for quantification of SA in saliva,using citrate-reduced silver nanoparticles （cit-Ag-NPs） as a surface-enhanced Raman spectroscopy （SERS） substrate.Quantification of SA was accomplished by measuring its intensity in saliva and comparing it with a calibration curve of SA standards.The mean SA concentration in saliva was found to be significantly higher among 100 breast cancer patients （18.3 ＆#177; 9.4 mg＆#183;dL-1;mean ＆#177; SD） than among 106 healthy controls （3.5 ＆#177; 1.0 mg＆#183;dL-1）.The SERS test showed sensitivity of 94% and specificity 98% for detection of patients with breast cancer,assuming that SA concentration 〉 7 mg＆#183;dL-1 is a cutoff for positive test results.Our findings prove the usefulness of this SERS technique as a simple,convenient,and highly sensitive method of quantitative analysis of SA in saliva.The simplicity of this nanotechnological test may help to substantially reduce the mortality among patients with breast cancer by providing women with a simple,noninvasive screening test that can be applied regardless of age or density of breast tissue.

Reproducibility in Surface-Enhanced Raman Spectroscopy

Surface-enhanced Raman spectroscopy（SERS） is an intense ongoing hot topic because it is an attractive tool for sensing or detecting molecules in trace amounts. Despite its high specificity and sensitivity, the SERS technique has not been established as a routine analytic method most likely due to the low reproducibility of the SERS signal. This review considers the influence factors to produce the poor reproducibility during the SERS measurement. This review starts with the discussion of calculation of surface-enhanced Raman intensity in order to explain the reason why it is so difficult to achieve a high reproducibility of SERS measurement from the origin of enhancement mechanism. Then we focus on the fabrication of SERS substrates generally including two types：① single particles and ② arrays on substrate that are directly used to detect molecules or other components.In addition, we discuss the molecule factors and optical system for the reproducibility for sample-to-sample or spot-to-spot on a substrate. In the final part of this review, some effects resulting in the irreproducibility of Raman bands＇ position from recent literatures are discussed.

Determination of primary aromatic amines using immobilized nanoparticles based surface-enhanced Raman spectroscopy

Primary aromatic amines （PAAs） are substances with toxicity and suspected human carcinogenicity. A facile method for highly sensitive detection of PAAs using surface-enhanced Raman spectroscopy （SERS） is reported. The immobilization of Au nanoparticles （AuNPs） on the glycidyl methacrylate-ethylene dimethacrylate （GMA-EDMA） materials makes the suhstrate a closely packed but not aggregated Au NP arrays which provides a prominent SERS enhancement. Four PAAs with different substituent groups, namely, p-toluidine, p-nitroaniline, benzidine and 4,4-methylene-bis-（2-chloroaniline） have been successfully identified and quantified. High sensitivity and good linear relationship between SERS signals and concentrations of PAAs are obtained for all four PAAs.

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.

Dual-step hybrid SERS scheme through the blending of CV and MoS_(2) NPs on the AuPt core-shell hybrid NPs

Along with a wide range of applications,the surface-enhanced Raman spectroscopy(SERS)is a promi-nent analytical technique to recognize and detect molecules and materials even at an extremely low mo-lar concentration.In this work,a unique hybrid SERS platform is demonstrated by the incorporation of molybdenum disulfate(MoS_(2))nanoparticles(NPs)onto the core-shell AuPt hybrid NPs(HNPs)for the en-hanced molecular Raman vibration of crystal violet(CV).The hybrid platform takes the advantage of both the electromagnetic mechanism(EM)offered by the AuPt HNPs and chemical mechanism(CM)owing to the MoS_(2)NPs.The distinctive core-shell morphology of AuPt HNPs with the high-density background Au NPs is attained by a unique two-step solid-state dewetting method,which can offer a high concentration of electromagnetic hot spots.At the same time,the MoS_(2)NPs can provide an ample charge transfer with abundant active sites.Through the hybrid SERS approach,a dramatic SERS enhancement of CV Raman vibration is demonstrated,and the SERS capability is thoroughly studied.In addition,the finite-difference time-domain(FDTD)simulations provide a deeper understanding of the electromagnetic field distributions for various configurations of nanostructures and their hybrid combinations:i.e.,HNPs,alloy NPs,MoS_(2)/HNPs configurations.

Study on the chemisorption kinetics of Methylene Blue using SERS technique

SERS technique wae used to study the chemiesorption kinetics of Methylene Blue (MB) on the HNO3-etched silver surface. The adsorption kinetic parameters were deduced from different vibrational modes at a low concentration of 3.5 × 10?6 mol/L, and it showed that MB adsorbed uniformly (monolayerly) on silver surface. However, the adsorptive behavior turned anomalous at relatively higher concentrations and a possible explanation was suggested. In addition, the influence of Cl? ions on the adsorption states of MB was investigated, and it was shown that MB molecules, adsorbed on the silver surface, tended to transform the “lying-down” state to the “end - on” 4 state after CI? ions were added.

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.

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.