Surface Enhanced Raman Spectroscopy Signal Research Articles

Ultrasensitive SERS aptasensor using Au@Ag bimetallic nanorod SERS tags for the selective detection of amantadine in foods

Herein, a novel surface enhanced Raman spectroscopy (SERS) aptasensor was developed for amantadine (AMD) detection, based on magnetite nanoparticles coated with polyethylenimine, silver nanoclusters and aptamers (Fe3O4@PEI@AgNC-apt) as the capture probe and complementary DNA-modified gold nanorods (AuNRs@4-MPBA@Ag-c-DNA containing 4-mercaptophenylboric acid molecules) as the reporter probe. In the presence of AMD, the AMD and the reporter probe competed for the aptamer on the surface of the capture probe, resulting in the reporter probe detaching from the capture probe leading to a decrease in intensity of the SERS signal at 1067 cm−1 for 4-MPBA. Under optimal conditions, a good linear relationship was established between the SERS intensity at 1067 cm−1 and the logarithm of the AMD concentration over the range 10−6-102 mg L−1, with a LOD of 0.50 × 10−6 mg L−1. The AMD levels in spiked samples were evaluated using the SERS aptasensor, with good recoveries ranging from 90.57% to 113.49% being obtained.

Controlled Growth of Silver Nanoparticles on Cotton Substrate for Enhanced SERS, Catalytic, and Antibacterial Performance

AbstractIn this study, we report the growth of surfactant‐free silver nanoparticles (NPs) on cotton through a facile chemical reduction method, iteratively applied to gradually increase and control the concentration of silver NPs. Our substrates showed enhanced performance in surface enhanced Raman spectroscopy (SERS), catalytic, and antibacterial properties, all attributable to the high concentration of NPs on the cotton and their surfactant‐free nature. While the antibacterial properties improve with increasing growth cycles, SERS and catalytic properties first increase from the first to fourth growth cycles and then decrease for the fifth growth cycle. For substrate with optimum deposition for SERS, rhodamine 6G (R6G) analyte down to nanomolar concentrations were detectable, with a linear correlation of intensity versus concentration and exhibit excellent uniformity in the SERS signal. Furthermore, the catalytic activity of our substrates against the degradation of methyl orange (MO) was impressive with a rate constant of 0.0866 min−1 for the first growth cycle, which increased by ~3.4‐fold to 0.2979 min−1 for the fourth growth cycle. Finally, the substrates showed excellent antibacterial activity towards both Gram‐negative (E. coli) and Gram‐positive (S. aureus) bacteria. For both bacteria, the zone of inhibition increased with increasing growth cycles.

A new strategy for constructing 3D hybrid graphene/Au/rectangular pyramids PMMA on a flexible SERS substrate for trace molecule detection

Surface enhanced Raman spectroscopy (SERS) has attracted interest in the fields of hazardous substance detection and food safety. However, its limited sensitivity and SERS signal consistency inhibit the widespread use of SERS technology. Herein, a novel approach for the fabrication of a graphene/Au NP/rectangular pyramid PMMA hybrid SERS substrate (Gr/Au/RP PMMA) with high uniformity and sensitivity is presented. The Gr/Au/RP PMMA substrate is machined by indentation firstly, then following wet etching of the copper substrate. The Raman enhancement of Gr/Au/RP PMMA is studied in terms of both electromagnetic enhancement and chemical enhancement. The field strength enhancement of the obtained Gr/Au/RP PMMA substrate is more than 4.9 times greater than that of the Gr/Au/flat PMMA substrate, established using a COMSOL simulation. By actively modulating the machining parameters on a Cu-Gr surface, the number of Gr layers, as well as the Gr/Au/RP PMMA topography, can be controlled, which can effectively influence the performance of the SERS substrate. Moreover, compared with other SERS substrates, including Gr/Au/RP PMMA, Gr/Au/flat PMMA, Au/Gr/RP Cu, Gr/RP PMMA, and Au/RP PMMA, the Raman intensities of R6G were strongest on the Gr/Au/RP PMMA. In addition, the minimum detectable concentrations of paraquat (PQ) and 2,4-d used in situ detection were 10−8 M and 10−6 M, respectively, after being covered with the Gr/Au/RP PMMA flexible substrate. To test its practical applicability with actual fruit surfaces, the Gr/Au/RP PMMA flexible substrate was used for the in situ SERS detection of PQ on apples. Clear Raman peaks of 10−7 M PQ were detected on the apple surface.

Investigation of Melphalan interaction as an alkylating agent with nucleotides by using surface enhanced Raman spectroscopy (SERS)

SERS (Surface Enhanced Raman Spectroscopy) is a new Raman spectroscopy which relies on Surface Plasmon Resonance (SPR) of metal nanoparticles. We have applied colloidal silver and gold nanoparticles as amplifier agents to enhance nucleotide Raman signals. It is observed that without these enhancing agents, it is impossible to investigate nucleotide spectrum due to weak Raman signals. Interaction mechanism of Melphalan, an anticancer drug with four nucleotides (Adenine, Cytosine, Guanine, Thymine) was investigated using SERS to detect and identify changes due to alkylating process in Raman spectra. After incubating Melphalan drug with nucleotides for 24 h at 37 °C, some changes occurred in SERS spectrum and interpretation of SERS spectra revealed the influence of the alkyl substitution on peaks and Raman shifts. After incubation of Melphalan with each nucleotide, intensity of relevant SERS signals assigned to Amid III group of Cytosine and Amid I of Thymine decreased significantly, confirming alkylating taking place. In this study, we also investigated the effect of nanoparticles type on nucleotide spectrum. We could not obtain useful information in the cases of guanine nucleotide. The SERS spectrum of Cytosine as an example of nucleotides in aqueous solution compared to solid state and results demonstrated that in solid state better signals were obtained than in liquid state.

Self-assembled core-shell nanoparticles with embedded internal standards for SERS quantitative detection and identification of nicotine released from snus products.

Surface enhanced Raman spectroscopy (SERS) is a unique analytical technique with excellent performance in terms of sensitivity, non-destructive detection and resolution. However, due to the randomness and poor repeatability of hot spot distribution, SERS quantitative analysis is still challenging. Meanwhile, snus is a type of tobacco product that can release nicotine and other components in the mouth without burning, and the rapid detection technique based on SERS can reliably evaluate the amount of nicotine released from snus, which is of great significance for understanding its characteristics and regulating its components. Herein, the strategy was proposed to solve the feasibility of SERS quantitative detection based on self-assembled core-shell nanoparticles with embedded internal standards (EIS) due to EIS signal can effectively correct SERS signal fluctuations caused by different aggregation states and measurement conditions, thus allowing reliable quantitative SERS analysis of targets with different surface affinity. By means of process control, after the Au nanoparticles (Au NPs) were modified with 4-Mercaptobenzonitrile (4-MBN) as internal standard molecules, Ag shell with a certain thickness was grown on the surface of the AuNP@4-MBN, and then the Au@4-MBN@Ag NPs were used to regulate and control the assembly of liquid-liquid interface. The high-density nano-arrays assembled at the liquid-liquid interface ensure high reproducibility as SERS substrates, and which could be used for SERS detection of nicotine released from snus products. In addition, time-mapping research shows that this method can also be used to dynamically monitor the release of nicotine. Moreover, such destruction-free evaluation of the release of nicotine from snus products opens up new perspectives for further research about the impact of nicotinoids-related health programs.

Silver Nanoflowers as an Interfacial Liquid-State Surface Enhanced Raman Spectroscopy (SERS) Sensor for Water Pollution

Water pollution has created a critical threat to the environment.‎‎ A lot of research has been done ‎recently to use surface-enhanced Raman spectroscopy (SERS) to detect multiple pollutants in water. This study aims to use Ag colloid nanoflowers as liquid SERS enhancer. Tri sodium phosphate (Na3PO4) was investigated as a pollutant using liquid SERS ‎based on colloidal Ag ‎nanoflowers. The chemical method was used to synthesize nanoflowers from silver ‎ions. Atomic Force Microscope (AFM), Scanning Electron Microscope (SEM), and X-ray diffractometer (XRD) were employed to characterize the silver nanoflowers. This ‎nanoflowers SERS action in detecting Na3PO4 was reported and analyzed concerning both shape and size using a 532 ‎nm laser. We observed that the nanoflower's structure produced strong SERS signals. The increase in the SERS signal is related to ‎the deposition of Na3PO4 molecules in the aggregated silver nanostructure ‎in the solution. The concentration of Na3PO4 plays a main role in detection since the Raman ‎signal becomes stronger as the concentration increases. The highest phosphate analytical enhancement factor obtained for SERS in colloidal nanoflowers was 1.7×103 at 0.7×10-6 M which was the lowest concentration.

Just laser irradiation of silver benzoate water solution — A direct way of Ag nanofibers synthesis for broadband SERS detection

Highly efficient, homogeneous and reproducible substrates for surface enhanced Raman spectroscopy (SERS) are in high demand for practical broadband sensing and the detection of various analytes. The most promising SERS structures in terms of morphology are nanofibers, forming homogeneous coatings with broadband electric field enhancement. However, existing synthesis methods for the formation of nanofibers are multistage, requiring the preliminary synthesis of templates, using additional components, such as surfactants and capping agents, species extraction from the reaction mixture, washing and sedimentation onto a substrate. Here, we present a simple and scalable synthesis approach allowing the fabrication of long winding silver nanofibers directly on a substrate surface, without any additional stages. The process proposed is ecologically friendly and based on laser irradiation of a substrate–solution interface using a low intensity continuous wave unfocused laser beam with a wavelength of 448 nm. As the liquid phase, a silver benzoate water solution without any additional chemicals was used. The deposited nanofibers formed a continuous coating with an area corresponding to the laser beam, ca. 3 mm2, and were characterized by an enhancement factor as high as 107 in the broad spectral region, a low experimental detection limit of 10−11 M and high reproducibility of the SERS signal with a variation of ∼10%.

Seeing Is Not Necessarily Believing: Is the Surface-Enhanced Raman Spectroscopy Signal Really from the Target?

Reagent purity is crucial to experimental research, considering that the ignorance of ultratrace impurities may induce wrong conclusions in either revealing the reaction nature or qualifying the target. Specifically, in the field of surface science, the strong interaction between the impurity and the surface will bring a non-negligible negative effect. Surface-enhanced Raman spectroscopy (SERS) is a highly surface-sensitive technique, providing fingerprint identification and near-single molecule sensitivity. In the SERS analysis of trace chloromethyl diethyl phosphate (DECMP), we figured out that the SERS performance of DECMP is significantly distorted by the trace impurities from DECMP. With the aid of gas chromatography-based techniques, one strongly interfering impurity (2,2-dichloro-N,N-dimethylacetamide), the byproduct during the synthesis of DECMP, was confirmed. Furthermore, the nonignorable interference of impurities on the SERS measurement of NaBr, NaI, or sulfadiazine was also observed. The generality ignited us to refresh and consolidate the guideline for the reliable SERS qualitative analysis, by which the potential misleading brought by ultratrace impurities, especially those strongly adsorbed on Au or Ag surfaces, could be well excluded.

Identification and Detection of Intracellular Reactive Sulfur Species Using a Reaction-Mediated Dual-Recognition Strategy.

Reactive sulfur species (RSS) are emerging as a potential key gasotransmitter in diverse physiological processes linking two signaling molecules H2S and SO2. However, the exact roles of H2S and SO2 remain unclear. A major hurdle is the shortage of accurate and robust approaches for sensing of H2S and SO2 in biological systems. Herein, we report a reaction-mediated dual-recognition strategy-based nanosensor, silver nanoparticles (AgNPs)-loaded MIL-101 (Fe) (ALM) hybrids, for the simultaneous detection of H2S and SO2 in a living cell. Upon exposure to H2S, AgNPs can be oxidized to form Ag2S, causing a decrease of surface enhanced Raman spectroscopy (SERS) signals of p,p'-dimercaptoazobenzene. Moreover, SO2 reacts with the amino moiety of MIL-101 to form charge-transfer complexes, resulting in an increment of fluorescent (FL) intensity. The ALM with dual-modal signals can simultaneously analyze H2S and SO2 at a concentration as low as 2.8 × 10-6 and 0.003 μM, respectively. Most importantly, the ALM sensing platform enables targeting mitochondria and detection multiple RSS simultaneously in living cells under external stimulation, as well as displays indiscernible crosstalk between SERS and FL signals, which is very beneficial for the comprehension of physiological issues related with RSS.

Optical response of Au films for reproducible Si nano-structuring and its application for efficient micro-drop SERS with portable Raman system

Si nanostructuring by metal assisted chemical etching is highly sensitive to morphology of thin metal film, here we demonstrate use of plasmon driven optical or dielectric response of Au films for predicting nanopore or nanowire Si prior to etching, ensuring the process reproducibility. By controlling growth temperature, it is shown that same mass thickness of Au films can produce either nanopore, nanowire or hybrid (mix of the two) Si nanostructures, useful for various applications. Ag nanoparticles coated nanostructure Si is shown to be efficient surface enhanced Raman spectroscopy (SERS) substrate for dry state measurements with micro-Raman system. In contrast, by exploiting super-hydrophilicity and strong light coupling of nanostructure Si, a novel micro-drop SERS using portable Raman spectrometer is demonstrated as low-cost, reliable and easy field-deployable technique. With very low sample volume about 50 μL of as prepared Au nanoparticles and analyte, it is capable of producing SERS signal in samples containing 120 pg thiram, 240 pg Rh6G, 455 pg malachite green and 48 pg methylene blue. With advantages of micro-drop SERS, mainly high intensity signal with 3D dynamic hot-spots at high laser power, longer shelf-life colloidal gold, reusable substrates with no prior sample preparation, this method is envisaged to be an inexpensive technique for on-site trace detection applications and importantly quick generation of large experimental SERS data-set for machine learning (ML) driven studies. This is demonstrated by principal component analysis with ML classifier for 100% accurate prediction of trace dyes, pesticide and their binary mixtures.

A SERS nanoswitch based on Cu(II)-mediated dual-ligand AuNPs reversible aggregation for pyrophosphate ions detection

Surface enhanced Raman spectroscopy (SERS) detection was not as accurate and reproducible as fluorometry due to some uncertainties such as operator's focus adjustment and difference between capillaries. Herein, the weak Raman signal (1640 cm−1) from water bending vibration is adopted as a benchmark to improve the practical applicability of Raman detection. Specifically, amygdalin and citrate sodium were applied as reducing and capping agent to synthesize dual-ligand gold nanoparticles (DL-AuNPs). Additionally, the cyano group of amygdalin can attach to the surface of DL-AuNPs and generate a primary SERS signal (2174 cm−1), which can be significantly enhanced by Cu(II) as DL-AuNPs aggregates. More importantly, the strong binding affinity between pyrophosphate ions (PPi) and Cu(II) redisperses DL-AuNPs and decreases the signal intensity, making the DL-AuNPs/Cu(II) SERS sensor promising for the detection of PPi. This proposed method presents a reliable SERS analysis with the stable water background calibration and broaden the application of SERS technique in aqueous solution target monitoring.

Ultra-trace detection of diverse analyte molecules using femtosecond laser structured Ag–Au alloy substrates and SERRS

Choosing a wavelength close to the electronic excitation of the analyte molecules is known to enhance the Surface Enhanced Raman Spectroscopy signal further. This technique is often referred to as Surface Enhanced Resonance Raman Spectroscopy (SERRS). Here we use SERRS for sensing different classes of molecules and demonstrate how it can be used for ultra-trace detection. Diverse SERS substrates were fabricated by femtosecond laser ablation of Ag–Au alloy (1:1) in the air by changing the angle of incidence. Further, we have examined the SERRS performance of each substrate. Often in laser ablation in air, the surface debris is considered undesirable. Here we have shown that this debris of nanoparticles can be used as an advantage for ultra-trace detection of different molecules. Further, with the advantage of having randomly stacked nanoparticles in debris and periodic substrates without debris from a single experiment, we have examined the much-debated relationship between enhancement and reproducibility in SERS and found that they are inversely correlated. The sensitivity of the substrate for rhodamine 6G, crystal violet, picric acid, and cysteine was found to be 10 fM, 100 fM, 100 nM, and 100 nM, respectively, with good reproducibility.

Strong π-Metal Interaction Enables Liquid Interfacial Nanoarray-Molecule Co-assembly for Raman Sensing of Ultratrace Fentanyl Doped in Heroin, Ketamine, Morphine, and Real Urine.

Toward the challenge on reliable determination of trace fentanyl to avoid opioid overdose death in drug crisis, here we realize rapid and direct detection of trace fentanyl in real human urine without pretreatment by a portable surface enhanced Raman spectroscopy (SERS) strategy on liquid/liquid interfacial (LLI) plasmonic arrays. It was observed that fentanyl could interact with the gold nanoparticles (GNPs) surface, facilitate the LLI self-assembly, and consequently amplify the detection sensitivity with a limit of detection (LOD) as low as 1 ng/mL in aqueous solution and 50 ng/mL spiked in urine. Furthermore, we achieve multiplex blind sample recognition and classification of ultratrace fentanyl doped in other illegal drugs, which has extremely low LODs at mass concentrations of 0.02% (2 ng in 10 μg of heroin), 0.02% (2 ng in 10 μg of ketamine), and 0.1% (10 ng in 10 μg of morphine). A logic circuit of the AND gate was constructed for automatic recognition of illegal drugs with or without fentanyl doping. The data-driven analog soft independent modeling model could quickly distinguish fentanyl-doped samples from illegal drugs with 100% specificity. Molecular dynamics (MD) simulation elucidates the underlying molecular mechanism of nanoarray-molecule co-assembly through strong π-metal interactions and the differences in the SERS signal of various drug molecules. It paves a rapid identification, quantification, and classification strategy for trace fentanyl analysis, indicating broad application prospects in response to the opioid epidemic crisis.

Evaporation-induced self-assembly of gold nanorods on a hydrophobic substrate for surface enhanced Raman spectroscopy applications

The controllable assembly of plasmonic nanoparticles has developed as one of the most significant approaches for surface enhanced Raman spectroscopy (SERS) applications. This study developed a simple approach to improve a large-scale ordered assembly of gold nanorods (GNRs) by controlling the droplet evaporation mode on hydrophobic substrates. The hydrophobic substrate was efficiently produced by spin coating the silicone oil onto the glass slides and annealing them. The analyte molecule rhodamine (R6G) was employed as a surface-enhanced Raman scattering probe to demonstrate the potential effects of the synthesized arrays. This hydrophobic platform enables the concentration and delivery of analyte molecules into the surface enhanced Raman spectroscopy sensitive site while suppressing the coffee ring effect generated by the smooth contraction motion of the base contact radius of the droplet without any pinning. Thus, the limit of detection (LOD) of the R6G analyte was lowered to 10−10 M and the homogenous dispersion of surface enhanced Raman spectroscopy hotspots within the self-assembly reproducible surface enhanced Raman spectroscopy signal. This new method enables a broad range of packing patterns and mechanisms by changing the host nanoparticles in the dispersion.

Performance evaluation of novel Ag@GO-biomaterial SERS substrates for the ultrasensitive detection of neomycin in foods

Many biomaterials are hydrophobic, making them attractive materials for the fabrication of surface enhanced Raman spectroscopy (SERS) substrates. Herein, we prepared a series of novel SERS substrates by loading graphene oxide (GO) and silver nanoparticles onto four different hydrophobic biomaterials (rose petals, lotus leaves, cicada wings or dragonfly wings). The obtained Ag@GO-biomaterial SERS substrates offered outstanding SERS performance. These substrates utilized both the electromagnetic mechanism and chemical mechanism to boost the SERS signal, as well as the concentrating effect owing to the hydrophobicity of biomaterials. The Ag@GO-rose petal SERS substrate showed the strongest signal enhancement capability, offering an LOD of 4.52 × 10-11 mol L-1 for the detection of the neomycin. Results encourage the wider use of hydrophobic biomaterials in SERS substrate construction and hazard monitoring.

Designed Growth of AgNP Arrays for Anti-counterfeiting Based on Surface-Enhanced Raman Spectroscopy Signals.

Based on etched PS sphere arrays, the different growths of Ag nanoparticles with tunable LSPR are designed when SiO2-25 nm/Ag-30 nm/SiO2-100 nm sandwich nanocavity structures are annealed at 500 °C, including the hexagonal silver nanoparticle rings, circular silver nanoparticle rings, and aggregated silver nanoparticles. The uniformity of particle size and regularity of position generate enhanced electromagnetic field and good surface-enhanced Raman spectroscopy signals as confirmed by UV-vis observation and finite difference time domain method simulation. The developed nanostructures are effectively used as stable, nonreproducible, and markable anti-counterfeiting signs.

A gold coating nanoporous anodized alumina oxide membrane as the substrate for rapid surface enhanced Raman spectroscopy detection of conjugated cyanide in fingertip blood

Rapid and sensitive detection of cyanide (free and conjugated) in blood samples is of vital significance for the clinical treatments and forensic verifications of cyanide poisoning. To overcome the disadvantages of conventional in-field detection methods, a facile, rapid and sensitive surface enhanced Raman spectroscopy (SERS) method for the analysis of free and conjugated cyanide using functionalized nanoporous anodic aluminium oxide (AAO) membrane coupled with hand-held Raman spectrometer has been developed in this study. A gold coating nanoporous AAO membrane with a high specific surface area, appropriate surface roughness and super-hydrophobicity has been prepared. The significant SERS signals enhancement benefiting from the high enrichment capacity and strong plasmonic hot-spots effects of the membrane has been achieved for hydrocyanic acid (HCN). Optimal parameters, including substrate modification, dissociation and capture conditions for blood samples have been investigated. The conjugated cyanide in the fingertip blood could be effectively liberated by the addition of H3PO4 and NaBH4, followed by the capture of HCN on the membrane and analyzed based on SERS. The whole detection procedure only needed 2 min, and the limit of detection could reach 10 ng/mL in only ∼ 50 μL fingertip blood. Therefore, this approach is expected to be a powerful point of care testing (POCT) tool for the diagnosis of cyanide poisoning in clinical and forensic applications.

MOF-derived AuNS/LDH with high adsorption ability for surface enhanced Raman spectroscopy detection

The sensitivity of surface enhanced Raman spectroscopy (SERS) depends on the construction of “hot spots” and the number of analyte molecules adsorbed onto the substrates. Herein, we have constructed a kind of SERS substrate based on gold nanostars (Au NSs) coated with nickel-cobalt layered double hydroxide (LDH) using a zeolitic imidazolate skeleton as sacrificial template via nickel ions etching. LDH was used as the absorption medium for target molecules, and concurrently prevented Au NSs from agglomeration to improve stability and uniformity of the substrate. Meanwhile, encapsulated Au NSs were used as the enhancement medium for Raman detection. The porous LDH shell around the Au NSs promoted the target molecules to approach the Au NSs, which was certified by the experimental results of UV–Vis absorption and simulation analysis using the density functional theory. The detection of Rhodamine 6G solution with a concentration of 10−9 M was realized by the AuNS/LDH, and the relative standard deviation of Raman signals was less than 10%. Therefore, this work provides a new idea and a suitable structure to improve SERS signal intensity by introducing adsorption medium into the SERS substrate.

An improved surface enhanced Raman spectroscopic method using a paper-based grape skin-gold nanoparticles/graphene oxide substrate for detection of rhodamine 6G in water and food.

Organic toxins are persistent chemicals of global concern capable of accumulating in environment and food. Surface enhanced Raman spectroscopy (SERS) is a promising technique that facilitates onsite detection of organic toxins. However, the fabrication of a SERS substrate is complicated and difficult to provide flexibility, fastness and cost-effectiveness. This study aims to develop a paper-based SERS method using grape skin-gold nanoparticles/graphene oxide (GE-AuNPs/GO) as SERS substrate and evaluate its efficiency with rhodamine 6G (Rh6G) as a model organic toxin and a real water and food contaminant. GE-AuNPs synthesized by green method using grape skin waste extract and GE-AuNPs/GO showed a surface plasmon resonance at 536 and 539nm, particle size 18.6 and 19.5nm, and zeta potential -44.6 and -59.7mV, respectively. Paper-based SERS substrates were prepared by coating a hydrophobic thin-film of 30% polydimethylsiloxane solution in hexane on Whatman no. 1 filter paper, followed by drop-casting GE-AuNPs or GE-AuNPs/GO and drying. The SERS signals of Rh6G showed an enhancement factor of 5.8×104 for GE-AuNPs and 1.92×109 for GE-AuNPs/GO, implying that a combination of electromagnetic surface plasmon, charge transfer and molecular resonances may be responsible for a higher enhancement of signal by the latter. A low detection limit of 7.33×10-11M in the linear range of 10-11-10-5M was obtained for GE-AuNPs/GO, while the relative standard deviation of repeatability and reproducibility was 9.6 and 12.6%, respectively. Paper-based GE-AuNPs/GO SERS substrate was highly stable as <20% loss in efficiency was shown over a 60-day storage period. Application to real samples showed a high recovery of Rh6G from tap water (93.9-100.8%) as well as food samples such as red chilli powder (91.0-95.4%), red glutinous rice ball (96.6-98.3%) and tomato ketchup (98.9-102.3%) after QuEChERS extraction. Collectively, the developed paper-based GE-AuNPs/GO can be a potential substrate for sensitive onsite detection of rhodamine 6G by SERS method.

Development and validation of an integrated microfluidic device with an in-line Surface Enhanced Raman Spectroscopy (SERS) detection of glyphosate in drinking water

Glyphosate, also known as N-(phosphonomethyl)glycine, is one of the most widely used herbicides in the world. However, the controversy surrounding the toxicity of glyphosate and its main breakdown product, aminomethylphosphonic acid (AMPA), remains a serious public concern. Therefore, there is a clear need to develop a rapid, sensitive and automated alternative method for the quantification of glyphosate and AMPA. In this context, surface enhanced Raman spectroscopy (SERS) coupled with a microfluidic system for the determination of glyphosate in tap water was developed, optimized and validated. The design of the microfluidic configuration for this application was built constructed to integrate the synthesis of the SERS substrate through to the detection of the analyte. To optimize the microfluidic setup, a design of experiments approach was used to maximize the SERS signal of glyphosate. Subsequently, an approach based on the European guideline document SANTE/11312/2021 was used to validate the method in the range of 78–480 μg/L using the normalized band intensities. The limit of detection and quantification obtained for glyphosate were 40 and 78 μg/L, respectively. Recoveries were in the range 76–117%, while repeatability and intra-day reproducibility were ≤17%. Finally, the method was also tested for the determination of AMPA in tap water matrix and for the simultaneous detection of AMPA and glyphosate.