Selective Surface-enhanced Raman Scattering Research Articles

Selective SERS Detection of TATB Explosives Based on Hydroxy-Terminal Nanodiamond-Multilayer Graphene Substrate.

Selective surface-enhanced Raman scattering (SERS) detection of target explosives with good reproducibility is very important for monitoring soldiers' health and ecological environment. Here, the specific charge transfer pathway was constructed between a stable nanodiamond-multilayer graphene (MGD) film substrate and the target explosives. Two-step wet chemical oxidation methods of H2O2 (30%) and HNO3 (65%) solutions were used to regulate the terminal structure of MGD films. The experimental results showed that the hydroxyl (-OH) functional groups are successfully modified on the surface of MGD thin films, and the MGD-OH substrates having good selectivity for 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) explosive in mixed solutions of the TATB, 2,2-dinitroethene-1,1-diamine, 2,4,6-trinitrotoluene, and 1,3,5-trinitroperhydro-1,3,5-triazine explosives compared with MGD substrates were demonstrated. Finally, first-principles density functional theory simulations revealed that the SERS enhancement of the MGD-OH substrate is mainly attributed to the transferred electrons between the -NO2 groups of TATB and the -OH groups of the MGD-OH substrate.

SnS2/AuNPs surface-enhanced Raman scattering sensor for rapid and selective quantification of methimazole in serum and meat samples

Rapid and selective quantification is a great challenge for on-site analysis and point-of-care detection. Herein, we developed a SnS2/AuNPs sensor for quick and selective surface-enhanced Raman scattering (SERS) determination of methimazole in clinic serum and meat samples. SnS2/AuNPs hybrid with adjustable size, electromagnetic field enhancement, and surface plasmon resonance was facilely prepared by ultrasonic assistance. The SnS2/AuNPs sensor exhibited good SERS sensing performances for methimazole detection: a high enhancement factor of 4.5 × 107, good intra-batch uniformity with RSD of 6.1 % (n = 27), good batch-to-batch stability with RSD of 6.6 % (n = 15), and good selectivity to thyroid antagonists possibly due to the lowest energy charge transfer. Subsequently, a rapid SERS sensing method was established for quantitative analysis of methimazole ranging from 5 to 1000 µg/L with a detection limit down to 2.7 µg/L. Clinic serum samples from eight patients were accurately found with concentrations of 86.5–345.9 µg/L, recoveries of 89.7–104.7 % and RSDs of 2.1–8.8 %. The whole analysis time of clinic serum samples could be finished in 10 min without any pretreatment. The sensor with good sensitivity, reproducibility, and selectivity possessed great values for rapid food safety analysis and point-of-care detection in clinic diagnosis.

2D MoO2/N-Doped-Carbon Nanosheets as SERS Tweezers: A Non-Noble Metal Reusable Substrate for Selective Organic Dye Detection

The design and synthesis of a highly sensitive and exceptionally selective surface-enhanced Raman scattering (SERS) substrate with an excellent reusable property are of significant interest because...

Intrinsic Raman signal amplification for rapid identification and detection of methylglyoxal in manuka honey

Methylglyoxal (MGO) is the primary material basis for the non-peroxide antibacterial activity (NPA) of manuka honey from New Zealand. Therefore, it is necessary to identify the quality or discriminate the grade of honey because no all manuka honeys on the market display the NPA. The current routine method employed for the detection of MGO involves high-performance liquid chromatography (HPLC) test. However, it requires long time (∼8 h) for sample derivatization. Herein, we report an intrinsic Raman signal amplification strategy for the rapid identification and detection of MGO by using silver-coated gold nanoparticles (Au@Ag NPs) along with a high selective surface-enhanced Raman scattering (SERS) probe 8-thioguanosine (8-TG). 8-TG is synthesized via the derivatization of 8-bromoguanosine (8-BG) with thiourea, and its Raman peak assignments were confirmed by computer simulation. The detection is performed through the Raman intensity ratio (I631/I700) variation of N2-(1-carboxyethyl)-thioguanosine (CETG) formed by the reaction between 8-TG and MGO on surface of Au@Ag NPs, where one CETG Raman intensity at 631 cm−1 increases while the other one at 700 cm−1 decreases oppositely. The opposite change not only yields an intrinsic Raman signal amplification, but also provides built-in correction. As a result, the proposed SERS method exhibits high sensitivity and accuracy. In addition, the whole analytical test is achieved within ∼20 min. The method can be used for the fast detection of MGO in manuka honey and discrimination of the honey grade.

Enzyme-Free Tandem Reaction Strategy for Surface-Enhanced Raman Scattering Detection of Glucose by Using the Composite of Au Nanoparticles and Porphyrin-Based Metal-Organic Framework.

In this work, an S hybrid nanosheet with multiple functions is synthesized by in situ modification of gold nanoparticles (AuNPs) onto two-dimensional (2D) metalloporphyrinic metal-organic framework (MOF) (Cu-tetra(4-carboxyphenyl)porphyrin chloride(Fe(III)), designated as AuNPs/Cu-TCPP(Fe). Cu-TCPP(Fe) nanosheets contribute peroxidase-like activity, and AuNPs have glucose oxidase (GOx) mimicking performance, which induce the cascade catalysis reactions to convert glucose into hydrogen peroxide (H2O2), and then, by using AuNP catalysis, H2O2 oxidizes the no Raman-active leucomalachite green (LMG) into the Raman-active malachite green (MG). Simultaneously, in the presence of AuNPs, sensitive and selective surface-enhanced Raman scattering (SERS) determination of glucose can be achieved. The bioenzyme-free SERS assay based on such AuNPs/Cu-TCPP(Fe) nanosheets is used for detection of glucose in saliva, showing good recovery from 96.9 to 100.8%. The work paves a new way to design a nanozyme-based SERS protocol for biomolecule analysis.

Determination of prostate cancer marker Zn2+ with a highly selective surface-enhanced Raman scattering probe on liquid–liquid self-assembled Au nanoarrays

As the concentration of Zn2+ in patients with prostate cancer is much less than that in healthy persons, Zn2+ concentration can be used as a marker to expediently screen prostate cancer. In this study, a sensitive and highly selective surface-enhanced Raman scattering (SERS) method to detect Zn2+ concentration in human prostatic fluids by utilizing water-insoluble 2-carboxyl-2′-hydroxyl-5′-sulfoformazylbenze (Zincon) as a SERS probe based on self-assembled Au nanoarrays at a liquid–liquid interface between n-hexane and Au colloids was proposed. Zincon showed remarkably different SERS bands before and after coordinating Zn2+ in the controlled conditions (70 μL of ethanol, 500 μL of n-hexane, pH value of 7.1 and 10 s of vortex mixing time), which can be used in quantifying Zn2+ with characteristic peaks. The proposed SERS method presented a good linear relationship ranging from 0.5 to 10 μmol/L and a satisfactory detection limit of 0.1 μmol/L as well as low interference with other metal ions. Moreover, the detection results are close to those of the conventional standard atomic absorption spectroscopy (AAS) method.

Determination of 2,6-Dichlorophenol by Surface-Enhanced Raman Scattering with Molecular Imprinting

ABSTRACTA novel method has been reported for 2,6-dichlorophenol using surface-enhanced Raman scattering (SERS). SiO2/gold composites were selected as the SERS substrates to provide the response of gold nanoparticles. Molecular imprinting was subsequently used for the development of a specific detector to 2,6-dichlorophenol with precipitation polymerization. The molecularly imprinted polymer provided sensitive and selective SERS detection for the determination of 2,6-dichlorophenol. The intensity and concentration obeyed a linear relationship from 1 × 10−5 to 1 × 10−9 mol L−1 2,6-dichlorophenol. The sensitivity of SERS with the molecularly imprinted polymers provides a promising approach for practical analysis.

Selective Surface Enhanced Raman Scattering for Quantitative Detection of Lung Cancer Biomarkers in Superparticle@MOF Structure.

Surface enhanced Raman scattering (SERS) is a trace detection technique that extends even to single molecule detection. Its potential application to the noninvasive recognition of lung malignancies by detecting volatile organic compounds (VOCs) that serve as biomarkers would be a breakthrough in early cancer diagnostics. This application, however, is currently limited by two main factors: (1) most VOC biomarkers exhibit only weak Raman scattering; and (2) the high mobility of gaseous molecules results in a low adsorptivity on solid substrates. To enhance the adsorption of gaseous molecules, a ZIF-8 layer is coated onto a self-assembly of gold superparticles (GSPs) in order to slow the flow rate of gaseous biomarkers and depress the exponential decay of the electromagnetic field around the GSP surfaces. Gaseous aldehydes that are released as a result of tumor-specific tissue composition and metabolism, thereby acting as indicators of lung cancer, are guided onto SERS-active GSPs substrates through a ZIF-8 channel. Through a Schiff base reaction with 4-aminothiophenol pregrafted onto gold GSPs, gaseous aldehydes are captured with a 10 ppb limit of detection, demonstrating tremendous prospects for in vitro diagnoses of early stage lung cancer.

Small and Sharp Triangular Silver Nanoplates Synthesized Utilizing Tiny Triangular Nuclei and Their Excellent SERS Activity for Selective Detection of Thiram Residue in Soil.

The great harm of thiram residue in soil to environment and human health is usually ignored. Due to the complexity of soil compositions, the detection of thiram residue in soil faces considerable difficulties. In this work, a highly sensitive and selective surface-enhanced Raman scattering (SERS) substrate based on the triangular silver nanoplates (TSNPs) with small size and sharp corners is developed and used for the detection of thiram residue in soil for the first time. These TSNPs are synthesized by replacing the conventional seeds in the seed-mediated chemical reduction route with the tiny and uniform triangular silver nuclei (TSN) which can provide more growing space for generating sharp corners during the growth of TSNPs. It is interesting that the TSNPs with the smaller size have the better SERS performance. The possible mechanism behind this phenomenon is explained by the electromagnetic enhancement theory. On the basis of the Raman activity of the smallest TSNPs, a SERS-active substrate is prepared for detecting the thiram residue in soil. The thiram solution detection shows that the limit of detection (LOD) of these smallest TSNPs is lower than other nanoparticles, such as nanospheres, nanocubes, etc. For sensing the thiram residue in soil, the addition of poly(sodium 4-styrenesulfonate) realizes the specific adsorption of thiram by TSNPs. This method exhibits a good linear response from 0.12 to 4.8 μg/g with a low LOD of 90 ng/g, which is better than conventional methods. This work shows the great potential of the small TSNPs as a novel SERS substrate and its broader applications in pesticides detection.

A Selective Surface-Enhanced Raman Scattering Sensor for Mercury(II) Based on a Porous Polymer Material and the Target-Mediated Displacement of a T-Rich Strand

A sensitive and selective surface-enhanced Raman scattering (SERS) sensor for mercury(II) was fabricated based on the target-mediated displacement of a T-rich oligonucleotide strand. A DNA/aptamer duplex was prepared by the hybridization between a tetramethylrhodamine(TMR)-labeled thymine(T)-rich Hg2+-specific aptamer (denoted as TMR-aptamer) and a thiolated adenine-rich capturing DNA. The duplex can be immobilized onto the SERS substrate of the Ag-moiety modified glycidyl methacrylate-ethylene dimethacrylate (denoted as Ag-GMA-EDMA) via self-assembly by the thiol anchor, in which the TMR-aptamer exists in a double-stranded chain. In this case, the label of the TMR moiety approaches the substrate surface and produces a strong SERS signal. Upon the addition of the target, a pair of TMR-aptamers could cooperatively coordinate with Hg2+ to form a stable duplex-like structure mediated by the T–Hg2+–T complex between two adjacent strands, which triggers the release of the TMR-aptamer from the SERS substrate surface, thus drawing the TMR tags away from the substrate with a significant decrease in the SERS signal. This optical sensor shows a sensitive response to Hg2+ in a concentration from 5 nM to 2.0 μM with a detection limit of 2.5 nM. The prepared sensor is negligibly responsive to other metal ions, can be easily regenerated, and shows good performance in real sample analysis.

Surface enhanced Raman scattering fiber optic sensor as an ion selective optrode: the example of Cd2+detection

Here in this work, we report the fabrication of a (metal) ion selective surface enhanced Raman scattering (SERS) optrode, the counterpart of an ion selective electrode, for the detection of metal ions in solution. Following our previous work, a layer-by-layer self-assembly strategy was used to fabricate the SERS optrode, followed by modification with an ion chelating reagent, 4-(4-phenylmethanethiol)-2,2′:6′,2′′-terpyridine (PMTTP). The SERS spectrum change after binding with metal ions was used to identify and detect metal ions in solution. Cd2+ in aqueous solution was chosen as a sample analyte. Similar to standard pH measurement, through simple single point known standard solution calibration, a quick (semi-)quantitative analysis of Cd2+ was realized.

Rational design of a bisphenol A aptamer selective surface-enhanced Raman scattering nanoprobe.

Surface-enhanced Raman scattering (SERS) optical nanoprobes offer a number of advantages for ultrasensitive analyte detection. These functionalized colloidal nanoparticles are a multifunctional assay component. providing a platform for conjugation to spectral tags, stabilizing polymers, and biorecognition elements such as aptamers or antibodies. We demonstrate the design and characterization of a SERS-active nanoprobe and investigate the nanoparticles’ biorecognition capabilities for use in a competitive binding assay. Specifically, the nanoprobe is designed for the quantification of bisphenol A (BPA) levels in the blood after human exposure to the toxin in food and beverage plastic packaging. The nanoprobes demonstrated specific affinity to a BPA aptamer with a dissociation constant Kd of 54 nM, and provided a dose-dependent SERS spectra with a limit of detection of 3 nM. Our conjugation approach shows the versatility of colloidal nanoparticles in assay development, acting as detectable spectral tagging elements and biologically active ligands concurrently.

Theragnostic pH-Sensitive Gold Nanoparticles for the Selective Surface Enhanced Raman Scattering and Photothermal Cancer Therapy

We report a nanoparticle-based probe that can be used for a "turn-on" theragnostic agent for simultaneous Raman imaging/diagnosis and photothermal therapy. The agent consists of a 10 nm spherical gold nanoparticle (NP) with pH-responsive ligands and Raman probes on the surface. They are engineered to exhibit the surface with both positive and negative charges upon mildly acidic conditions, which subsequently results in rapid aggregations of the gold NPs. This aggregation simultaneously provides hot spots for the SERS probe with the enhancement factor reaching 1.3 × 10(4) and shifts the absorption to far-red and near-infrared (which is optimal for deep tissue penetration) by the coupled plasmon resonances; this shift was successfully exploited for low-threshold photothermal therapy. The theragnostic gold NPs are cancer-specific because they aggregate rapidly and accumulate selectively in cancerous cells. As the result, both Raman imaging and photothermal efficacy were turned on under a cancerous local environment. In addition, the relatively small hydrodynamic size can have the potential for better access to targeted delivery in vivo and facilitated excretion after therapy.

Relationship between resonant Raman scattering in Ag–C2H4 complexes and SERS

AbstractConcentrations less than 10−2 of silver dispersed in C2H4 matrices (ratio of Ag atoms and C2H4 molecules in the matrix) induce an absorption band in the visible range by electron transfer excitation and (with the exception of the C–H stretch vibrations) shifted Raman bands, assigned to resonant enhancement by two orders of magnitude by electron transfer in Ag–C2H4 complexes. Both phenomena are absent for Ag dispersed in C2H6. These results are analogous to the chemical specific and vibrational selective surface‐enhanced Raman scattering (SERS) of C2H4 and C2H6. The loss of the electron transfer excitation by mixing oxygen into the Ag–C2H4 matrix (as measured by Ozin et al.) corresponds to the quenching of SERS by oxygen.