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In this work, a highly sensitive and selective molecularly imprinted electrochemical sensor is exploited to detect zearalenone (ZEA) by the synergistic effect of reduced graphene nanoribbons (rGNRs) and gold nanoparticles (AuNPs). The oxidized GNRs are firstly produced by an improved Hummers' oxidation method, and then reduced and modified together with AuNPs onto a glassy carbon electrode by electrodeposition technique to realize collaborative amplification of electrochemical signal. The molecularly imprinted polymer film with specific recognition sites can be generated on the modified electrode by electropolymerization. The effect of experimental conditions is systematically investigated to obtain the best detection performance. It is found that the constructed sensor shows a wide linear range of 1-500 ng·mL -1 for ZEA with a detection limit as low as 0.34 ng·mL -1 . Obviously, our constructed molecularly imprinted electrochemical sensor shows great potential in the application of precisely detecting ZEA in food., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Surface enhanced Raman spectroscopy (SERS) is a promising technique for trace determination. More and more attention is focused on hybrid SERS substrates, which coupled with noble metal nanoparticles and carbon-based materials. Herein, expanded graphite (EG) is used to prepare EG-covered support by ultrasonic washing and filtration. Such support is flexible and can be cut into any shape. And the contact angle (θe) for Au nanorods (Au NRs) sol on the EG-covered support was 108.2° and the hydrophobic surface is helpful for Au NRs to construct 'hot spots' during evaporation. The limits of detection (LOD) for crystal violet (CV), thiram, malachite green (MG) and methylene blue (MB) were as low as 1 ppb, 50 ppb, 1 ppb and 1 ppb, respectively. Moreover, a fast and convenient 'paste-sampling' method could be employed for trace contaminants on real samples, because EG-based Au NRs substrate is of flexibility and porosity. Thus, CV residue on shrimp could be determined lower than 1 ppb and thiram residue on grapes could be identified lower than 50 ppb. In addition to high sensitivity, the stability of EG-based Au NRs substrate is also very good. Even after acid/alkali pretreatment (pH = 4∼10) or 30 min of thermal treatment (T = 20∼100 °C), the enhancement of the substrate remained stable. What's more, the substrate could be stored as long as 30 days. The highly stable, sensitive, cost-effective and easy-to-produce EG-based Au NRs substrates exhibit a great potential to promote application of SERS for routine analysis., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Aggregation and fibrillation of β-amyloid peptides (Aβ) as well as accumulation of toxic metal ions have been believed to be the central events to cause Alzheimer's disease (AD). Thus, an attractive therapeutic tactic for AD is to design and synthesize inhibitors and metal chelators to prevent Aβ aggregation and chelate toxic metal ions. In this study, the polypeptide functionalized gold nanoparticles (PFGNP) were obtained by modifying polypeptides Cys-Gly-Gly-Gly-Leu-Pro-Phe-Phe-Asp (CGGGLPFFD) and Cys-Gly-Gly-Gly-Gly-Gly-His (CGGGGGH) onto gold nanoparticles through gold-sulfur bond. The inhibitory properties of PFGNP toward Aβ 1-42 fibril formation was assessed by thioflavin T (ThT) fluorescence method and corroborated by atomic force microscopy analysis. The ability of PFGNP to complex copper ions was studied by electrochemical method. The experimental results reveal that PFGNP can effectively chelate copper ions and significantly inhibit the fibrillation of Aβ 1-42 . Moreover, PFGNP exhibits significantly protective effect on Aβ-induced cytotoxicity toward human neuroblastoma SH-SY5Y cells., (© 2022 Wiley-VHCA AG, Zurich, Switzerland.)

Sensitivity and credibility detecting histamine (HA) as an important neurotransmitter in biofluids is of importance in analytical science and physiology. Surface-enhanced Raman spectroscopy (SERS) is able to realize the high sensitivity with single molecules level, but providing the high sensitivity for HA with a small cross section remains a challenge. Here we develop the metal complex-based SERS nanoprobe nitrilotriacetic acid-Ni 2+ (NTA-Ni 2+ ) combined with self-assemble Au NPs active substrates for sensitive detection of HA. The NTA-Ni 2+ can capture the HA molecules close to Au NPs substrates and then amplify the Raman signals of HA owing to the formation of a complex of NTA-Ni 2+ -HA. The self-assemble Au film through the evaporation-driven method can provide the high-density hot spots substrate with high stability and reproducibility. The NTA-Ni 2+ decorated Au NPs as nanoprobe responds to HA with 1 μM level of sensitivity. More importantly, the developed SERS nanoprobe composing of NTA-Ni 2+ and self-assemble Au NPs can be utilized to detect and monitor the HA spiked into serum, indicating the potential prospect in analysis of HA in complex specimen., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Morphologically and dimensionally controlled growth of Ag nanocrystals has long been plagued by surfactants or capping agents that complicate downstream applications, unstable Ag salts that impaired the reproducibility, and multistep seed injection that is troublesome and time-consuming. Here, we report a one-pot electro-chemical method to fast (∼2 min) produce Ag nanoparticles from commercial bulk Ag materials in a nitric acid solution, eliminating any need for surfactants or capping agents. Their size can be easily manipulated in an unprecedentedly wide range from 35 to 660 nm. Furthermore, the Ag nanoparticles are directly grown on the Ag substrate, highly desirable for promising applications such as catalysis and plasmonics. The mechanistic studies reveal that the concentration of Ag + in the diffusion layer nearby the surface, controlled by the magnitude and duration of voltage, is critical in governing the nanoparticle formation (<1.3 mM) and its dimensional adjustability., (© 2021 Wiley-VCH GmbH.)

Surface enhanced Raman spectroscopy (SERS) is a powerful spectroscopic technique with unique vibrational fingerprints, making it an ideal candidate for in situ multiphase detection. However, it is a great challenge to determine how to guide the SERS sensor to target molecules of interest in multiphase heterogeneous samples with minimal disturbance. Here, we present a portable ultrasensitive and highly repeatable SERS sensor for in situ multiphase detection. The sensor is composed of commercial Ag acupuncture needle and PVP-Au nanoparticles (Au NPs). The PVP on the Au NPs can adsorb and induce the Au NPs into a highly uniform array on the surface of the Ag needle because of its adhesiveness and steric nature. The Au NPs-Ag Needle system (Au-AgN) holds a huge SERS effect, which is enabled by the multiple plasmonic couplings from particle-film and interparticle. The PVP, as the amphiphilic polymer, promotes the target molecules to adsorb on surface of the Au-AgN whether in the oil phase or in the water phase. In this work, the Au-AgN sensor was directly inserted into the multiphase system with the laser in situ detection, and SERS detection at different spots of the Au-AgN sensor provided Raman signal of targets molecule in the different phase. In situ multiphase detection can minimize the disturbance of sampling and provide more accurate information. The facile fabrication and amphiphilic functionalization make Au-AgN sensor as generalized SERS detection platform for on-site testing of aqueous samples, organic samples, even the multiphase heterogeneous samples.

Liquid interfacial self-assembly of metal nanoparticles holds great promise for its various applications, such as in tunable optical devices, plasmonics, sensors, and catalysis. However, the construction of large-area, ordered, anisotropic, nanoparticle monolayers and the acquisition of self-assembled interface films are still significant challenges. Herein, a rapid, validated method to fabricate large-scale, close-packed nanomaterials at the cyclohexane/water interface, in which hydrophilic cetyltrimethylammonium bromide coated nanoparticles and gold nanorods (AuNRs) self-assemble into densely packed 2D arrays by regulating the surface ligand and suitable inducer, is reported. Decorating AuNRs with polyvinylpyrrolidone not only extensively decreases the charge of AuNRs, but also diminishes repulsive forces. More importantly, a general, facile, novel technique to transfer an interfacial monolayer through a designed in situ reaction cell linked to a microfluidic chip is revealed. The self-assembled nanofilm can then automatically settle on the substrate and be directly detected in the reaction cell in situ by means of a portable Raman spectrometer. Moreover, a close-packed monolayer of self-assembled AuNRs provides massive, efficient hotspots to create great surface-enhanced Raman scattering (SERS) enhancement, which provides high sensitivity and reproducibility as the SERS-active substrate. Furthermore, this strategy was exploited to detect drug molecules in human urine for cyclohexane-extracted targets acting as the oil phase to form an oil/water interface. A portable Raman spectrometer was employed to detect methamphetamine down to 100 ppb levels in human urine, exhibiting excellent practicability. As a universal platform, handy tool, and fast pretreatment method with a good capability for drug detection in biological systems, this technique shows great promise for rapid, credible, and on-spot drug detection., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Intramolecular proton transfer of hypoxanthine, induced by application of a laser on the surface of a bare noble nanomaterial, was monitored in real time using surface-enhanced Raman spectroscopy (SERS). This monitoring demonstrated the dependence of the reaction on the identity of the nanomaterial and on the laser power density. The results pave the way for monitoring the proton transfer reaction in various relevant fields. In addition, we observed the presence of the proton transfer phenomenon of hypoxanthine in serum, providing a way to avoid the effect of proton transfer and hence achieve more reliable spectra of sera for clinical diagnosis.

This article presents a general method for the detection of protein kinase with a peptide-like kinase inhibitor as the bioreceptor, and it was done by converting gold nanoparticles (AuNPs)-based colorimetric assay into sensitive electrochemical analysis. In the colorimetric assay, the kinase-specific aptameric peptide triggered the aggregation of AuNPs in solution. However, the specific binding of peptide to the target protein (kinase) inhibited its ability to trigger the assembly of AuNPs. In the electrochemical analysis, peptides immobilized on a gold electrode and presented as solution triggered together the in situ formation of AuNPs-based network architecture on the electrode surface. Nevertheless, the formation of peptide-kinase complex on the electrode surface made the peptide-triggered AuNPs assembly difficult. Electrochemical impedance spectroscopy was used to measure the change in surface property in the binding events. When a ferrocene-labeled peptide (Fc-peptide) was used in this design, the network of AuNPs/Fc-peptide produced a good voltammetric signal. The competitive assay allowed for the detection of protein kinase A with a detection limit of 20 mU/mL. This work should be valuable for designing novel optical or electronic biosensors and likely lead to many detection applications., Competing Interests: Disclosure The authors report no conflicts of interest in this work.

A novel and rapid method to detect cocaine in human urine has been developed by using self-assembly ordered two dimensional (2D) gold nanoparticles (GNPs) film as surface-enhanced Raman spectroscopy (SERS) substrates. In order to obtain high sensitivity, uniformity, and reproducibility of SERS platform, quasi-spherical, uniform GNPs were firstly synthesis using seed growth method, in which the GNPs have been functionalized with CTAB to form orderly close-packed GNPs film as SERS substrate. Importantly, the high-performance GNPs on solid substrates can produce a high yield of sub-10-nm gaps which can generate gigantic signals enhancement for analytes adsorbed GNPs surface. In view of the complex component of human urine, we develop a rapid and efficient pretreatment strategy for separation and purification of cocaine by using hexane extraction in real human urine samples within 3min. With the advantages of better extraction rates (>75%) examined by ultraperformance liquid chromatography (UPLC) and the excellent signal-to-noise ratio detected by SERS, our pretreatment procedure can efficiently lower the interference of complex biological components in urine. To reach on-spot analyzer, a handheld Raman spectrometer was used for feasible SERS detection of cocaine in real human urine. The favorable results demonstrated our pretreatment strategy combined with SERS platform will be a great prospective method toward rapid, reliable, and on-spot cocaine detection for public safety., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Beta-amyloid (Aβ) peptides are the major constituents of senile plaques in the brains of Alzheimer's disease (AD) patients. Aβ monomers (AβMs) can coalesce to form small, soluble oligomers (AβOs), followed by reorganization and assembly into long, thread-like fibrils (AβFs). Recently, soluble AβOs have been regarded as reliable molecular biomarkers for the diagnosis of AD because of their high toxicity for neuronal synapse and high concentration levels in the brains of AD patients. In this work, we reported a label-free, sensitive and selective method for visual and fluorescent detection of AβOs based on the inner filter effect (IFE) of gold nanoparticles (AuNPs) on the fluorescence of CdTe quantum dots (QDs). Specifically, the fluorescence of CdTe QDs was quenched significantly by AuNPs through the IFE. PrP(95-110), an AβOs-specific binding peptide from cellular prion protein, triggered the aggregation and color change of AuNPs suspension; thus, the IFE of AuNPs on the fluorescence of CdTe QDs was weakened and the fluorescence intensity was recovered. However, in the presence of AβOs, the specific interaction of AβOs and PrP(95-110) prevented the absorption of PrP(95-110) onto the surface of AuNPs. As a result, the aggregation of AuNPs was inhibited and the fluorescence intensity of CdTe QDs was quenched again. This label-free method is specific for detection of AβOs but not for AβMs and AβFs. The detection limits were found to be 0.5nM for the visual assay and 0.2nM for the fluorescent detection. We believe that this work would be valuable for many investigations related to AD diagnosis and drug discovery., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Amyloid-β oligomers (AβOs) are the most important toxic species in the brain of Alzheimer's disease (AD) patient. AβOs, therefore, are considered reliable molecular biomarkers for the diagnosis of AD. Herein, we reported a simple and sensitive electrochemical method for the selective detection of AβOs using silver nanoparticles (AgNPs) as the redox reporters and PrP(95-110), an AβOs-specific binding peptide, as the receptor. Specifically, adamantine (Ad)-labeled PrP(95-110), denoted as Ad-PrP(95-110), induced the aggregation and color change of AgNPs and the follow-up formation of a network of Ad-PrP(95-110)-AgNPs. Then, Ad-PrP(95-110)-AgNPs were anchored onto a β-cyclodextrin (β-CD)-covered electrode surface through the host-guest interaction between Ad and β-CD, thus producing an amplified electrochemical signal through the solid-state Ag/AgCl reaction by the AgNPs. In the presence of AβOs, Ad-PrP(95-110) interacted specifically with the AβOs, thus losing the capability to bind AgNPs and to induce the formation of an AgNPs-based network on the electrode surface. Consequently, the electrochemical signal decreased with an increase in the concentration of AβOs in the range of 20 pM to 100 nM. The biosensor had a detection limit of 8 pM and showed no response to amyloid-β monomers (AβMs) and fibrils (AβFs). On the basis of the well-defined and amplified electrochemical signal of the AgNPs-based network architecture, these results should be valuable for the design of novel electrochemical biosensors by marrying specific receptors.

An aniline-GGAAKLVFF peptide (AFP) was prepared by solid-phase synthesis. The peptide can readily self-assemble into fibrils. Platinum nanoparticles (Pt NPs) were directly immobilized on the surface of the AFP fibrils via electrostatic interaction. Compared to other currently available techniques for the fabrication of metal-peptide fibrils, the noncovalent functionalization strategy is able to deposit nanoparticles on peptide fibrils with different morphologies and high metal loading, which is important for applications in catalysis, electronic materials and other corresponding fields. The Pt-AFP fibrils were employed to modify the electrode, which exhibits high electrocatalytic activities towards oxygen reduction. Thus, the Pt-AFP fibrils hold great potential for polymer electrolyte fuel cells and other electrochemical applications.

Abstract: Liquid interfacial self‐assembly of metal nanoparticles holds great promise for its various applications, such as in tunable optical devices, plasmonics, sensors, and catalysis. However, the construction of large‐area, ordered, anisotropic, nanoparticle monolayers and the acquisition of self‐assembled interface films are still significant challenges. Herein, a rapid, validated method to fabricate large‐scale, close‐packed nanomaterials at the cyclohexane/water interface, in which hydrophilic cetyltrimethylammonium bromide coated nanoparticles and gold nanorods (AuNRs) self‐assemble into densely packed 2D arrays by regulating the surface ligand and suitable inducer, is reported. Decorating AuNRs with polyvinylpyrrolidone not only extensively decreases the charge of AuNRs, but also diminishes repulsive forces. More importantly, a general, facile, novel technique to transfer an interfacial monolayer through a designed in situ reaction cell linked to a microfluidic chip is revealed. The self‐assembled nanofilm can then automatically settle on the substrate and be directly detected in the reaction cell in situ by means of a portable Raman spectrometer. Moreover, a close‐packed monolayer of self‐assembled AuNRs provides massive, efficient hotspots to create great surface‐enhanced Raman scattering (SERS) enhancement, which provides high sensitivity and reproducibility as the SERS‐active substrate. Furthermore, this strategy was exploited to detect drug molecules in human urine for cyclohexane‐extracted targets acting as the oil phase to form an oil/water interface. A portable Raman spectrometer was employed to detect methamphetamine down to 100 ppb levels in human urine, exhibiting excellent practicability. As a universal platform, handy tool, and fast pretreatment method with a good capability for drug detection in biological systems, this technique shows great promise for rapid, credible, and on‐spot drug detection. [ABSTRACT FROM AUTHOR]