Ultra-Sensitive and Selective Detection of Arsenic(III) via Electroanalysis over Cobalt Single-Atom Catalysts.

Achieving highly sensitive and selective detection of trace-level As(III) and clarifying the underlying mechanism is still a intractable problem. The electroanalysis of As(III) relies on the electrocatalytic ability of the sensing interface. Herein, we first adopt single-atom catalysts as the electrocatalyst in As(III) detection. Cobalt single-atoms anchored on nitrogen-doped carbon material (Co SAC) were found to have an extraordinary sensitivity of 11.44 µA ppb-1 with excellent stability and repeatability, which so far is the highest among non-noble metal nanomaterials. Co SAC also exhibited a superior selectivity toward As(III) compared with some bivalent heavy metal ions (HMIs). Combining X-ray absorption spectroscopy (XAFS), density functional theory (DFT) calculation, and reaction kinetics simulation, we demonstrated that Co single atoms stabilized in N2C2 support serve as active sites to catalyze H3AsO3 reduction via the formation of Co-O hybridization bond, leading to a lower energy barrier, promoting the breakage of As-O bonds. Importantly, the first electron transfer is the rate-limiting step of arsenic reduction and is found to be more favorable on Co-SAC both thermodynamically and kinetically. This work not only expands the potential applicaiton of single-atom catalysts in the detection and treatment of As(III), but also provides atomic-level catalytic insights into HMIs sensing interfaces.

Identifying Phase-Dependent Electrochemical Stripping Performance of FeOOH Nanorod: Evidence from Kinetic Simulation and Analyte-Material Interactions.

Metal hydroxide nanomaterials are widely applied in the energy and environment fields. The electrochemical performance of such materials is strongly dependent on their crystal phases. However, as there are always multiple factors relating to the phase-dependent electrochemistry, it is still difficult to identify the determining one. The well-defined crystal phases of α- and ß-FeOOH nanorods are characterized through the transmission electron microscopy by a series of rotation toward one rod, where the cross-section shape and the growth direction along the [001] crystalline are first verified for 1D FeOOH nanostructures. The electrosensitivity of the two materials toward Pb(II) is tested, where α-FeOOH performs an outstanding sensitivity whilst it is only modest for ß-FeOOH. Experiments via Fourier transform infrared spectroscopy, X-ray absorption fine structure (XAFS), etc., show that α-FeOOH presents a larger Pb(II) adsorption capacity due to more surficial hydroxyl groups and weaker PbO bond strength. The reaction kinetics are simulated and the adsorption capacity is found to be the determining factor for the distinct Pb(II) sensitivities. Combining experiment with simulation, this work reveals the physical insights of the phase-dependent electrochemistry for FeOOH and provides guidelines for the functional application of metal hydroxide nanomaterials.

Metal coordination-functionalized Au-Ag bimetal SERS nanoprobe for sensitive detection of glutathione.

We demonstrated a surface-enhanced Raman spectroscopy (SERS) nanoprobe, neocuproine-Cu (Nc-CuII)-functionalized Au-Ag "nanobowls" (Au-Ag NBs/Nc-CuII), for detection of glutathione (GSH). Detection was accomplished with alternation of SERS spectra from Nc-CuII into Nc-CuI resulting from the reaction of GSH with Nc-CuII on Au-Ag NBs. This nanoprobe exhibited high selectivity and sensitivity (µM) towards GSH.

A nanoscale "yarn ball"-like heteropoly blue catalyst for extremely efficient elimination of antibiotics and dyes.

Fenton system is one of the most popular methods to eliminate antibiotics and dyes in aquatic environment. However, the existed Fenton system is limited by various factors such as potential second pollution and narrow pH range. In this study, we report that the bottlenecks for high strength antibiotics and dyes wastewater treatment at a wide pH range can be well tackled by the nanoscale "yarn ball"-like Mo/W-containing heteropoly blue (HPB) catalyst Mg2Ti6Mo23O119SiW12 (1). This novel catalyst displayed extremely efficient elimination for several typical organic contaminants such as malachite green (MG), tetracycline (TC) and methyl orange (MO). Compared with other materials reported in previous papers, the catalytic performance of 1 in degradation of the organic contaminants of high concentrations increased several times. More than 90% of antibiotics and dyes are degraded within 60 min. Electron spin resonance (ESR) experiments and UV-vis spectra confirmed that the catalytic mechanisms of 1 could mainly ascribe to the 1/H2O2 process and the possible photocatalytic oxidation of adsorbed H2O by holes (h+) in the valence band (VB) of 1 surface generated ·OH for extremely efficient degradation of organic contaminants. This work widens the optimal pH values up to neutral condition and it's significant for the expansion of the heterogeneous Fenton-like catalyst family and its application in the field of water treatment.

Noble-Metal-Free Co0.6Fe2.4O4 Nanocubes Self-Assembly Monolayer for Highly Sensitive Electrochemical Detection of As(III) Based on Surface Defects.

Nanocrystals generally suffer from agglomeration because of the spontaneous reduction of the system surface energy, resulting in blocking the active sites from reacting with target ions, and then severely reducing the electrochemical sensitivity. In this article, a highly ordered self-assembled monolayer array is successfully constructed using ∼14 nm Co0.6Fe2.4O4 nanocubes uniformly and controllably distributed on the surface of a working electrode (glass carbon plate). The large area and high exposure of the surface defects on Co0.6Fe2.4O4 nanocubes are clearly characterized by high-resolution transmission electron microscopy (HRTEM) and atomic-resolution high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM). Expectedly, a considerable sensitivity of 2.12 µA ppb-1 and a low limit of detection of 0.093 ppb are achieved for As(III) detection on this highly homogeneous sensing interface; this excellent electroanalysis performance is even better than that of noble metals electrodes. Most importantly, this approach of uniformly distributing the small-sized defective nanoparticles on the electrode surface provides a new opportunity for modifying the electrodes, as well as the realization of their applications in the field of environmental electroanalysis for heavy metal ions.

Surface Fe(II)/Fe(III) Cycle Promoted Ultra-Highly Sensitive Electrochemical Sensing of Arsenic(III) with Dumbbell-Like Au/Fe3O4 Nanoparticles.

Developing a new ultrasensitive interface to detect As(III) is highly desirable because of its seriously toxic and low concentration in drinking water. Recently, Fe3O4 nanoparticles of high adsorption toward As(III) become very promising to be such an interface, which is still limited by the poor understanding of their surface physicochemical properties. Herein, we report that dumbbell-like Au/Fe3O4 nanoparticles, when being modified the screen-printed carbon electrode, can serve as an efficient sensing interface for As(III) detection with an excellent sensitivity of 9.43 µA ppb-1 and a low detection limit of 0.0215 ppb. These outstanding records were attributed to the participation of Fe(II)/Fe(III) cycle on Fe3O4 surface in the electrochemical reaction of As(III) redox, as revealed by X-ray photoelectron spectroscopy, X-ray absorption near edge structure, and extended X-ray absorption fine structure. This work provides new insight into the mechanism of electroanalysis from the viewpoint of surface active atoms, and also helps to predict the construction of ultrahighly sensitive electrochemical sensors for other heavy metal ions with nonprecious redox active materials.

Amphiphilic Functionalized Acupuncture Needle as SERS Sensor for In Situ Multiphase Detection.

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.

High Electrochemical Sensitivity of TiO2- x Nanosheets and an Electron-Induced Mutual Interference Effect toward Heavy Metal Ions Demonstrated Using X-ray Absorption Fine Structure Spectra.

Mutual interference is a severe issue that occurs during the electrochemical detection of heavy metal ions. This limitation presents a notable drawback for its high sensitivity to specific targets. Here, we present a high electrochemical sensitivity of ∼237.1 µA cm-2 µM-1 toward copper(II) [Cu(II)] based on oxygen-deficient titanium dioxide (TiO2- x) nanosheets. We fully demonstrated an atomic-level relationship between electrochemical behaviors and the key factors, including the high-energy (001) facet percentage, oxygen vacancy concentration, surface -OH content, and charge carrier density, is fully demonstrated. These four factors were quantified using Raman, electron spin resonance, X-ray photoelectron spectroscopy spectra, and Mott-Schottky plots. In the mutual interference investigation, we selected cadmium(II) [Cd(II)] as the target ion because of the significant difference in its stripping potential (∼700 mV). The results show that the Cd(II) can enhance the sensitivity of TiO2- x nanosheets toward Cu(II), exhibiting an electron-induced mutual interference effect, as demonstrated by X-ray absorption fine structure spectra.

Natural Deposition Strategy for Interfacial, Self-Assembled, Large-Scale, Densely Packed, Monolayer Film with Ligand-Exchanged Gold Nanorods for In Situ Surface-Enhanced Raman Scattering Drug Detection.

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.

Size-tunable Ag nanoparticles sensitized porous ZnO nanobelts: controllably partial cation-exchange synthesis and selective sensing toward acetic acid.

Porous ZnO nanobelts sensitized with Ag nanoparticles have been prepared via a partial cation-exchange reaction assisted by a thermal oxidation treatment, employing ZnSe·0.5N2H4 nanobelts as precursors. After partially exchanged with Ag+ cations, the belt-like morphology of the precursors is still preserved. Continuously calcined in air, they are in situ transformed into Ag nanoparticles sensitized porous ZnO nanobelts. The size of the Ag nanoparticles can be tuned through manipulating the amount of exchanging Ag+ cations. Considering the porous and belt-like nanostructure, sensing characteristics of ZnO and the catalytic activity of Ag nanoparticles, the gas sensing performances of the as-prepared Ag nanoparticles sensitized porous ZnO nanobelts have been carefully investigated. The results indicate that Ag nanoparticles significantly enhance the sensing performances of porous ZnO nanobelts toward typical volatile organic compounds. Especially, a good selectivity has been demonstrated toward acetic acid gas with a low detection limit less than 1 ppm. Furthermore, they also display a good reproducibility with a short response/recovery time due to the thin, uniform and porous sensing film, which is fabricated with the assembled technique and in situ calcined approach. Finally, their sensing mechanism has been further discussed.

EDTA-Fe(III) Fenton-like oxidation for the degradation of malachite green.

Industrial waste, urban sewage and aquaculture have led to severely increased grades of environment pollutants such as dyes, pesticides and fertilizer. The use of technologies for purifying contaminated waters can be difficult and toxic due to the anti-photolysis, anti-oxidation and anti-bio-oxidation characteristics of organic pollutants, and there is therefore a significant need for new approaches. Here, we report methods of Fenton oxidation and EDTA-Fe(III) Fenton-like oxidation which can be used to degrade malachite green (MG: a dye and antibiotic-like substance) from contaminated water. Compared with the degradation rate (59.34%) of the Fe(III)/H2O2 Fenton process, the EDTA-Fe(III) Fenton-like oxidation got a better degradation rate (92.7%) at neutral pH conditions. By conducting a series of parallel controlled experiments (changing parameters such as the reactant concentration, temperature, and pH), we report the relationships between the degradation effect and different parameters, and we fitted their pseudo first order kinetic curves. Furthermore, we repeated to adjustment of the concentrations of MG in solutions to test the cycle performance and catalytic activities of EDTA-Fe(III)/H2O2 system and it showed good repeatability in the first five rounds and all of them keep the degradation efficiencies greater than 80%. By conducting comparative spin-trapping electron paramagnetic resonance (EPR) experiments, we showed indirectly that the OH contributes to the degradation of MG. Additionally, the results of the EPR experiments showed that EDTA contributes to the generation of OH in the EDTA-Fe(III)/H2O2 Fenton-like system. By conducting total organic carbon (TOC) analysis experiments, we found that EDTA was also oxidized to some extent during the degradation of MG. In all, the findings of this work widen the range of the optimal pH values up to neutral condition for degradation of MG by use of EDTA-Fe(III) Fenton-like system. And this system could be used as one approach for the degradation of organic pollutants at neutral conditions and provide some initial information regarding EDTA-Fe(III) Fenton-like oxidations. It's significant for the expansion of the homogenous Fenton-like family and its application in the field of water treatment.

Surface-Electronic-State-Modulated, Single-Crystalline (001) TiO2 Nanosheets for Sensitive Electrochemical Sensing of Heavy-Metal Ions.

Intrinsically low conductivity and poor reactivity restrict many semiconductors from electrochemical detection. Usually, metal- and carbon-based modifications of semiconductors are necessary, making them complex, expensive, and unstable. Here, for the first time, we present a surface-electronic-state-modulation-based concept applied to semiconductors. This concept enables pure semiconductors to be directly available for ultrasensitive electrochemical detection of heavy-metal ions without any modifications. As an example, a defective single-crystalline (001) TiO2 nanosheet exhibits high electrochemical performance toward Hg(II), including a sensitivity of 270.83 µA µM-1 cm-2 and a detection limit of 0.017 µM, which is lower than the safety standard (0.03 µM) of drinking water established by the World Health Organization (WHO). It has been confirmed that the surface oxygen vacancy adsorbs an O2 molecule while the Ti3+ donates an electron, forming the O2•- species that facilitate adsorption of Hg(II) and serve as active sites for electron transfer. These findings not only extend the electrochemical sensing applications of pure semiconductors but also stimulate new opportunities for investigating atom-level electrochemical behaviors of semiconductors by surface electronic-state modulation.

Tin Oxide Crystals Exposed by Low-Energy {110} Facets for Enhanced Electrochemical Heavy Metal Ions Sensing: X-ray Absorption Fine Structure Experimental Combined with Density-Functional Theory Evidence.

Herein, we revealed that the electrochemical behaviors on the detection of heavy metal ions (HMIs) would largely rely on the exposed facets of SnO2 nanoparticles. Compared to the high-energy {221} facet, the low-energy {110} facet of SnO2 possessed better electrochemical performance. The adsorption/desorption tests, density-functional theory (DFT) calculations, and X-ray absorption fine structure (XAFS) studies showed that the lower barrier energy of surface diffusion on {110} facet was critical for the superior electrochemical property, which was favorable for the ions diffusion on the electrode, and further leading the enhanced electrochemical performance. Through the combination of experiments and theoretical calculations, a reliable interpretation of the mechanism for electroanalysis of HMIs with nanomaterials exposed by different crystal facets has been provided. Furthermore, it provides a deep insight into understanding the key factor to improve the electrochemical performance for HMIs detection, so as to design high-performance electrochemical sensors.

Optimal Hotspots of Dynamic Surfaced-Enhanced Raman Spectroscopy for Drugs Quantitative Detection.

Surface-enhanced Raman spectroscopy (SERS) as a powerful qualitative analysis method has been widely applied in many fields. However, SERS for quantitative analysis still suffers from several challenges partially because of the absence of stable and credible analytical strategy. Here, we demonstrate that the optimal hotspots created from dynamic surfaced-enhanced Raman spectroscopy (D-SERS) can be used for quantitative SERS measurements. In situ small-angle X-ray scattering was carried out to in situ real-time monitor the formation of the optimal hotspots, where the optimal hotspots with the most efficient hotspots were generated during the monodisperse Au-sol evaporating process. Importantly, the natural evaporation of Au-sol avoids the nanoparticles instability of salt-induced, and formation of ordered three-dimensional hotspots allows SERS detection with excellent reproducibility. Considering SERS signal variability in the D-SERS process, 4-mercaptopyridine (4-mpy) acted as internal standard to validly correct and improve stability as well as reduce fluctuation of signals. The strongest SERS spectra at the optimal hotspots of D-SERS have been extracted to statistics analysis. By using the SERS signal of 4-mpy as a stable internal calibration standard, the relative SERS intensity of target molecules demonstrated a linear response versus the negative logarithm of concentrations at the point of strongest SERS signals, which illustrates the great potential for quantitative analysis. The public drugs 3,4-methylenedioxymethamphetamine and α-methyltryptamine hydrochloride obtained precise analysis with internal standard D-SERS strategy. As a consequence, one has reason to believe our approach is promising to challenge quantitative problems in conventional SERS analysis.

In Situ Underwater Laser-Induced Breakdown Spectroscopy Analysis for Trace Cr(VI) in Aqueous Solution Supported by Electrosorption Enrichment and a Gas-Assisted Localized Liquid Discharge Apparatus.

Traditional laser-induced breakdown spectroscopy (LIBS) always fails to directly detect target in aqueous solution due to rapid quenching of emitted light and adsorption of pulse energy by surrounding water. A method is proposed for the in situ underwater LIBS analysis of Cr(VI) in aqueous solution freed from the common problems mentioned above by combining a gas-assisted localized liquid discharge apparatus with electrosorption for the first time. In this approach, the introduction of the gas-assisted localized liquid discharge apparatus provides an instantaneous gaseous environment for underwater LIBS measurement (that is, the transfer of sampling matrix is not needed from aqueous solution to dry state). The preconcentration of Cr(VI) is achieved by electrosorption with a positive potential applied around adsorbents, which can promote the adsorption of Cr(VI) and inhibit that of the coexisting cations leading to a good anti-interference. Amino groups functionalized chitosan-modified graphene oxide (CS-GO) is utilized for Cr(VI) enrichment, which can be protonated to form NH3+ in acidic condition promoting the adsorption toward Cr(VI) by electrostatic attraction. The highest detection sensitivity of 5.15 counts µg-1 L toward Cr(VI) is found for the optimized electrosorption potential (EES = 1.5 V) and electrosorption time (tES = 600 s) without interference from coexisting metal ions. A corresponding limit of detection (LOD) of 12.3 µg L-1 (3σ method) is achieved, which is amazingly improved by 2 or even 3 orders of magnitude compared to the previous reports of LIBS.

Functionalized Acupuncture Needle as Surface-Enhanced Resonance Raman Spectroscopy Sensor for Rapid and Sensitive Detection of Dopamine in Serum and Cerebrospinal Fluid.

It is a challenge to develop a robust sensor for simple, rapid operation and sensitive detection of neurotransmitters in complex specimens. Herein, ferric citrate functionalized gold nanoparticles (CA-FeIII /Au NPs) are utilized to develop a facile sensor based on surface-enhanced resonance Raman spectroscopy (SERRS) for sensitive detection of dopamine (DA). The sensor is prepared by decorating the acupuncture needle with Au NPs, which enables sufficient surface-enhanced Raman spectroscopy enhancement. The CA-FeIII structure is highly sensitive and selective for DA due to the formation of the CA-FeIII -DA resonant structure; this indicates the advantages of capturing, carrying, and separating DA molecules from complicated samples in a simple operation. Furthermore, the practical application of the fabricated sensor is validated by the detection of DA in pretreated serum and cerebrospinal fluid of acupuncture-treated mice with detection limits of 0.1 and 2.5 nm DA, respectively. The developed active acupuncture needle sensor has potential benefits for sensitive detection and qualitative identification of DA molecules from biological samples.

Trimethylamine Sensors Based on Au-Modified Hierarchical Porous Single-Crystalline ZnO Nanosheets.

It is of great significance for dynamic monitoring of foods in storage or during the transportation process through on-line detecting trimethylamine (TMA). Here, TMA were sensitively detected by Au-modified hierarchical porous single-crystalline ZnO nanosheets (HPSCZNs)-based sensors. The HPSCZNs were synthesized through a one-pot wet-chemical method followed by an annealing treatment. Polyethyleneimine (PEI) was used to modify the surface of the HPSCZNs, and then the PEI-modified samples were mixed with Au nanoparticles (NPs) sol solution. Electrostatic interactions drive Au nanoparticles loading onto the surface of the HPSCZNs. The Au-modified HPSCZNs were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive spectrum (EDS), respectively. The results show that Au-modified HPSCZNs-based sensors exhibit a high response to TMA. The linear range is from 10 to 300 ppb; while the detection limit is 10 ppb, which is the lowest value to our knowledge.

High Volumetric Capacity Three-Dimensionally Sphere-Caged Secondary Battery Anodes.

High volumetric energy density secondary batteries are important for many applications, which has led to considerable efforts to replace the low volumetric capacity graphite-based anode common to most Li-ion batteries with a higher energy density anode. Because most high capacity anode materials expand significantly during charging, such anodes must contain sufficient porosity in the discharged state to enable the expansion, yet not excess porosity, which lowers the overall energy density. Here, we present a high volumetric capacity anode consisting of a three-dimensional (3D) nanocomposite formed in only a few steps which includes both a 3D structured Sn scaffold and a hollow Sn sphere within each cavity where all the free Sn surfaces are coated with carbon. The anode exhibits a high volumetric capacity of ∼1700 mA h cm(-3) over 200 cycles at 0.5C, and a capacity greater than 1200 mA h cm(-3) at 10C. Importantly, the anode can even be formed into a commercially relevant ∼100 µm thick form. When assembled into a full cell the anode shows a good compatibility with a commercial LiMn2O4 cathode. In situ TEM observations confirm the electrode design accommodates the necessary volume expansion during lithiation.

Surface-Enhanced Raman Spectroscopy on Liquid Interfacial Nanoparticle Arrays for Multiplex Detecting Drugs in Urine.

The design and application of liquid interfacial plasmonic platform is still in its infancy but is an exciting topic in tunable optical devices, sensors, and catalysis. Here, we developed an interfacial surface-enhanced Raman scattering (SERS) platform through the large-scale self-assembly of gold nanoparticle (GNP) arrays at the cyclohexane (CYH)/water interface for detecting trace drug molecules in the urine of humans. The molecules extracted by the CYH phase from a urine sample were directly localized into the self-organized plasmonic hotspots, yielded excellent Raman enhancement, and realized the substrate-free interfacial SERS detection. Synchrotron radiation small-angle X-ray scattering (SR-SAXS) experiments reveals a good uniformity of approximately 2-3 nm interparticle distance in the GNP arrays. SERS colocalization experiments demonstrated that amphetamine molecules of different concentration levels could be loaded into the interfacial GNP arrays and realized the coassembly together with nanoparticles at the liquid/liquid interface. Interfacial GNP arrays with dynamic nanogaps in liquid interfacial structure can make surrounding molecules easily diffuse into the nanogaps. In contrast, the fixed GNP arrays on Si wafer were more irregular, such as multilayer stack, random aggregates, and voids, during the drying process. When the drugs directly participate in the self-assembly process, it becomes easier for analytes diffusing into the nanogaps of GNP arrays, produces a concentration effect, and amplified the SERS sensitivity. This feature also enables molecules to be adsorbed evenly in the arrays and makes a more uniform distribution of both the analytes and GNPs in the liquid interface and realizes the significant increase in signal reproducibility. Interfacial SERS produced a standard deviation of 12.5% at 1001 cm(-1) peak of methamphetamine (MAMP) molecules under the concentration of 1 ppm, implying a good reproducibility. Moreover, dual-analyte detection at organic and aqueous phases was also realized and confirmed a good capability for analytes detection by liquid interfacial SERS platform, which promises nonengineering detection of analytes dissolved in often-inaccessible environments.

Adsorbent Assisted in Situ Electrocatalysis: An Ultra-Sensitive Detection of As(III) in Water at Fe3O4 Nanosphere Densely Decorated with Au Nanoparticles.

Most gold nanoparticle-based electrodes have been utilized for the analysis of highly toxic As(III), while nano-Fe3O4 materials are currently attracting considerable interest as an adsorbent for the removal of As(III). However, the combination of gold nanoparticles with Fe3O4 nanoadsorbents for stripping voltammetry is, to the best of our knowledge, unexplored. Here, a sensing interface for ultrasensitive detection of As(III) is designed and constructed by abundantly dispersing Au nanoparticles (Au NPs) on the surface of the Fe3O4 nanosphere. The Au@Fe3O4 nanospheres are covered by the room temperature ionic liquid (RTIL) and then modified on the screen-printed carbon electrode (SPCE). By combining the excellent catalytic properties of the Au nanoparticles (∼3-9 nm in diameter) with the good adsorption capacity of Fe3O4 nanospheres toward As(III), as well as the good conductivity of RTIL, the Au@Fe3O4-RTIL shows excellent performance in the detection of arsenic under nearly neutral conditions without modifying the morphology of the sensing interface. Through optimization of the experimental conditions, an ultrahigh sensitivity of 458.66 µA ppb(-1) cm(-2) from 0.1 to 1 ppb with a detection limit (3σ method) of 0.0022 ppb was obtained. The reproducibility and reliability of the Au@Fe3O4-RTIL sensing interface was also evaluated with good results. Finally, we used this platform to analyze real samples.