One-pot synthesis of ion-imprinted three-dimensional porous material based on graphene oxide for the selective adsorption of copper(II).

Molecularly imprinted polymers (MIPs) are synthetic polymers with predetermined selectivity for a given analyte. One major problem associated with MIPs is the inaccessibility of a large fraction of the recognition sites that remain buried within the polymeric matrix. To address this problem, the high selectivity imparted by the imprinting technique and the porosity of three-dimensional (3D) graphene oxide (GO)-based porous materials were utilized in this work to prepare a 3D GO-based Cu(II)-ion-imprinted material (hereafter denoted as IIM) via one-pot reactions of GO, chitosan (CS), and glutaraldehyde in the presence of Cu(II). Results of equilibrium binding experiments show that IIM has a high template-ion binding capacity (1.75 mmol g-1) and good imprinting factor (2.19). Further, results of selectivity tests indicate that IIM has a high Cu(II)-recognition ability. IIM also has a fast binding rate and satisfactory reusability. In addition, the Langmuir isotherm model was well fitted with the experimental data, indicating the monolayer adsorption of Cu(II) ions. The present work provided a convenient approach to prepare 3D GO-based imprinted materials that are promising for enrichment or recycling of target compounds from wastewater.

Fluorescent porous organic cage with good water solubility for ratiometric sensing of gold(III) ion in aqueous solution.

Fluorescent porous organic cage with good water solubility is of great interest but still challenging for its fluorescent sensing application. Poor water solubility and single signal of most previous probes are unfavorable for the monitoring of Au3+ generated from the potential dissociation of gold nanoparticles in environmental and biological samples. Here we report a water-soluble porous organic cage as a ratiometric fluorescent probe for Au3+ in aqueous solution. The prepared porous organic cage with good water solubility showed specific redox interaction with Au3+ in pH 5, leading to the change of dual emission at 420 and 484 nm. Based on the change of fluorescence ratio, a simple ratiometric sensing method for Au3+ from the dissociation of gold nanoparticles in aqueous solution was developed. The proposed method gave a calibration function of F484/F420 = 0.0370[Au3+] + 0.5689 (where F484/F420 is the intensity ratio of fluorescence at 484 nm to that at 420 nm; [Au3+] in µM) (R2 = 0.9975) in the concentration range of 1-60 µM, the limit of detection (3s) of 8 nM, and the relative standard deviation of 0.26% for 10 replicate detections of 50 µM Au3+. The recoveries of spiked Au3+ in domestic wastewater and human serum samples ranged from 94.66% to 105.61%.

An Electrochemical Sensor Based on a Nitrogen-Doped Carbon Material and PEI Composites for Sensitive Detection of 4-Nitrophenol.

A glassy carbon electrode (GCE) was modified with nitrogen-doped carbon materials (NC) and polyethyleneimine (PEI) composites to design an electrochemical sensor for detecting 4-nitrophenol (4-NP). The NC materials were prepared by a simple and economical method through the condensation and carbonization of formamide. The NC materials were dispersed in a polyethyleneimine (PEI) solution easily. Due to the excellent properties of NC and PEI as well as their synergistic effect, the electrochemical reduction of the 4-NP on the surface of the NC-PEI composite modified electrode was effectively enhanced. Under the optimized conditions, at 0.06-10 µM and 10-100 µM concentration ranges, the NC-PEI/GCE sensor shows a linear response to 4-NP, and the detection limit is 0.01 µM (the signal-to-noise ratio is three). The reliability of the sensor for the detection of 4-NP in environmental water samples was successfully evaluated. In addition, the sensor has many advantages, including simple preparation, fast response, high sensitivity and good repeatability. It may be helpful for potential applications in detecting other targets.

Simultaneous and sensitive determination of ascorbic acid, dopamine and uric acid via an electrochemical sensor based on PVP-graphene composite.

A method with high sensitivity, good accuracy and fast response is of ever increasing importance for the simultaneous detection of AA, DA and UA. In this paper, a simple and sensitive electrochemical sensor, which based on the polyvinylpyrrolidone (PVP)-graphene composite film modified glassy carbon electrode (PVP-GR/GCE), was presented for detecting ascorbic acid (AA), dopamine (DA) and uric acid (UA) simultaneously. The PVP-GR/GCE has excellent electrocatalytic activity for the oxidation of AA, DA and UA. The second-order derivative linear sweep voltammetry was used for the electrochemical measurements. The peak potential differences of DA-AA, DA-UA, and UA-AA (measured on the PVP-GR/GCE) were 212, 130 and 342 mV respectively. Besides, the over potential of AA, DA and UA reduced obviously, so did the peak current increase. Under the optimum conditions, the linear ranges of AA, DA and UA were 4.0 µM-1.0 mM, 0.02-100 µM, and 0.04-100 µM, respectively. The detection limits were 0.8 µM, 0.002 µM and 0.02 µM for AA, DA, and UA. The electrochemical sensor presented the advantages of high sensitivity and selectivity, excellent reproducibility and long-term stability. Furthermore, the sensor was successfully applied to the analysis of real samples.

Facile Fabrication of CeO2/Electrochemically Reduced Graphene Oxide Nanocomposites for Vanillin Detection in Commercial Food Products.

In this paper, CeO2 nanoparticles were synthesized by the solvothermal method and dispersed uniformly in graphene oxide (GO) aqueous solution by ultrasonication. The homogeneous CeO2-GO dispersion was coated on the surface of a glassy carbon electrode (GCE), and the CeO2/electrochemically reduced graphene oxide modified electrode (CeO2/ERGO/GCE) was obtained by potentiostatic reduction. The results of X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) showed that CeO2 nanocrystals were uniformly coated by gossamer like ERGO nanosheets. The electrochemical behavior of vanillin on the CeO2/ERGO/GCE was studied by cyclic voltammetry (CV). It was found that the CeO2/ERGO/GCE has high electrocatalytic activity and good electrochemical performance for vanillin oxidation. Using the second derivative linear sweep voltammetry (SDLSV), the CeO2/ERGO/GCE provides a wide range of 0.04-20 µM and 20 µM-100 µM for vanillin detection, and the detection limit is estimated to be 0.01 µM after 120 s accumulation. This method has been successfully applied to the vanillin detection in some commercial foods.

Rapid recognition and determination of tryptophan by carbon nanotubes and molecularly imprinted polymer-modified glassy carbon electrode.

A tryptophan (Trp) molecularly imprinted electrochemical sensor was fabricated by drop-coating an imprinted chitosan film on the surface of a glassy carbon electrode modified with multi-walled carbon nanotubes (MIP-MWCNTs/GCE). The surface morphology and electrochemical properties of the MIP-MWCNTs/GCE were characterized by scanning electron microscopy (SEM) and cyclic voltammetry (CV), respectively. The formation of hydrogen bonds between the functional polymer and the template molecule was confirmed by infrared spectroscopy. The electrochemical performance of the MIP-MWCNTs/GCE with Trp showed that the signal of the oxidation current of Trp obtained with MIP-MWCNTs/GCE was significantly enhanced relative to that of the uncovered GCE, indicating that the modified electrode can accelerate electron transfer and has strong selectivity for Trp. The experimental conditions were optimized in parallel, and under the optimal conditions, the MIP-MWCNTs/GCE showed a good linear relationship between the Trp oxidation peak current and Trp concentrations in the ranges of 2.0 nM-0.2 µM, 0.2 µM-10 µM and 10 µM-100 µM The limit of detection (LOD) was 1.0 nM (S/N = 3), and the modified electrode had good reproducibility and stability. Finally, the MIP-MWCNTs/GCE was successfully applied to the determination of Trp in the human serum samples.

A Simple and Efficient Molecularly Imprinted Electrochemical Sensor for the Selective Determination of Tryptophan.

In this paper, a tryptophan (Trp) molecularly imprinted chitosan film was prepared on the surface of an acetylene black paste electrode using chitosan as the functional polymer, Trp as the template molecule and sulfuric acid as the crosslinking agent. The surface morphologies of non-imprinted and imprinted electrodes were characterized by scanning electron microscopy (SEM). The formation of hydrogen bonds between the functional polymer and the template molecule was confirmed by infrared spectroscopy. Some factors affecting the performance of the imprinted electrode such as the concentration of chitosan, the mass ratio of chitosan to Trp, the dropping amount of the chitosan-Trp mixture, the solution pH, and the accumulation potential and time were discussed. The experimental results show that the imprinted electrode exhibit good affinity and selectivity for Trp. The dynamic linear ranges of 0.01-4 M, 4-20 M and 20-100 M were obtained by second derivative linear sweep voltammetry, and the detection limit was calculated to be 8.0 nM. The use of the imprinted electrode provides an effective method for eliminating the interference of potentially interfering substances. In addition, the sensor has high sensitivity, reproducibility and stability, and can be used for the determination of Trp in pharmaceutical preparations and human serum samples.

Facile Preparation of Cu2O Nanoparticles and Reduced Graphene Oxide Nanocomposite for Electrochemical Sensing of Rhodamine B.

In this paper, the preparation, characterization, and electrochemical application of Cu2O nanoparticles and an electrochemical reduced graphene oxide nanohybrid modified glassy carbon electrode (denoted as Cu2O NPs‒ERGO/GCE) are described. This modified electrode was used as an electrochemical sensor for the catalytic oxidation of rhodamine B (RhB), and it exhibited an excellent electrochemical performance for RhB. The oxidation potential of RhB was decreased greatly, and the sensitivity to detect RhB was improved significantly. Under optimum conditions, a linear dynamic range of 0.01-20.0 µM and a low detection limit of 0.006 µM were obtained with the Cu2O NPs‒ERGO/GCE by using second‒order derivative linear sweep voltammetry. In addition, the selectivity of the prepared modified electrode was analyzed for the determination of RhB. The practical application of this sensor was investigated for the determination of RhB in food samples, and satisfactory results were obtained.

Facile Preparation of Fe3O4/C Nanocomposite and Its Application for Cost-Effective and Sensitive Detection of Tryptophan.

In this study, we reported facile synthesis of Fe3O4/C composite and its application for the cost-effective and sensitive determination of tryptophan (Trp) in human serum samples. Fe3O4/C composites were prepared by a simple one-pot hydrothermal method followed by a mild calcination procedure, using FeCl3∙6H2O as Fe3O4 precursor, and glucose as reducing agent and carbon source simultaneously. The Fe3O4/C composite modified glassy carbon electrode (Fe3O4/C/GCE) was prepared by drop-casting method. The microstructure and morphology of Fe3O4/C composite was characterized by powder X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. Due to large specific surface area and synergistic effect from Fe3O4 nanoparticles and carbon coating, Fe3O4/C composite showed excellent electrocatalytic activity toward the oxidation of Trp. As a result, the proposed Fe3O4/C/GCE displayed superior analytical performances toward Trp determination, with two wide detection ranges (1.0-80 µM and 80-800 µM) and a low detection limit (0.26 µM, S/N = 3). Moreover, successful detection of Trp in human serum samples further validate the practicability of the proposed sensor.

Electrochemical Sensor for Rapid and Sensitive Detection of Tryptophan by a Cu2O Nanoparticles-Coated Reduced Graphene Oxide Nanocomposite.

In this paper, a nanocomposite of cuprous oxide and electrochemically reduced graphene oxide (Cu2O‒ERGO) was prepared by a simple and low-cost method; hereby, a new method for the electrochemical determination of tryptophan (Trp) by this composite modified glassy carbon electrode (GCE) is proposed. The prepared materials and modified electrodes were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and cyclic voltammetry (CV). The results showed that Cu2O‒ERGO/GCE had good electrocatalytic activity for Trp. The effects of supporting electrolyte, scanning rate, accumulation potential, and accumulation time on the determination of Trp were studied. Under the optimum experimental conditions, Trp was quantitatively analyzed by square-wave voltammetry (SWV). The oxidation peak current of Trp had a good linear relationship with its concentration in the range of 0.02‒20 µM, and the detection limit was 0.01 µM (S/N = 3). In addition, the modified electrode has high sensitivity, good repeatability, and long-term stability. Finally, the proposed method has been successfully applied in the determination of Trp concentration in practical samples.

A Novel Modified Electrode for Detection of the Food Colorant Sunset Yellow Based on Nanohybrid of MnO2 Nanorods-Decorated Electrochemically Reduced Graphene Oxide.

The nanohybrid of electrochemically-reduced graphene oxide (ERGO) nanosheets decorated with MnO2 nanorods (MnO2 NRs) was modified on the surface of a glassy carbon electrode (GCE). Controlled potential reduction was applied for the reduction of graphene oxide (GO). The characterization was performed by scanning electron microscopy, X-ray diffraction and cyclic voltammetry. Compared with the poor electrochemical response at bare GCE, a well-defined oxidation peak of sunset yellow (SY) was observed at the MnO2 NRs-ERGO/GCE, which was attributed to the high accumulation efficiency as well as considerable electrocatalytic activity of ERGO and MnO2 NRs on the electrode surface. The experimental parameters for SY detection were optimized in detail. Under the optimized experiment conditions, the MnO2 NRs-ERGO/GCE showed good linear response to SY in concentration range of 0.01⁻2.0 µM, 2.0⁻10.0 µM and 10.0⁻100.0 µM with a detection limit of 2.0 nM. This developed method was applied for SY detection in soft drinks with satisfied detected results.

Facile and Ultrasensitive Determination of 4-Nitrophenol Based on Acetylene Black Paste and Graphene Hybrid Electrode.

4-nitrophenol (4-NP) is a hazardous waste and a priority toxic pollutant identified by US Environmental Protection Agency (EPA). Hence, in this paper, a voltammetric sensor was proposed for the direct and sensitive detection of 4-nitrophenol (4-NP) at nanomolar level in complex matrices by using graphene and acetylene black paste hybridized electrode (GR/ABPE). Under optimal conditions, the calibration curve demonstrates a linear relationship for 4-NP in the range from 20 nM to 8.0 µM and 8.0 µM to 0.1 mM separately with the detection limit of 8.0 nM. In addition to it, the performance of the GR/ABPE in practical applications was evaluated by detecting 4-NP in various water samples, and satisfactory recoveries were realized. Therefore, GR/ABPE may have a great potential application for facile and sensitive detection of 4-NP in complex matrices at nanomolar level.

Facile Electrochemical Sensor for Nanomolar Rutin Detection Based on Magnetite Nanoparticles and Reduced Graphene Oxide Decorated Electrode.

A new electrochemical sensor for nanomolar rutin detection based on amine-functionalized Fe3O4 nanoparticles and electrochemically reduced graphene oxide nanocomposite modified glassy carbon electrode (NH2-Fe3O4 NPs-ErGO/GCE) was fabricated through a simple method, and the X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), transmission electron microscope (TEM), vibrating sample magnetometer (VSM) and electrochemical technique were used to characterize the modified electrode. The electrochemical behavior of rutin on the Fe3O4 NPs-ErGO/GCE was studied in detail. The electrochemical response of rutin at this modified electrode was remarkably higher than that of the bare GCE or other modified GCE (GO/GCE, Fe3O4 NPs-GO/GCE, and ErGO/GCE). Under the optimum determination conditions, Fe3O4 NPs-ErGO/GCE provided rutin with a broader detection range of 6.0 nM⁻0.1 µM; 0.1⁻8.0 µM and 8.0⁻80 µM, a minimum detectable concentration of 4.0 nM was obtained after 210 s accumulation. This novel method was applied in determination of rutin in pharmaceutical tablets and urine samples with satisfactory results.

Modification of mesoporous silica with molecular imprinting technology: A facile strategy for achieving rapid and specific adsorption.

In order to improve the diffusion kinetics of molecularly imprinted materials (MIMs), applying imprinting technology to mesoporous materials is a promising strategy. In the present study, an imprinting approach based on the combination of mesoporous silica materials and molecular imprinting technology is reported. Molecularly imprinted material (MIM) for 2,4-dichlorophenoxyacetic acid (2,4-D) was prepared by using 2,4-D as the template molecule, alkyne-modified ß-cyclodextrin and propargyl amine as the combinatorial functional monomers and SBA-15 as the supporter. The functional monomers were anchored to the azide-modified SBA-15 by azide-alkyne Click reaction. The synthesized MIM was characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), elemental analysis (EA), thermal gravimetric analysis (TGA), low-angle X-ray diffraction (XRD) and N2 adsorption-desorption analysis. The interactions between template and functional monomers were studied by proton NMR analysis and UV-vis experiments. The results of the equilibrium binding experiments and selective tests showed that the prepared MIM has binding affinity and specificity for a group of analytes which have similar size and shape to those of template. Binding kinetic experiments demonstrated that the present imprinting approach can effectively enhance the mass transfer rate. The solid phase extraction of 2,4-D using MIM as the adsorbent was investigated. The extraction conditions for the processes of loading, washing and eluting were optimized. The recoveries of the molecularly imprinted solid phase extraction (MISPE) column for 2,4-D were 76.3-88.9% with relative standard deviations (RSD) of 3.48-7.64%.

Manganese dioxide Nanorods/electrochemically reduced graphene oxide nanocomposites modified electrodes for cost-effective and ultrasensitive detection of Amaranth.

A novel manganese dioxide nanorods-electrochemically graphene oxide nanocomposites modified glassy carbon electrode (MnO2NRs-ErGO/GCE) was developed for the rapid and sensitive detection of Amaranth in foodstuffs. The morphology, structure and composition of MnO2NRs, ErGO, and MnO2/ErGO were characterized by SEM and XRD. The electrochemical behavior of Amaranth on the bare GCE, ErGO/GCE, and MnO2NRs-ErGO/GCE were investigated by cyclic voltammetry and electrochemical impedance spectroscopy. The voltammetric conditions (including pH, scan rate, accumulation potential as well as time) were optimized systematically. Due to large electrochemical active area and low charge transfer resistance, the MnO2NRs-ErGO/GCE exhibited a great enhancement effect on the oxidation of Amaranth, and significant increased the oxidation peak current ipa (approximately 38-fold increase compared to that of bare GCE). Under the optimum voltammetric conditions, the ipa varied linearly with Amaranth concentration in the range of 0.02 µM-10 µM, and 10 µM-400 µM with a low detection limit of 1.0 nM (S/N = 3). Moreover, satisfactory results were obtained in the analysis of real samples. Together with the merits of rapidness, cost-effectivity, high sensitivity and selectivity, the result suggests the proposed MnO2NRs-ErGO/GCE have broad application prospects on the sensitive detection of Amaranth in various real samples.

Novel Electrochemical Sensors Based on Cuprous Oxide-Electrochemically Reduced Graphene Oxide Nanocomposites Modified Electrode toward Sensitive Detection of Sunset Yellow.

Control and detection of sunset yellow is an utmost demanding issue, due to the presence of potential risks for human health if excessively consumed or added. Herein, cuprous oxide-electrochemically reduced graphene nanocomposite modified glassy carbon electrode (Cu2O-ErGO/GCE) was developed for the determination of sunset yellow. The Cu2O-ErGO/GCE was fabricated by drop-casting Cu2O-GO dispersion on the GCE surface following a potentiostatic reduction of graphene oxide (GO). Scanning electron microscope and X-ray powder diffractometer was used to characterize the morphology and microstructure of the modification materials, such as Cu2O nanoparticles and Cu2O-ErGO nanocomposites. The electrochemical behavior of sunset yellow on the bare GCE, ErGO/GCE, and Cu2O-ErGO/GCE were investigated by cyclic voltammetry and second-derivative linear sweep voltammetry, respectively. The analytical parameters (including pH value, sweep rate, and accumulation parameters) were explored systematically. The results show that the anodic peak currents of Cu2O-ErGO /GCE are 25-fold higher than that of the bare GCE, due to the synergistic enhancement effect between Cu2O nanoparticles and ErGO sheets. Under the optimum detection conditions, the anodic peak currents are well linear to the concentrations of sunset yellow, ranging from 2.0 × 10-8 mol/L to 2.0 × 10-5 mol/L and from 2.0 × 10-5 mol/L to 1.0 × 10-4 mol/L with a low limit of detection (S/N = 3, 6.0 × 10-9 mol/L). Moreover, Cu2O-ErGO/GCE was successfully used for the determination of sunset yellow in beverages and food with good recovery. This proposed Cu2O-ErGO/GCE has an attractive prospect applications on the determination of sunset yellow in diverse real samples.

Sensitive and Selective Detection of Tartrazine Based on TiO2-Electrochemically Reduced Graphene Oxide Composite-Modified Electrodes.

TiO2-reduced graphene oxide composite-modified glassy carbon electrodes (TiO2⁻ErGO⁻GCE) for the sensitive detection of tartrazine were prepared by drop casting followed by electrochemical reduction. The as-prepared material was characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). Cyclic voltammetry and second-order derivative linear scan voltammetry were performed to analyze the electrochemical sensing of tartrazine on different electrodes. The determination conditions (including pH, accumulation potential, and accumulation time) were optimized systematically. The results showed that the TiO2⁻ErGO composites increased the electrochemical active area of the electrode and enhanced the electrochemical responses to tartrazine significantly. Under the optimum detection conditions, the peak current was found to be linear for tartrazine concentrations in the range of 2.0 × 10−8⁻2.0 × 10−5 mol/L, with a lower detection limit of 8.0 × 10−9 mol/L (S/N = 3). Finally, the proposed TiO2⁻ErGO⁻GCEs were successfully applied for the detection of trace tartrazine in carbonated beverage samples.

Fabrication of Amine-Modified Magnetite-Electrochemically Reduced Graphene Oxide Nanocomposite Modified Glassy Carbon Electrode for Sensitive Dopamine Determination.

Amine-modified magnetite (NH2-Fe3O4)/reduced graphene oxide nanocomposite modified glassy carbon electrodes (NH2-Fe3O4/RGO/GCEs) were developed for the sensitive detection of dopamine (DA). The NH2-Fe3O4/RGO/GCEs were fabricated using a drop-casting method followed by an electrochemical reduction process. The surface morphologies, microstructure and chemical compositions of the NH2-Fe3O4 nanoparticles (NPs), reduced graphene oxide (RGO) sheets and NH2-Fe3O4/RGO nanocomposites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-Ray diffraction (XRD) and Fourier-transform infrared (FTIR) spectroscopy. The electrochemical behaviors of DA on the bare and modified GCEs were investigated in phosphate buffer solution (PBS) by cyclic voltammetry (CV). Compared with bare electrode and RGO/GCE, the oxidation peak current (ipa) on the NH2-Fe3O4/RGO/GCE increase significantly, owing to the synergistic effect between NH2-Fe3O4 NPs and RGO sheets. The oxidation peak currents (ipa) increase linearly with the concentrations of DA in the range of 1 × 10-8 mol/L - 1 × 10-7 mol/L, 1 × 10-7 mol/L - 1 × 10-6 mol/L and 1 × 10-6 mol/L - 1 × 10-5 mol/L. The detection limit is (4.0 ± 0.36) ×10-9 mol/L (S/N = 3). Moreover, the response peak currents of DA were hardly interfered with the coexistence of ascorbic acid (AA) and uric acid (UA). The proposed NH2-Fe3O4/RGO/GCE is successfully applied to the detection of dopamine hydrochloride injections with satisfactory results. Together with low cost, facile operation, good selectivity and high sensitivity, the NH2-Fe3O4/RGO/GCEs have tremendous prospects for the detection of DA in various real samples.

Preparation of Cu2O-Reduced Graphene Nanocomposite Modified Electrodes towards Ultrasensitive Dopamine Detection.

Cu2O-reduced graphene oxide nanocomposite (Cu2O-RGO) was used to modify glassy carbon electrodes (GCE), and applied for the determination of dopamine (DA). The microstructure of Cu2O-RGO nanocomposite material was characterized by scanning electron microscope. Then the electrochemical reduction condition for preparing Cu2O-RGO/GCE and experimental conditions for determining DA were further optimized. The electrochemical behaviors of DA on the bare electrode, RGO- and Cu2O-RGO-modified electrodes were also investigated using cyclic voltammetry in phosphate-buffered saline solution (PBS, pH 3.5). The results show that the oxidation peaks of ascorbic acid (AA), dopamine (DA), and uric acid (UA) could be well separated and the peak-to-peak separations are 204 mV (AA-DA) and 144 mV (DA-UA), respectively. Moreover, the linear response ranges for the determination of 1 × 10-8 mol/L~1 × 10-6 mol/L and 1 × 10-6 mol/L~8 × 10-5 mol/L with the detection limit 6.0 × 10-9 mol/L (S/N = 3). The proposed Cu2O-RGO/GCE was further applied to the determination of DA in dopamine hydrochloride injections with satisfactory results.

Facile synthesis of MnO2-embedded flower-like hierarchical porous carbon microspheres as an enhanced electrocatalyst for sensitive detection of caffeic acid.

Tailored designs/fabrications of hierarchical porous advanced electrode materials are of great importance for developing high-performance electrochemical sensors. Herein, we demonstrate a simple and low-cost in situ chemical approach for the facile synthesis of MnO2-embedded hierarchical porous carbon microspheres (MnO2/CM). By the characterizations of scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray powder diffraction and energy dispersive spectroscopy, we evidenced that the synthesized product were flower-like carbon microspheres (CM) assembled by the bent flakes with thickness of about several nanometers and MnO2 nanorods were highly dispersed and successfully decorated on the CM layers, resulting in a rough surface and three-dimensional microstructure. The greatest benefit from the combined porous CM with MnO2 nanorods is that the MnO2/CM modified electrode has the synergetic catalysis effect on the electro-oxidation of caffeic acid, leading to the remarkable increase in the electron transfer rate and significant decrease in the over-potential for the caffeic acid oxidation in contrast to the bare electrode and CM modified electrode. This implies that the prepared MnO2/CM can be employed as an enhanced electrocatalyst for the sensitive detection of caffeic acid. Under the optimum conditions, the anodic peak current of caffeic acid is linear with its concentration in the range of 0.01-15.00 µmol L-1, and a detection limit of 2.7 nmol L-1 is achieved based on S/N = 3. The developed sensor shows good selectivity, sensitivity, reproducibility, and also excellent recovery in the detections of real samples, revealing the promising practicality of the sensor for the caffeic acid detection.