Photoelectrochemical detection of copper ions based on a covalent organic framework with tunable properties.

Copper ions (Cu2+) play an essential role in various cellular functions, including respiration, nerve conduction, tissue maturation, oxidative stress defense, and iron metabolism. Covalent organic frameworks (COFs) are a class of porous crystalline materials with directed structural designability and high stability due to the combination of different monomers through covalent bonds. In this study, we synthesized a porphyrin-tetrathiazole COF (TT-COF(Zn)) with Zn-porphyrin and tetrathiafulvalene (TTF) as monomers and used it as a photoactive material. The strong light absorption of metalloporphyrin and the electron-rich properties of supplied TTF contribute to its photoelectrochemical performance. Additionally, the sulfur (S) in the TTF can coordinate with Cu2+. Based on these properties, we constructed a highly sensitive photoelectrochemical sensor for detecting Cu2+. The sensor exhibited a linear range from 0.5 nM to 500 nM (R2 = 0.9983) and a detection limit of 0.15 nM for Cu2+. Notably, the sensor performed well when detecting Cu2+ in water samples.

Selective identification of p-nitroaniline by bromine-mediated polarization of carbon dots.

A fluorometric method based on boron, bromide-codoped carbon dots (BBCNs) was developed for the first time for the highly selective detection of p-nitroaniline (PNA) in wastewater samples. It should be noted that the introduction of bromine greatly increases the molecular polarizability of the probe, which can regulate the energy level matching between the probe and PNA, resulting in the interaction between BBCNs and PNA. In the presence of PNA, the fluorescence of BBCNs is obviously quenched and accompanied by a red shift of the fluorescence band, which might be attributed to the formation of aggregates caused by the polar adsorption of BBCNs and PNA. It is beneficial for constructing a highly selective sensing platform for PNA determination compared to its isomers (o-nitroaniline and m-nitroaniline) through atomic bromine-mediated polarization of the BBCNs. With the help of this mechanism, an excellent linear range of 0.5-300 µM with a low detection limit of 0.24 µM toward PNA was obtained. This work further confirms that there is a significant relationship between the nature of doping elements and the optical and physicochemical properties of fluorescent materials.

A single-site porphyrin (Cu)-based COF electrocatalyst for the electrochemical detection of gallic acid sensitively.

Sensitive and convenient determination of gallic acid (GA) is vital for food safety. Here, a novel porphyrin (Cu)-based covalent organic framework named as COF(Cu) was successfully synthesized by condensing pre-metalated 5,10,15,20-tetrakis (para-aminophenyl) porphyrin copper (II) and 2,3,6,7-tetra (4-formylphenyl) tetrathiafulvalene ligands. By combining the advantages of porphyrin with tetrathiafulvalene, it may be possible to create a COF with an intrinsically effective charge-transfer channel. In addition, the Cu-N4 type in the COF(Cu) can be regarded as the single-site electrocatalyst. Benefiting from these advantages, the COF(Cu) based electrochemical sensor demonstrated outstanding response to gallic acid (GA). Under the optimal conditions by square wave voltammetry technique, the COF(Cu) modified electrode showed a wide linear range (0.01-1000 µM), a low detection limit (2.81 nM), good reproducibility, acceptable selectivity as well as high stability. Moreover, the established approach was adopted to detect GA in real tea samples with good recoveries, indicating that the COF(Cu) based electrochemical sensor may pave the way for the application in food analysis.

An eco-friendly fluorometric assay for high-sensitive meloxicam quantitation in biological matrices.

Meloxicam (Mel), as a powerful and effective anti-inflammatory drug, is commonly employed for the treatment of various inflammatory diseases; however, the use of Mel at high doses or for extended periods could cause severe side effects in human visceral organs. Therefore, a simple, rapid, and reliable method is urgently needed to monitor Mel in biological samples. Herein, novel water-soluble luminescent nano-carbon dots (nano-Cdots) with outstanding physicochemical properties were prepared by a one-pot high-temperature hydrothermal process of ellagic acid and guanidine. The nano-Cdots were further used as an optical probe for the sensitive detection of Mel in serum samples through the cooperative mechanisms of the inner filter effect and photoelectron transfer. By employing this sensor, an excellent linear correlation was achieved between the relative luminescent intensity [(PL0 - PL)/PL0] and the concentration of Mel in the range of 0.1 to 200 µM, with a limit of detection of 34.68 nM (3σ/k). This sensor was effectively employed for the analysis of Mel in real serum samples, implying its potential development prospects for the advancement of drug analysis with carbon-based probes.

Organic Molecular Probe Enabled Ionic Current Rectification toward Subcellular Detection of Glutathione with High Selectivity, Sensitivity, and Recyclability.

Single-cell interrogation with the solid-state nanoprobes enables understanding of the linkage between cellular behavior and heterogeneity. Herein, inspired by the charge property of the organic molecular probe (OMP), a generic ionic current rectification (ICR) single-cell methodology is established, exemplified by subcellular detection of glutathione (GSH) with high selectivity, sensitivity, and recyclability. The as-developed nanosensor can transduce the subcellular OMP-GSH interaction via a sensitive ionic response, which stems from the superior specificity of OMP and its essential charge property. In addition, the nanosensor exhibits good reversibility, since the subsequent tandem reaction after the recognition can well recover the sensing surface. Given the diverse structures and tailorable charge properties of OMP, this work underpins a new and general method of OMP-based ICR single-cell analysis.

Ratiometric detection of p-nitrophenol and its derivatives using a dual-emissive neuron cell-like carbonized probe based on a ππ stacking quenching mechanism.

p-Nitrophenol and its derivatives can cause serious harm to the health of mankind and the earth's ecosystem. Therefore, it is necessary to develop a novel and rapid detection technology for p-nitrophenol and its derivative. Herein, excellent water-soluble, large-size and dual-emissive neuron cell-analogous carbon-based probes (NCNPs) have been prepared via a solvothermal approach, using o-phenylenediamine as the only precursor, which exhibit two distinctive fluorescence (FL) peaks at 420 and 555 nm under 345 nm excitation. The NCNPs show a neuron cell-like branched structure, are cross-connected, and are in the range of 10-20 nm in skeleton diameter. Interestingly, their blue-green dual-colour fluorescence is quenched by p-nitrophenol or its derivative due to the specific mechanism of the ππ stacking interactions or internal filtration effect. Accordingly, a simple, rapid, direct and free-label ratiometric FL detection of p-nitrophenol is proposed. An excellent linear relationship shows linear regions over the range of 0.1-50 µM between the ratio of the FL intensity (FL555 nm/FL420 nm) and the concentrations of p-nitrophenol. The detection limit is as low as 43 nM (3σ). Importantly, the NCNP-based probe also shows acceptable repeatability and reproducibility for the detection of p-nitrophenol and its derivatives, and the recovery results for p-nitrophenol in real wastewater samples are favourable.

Green synthesis of a deep-ultraviolet carbonized nanoprobe for ratiometric fluorescent detection of feroxacin and enrofloxacin in food and serum samples.

Recently, the development of a novel fluorescent (FL) nanoprobe for ratiometric detection of antibiotics in real-world samples has received more and more attention. In this article, the distinctive optical properties of deep-ultraviolet emission, a narrowed full width at half maximum (∼20 nm) and excitation-independent emission of a carbonized nanoprobe (CNP) were easily prepared by an environmentally friendly approach of solvothermal treatment using melamine as the precursor and H2O as the solvent. The obtained CNP can be further utilized as an efficient ratiometric FL nanoprobe for enrofloxacin (EFC) and feroxacin (FXC) detection based on the fact that the FL quenching of the CNP was accompanied by an FL increase with EFC/FXC based on the inner filter effect (IFE). Under the optimal conditions, excellent linear relationships existed between the relative FL intensity (FL290 nm/FL412 nm, CNP for FL290 nm and antibiotics for FL412 nm) and the concentrations of FXC and EFC in the range of 0.05-500.0 µM and 0.05-200.0 µM, with limits of detection of 21.74 and 22.43 nM (3σ/k), respectively. With the proposed ratiometric FL sensor, FXC and EFC in milk and serum samples can be rapidly and selectively analyzed without tedious pretreatment processes for real-world samples.

UV-assisted one-pot synthesis of bimetallic Ag-Pt decorated reduced graphene oxide for colorimetric determination of hydrogen peroxide.

Bimetallic Ag-Pt nanoparticles decorated on the surface of reduced graphene oxide (Ag-Pt/rGO) were designed and selected as a nanozyme for the assay of hydrogen peroxide. The nanocomposites were prepared through a one-pot reduction of potassium chloroplatinate, silver nitrate, and graphene oxide under ultraviolet irradiation without using any extra chemical reducing agents or surfactants. The successful formation of Ag-Pt/rGO nanocomposites was confirmed by transmission electron microscopy, energy disperse spectroscopy mapping, X-ray photoelectron spectroscopy, and X-ray diffraction analysis. Significantly, Ag-Pt/rGO nanocomposites possessed excellent peroxidase-like activity toward the catalytic oxidation of 3,3',5,5'-tetramethylbenzidine to form a blue product in the presence of hydrogen peroxide. Steady-state kinetics studies suggested that Ag-Pt/rGO nanocomposites had high affinity to hydrogen peroxide. Based on these properties, a convenient and sensitive method for the colorimetric determination of hydrogen peroxide was developed. Under optimal conditions, the absorbance at 652 nm increases linearly in the 10-100 µM and 100 µM-1 mM ranges of hydrogen peroxide concentration, and the detection limit is 0.9 µM (S/N = 3). The method was successfully applied to the determination of hydrogen peroxide in real water samples. Graphical abstract Ag-Pt/rGO nanocomposites were prepared by a one-pot UV irradiation method and used as a novel nanozyme for colorimetric determination of H2O2.

Au-Hg/rGO with enhanced peroxidase-like activity for sensitive colorimetric determination of H2O2.

The Au-Hg amalgam anchored on the surface of reduced graphene oxide nanosheets (Au-Hg/rGO) has been synthesized successfully and characterized by various techniques such as transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. The Au-Hg/rGO nanocomposites were found to possess excellent peroxidase-like catalytic activity and can quickly catalyze the oxidation of colorless 3,3',5,5'-tetramethylbenzidine (TMB) to blue oxTMB in the presence of H2O2. The obvious color change offered accurate determination of the H2O2 concentration by recording the absorbance at 652 nm using a UV-vis spectrophotometer. The linear response range for H2O2 was from 5 µM to 100 µM and the detection limit was 3.25 µM (S/N = 3). Furthermore, a kinetic study indicated that the catalytic behavior of Au-Hg/rGO nanocomposites followed the typical Michaelis-Menten theory and Au-Hg/rGO nanocomposites showed good affinity for H2O2. We envision that the simple and sensitive colorimetric detection system holds great promising applications in clinical diagnostics and food and environment monitoring.

A voltammetric sensor based on reduced graphene oxide-hemin-Ag nanocomposites for sensitive determination of tyrosine.

A novel voltammetric sensor was designed and used for the determination of l-tyrosine (l-Tyr) by surface modification of a glassy carbon electrode with reduced graphene oxide-hemin-Ag (rGO-H-Ag) nanocomposites. The nanocomposites were synthesized by a facile one-pot hydrothermal method and characterized by means of transmission electron microscopy and Raman spectroscopy. The determination of l-Tyr was investigated by cyclic voltammetry and further quantified using differential pulse voltammetry. The results revealed a significant enhanced electrochemical oxidation effect for l-Tyr at the nanocomposites modified electrode. Two linear ranges from 0.1 to 100 µM and 100 to 1000 µM as well as a low detection limit of 30 nM (S/N = 3) were obtained. In addition, the sensor also demonstrated good selectivity, reproducibility and stability.

Aggregation-Induced Emission Behavior of Dual-NIR-Emissive Zinc-Doped Carbon Nanosheets for Ratiometric Anthrax Biomarker Detection.

The development of near-infrared (NIR) emission nanoprobes for the ratiometric fluorescent determination of living cells in vitro/vivo is of great analytical importance. In this work, dual-NIR-emissive Zn-doped carbon-based nanosheets (Zn-CNSHs) were prepared with a beneficial and special donor-π-acceptor-conjugated (D-π-A-conjugated) spatial framework, which resulted in not only a much lower HOMO-LUMO energy level but also excellent biocompatibility and physicochemical properties. The Zn-CNSHs were prepared by simple one-pot solvothermal synthesis with zinc gluconate (ZGN) and a strong acid and exhibited two distinctive photoluminescence (PL) peaks at 620 and 720 nm with the 600 nm excitation. The 620 nm peak intensity was dependent on dipicolinic acid (DPA) owing to the aggregation-induced emission enhancement effect via the strong intersheet hydrogen bonds between Zn-CNSHs and DPA, enabling the ratiometric fluorescent determination of DPA, an important clinical anthrax biomarker. An excellent calibration curve showed linear regions over the range of 0.05-500 µM between the ratio of PL intensity (PL620 nm/PL720 nm) and the concentrations of DPA. The detection limit was down to 21.7 nM. Based on the high stability, low cytotoxicity, high selectivity, and outstanding PL-reliant sensitivity for the DPA assay, the nanoprobe has been successfully used to monitor DPA in serum, wastewater, and cells.

Self-Assembled Peptide Nanostructures for Photoelectrochemical Bioanalysis Application: A Proof-of-Concept Study.

Currently, one of important research directions of photoelectrochemical (PEC) bioanalysis is to exploit innovative photoactive species and their elegant implementations for selective detection and signal transduction. Different from existing candidates for photoelectrode development, this study, exemplified by the cationic dipeptide nanoparticles (CDNPs), reports the first demonstration of self-assembled peptide nanostructures (SAPNs) for the PEC bioanalysis. Specifically, the CDNPs were prepared as representative materials and then immobilized onto the indium tin oxide (ITO) electrode for the PEC differentiation of several commonly involved biomolecules such as ascorbic acid (AA) and l-cysteine. Significantly, the experimental results disclosed that the CDNPs possessed unique photocathodic responses and good analytical performance toward AA detection in terms of rapid response, high stability, and excellent selectivity. This work demonstrates the great potential of the large SAPN family for the future PEC bioanalysis development and has not been reported to our knowledge.

An OFF-ON detection method for copper(ii) ions using a AgAu-NG nanocomposite modified electrode.

An OFF-ON detection method for Cu2+ was developed at the AgAu bimetallic nanoparticle decorated nitrogen-doped graphene (AgAu-NG) nanocomposite modified electrode. The measurement was based on the copper-catalyzed oxidation of cysteamine (Cys) to regulate the oxidation peak current of Ag. In the absence of Cu2+, Cys can bind to the surface of AgAu-NG via the Ag-S or Au-S bond, thus leading to an obvious decrease of the oxidation peak current of Ag. However, in the presence of Cu2+, Cu2+ can greatly catalyze the oxidation of Cys by dissolved O2 to form cystamine, which would fall off the surface of AgAu-NG nanocomposites, leading to the partial recovery of the oxidation peak current of Ag. With the increase in the concentration of Cu2+, the oxidation peak current of Ag in the presence of Cys increases accordingly. So, the concentration of Cu2+ can be measured. By using the optimum conditions, this method can detect Cu2+ concentrations down to 0.3 nM (S/N = 3) with a linear response range of 1 nM-1 mM. Furthermore, this method was applied to determine Cu2+ concentrations in river water samples and showed excellent analytical performance.

A novel electrochemical sensor based on Au nanoparticles/8-aminoquinoline functionalized graphene oxide nanocomposite for paraquat detection.

In this paper, a novel electrochemical sensor based on Au nanoparticles/8-aminoquinoline functionalized graphene oxide (AuNPs/GAQ) nanocomposite was developed and tested for the first time for detection of paraquat (PQ). The morphology and composition of AuNPs/GAQ nanocomposite were characterized by various techniques, including transmission electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, and x-ray photoelectron spectroscopy. Cyclic voltammetry and differential pulse voltammetry were utilized to investigate the electrochemical performances of AuNPs/GAQ nanocomposite modified glassy carbon electrode. The obtained modified electrode exhibited excellent electrocatalytic activity towards detection of PQ. Under the optimized conditions, the proposed sensor showed low detection limit (6 nM, S/N = 3), wide linear range (0.02-24 µM), high selectivity and good stability. In addition, it was successfully applied for detection of PQ in natural water samples with satisfactory results.

Nanoporous Semiconductor Electrode Captures the Quantum Dots: Toward Ultrasensitive Signal-On Liposomal Photoelectrochemical Immunoassay.

Liposomal photoelectrochemical (PEC) bioanalysis has recently emerged and exhibited great potential in sensitive biomolecular detection. Exploration of the facile and efficient route for advanced liposomal PEC bioanalysis is highly appealing. In this work, we report the split-type liposomal PEC immunoassay system consisting of sandwich immunorecognition, CdS quantum dots (QDs)-loaded liposomes (QDLL), and the release and subsequent capture of the QDs by a separated TiO2 nanotubes (NTs) electrode. The system elegantly operated upon the protein binding and lysis treatment of CdS QDLL labels within the 96-well plate, and then the CdS QDs-enabled sensitization of TiO2 NTs electrode. Exemplified by cardiac markers troponin I (cTnI) as target, the proposed system achieved efficient activation of TiO2 NTs electrode and thus the signal generation toward the split-type PEC immunoassay. This work features the first use of QDs for liposomal PEC bioanalysis and is expected to inspire more interests in the design and implementation of numerous QDs-involved liposomal PEC bioanalysis.

Voltammetric simultaneous determination of catechol and hydroquinone using a glassy carbon electrode modified with a ternary hybrid material composed of reduced graphene oxide, magnetite nanoparticles and gold nanoparticles.

An electrochemical sensor is described for the simultaneous determination of the pollutants catechol (CC) and hydroquinone (HQ). A glassy carbon electrode (GCE) was modified with reduced graphene oxide, Fe3O4 and gold nanoparticles and then showed a pair of well-defined voltammetric peaks for CC and HQ. Its oxidation peak potentials (located at 0.21 and 0.10 V vs. Ag/AgCl) are well separated, and this makes it suitable for simultaneous determination of the two isomers. Under optimal conditions, the oxidation peak currents of CC and HQ increase linearly in the 0.05-550 µM and 0.1-500 µM concentration ranges, even in the presence of 0.1 mM of the respective other isomer. The detection limits are 0.02 and 0.17 µM (at S/N = 3), respectively. The modified GCE exhibits good selectivity and recovery when applied for the analysis of spiked wastewater. Graphical abstract Ternary hybrid nanomaterials of rGO-Fe3O4-Au was developed for simultaneous electrochemical determination of catechol (CC) and hydroquinone (HQ).