Materials Containing Single-, Di-, Tri-, and Multi-Metal Atoms Bonded to C, N, S, P, B, and O Species as Advanced Catalysts for Energy, Sensor, and Biomedical Applications.

Modifying the coordination or local environments of single-, di-, tri-, and multi-metal atom (SMA/DMA/TMA/MMA)-based materials is one of the best strategies for increasing the catalytic activities, selectivity, and long-term durability of these materials. Advanced sheet materials supported by metal atom-based materials have become a critical topic in the fields of renewable energy conversion systems, storage devices, sensors, and biomedicine owing to the maximum atom utilization efficiency, precisely located metal centers, specific electron configurations, unique reactivity, and precise chemical tunability. Several sheet materials offer excellent support for metal atom-based materials and are attractive for applications in energy, sensors, and medical research, such as in oxygen reduction, oxygen production, hydrogen generation, fuel production, selective chemical detection, and enzymatic reactions. The strong metal-metal and metal-carbon with metal-heteroatom (i.e., N, S, P, B, and O) bonds stabilize and optimize the electronic structures of the metal atoms due to strong interfacial interactions, yielding excellent catalytic activities. These materials provide excellent models for understanding the fundamental problems with multistep chemical reactions. This review summarizes the substrate structure-activity relationship of metal atom-based materials with different active sites based on experimental and theoretical data. Additionally, the new synthesis procedures, physicochemical characterizations, and energy and biomedical applications are discussed. Finally, the remaining challenges in developing efficient SMA/DMA/TMA/MMA-based materials are presented.

Facile synthesis of petal-like VS2 anchored onto graphene nanosheets for the rapid sensing of toxic pesticide in polluted water.

Fenitrothion (FT) is a toxic phosphorothioate insecticide that can easily contaminate aquatic environments, leading to a detrimental effect on the aquatic species and harmful endocrine disrupter effects on human health. Therefore, it is vital to develop a reliable methodology for the accurate and precise real-time sensing of carcinogenic FT in water samples at trace concentration to ensure environmental safety. We aim to fabricate the low-cost VS2-attached reduced graphene oxide (RGO) sheets via a simple hydrothermal approach. It was further applied for the rapid and accurate sensing of toxic FT. The VS2/RGO-composite delivers a more favorable microenvironment for the rapid electrocatalytic sensing performance towards toxic FT reduction than the VS2 and RGO modified electrodes. The electron transfer rate constant (ks) and the saturating absorption capacity (Γ) value of FT was evaluated to be 1.52 s-1 and 2.18 × 10-10 mol cm-2, respectively. The constructed sensor exhibits a wide linear relationship after amperometry between the cathodic current densities and the concentrations of FT in the range of 5-90 nM and high sensitivity (5.569 µA nM-1 cm-2); moreover, the detection limit was 0.07 nM (S/N = 3). The fabricated sensor has excellent anti-interference ability and reproducibility for the direct sensing of FT in river water, seawater, and lake water samples with acceptable recoveries. It is a promising sensing device for in-situ quantification of FT in agricultural products and ecological systems.

Pd-Cu nanospheres supported on Mo2C for the electrochemical sensing of nitrites.

The improper disposal in agricultural and industrial wastewater leads to high NO2- concentrations in the aquatic environment, which can cause cancer in humans and animals; thus, their quick and accurate detection is urgently needed to ensure public health and environmental safety. In this study, a reliable and selective electrochemical sensor consisting of Pd-Cu nanospheres (NSs) supported on molybdenum carbide was prepared via simple ultrasonication. Then, a glassy carbon electrode was realized using this composite (Pd-Cu-Mo2C-modified GCE) to test its electrocatalytic sensing for NO2- in a 0.1 M phosphate-buffered solution (PBS) solution via cyclic voltammetry and amperometry; at a low oxidation potential, the anodic peak current of NO2- detected by this electrode was significantly higher than that of its unmodified and other modified electrodes. The sensor showed a broad linear response in the 5-165-nM NO2- concentration range, with a low detection limit (0.35 nM in 0.1 M PBS) and high sensitivity (3.308 µAnM-1 cm-2). Moreover, the fabricated electrode was successfully applied for detecting nitrites in sausages, river water, and milk, showing also good recovery.

Improved conductivity of flower-like MnWO4 on defect engineered graphitic carbon nitride as an efficient electrocatalyst for ultrasensitive sensing of chloramphenicol.

Environmental hazards caused by chloramphenicol has attained special attention. Fast, accurate and reliable detection of chloramphenicol in foodstuffs and water samples is of utmost importance. Herein, we developed a g-C3N4/MnWO4 composite for the selective and sensitive detection of chloramphenicol. Successful fabrication of g-C3N4/MnWO4 composite was verified by using scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, Fourier transform infrared spectroscopy (FT-IR), x-ray diffraction (XRD) and x-ray photo electron spectroscopy (XPS) techniques. Electrochemical characteristics were evaluated by using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and differential pulse voltammetry (DPV). The g-C3N4/MnWO4 modified glassy carbon electrode has shown the highest electrocatalytic activity towards chloramphenicol with a decreased reduction potential of -0.547 V and increased cathodic peak current. The developed sensor has shown excellent performance for the detection of chloramphenicol with a sensitivity of 0.9986 µA nM-1 cm-2 and LOD of 1.03 nM in a broad linear range of 4.0-71 nM. In addition, the fabricated sensor has achieved anti-interference ability, good stability, excellent repeatability and remarkable reproducibility for the detection of chloramphenicol. The fabricated sensor applied for the determination of chloramphenicol in milk, human blood serum and sewage samples, in which significant and satisfactory results were achieved.

Efficient electron-mediated electrochemical biosensor of gold wire for the rapid detection of C-reactive protein: A predictive strategy for heart failure.

C-reactive protein (CRP) is considered a promising biomarker for the rapid and high-throughput real-time monitoring of cardiovascular disease and inflammation in unprocessed clinical samples. Implementation of this monitoring would enable various transformative biomedical applications. We have fabricated a highly specific sensor chip to detect CRP with a detection limit of 2.25 fg/mL. The protein was immobilized on top of a gold (Au) wire/polycarbonate (PC) substrate using 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride/N-hydroxy succinimide-activated 3-mercaptoproponic acid (MPA) as a self-assembled monolayer agent and bovine serum albumin (BSA) as a blocking agent. In contrast to the bare PC substrate, the CRP/BSA/anti-CRP/MPA/Au substrate exhibited a considerably high electrochemical signal toward CRP. The influence of the experimental parameters on CRP detection was assessed via various analysis methods, and these parameters were then optimized. The linear dynamic range of the CRP was 5-220 fg/mL for voltammetric and impedance analysis. Morever, the strategy exhibited high selectivity against various potential interfering species and was capable of directly probing trace amounts of the target CRP in human serum with excellent selectivity. The analytical assay based on the CRP/BSA/anti-CRP/MPA/Au substrate could be exploited as a potentially useful tool for detecting CRP in clinical samples.

The facile and simple synthesis of poly(3,4ethylenedioxythiophene) anchored reduced graphene oxide nanocomposite for biochemical analysis.

In this article, we demonstrate the potentiostatic electrodeposition of poly(3,4-ethylenedioxythiophene) (PEDOT) on reduced graphene oxide (RGO) to develop a nanocomposite-modified electrode that separates three coexisting biofluids - ascorbic acid (AA), dopamine (DA), and uric acid (UA) - in a 0.1 M Phosphate buffer solution at a physiological pH (7.4). The texture, physicochemical properties, and electrochemical behavior of the PEDOT-RGO were explored using UV-visible spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, electron microscopic techniques, and electrochemical impedance spectroscopy (EIS). A PEDOT-RGO/GCE was evaluated with respect to a bare GCE, RGO/GCE, and PEDOT/GCE for the simultaneous sensing of AA, DA, and UA. The difference in voltammetric peak potentials was about 180 mV between AA and DA and 120 mV between DA and UA. The differential pulse voltammetric sensor provided a linear calibration for a wide concentration range (0.1-907 µM for AA, 0.1-901 µM for DA, and 0.1-701 µM for UA) with detection limits of 1.5 µM, 0.6 µM, and 0.2 µM for AA, DA, and UA, respectively. The developed sensor was validated by the detection of AA, DA, and UA in a vitamin C tablet, a dopamine hydrochloride injection, and human serum samples.

Correction to: Recent advances in molybdenum disulfide-based electrode materials for electroanalytical applications.

The original version of this article unfortunately missed Prof. A.T. Ezhil Vilian's project number in Acknowledgements. The missing project number is 2017R1D1A1B03034977.

Recent advances in molybdenum disulfide-based electrode materials for electroanalytical applications.

The primary objective of this review article is to summarize the development and structural diversity of 2D/3D molybdenum disulfide (MoS2) based modified electrodes for electrochemical sensors and biosensor applications. Hydrothermal, mechanical, and ultrasonic techniques and solution-based exfoliation have been used to synthesize graphene-like 2D MoS2 layers. The unique physicochemical properties of MoS2 and its nanocomposites, including high mechanical strength, high carrier transport, large surface area, excellent electrical conductivity, and rapid electron transport rate, render them useful as efficient transducers in various electrochemical applications. The present review summarizes 2D/3D MoS2-based nanomaterials as an electrochemical platform for the detection and analysis of various biomolecules (e.g., neurotransmitters, NADH, glucose, antibiotics, DNA, proteins, and bacteria) and hazardous chemicals (e.g., heavy metal ions, organic compounds, and pesticides). The substantial improvements that have been achieved in the performance of enzyme-based amperometry, chemiluminescence, and nucleic acid sensors incorporating MoS2-based chemically modified electrodes are also addressed. We also summarize key sensor parameters such as limits of detection (LODs), sensitivity, selectivity, response time, and durability, as well as real applications of the sensing systems in the environmental, pharmaceutical, chemical, industrial, and food analysis fields. Finally, the remaining challenges in designing MoS2 nanostructures suitable for electroanalytical applications are outlined. Graphical abstract • MoS2 based materials exhibit high conductivity and improved electrochemical performance with great potential as a sensing electrode. • The role of MoS2 nanocomposite films and their detection strategies were reviewed. • Biomarkers detection for disease identification and respective clinical treatments were discussed. • Future Challenges, as well as possible research development for "MoS2 nanocomposites", are suggested.

Salt-templated three-dimensional porous carbon for electrochemical determination of gallic acid.

We report an electrochemical sensor based on three-dimensional porous amorphous carbon (3DPAC) for the sensitive and selective determination of gallic acid (GA). The tailor-made carbon was prepared via salt-templating in which the organic molecular precursor, i.e., glucose, was simply ground and carbonized with a eutectic mixture of LiBr and KBr at 800 °C in an inert atmosphere. Salt removal from the carbon-salt mixture with water yielded 3DPAC with a hierarchical porous structure and oxygen-containing functional groups. When employed as an electrochemical sensor, 3DPAC exhibited remarkable sensitivity (0.1045 µA pM-1 cm-2) with a lower detection limit of 0.434 pM at a signal-to-noise ratio of 3 and a linear response up to 1-150 pM for determination of GA. Under optimized test conditions, 3DPAC showed a superior peak current response for GA as compared to the glassy carbon electrode. In addition, ascorbic, uric, and caffeic acids did not interfere with the voltammetric detection of GA in terms of selectivity, stability, and repeatability. We envision that 3DPAC can provide a promising platform for the development of electrochemical sensors.

Palladium Supported on an Amphiphilic Triazine-Urea-Functionalized Porous Organic Polymer as a Highly Efficient Electrocatalyst for Electrochemical Sensing of Rutin in Human Plasma.

Metal nanoparticle-containing porous organic polymers have gained great interest in chemical and pharmaceutical applications owing to their high reactivity and good recyclability. In the present work, a palladium nanoparticle-decorated triazine-urea-based porous organic polymer (Pd@TU-POP) was designed and synthesized using 1,3-bis(4-aminophenyl)urea with cyanuric chloride and palladium acetate. The porous structure and physicochemical properties of the electrode material Pd@TU-POP were observed using a range of standard techniques. The Pd@TU-POP material on the electrode surface showed superior sensing ability for rutin (RT) because the Pd dispersion facilitated the electrocatalytic performance of TU-POP by reducing the overpotential of RT oxidation dramatically and improving the stability significantly. Furthermore, TU-POP provides excellent structural features for loading Pd nanoparticles, and the resulting Pd@TU-POP exhibited enhanced electron transfer and outstanding sensing capability in a linear range between 2 and 200 pM having a low detection value of 5.92 × 10-12 M (S/N = 3). The abundant porous structure of Pd@TU-POP not only provides electron transport channels for RT diffusion but also offers a facile route for quantification sensing of RT with satisfactory recoveries in aqueous electrolyte containing human plasma and red wine. These data reveal that the synthetic Pd@TU-POP is an excellent potential platform for the detection of RT in biological samples.

Development of gold nanoparticle-aptamer-based LSPR sensing chips for the rapid detection of Salmonella typhimurium in pork meat.

A non-labeled, portable plasmonic biosensor-based device was developed to enable the ultra-sensitive and selective detection of Salmonella typhimurium in pork meat samples. Specifically, a plasmonic sensor, using the self-assembly of gold nanoparticles (AuNPs) to achieve a regulated diameter of 20 nm for the AuNP monolayers, was used to conduct high-density deposition on a transparent substrate, which produced longitudinal wavelength extinction shifts via a localized surface plasmon resonance (LSPR) signal. The developed aptamers conjugated to the LSPR sensing chips revealed an ultra-sensitive upper limit of detection (LOD) of approximately 104 cfu/mL for S. typhimurium in pure culture under the optimal assay conditions, with a total analysis time of 30-35 min. When the LSPR sensing chips were applied on artificially contaminated pork meat samples, S. typhimurium in the spiked pork meat samples was also detected at an LOD of 1.0 × 104 cfu/mL. The developed method could detect S. typhimurium in spiked pork meat samples without a pre-enrichment step. Additionally, the LSPR sensing chips developed against S. typhimurium were not susceptible to any effect of the food matrix or background contaminant microflora. These findings confirmed that the developed gold nanoparticle-aptamer-based LSPR sensing chips could facilitate sensitive detection of S. typhimurium in food samples.

Cesium-induced inhibition of bacterial growth of Pseudomonas aeruginosa PAO1 and their possible potential applications for bioremediation of wastewater.

Radioactive isotopes and fission products have attracted considerable attention because of their long lasting serious damage to the health of humans and other organisms. This study examined the toxicity and accumulation behavior of cesium towards P. aeruginosa PAO1 and its capacity to remove cesium from waste water. Interestingly, the programmed bacterial growth inhibition occurred according to the cesium environment. The influence of cesium was analyzed using several optical methods for quantitative evaluation. Cesium plays vital role in the growth of microorganisms and functions as an anti-microbial agent. The toxicity of Cs to P. aeruginosa PAO1 increases as the concentration of cesium is increased in concentration-dependent manner. P. aeruginosa PAO1 shows excellent Cs removal efficiency of 76.1% from the contaminated water. The toxicity of cesium on the cell wall and in the cytoplasm were studied by transmission electron microscopy and electron dispersive X-ray analysis. Finally, the removal of cesium from wastewater using P. aeruginosa PAO1 as a potential biosorbent and the blocking of competitive interactions of other monovalent cation, such as potassium, were assessed. Overall, P. aeruginosa PAO1 can be used as a high efficient biomaterial in the field of radioactive waste disposal and management.

Pd nanospheres decorated reduced graphene oxide with multi-functions: Highly efficient catalytic reduction and ultrasensitive sensing of hazardous 4-nitrophenol pollutant.

We illustrate a facile approach for in situ synthesis of Pd-gum arabic/reduced graphene oxide (Pd-GA/RGO) using GA as the reducing agent, which favors the instantaneous reduction of both Pd ions and GO into Pd nanoparticles (NPs) and RGO. From the morphological analysis of Pd-GA/RGO, we observed highly dispersed spherical 5nm Pd NPs decorated over RGO. The as-synthesized Pd-GA/RGO composite was employed for the catalytic reduction and the electrochemical detection of 4-nitrophenol (4-NP), respectively. The catalytic reduction of 4-NP was highly pronounced for Pd-GA/RGO (5min) when compared to Pd NPs (140min) and Pd/RGO (36min). This enhanced catalytic activity was attributed to the synergistic effect of Pd NPs and the presence of various functional groups of GA. Significantly, the fabricated sensor offered a low detection limit (9fM) with a wider linear range (2-80 pM) and long-term stability. The simple construction technique, high sensitivity, and long-term stability with acceptable accuracy in wastewater samples were the main advantages of the developed sensor. The results indicated that the as-prepared Pd-GA/RGO exhibited better sensing ability than the other graphene-based modified electrodes. Therefore, the proposed sensor can be employed as a more convenient sensing platform for environmental and industrial pollutants.

Fabrication of 3D honeycomb-like porous polyurethane-functionalized reduced graphene oxide for detection of dopamine.

A three dimensional reduced graphene oxide/polyurethane (RGO-PU) porous material with connected pores was prepared by physical adsorption of RGO onto the surface of porous PU. The porous PU was prepared by directional melt crystallization of a solvent, which produced high pores with controlled orientation. The prepared RGO-PU was characterized by scanning electron microscopy, spectroscopy and electro-chemical methods. The RGO-PU porous material revealed better electrochemical performance, which might be attributed to the robust structure, superior conductivity, large surface area, and good flexibility. Differential pulse voltammetry (DPV) analysis of DA using the RGO-PU exhibited a linear response range over a wide DA concentration of 100-1150pM, with the detection limit of 1pM. This sensor exhibited outstanding anti-interference ability towards co-existing molecules with good stability, sensitivity, and reproducibility. Furthermore, the fabricated sensor was successfully applied for the quantitative analysis of DA in human serum and urine samples with acceptable recovery, which indicates its feasibility for practical application.

Fabrication of Palladium Nanoparticles on Porous Aromatic Frameworks as a Sensing Platform to Detect Vanillin.

Here, we report the fabrication of palladium nanoparticles on porous aromatic frameworks (Pd/PAF-6) using a facile chemical approach, which was characterized by various spectro- and electrochemical techniques. The differential pulse voltammetry (DPV) response of Pd/PAF-6 toward the vanillin (VA) sensor shows a linear relationship over concentrations (10-820 pM) and a low detection limit (2 pM). Pd/PAF-6 also exhibited good anti-interference performance toward 2-fold excess of ascorbic acid, nitrophenol, glutathione, glucose, uric acid, dopamine, ascorbic acid, 4-nitrophenol, glutathione, glucose, uric acid, dopamine, and 100-fold excess of Na(+), Mg(2+), and K(+) during the detection of VA. The developed electrochemical sensor based on Pd/PAF-6 had good reproducibility, as well as high selectivity and stability. The established sensor revealed that Pd/PAF-6 could be used to detect VA in biscuit and ice cream samples with satisfactory results.

Immobilization of myoglobin on Au nanoparticle-decorated carbon nanotube/polytyramine composite as a mediator-free H2O2 and nitrite biosensor.

A novel composite film was designed for use as a highly selective mediator-free amperometric biosensor, and a method was created for accomplishing direct electrochemistry of myoglobin on a multi-walled carbon nanotube and tyramine-modified composite decorated with Au nanoparticles on a glassy carbon electrode. The ultraviolet-visible and electrochemical impedance spectroscopy results showed that myoglobin retained its native conformation in the interaction with Au-PTy-f-MWCNT. The surface coverage of Mb-heme-Fe((II)/(III)) immobilized on Au-PTy-f-MWCNT and the heterogeneous electron-transfer rate constant were 2.12 × 10(-9) mol cm(-2) and 4.86 s(-1), respectively, indicating a higher loading capacity of the nanocomposite for direct electron transfer of Mb onto the electrode surface. The proposed Mb/Au-PTy-f-MWCNT biofilm exhibited excellent electrocatalytic behavior toward the reduction of H2O2 and the oxidation of nitrite with linear ranges of 2 to 5000 µM and 1 to 8000 µM and lower detection limits of 0.01 µM and 0.002 µM, respectively. An apparent Michaelis-Menten constant of 0.12 mM indicated that the Mb immobilized on the Au-PTy-f-MWCNT film retained its native activity. This biosensor can be successfully applied to detect H2O2 and nitrite in disinfectant cream, eye drops, pickle juice, and milk samples.

An electrocatalytic oxidation and voltammetric method using a chemically reduced graphene oxide film for the determination of caffeic acid.

The present work describes the characterization of a chemically reduced graphene oxide (CRGO) modified glassy carbon electrode (GCE) for electrochemical investigation of caffeic acid (CA). Cyclic voltammetry (CV), differential pulse voltammetry (DPV), amperometry, and electrochemical impedance spectroscopy (EIS) techniques were used to characterize the properties of the electrode. There was an obvious enhancement of the current response and a decreased over potential for the oxidation of CA. The interfacial electron transfer rate of CA was studied by EIS. Under optimal conditions, the CRGO displayed a linear response range of 1×10(-8) to 8×10(-4) M and the detection limit was 2×10(-9) M (S/N=3), with a sensitivity of 192.21 µA mM(-1) cm(-2) at an applied potential of +0.2V (vs. Ag/AgCl reference), which suggests that the CRGO is a promising sensing materials for the electrochemical investigation of CA. The results showed the good sensitivity, selectivity and high reproducibility of the CRGO modified electrode. Moreover, this modified electrode was further applied to investigate the CA in real samples of wine with satisfactory results.