Achieving Long Cycle Life of Zn-Ion Batteries through Three-Dimensional Copper Foam.

Metallic zinc anodes in aqueous zinc-ion batteries (ZIBs) suffer from dendritic growth, low Coulombic efficiency, and high polarization during cycling. To mitigate these challenges, current collectors based on three-dimensional (3D) commercial copper foam (CCuF) are generally preferred. However, their utilization is constrained by their thickness, low electroactive surface area, and increased manufacturing expenses. In this study, the synthesis of cost-effective current collectors with exceptionally large surface areas designed for ZIBs that can be cycled hundreds of times is reported. A zinc-coated CuF anode (Zn/CuF) was prepared with a 3D porous CuF current collector produced by the dynamic hydrogen bubble template (DHBT) method. Electrochemically generated copper foam could be obtained within seconds while offering a thickness as low as 30-40 µm (CuF5 achieved a thickness of ∼38 µm in 5 s) via the DHBT method. The excellent electrical conductivity and open pore structure of the 3D porous copper scaffold ensured the uniform deposition/stripping of Zn during cycling. During the 500 h Zn deposition/stripping process, the as-synthesized CuF5 current collector offered fast electrochemical kinetics and low polarization as well as a relatively high average Coulombic efficiency of 99% (at a current density of 5 mA cm-2 and a capacity of 1 mAh cm-2). Furthermore, the symmetric cell exhibited low voltage polarization and a stable voltage profile for 1000 h at a current density of 0.1 mA cm-2. In addition, full cells containing the Zn/CuF anode coupled with an as-synthesized α-MnO2 nanoneedle cathode in aqueous electrolyte were also prepared. Capacities of 266 mAh g-1 at 0.1 A g-1 and 94 mAh g-1 at 2 A g-1 were achieved after 200 charge/discharge cycles with a stable Coulombic efficiency value close to 99.9%.

Electrochemical aptasensors for pathogenic detection toward point-of-care diagnostics.

A biosensor system refers to a biomedical device, which detects biological, chemical, or biochemical components by converting those signals to an electrical signal by utilizing and uniting physical or chemical transducer with biorecognition elements. An electrochemical biosensor is generally based on the reaction of either production or consumption of electrons under a three-electrode system. Biosensor systems are exploited in a wide range of areas, such as medicine, agriculture, husbandry, food, industry, environment protection, quality control, waste disposal, and the military. Pathogenic infections are the third leading cause of death worldwide after cardiovascular diseases and cancer. Therefore, there is an urgent need for effective diagnostic tools to control food, water, and soil contamination result in protecting human life and health. Aptamers are peptide or oligonucleotide-based molecules that show very high affinity to their targets that are produced from large pools of random amino acid or oligonucleotide sequences. Generally, aptamers have been utilized for fundamental sciences and clinical implementations for their target-specific affinity and have been intensely exploited for different kinds of biosensor applications for approximately 30 years. The convergence of aptamers with biosensor systems enabled the construction of voltammetric, amperometric, and impedimetric biosensors for the detection of specific pathogens. In this review, electrochemical aptamer biosensors were evaluated by discussing the definition, types, and production techniques of aptamers, the advantages of aptamers as a biological recognition element against their alternatives, and a wide range of aptasensor examples from literature in the detection of specific pathogens.

A novel comparative study for electrochemical urea biosensor design: Effect of different ferrite nanoparticles (MFe2O4, M: Cu, Co, Ni, Zn) in urease immobilized composite system.

A new enzymatic electrochemical biosensor has been developed with the PANI/Nafion composite system containing ferrite nanoparticles with four different transition metals. The ferrite nanoparticles containing copper, cobalt, nickel, and zinc metals were synthesized by the co-precipitation method and their surfaces were modified with tetraethoxysilane and (3-aminopropyl) triethoxysilane to obtain -NH2 function in order to develop the purposed sensing system. The modified and unmodified ferrite nanoparticles were characterized by physically, chemically, and morphologically. Ferrite nanoparticles with suitable for enzyme immobilization were integrated on the GCE surface and covered with PANI/Nafion. According toelectrochemical measurements, it was determined that copper ferrite nanoparticles, which have the lowest bandgap value, significantly increased the biosensor performance. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were used to monitor biosensor production and evaluate its performance. A detection limit of 0.17 µM and a wide linear range of 0.5-45.0 µM were obtained for the urea detection with the DPV method with the sensing system (Nf/PANI/CuF/Urs). The biosensor has been successfully applied to soil and milk samples with high accuracy. In addition, it has been determined that the proposed method has good reproducibility, selectivity, and stability.

Direct and selective determination of p-coumaric acid in food samples via layered Nb4AlC3-MAX phase.

Phenolic compounds that are naturally found in food samples are not only an important part of the human diet but also useful bioactive substances for health. Among these, para-coumaric acid (p-CA) has antibacterial and antioxidant properties and is used in many industrial processes. In this study, the novel MAX-phase material, Nb4AlC3, was successfully prepared and characterized in detail with various spectroscopic, microscopic and thermal techniques. The sensor performance of Nb4AlC3 modified glassy carbon electrode (Nb4AlC3@GCE) was evaluated and analytical parameters were calculated. Experimental conditions such as pH and amount of modifier were optimized with differential pulse voltammetry (DPV) measurements. The real samples analyses of lemon, apple and pomegranate were applied for determination of p-CA with Nb4AlC3@GCE sensing system under the optimized conditions. The accuracy was evaluated by spike/recovery and high-performance liquid chromatography analysis, which accounted for high accuracy of the Nb4AlC3@GCE sensing system. The limit of detection, limit of quantification, linear working range and relative standard deviation (%) of the Nb4AlC3@GCE sensing system were determined as 0.28 and 0.85 µmol/L, 0.8-80.0 µmol/L, 3.17 %, respectively. The results showed that the proposed sensing system has the high precision at lower concentration of p-CA.

Ultrasensitive electrochemical sensor for detection of rutin antioxidant by layered Ti3Al0.5Cu0.5C2 MAX phase.

MAX phases have attracted great attention due to unique features such as thermal and electrical conductivity, easy fabrication, heat resistant, and lightweight. In this study, an easy and green method was employed to successfully develop a Ti3Al0.5Cu0.5C2 MAX phase structure, and a Ti3Al0.5Cu0.5C2 based glassy carbon electrode (GCE) was applied for the electrochemical determination of rutin antioxidants in mandarin and kiwi samples. The developed Ti3Al0.5Cu0.5C2 MAX phase was characterized by different techniques such as X-ray photoelectron spectroscopy (XPS), thermogravimetry and differential scanning calorimetry (TG-DSC), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), diffuse reflectance spectroscopy (DRS), transmission electron microscopy (TEM), and scanning electron microscopy (SEM) to obtain information on the structural and morphological properties. Electrochemical methods such as cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were employed for the determination of rutin using Ti3Al0.5Cu0.5C2/GCE. The GCE modified with Ti3Al0.5Cu0.5C2 demonstrated amplified electrochemical response (ca. 4.25 times) in comparison to the bare GCE towards rutin, and exhibited ultra-sensitivity and selectivity in the presence of other interfering antioxidants. Under the optimum conditions, good linearity in the range of 0.02-50.00 µmol L-1 was obtained for rutin analysis by the Ti3Al0.5Cu0.5C2-based sensor with a limit of detection (LOD, 3σ/K) as low as 0.015 µmol L-1. The fabricated Ti3Al0.5Cu0.5C2 MAX phase was applied to determine trace levels of rutin in mandarin and kiwi samples with validation by high-performance liquid chromatography (HPLC), thus highlighting its potential for the electrochemical determination of small molecules in the agricultural field.

An electrochemical sensor for detection of trace-level endocrine disruptor bisphenol A using Mo2Ti2AlC3 MAX phase/MWCNT composite modified electrode.

Bisphenol A (BPA) is an industrially preferred material for the production of plastic and polycarbonate as well as a used material for the interior of food and beverage cans. In this study, synthesis and electrochemical sensor application of Mo2Ti2AlC3/MWCNT (multi-walled carbon nanotube) nanocomposite for BPA sensing was evaluated. Mo2Ti2AlC3 was used as MAX phase material in the design of the sensor, and MWCNT was preferred to increase conductivity and sensitivity. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were used to determine Mo2Ti2AlC3/MWCNT nanocomposite's electrochemical sensor performances which had LOD of 2.7 nM and LOQ of 8.91 nM in the linear working range of 0.01-8.50 µM calculated from DPV. The composite showed a single oxidation step against BPA which is diffusion-controlled and irreversible. The sensor was successfully applied for the determination of BPA in milk pack, plastic bottle, and can with recoveries ranging from 95.67% to 100.60%. In addition, sensor performance was examined through selectivity, repeatability, and reusability studies. HPLC as a standard determination method was carried out for accuracy of the voltammetric determination method in the real samples. The developed sensor could be applied to different areas from industry quality control to clinical analysis for the detection of BPA.

A synergetic and sensitive physostigmine pesticide sensor using copper complex of 3D zinc (II) phthalocyanine-SWCNT hybrid material.

2,3,9,10,16,17,23,24-Octakis (4-methyl-2,6-bis((prop-2-yn-1-yloxy)methyl)phenoxy) phthalocyaninato zinc(II) (Pc) bearing sixteen terminal ethynyl groups was synthesized and attached to SWCNT (Single-walled carbon nanotube) covalently to obtain three dimensional porous hybrid material (SWCNT-Pc 3D) and its copper complex (Cu-SWCNT-Pc 3D). The structural characterization and electrochemical sensor features of the Cu-SWCNT-Pc hybrid towards to physostigmine pesticide were performed. A fast, direct and suitable determination method for physostigmine detection was offered. The designed sensor, Cu-SWCNT-Pc 3D/GCE (glassy carbon electrode) shows sensitivity ca 1.8, 4.3 and 2.8 times more than that of SWCNT/GCE, SWCNT-Pc-noncovalent/GCE and SWCNT-Pc 3D/GCE in terms of peak heights while bare and Pc/GCE had almost no voltammetric response to 2 µM physostigmine in PBS at a pH of 7.0. The limit of detection and quantification of physostigmine determination with Cu-SWCNT-Pc 3D/GCE were found to be 53 and 177 nM in the range of 0.1-4.8 µM, respectively. This study demonstrated that the modification of the GCE with Cu-SWCNT-Pc 3D as an electrochemical sensor was acted as catalytic role toward physostigmine presence of other interfering pesticides as high sensitivity and selectivity. The electrochemical determination of physostigmine in real samples was performed under the optimized conditions, also accuracy of the electrochemical determination method was evaluated with HPLC as a standard determination method.

Sensitive, simple and fast voltammetric determination of pesticides in juice samples by novel BODIPY-phthalocyanine-SWCNT hybrid platform.

The present work describes the first synthesis of novel asymmetric zinc (II) phthalocyanine (ZnPc) including three boron dipyrromethene (BODIPY) and one ethyloxy azido moieties. Moreover, single walled carbon nanotube (SWCNT) surface was functionalized by this ZnPc containing BODIPY; using the azide-alkyne Huisgen cycloaddition (Click) reaction to obtain SWCNT-ZnPc hybrid material. Structural, thermal and morphological characterizations of both ZnPc and SWCNT-ZnPc hybrid were carried out in-depth by spectroscopic, thermal and microscopic techniques. In this study, the synthesized SWCNT-ZnPc material was decorated on composite glassy carbon electrode (GCE) by means of an easy and a practical drop cast method. The modified electrode was tested as a non-enzymatic electrochemical sensor in various common pesticides such as methyl parathion, deltamethrin, chlorpyrifos and spinosad. Electrochemical behavior of non-enzymatic electrode (GCE/SWCNT-ZnPc) was determined via cyclic voltammetry and differential pulse voltammetry. The non-enzymatic sensor demonstrated high selectivity for methyl parathion in a wide linear range (2.45 nM-4.0 × 10-8 M), low limit of detection value (1.49 nM) and high sensitivity (0.1847 µA nM-1). Also, the developing non-enzymatic sensor exhibited good repeatability (RSD = 2.3% for 10 electrodes) and stability (85.30% for 30 days). Validation guidelines by HPLC and statistical analysis showed that the proposed voltammetric method were precise, accurate, sensitive, and can be used for the routine quality control of methyl parathion determination in juice samples.

Fluorescence determination of trace level of cadmium with pyrene modified nanocrystalline cellulose in food and soil samples.

Cadmium is one of the most toxic metal that accumulates in the human body via food chain, industrial/agricultural activites. It also has negative effects in organs such as the brain, liver and central nervous system. Therefore, International Agency for Research on Cancer is classified cadmium as "carcinogenic to humans" (group 1). In this work, novel pyrene modified nanocrystalline cellulose (NP-1) was designed as a fluorescence sensor for selective determination of Cd2+ in food and soil samples. FTIR, UV-Vis, SEM, TEM and TGA were used for structural, morphological characterizations and thermal properties of NP-1. The experimental conditions such as selectivity, pH, sensor concentration, photostability, time and interaction mechanism were examined and optimized. The LOD was determined as 0.09 µM (10.70 µg/L) which was lower than WHO's permissible limit of cadmium in plant with 0.10-60.00 µM linear working range. Validation of the present method was performed by spike/recovery test and ICP-MS, then fluorescence determination of Cd2+ in food and soil samples was succesfully applied. The results indicated that the proposed method based on "turn-on" fluorescence of NP-1 was a simple, sensitive and reliable for rapid determination of Cd2+ in real samples with high applicability and stability.

A Hybrid Nanomaterial Based on Single Walled Carbon Nanotubes Cross-Linked via Axially Substituted Silicon (IV) Phthalocyanine for Chemiresistive Sensors.

In this work, the novel hybrid nanomaterial SWCNT/SiPc made of single walled carbon nanotubes (SWCNT) cross-linked via axially substituted silicon (IV) phthalocyanine (SiPc) was studied as the active layer of chemiresistive layers for the detection of ammonia and hydrogen. SWCNT/SiPc is the first example of a carbon-based nanomaterial in which an axially substituted phthalocyanine derivative is used as a linker. The prepared hybrid material was characterized by spectroscopic methods, thermogravimetry, scanning and transmission electron microscopies. The layers of the prepared hybrid were tested as sensors toward ammonia and hydrogen by a chemiresistive method at different temperatures and relative humidity as well as in the presence of interfering gases like carbon dioxide, hydrogen sulfide and volatile organic vapors. The hybrid layers exhibited the completely reversible sensor response to both gases at room temperature; the recovery time was 100-200 s for NH3 and 50-120 s in the case of H2 depending on the gas concentrations. At the relative humidity (RH) of 20%, the sensor response was almost the same as that measured at RH 5%, whereas the further increase of RH led to its 2-3 fold decrease. It was demonstrated that the SWCNT/SiPc layers can be successfully used for the detection of both NH3 and H2 in the presence of CO2. On the contrary, H2S was found to be an interfering gas for the NH3 detection.

Highly selective and ultra-sensitive electrochemical sensor behavior of 3D SWCNT-BODIPY hybrid material for eserine detection.

In this work, 4,4-difluoro-8-(4-hydroxyphenyl)- 2,6-diethynly-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene (BODIPY) having double terminal ethynyl groups was synthesized. Three dimensional single walled carbon nanotube (SWCNT)-BODIPY hybrid material (3D SWCNT-BODIPY) was synthesized by the reaction of BODIPY bearing double terminal ethynyl groups with azido containing SWCNTs via "Click" reaction. The structural properties and electrochemical detection of eserine (a pesticide) on BODIPY functionalized SWCNTs as a three dimensional (3D) material were investigated. A glassy carbon electrode (GCE) was modified by 3D SWCNT-BODIPY hybrid material for the determination of eserine in the range of 0.25-2.25 µM. In the study by the square wave voltammetry (SWV), the bare GCE showed no response, while the new peak at - 0.6 V appeared in the case of the modified electrode. The detection limit and quantification were determined as 160 nM and 528 nM for eserine on the 3D SWCNT-BODIPY modified electrode, respectively. Eserine was also determined with a standard addition method in different brands of orange juices, and the recovery of eserine was obtained to be in the range of 102.09% and 103.22%. This study clearly indicates that the 3D SWCNT-BODIPY modified electrode tested as an electrochemical sensor was found to be highly selective and sensitive to eserine.

Synthesis and organic solar cell performance of BODIPY and coumarin functionalized SWCNTs or graphene oxide nanomaterials.

The synthesis and characterization of new hybrid materials based on reduced graphene oxide (rGO) or single walled carbon nanotubes (SWCNTs) covalently functionalized by 4,4'-difluoro-8-(4-propynyloxy)-phenyl-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene (BODIPY) (2) or 7-(prop-2-yn-1-yloxy)-3-(3',4',5'-trimethoxyphenyl)-coumarin (4) as light harvesting groups have been described. The organic solar cell performances of these novel nanomaterials in P3HT:PCBM blends were investigated. These covalently bonded hybrid materials (reduced graphene oxide:BODIPY (GB), reduced graphene oxide:Coumarin (GC), SWCNTs:BODIPY (CB) and SWCNTs:Coumarin (CC)) were prepared by an azide-alkyne Huisgen cycloaddition (click) reaction between the azide bearing SWCNTs or rGO and terminal ethynyl functionalized BODIPY (2) or coumarin (4) derivatives. The formation of novel nanomaterials was confirmed by FT-IR, UV-Vis and Raman spectroscopies and thermogravimetric analysis. The best performance on P3HT:PCBM organic solar cells was produced by SWCNTs:Coumarin (CC) hybrids which were coated on an indium tin oxide coated polyethylene terephthalate film (ITO-PET). The reference device based on the P3HT:PCBM blend without CC showed a power conversion efficiency (PCE) of 1.16%, an FF of 35% and a short-circuit current density (Jsc) of 5.51 mA cm-2. The reference device with CC hybrids within the P3HT:PCBM blend increased the values significantly to 1.62% for PCE, 40% for FF and 6.8 mA cm-2 for Jsc.