A new method for the preparation of MgAl layered double hydroxide-copper metal-organic frameworks structures: application to electrocatalytic oxidation of formaldehyde.

In this research, we present a novel design protocol for the in-situ synthesis of MgAl layered double hydroxide-copper metal-organic frameworks (LDH-MOFs) nanocomposite based on the electrocoagulation process and chemical method. The overall goal in this project is the primary synthesis of para-phthalic acid (PTA) intercalated MgAl-LDH with Cu (II) ions to produce the paddle-wheel like Cu-(PTA) MOFs nanocrystals on/in the MgAl-LDH structure. The physicochemical properties of final product; Cu-(PTA) MOFs/MgAl-LDH, were characterized by the surface analysis and chemical identification methods (SEM, EDX, TEM, XRD, BET, FTIR, CHN, DLS, etc.). The Cu-(PTA) MOFs/MgAl-LDH nanocomposite was used to modification of the carbon paste electrode (CPE); Cu-(PTA) MOFs/MgAl-LDH/CPE. The electrochemical performance of Cu-(PTA) MOFs/MgAl-LDH/CPE was demonstrated through the utilization of electrochemical methods. The results show a stable redox behavior of the Cu (III)/Cu (II) at the surface of Cu-(PTA) MOFs/MgAl-LDH/CPE in alkaline medium (aqueous 0.1 M NaOH electrolyte). Then, the Cu-(PTA) MOFs/MgAl-LDH/CPE was used as a new electrocatalyst toward the oxidation of formaldehyde (FA). Electrochemical data show that the Cu-(PTA) MOFs/MgAl-LDH/CPE exhibits superior electrocatalytic performance on the oxidation of FA. Also the diffusion coefficient, exchange current density (J°) and mean value of catalytic rate constant (Kcat) were found to be 1.18 × 10-6 cm2 s-1, 23 mA cm-2 and 0.4537 × 104 cm3 mol-1 s-1, respectively. In general, it can be said the Cu-(PTA) MOFs/MgAl-LDHs is promising candidate for applications in direct formaldehyde fuel cells.

An amplified electrochemical sensor employing one-step synthesized nickel-copper-zinc ferrite/carboxymethyl cellulose/graphene oxide nanosheets composite for sensitive analysis of omeprazole.

In this work, a signal amplification strategy was designed by the fabrication of a highly sensitive and selective electrochemical sensor based on nickel-copper-zinc ferrite (Ni0.4Cu0.2Zn0.4Fe2O4)/carboxymethyl cellulose (CMC)/graphene oxide nanosheets (GONs) composite modified glassy carbon electrode (GCE) for determination of omeprazole (OMP). The one-step synthesized Ni0.4Cu0.2Zn0.4Fe2O4/CMC/GONs nanocomposite was characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy and X-ray diffraction techniques. Then, the Ni0.4Cu0.2Zn0.4Fe2O4/CMC/GONs/GCE was applied to study the electrochemical behavior of the OMP. Electrochemical data show that the Ni0.4Cu0.2Zn0.4Fe2O4/CMC/GONs/GCE exhibits superior electrocatalytic performance on the oxidation of OMP compared with bare GCE, GONs/GCE, CMC/GONs/GCE and MFe2O4/GCE (M = Cu, Ni and Zn including single, double and triple of metals) which can be attributed to the synergistic effects of the nanocomposite components, outstanding electrical properties of Ni0.4Cu0.2Zn0.4Fe2O4 and high conductivity of CMC/GONs as well as the further electron transport action of the nanocomposite. Under optimal conditions, the Ni0.4Cu0.2Zn0.4Fe2O4/CMC/GONs/GCE offers a high performance toward the electrodetermination of OMP with the wide linear-range responses (0.24-5 and 5-75 µM), lower detection limit (0.22 ± 0.05 µM), high sensitivity (1.1543 µA µM-1 cm-2), long-term signal stability and reproducibility (RSD = 2.54%). It should be noted that the Ni0.4Cu0.2Zn0.4Fe2O4/CMC/GONs/GCE sensor could also be used for determination of OMP in drug and biological samples, indicating its feasibility for real analysis.

3D printed solid phase microextraction scaffolds as novel tool for sample preparation; application in antifungal drugs analysis.

3D printed solid phase microextraction scaffolds as a novel sorbent were introduced for the extraction of antifungal drugs in wastewater and human plasma prior to their determination by HPLC-UV. The designed adsorbent was prepared as cubic scaffolds using fused deposition modeling (FDM) 3D printer and Polylactic acid (PLA) filament. Scaffold surface was chemically modified using alkaline ammonia solution (Alkali treatment). The application of this new design in the extraction of three antifungal drugs ketoconazole, clotrimazole and miconazole was investigated. Alkali surface modification time was optimized (0.5-5hr) and 4hr selected as the best-modification time. Morphology of the modified surface and its chemical changes were studied using Field Emission Scanning Electron Microscope (FE-SEM) and Attenuated Total Reflectance Fourier Transform Infrared spectroscopy (ATR-FTIR), respectively. Surface wettability of scaffolds was measured by Water Contact Angel (WCA) and the porosity created in the scaffolds was studied by N2 adsorption/desorption studies analysis. Analytical performance of the method, under optimum conditions (extraction time: 25 min, desorption solvent: methanol, volume of desorption solvent: 2 mL, desorption time: 10 min, solution pH: 8, solution temperature: 40 °C, salt concentration: 3 mol L-1) were obtained as 3.10 and 10.0 µg L-1 for LOD and LOQ, respectively. The calibration graphs were linear in the range of 10-150 µg L-1 and 10-100 µg L-1 for wastewater and plasma, respectively.

A sensitive nanocomposite design via carbon nanotube and silver nanoparticles: Selective probing of Emedastine Difumarate.

In this study, a novel and sensitive nanocomposite of carboxylate-functionalized multiwalled carbon nanotube (COOH-fMWCNT) and silver nanoparticles (AgNPs) was fabricated and used to modify a glassy carbon electrode (GCE) by a simple drop casting method. Modified electrode was then applied for selective determination of emedastine difumarate (EDD). The COOH-fMWCNT/AgNPs nanocomposite was characterized by electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX) and cyclic voltammetry (CV). EDD showed two oxidation peaks at 0.634 and 1.2 V on the GCE surface. CV results of COOH-fMWCNT/AgNPs/GCE displayed superior electrocatalytic performance in terms of anodic peak current of EDD when compared to AgNPs/GCE, MWCNT/GCE, and COOH-fMWCNT/GCE. The experimental conditions such as effect of pH, supporting electrolyte, effect of accumulation time and potential, scan rate were optimized for getting intense current signals of the target analyte. Under optimized conditions, COOH-fMWCNT/AgNPs/GCE showed a linear current response for oxidation of EDD in the range of 1.0 × 10-7-1.0 × 10-4 M, with a limit of detection (LOD) and quantification (LOQ) of 5.25 nM, 15.9 nM, respectively, in 0.1 M phosphate buffer solution at pH 2.0 using differential pulse adsorptive stripping voltammetry technique. The proposed method was successfully applied for determination of EDD in pharmaceutical dosage form. Satisfactory recovery percentages were achieved from eye drop sample with acceptable RSD values (less than 2 %). Furthermore, the reproducibility, stability and repeatability of the modified electrode were studied.

Application of surface molecular imprinted magnetic graphene oxide and high performance mimetic behavior of bi-metal ZnCo MOF for determination of atropine in human serum.

Herein, high performance peroxidase-like activity of zinc and cobalt bi-metal metal-organic framework (ZnCo MOF) is reported and applied for the sensitive measurement of atropine. ZnCo MOF was synthesized by the reaction of 2-methylimidazole with Zn and Co (II) cations in aqueous media. The colorimetric and fluorometric experiments were applied to investigate the catalytic activity of obtained MOF, using o-phenylenediamine (OPD) and terephthalic acid (TA) peroxidase substrates, respectively. The results demonstrated the more efficient mimetic behavior of ZnCo MOF compared with common Zn or Co MOFs. Besides, it was found that atropine hindered the catalytic action of ZnCo MOF and this effect was intensified by increasing the atropine concentration. So, it was considered to design a sensitive analytical assay for atropine detection. To assure a high specific recognition, molecularly imprinted polymer (MIP)-based extraction using magnetic graphene oxide supports was applied to extract atropine before its determination. The combination between the high specific extraction and great catalytic activity of ZnCo MOF led to the ultrasensitive and reliable determination of atropine. The best linear range of calibration graph was achieved using fluorometric detection system for 0.1-45 ng mL-1 atropine concentrations, and detection limit (3Sb/m) was 27 pg mL-1. The relative standard deviations (RSD %) for the determination of 1, and 10 ng mL-1 atropine (n = 5) were 2.13% and 3.08%, respectively. The explained fluorometric assay was examined for the measurement of atropine in biological fluids (Recoveries were in the range of 95.90-103.57%), and the results were validated by an official method.

NiCo alloy nanoparticles electrodeposited on an electrochemically reduced nitrogen-doped graphene oxide/carbon-ceramic electrode: a low cost electrocatalyst towards methanol and ethanol oxidation.

In this work, nickel-cobalt alloy nanoparticles were electrodeposited on/in an electrochemically reduced nitrogen-doped graphene oxide (ErN-GO)/carbon-ceramic electrode (CCE) and the resulting nanocomposite (NiCo/ErN-GO/CCE) was evaluated as a low cost electrocatalyst for methanol and ethanol electrooxidation. Field-emission scanning electron microscopy coupled with energy dispersive X-ray spectroscopy, X-ray diffraction, and Fourier-transform infrared spectroscopy were used for the physical characterization of the electrocatalyst. To study the electrochemical behavior and electrocatalytic activity of the prepared electrocatalyst towards the oxidation of methanol and ethanol in alkaline media, cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy were utilized. Electrochemical investigation of the introduced electrocatalysts (NiCo alloy and Ni nanoparticles alone electrodeposited on/in different substrates) indicated that NiCo/ErN-GO/CCE has highest activity and stability towards methanol (J p = 88.04 mA cm-2) and ethanol (J p = 64.23 mA cm-2) electrooxidation, which highlights its potential use as an anodic material in direct alcohol fuel cells.

Sensitive biosensing of organophosphate pesticides using enzyme mimics of magnetic ZIF-8.

Development of a sensitive detection method for the reliable screening of widely used organophosphorus (OP) toxins is a crucial request to control their side-effects. Herein, a novel fluorometric assay based on the acetylcholinesterase (AChE) inhibited enzymatic activity and the new peroxidase-like Fe3O4 nanoparticles@ZIF-8 composite (Fe3O4 NPs@ZIF-8) was developed for the determination of OPs. Magnetic Fe3O4 NPs were encapsulated into ZIF-8 and the high mimetic activity of produced composite was assessed on the oxidation of substrates. This observation was applied to the rapid detection of diazinon as a model OP compound. The sensing tool contains AChE and choline oxidase (CHO) enzymes, peroxidase colorimetric or fluorometric substrate, and Fe3O4 NPs@ZIF-8 as the catalyst. In the presence of mimic Fe3O4 NPs@ZIF-8, the generated H2O2 from the enzymatic reactions of acetylcholine is decomposed to hydroxyl radicals. The radicals oxidize the peroxidase substrates to generate a detectable signal. However, due to the inhibition effect of OPs on the enzymatic activity of AChE, lower H2O2 amounts are produced in the presence of diazinon. Using the fluorometric detection system, the generated signal is decreased proportionally by increasing diazinon concentration in the range of 0.5-500 nM. The limit of detection was obtained 0.2 nM. Consequently, the usage of high performance peroxidase-mimic Fe3O4 NPs@ZIF-8 provided a sensitive bio-assay with a potential to be applied as screening tool for toxic OP compounds. The developed assay was successfully applied for the determination of diazinon in water and fruit juices.

Ultrasensitive immunoassay of glycoprotein 125 (CA 125) in untreated human plasma samples using poly (CTAB­chitosan) doped with silver nanoparticles.

CA 125 is a Mucin glycoprotein and its concentration in human serum correlates with a woman's risk of developing ovarian cancer and also indicates response to therapy in diagnosed patients. Accurate detection of this large, complex protein in patient biofluids is of great clinical relevance. In this work, an innovative immunoassay for quantitation of CA 125 based on signal amplification strategy was proposed. In this work, Horseradish peroxidase (HRP) labeled CA 125-antibody (anti-CA 125) was immobilized onto a green and biocompatible nanocomposite containing poly cetyl trimethyl ammonium bromide (P (CTAB) as conductive matrix, chitosan (CS) as biocompatible agent and sliver nanoparticles (Ag NPs) as signal amplification element. Therefore, a novel nanocomposite film based P (CTAB-CS) and Ag NPs was exploited to develop a highly sensitive immunosensor for detection of CA 125 protein. Importantly, Ag NPs prepared by electrodeposition method which lead to compact morphology. Fully electrochemical methodology was used to prepare a new transducer on a glassy carbon surface which provided a high surface area to immobilize a high amount of the anti-CA 125. The surface morphology of electrode was characterized by high-resolution field emission scanning electron microscope (FE-SEM) and energy dispersive spectroscopy (EDS). The immunosensor was employed for the detection of CA 125 using cyclic voltammetry (CV) and differential pulse voltammetry (DPVs) techniques. Under optimized condition the calibration curve for CA 125 concentration by SWV and DPV was linear in 0.01-400 U/mL with lower limit of quantification of 0.001 U/mL. The method was successfully applied assay of the CA 125 in unprocessed human plasma samples.

Visual detection of peroxide-based explosives using novel mimetic Ag nanoparticle/ZnMOF nanocomposite.

A simple and selective colorimetric method for the detection of perilous peroxide explosives was developed using the peroxidase mimetic activity of silver nanoparticles/flake-like zinc metal-organic framework nanocomposite (Ag@ZnMOF). The synthesis of Ag@ZnMOF contained the formation of silver nanoparticles (AgNPs) inside the fine pores of Zn metal-organic framework (ZnMOF). High reactive AgNPs as well as great surface area of MOFs provided a synergetic and high improved catalytic activity for the composite which was studied as a peroxidase mimic in hydrogen peroxide (H2O2)-based oxidations. The achieved system was used for detection of Triacetone triperoxide (TATP) as one of the most hazardous peroxide explosives. TATP was decomposed in an acidic condition to generate H2O2, which was then applied to oxidize 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of the Ag@ZnMOF as a catalyst. This reaction led to the production of well-known blue colored charge transfer complex (oxTMB), which was recognized by the colorimetric technique. A linear relationship was obtained between the absorption intensity of the produced blue solution and the TATP concentration in the range of 0.4-15 mg L-1, with a detection limit of 0.1 mg L-1. A portable test kit was prepared using the same reagents for TATP measurement in real samples.

Motor Oil Classification Using Color Histograms and Pattern Recognition Techniques.

Motor oil classification is important for quality control and the identification of oil adulteration. In this work, we propose a simple, rapid, inexpensive and nondestructive approach based on image analysis and pattern recognition techniques for the classification of nine different types of motor oils according to their corresponding color histograms. For this, we applied color histogram in different color spaces such as red green blue (RGB), grayscale, and hue saturation intensity (HSI) in order to extract features that can help with the classification procedure. These color histograms and their combinations were used as input for model development and then were statistically evaluated by using linear discriminant analysis (LDA), quadratic discriminant analysis (QDA), and support vector machine (SVM) techniques. Here, two common solutions for solving a multiclass classification problem were applied: (1) transformation to binary classification problem using a one-against-all (OAA) approach and (2) extension from binary classifiers to a single globally optimized multilabel classification model. In the OAA strategy, LDA, QDA, and SVM reached up to 97% in terms of accuracy, sensitivity, and specificity for both the training and test sets. In extension from binary case, despite good performances by the SVM classification model, QDA and LDA provided better results up to 92% for RGB-grayscale-HSI color histograms and up to 93% for the HSI color map, respectively. In order to reduce the numbers of independent variables for modeling, a principle component analysis algorithm was used. Our results suggest that the proposed method is promising for the identification and classification of different types of motor oils.

Mimetic Ag nanoparticle/Zn-based MOF nanocomposite (AgNPs@ZnMOF) capped with molecularly imprinted polymer for the selective detection of patulin.

Here, Ag nanoparticle/flake-like Zn-based MOF nanocomposite (AgNPs@ZnMOF) with great peroxidase-like activity was applied as an efficient support for molecularly imprinted polymer (MIP) and successfully used for selective determination of patulin. AgNPs@ZnMOF was simply synthesized by creating Ag nanoparticles (Ag NPs) inside the nano-pores of flake-like (Zn)MOF. The high surface area of MOF remarkably improved the catalytic activity of Ag NPs which was assessed by fluorometric, colorimetric and electrochemical techniques. Furthermore, it was observed that patulin could strangely reduce the catalytic activity of AgNPs@ZnMOF, probably due to its electron capturing features. This outcome was the motivation to design an assay for patulin detection. In order to make a selective interaction with patulin molecules, MIP layer was created on the surface of AgNPs@ZnMOF by co-polymerization reaction of 3-aminopropyl triethoxysilane (APTES) and tetraethyl orthosilicate (TEOS) monomers wherein patulin was applied as template agent. Combination between the selective identifying feature of MIP and outstanding peroxidase-like activity of novel AgNPs@ZnMOF nanocomposite as well as the sensitive fluorescence detection system was led to the design of a reliable probe for patulin. The prepared MIP-capped AgNPs@ZnMOF catalyzed the H2O2-terephthalic acid reaction which produced a high florescent product. In the presence of patulin, the fluorescence intensity was decreased proportional to its concentration in the range of 0.1-10µmolL-1 with a detection limit of 0.06µmolL-1. The proposed method was able to selectively measure patulin in a complex media without significant interfering effects from analogue compounds.

Synthesis and characterization of graphene quantum dots/CoNiAl-layered double-hydroxide nanocomposite: Application as a glucose sensor.

In the present work, a novel nanocomposite based on the graphene quantum dots and CoNiAl-layered double-hydroxide was successfully synthesized by co-precipitation method. To achieve the morphological, structural and compositional information, the resulted nanocomposite was characterized by scanning electron microscopy X-ray diffraction, thermal gravimetric analysis, Fourier transform infrared spectroscopy, and photoluminescence. Then, the nanocomposite was used as a modifier to fabricate a modified carbon paste electrode as a non-enzymatic sensor for glucose determination. Electrochemical behavior and determination of glucose at the nanocomposite modified carbon paste electrode were investigated by cyclic voltammetry and chronoamperometry methods, respectively. The prepared sensor offered good electrocatalytic properties, fast response time, high reproducibility and stability. At the optimum conditions, the constructed sensor exhibits wide linear range; 0.01-14.0 mM with a detection limit of 6 µM (S/N = 3) and high sensitivity of 48.717 µAmM-1. Finally, the sensor was successfully applied to determine the glucose in real samples which demonstrated its applicability.

A novel and facile synthesis of carbon quantum dots via salep hydrothermal treatment as the silver nanoparticles support: Application to electroanalytical determination of H2O2 in fetal bovine serum.

A simple, low-cost, and green process was used for the synthesis of carbon quantum dots (CQDs) through the hydrothermal treatment of salep as a novel bio-polymeric carbon source in presence of only pure water. The silver nanoparticles (AgNPs) were embedded on the surface of CQDs by ultra-violate (UV) irradiation to the CQDs and silver nitrate mixture solution. The as-synthesized CQDs and AgNPs decorated CQDs nanohybrid (AgNPs/CQDs) were characterized by UV-vis and photoluminescence spectroscopy, Fourier transform-infrared spectroscopy, transmission electron microscopy, atomic force microcopy, X-ray diffraction, and field emission scanning electron microscopy. Then, the AgNPs/CQDs nanohybrid was casted on the glassy carbon electrode in order to prepare an amperometric hydrogen peroxide (H2O2) sensor. The electrochemical investigations show that the AgNPs/CQDs nanohybrid possesses an excellent performance toward the H2O2 reduction. In the optimum condition, the linear range of H2O2 determination was achieved from 0.2 to 27.0µM with high sensitivity (1.5µA/µM) and the limit of detection was obtained about 80nM (S/N=3). Finally, the prepared nanohybrid modified electrode was effectively applied to the H2O2 detection in the disinfected fetal bovine serum samples, and the recovery was obtained about 98%. The achieved results indicate that the AgNPs/CQDs nanohybrid with high reproducibility, repeatability, and stability has a favorable capability in electrochemical sensors improvement.

Simultaneous determination of codeine and caffeine using single-walled carbon nanotubes modified carbon-ceramic electrode.

In the present paper, the simultaneous determination of codeine (CO) and caffeine (CF) is described by the use of single-walled carbon nanotubes modified carbon-ceramic electrode (SWCNT/CCE); prepared via a simple and rapid method. The results show that the SWCNT/CCE exhibits excellent electrochemical catalytic activity toward the oxidation of these compounds with respect to the bare CCE and offers two anodic peaks at 1.05 and 1.38 V vs. saturated calomel electrode for oxidation of CO and CF, respectively. Differential pulse voltammetry was used for simultaneous determination of CO and CF at micromolar concentration level. In the optimum conditions, it is found that the calibration graphs for CO and CF are linear in the concentration ranges 0.2-230 and 0.4-300 µM with detection limits of 0.11 and 0.25 µM for CO and CF, respectively. The SWCNT/CCE presents good stability, reproducibility, and repeatability and the proposed method has been successfully applied for determination of CO and CF in some pharmaceutical, drinking and biological samples with high recovery rate.

Differential pulse voltammetric simultaneous determination of acetaminophen and ascorbic acid using single-walled carbon nanotube-modified carbon-ceramic electrode.

Single-walled carbon nanotube-modified carbon-ceramic electrode (SWCNT/CCE) was employed for the simultaneous determination of acetaminophen (APAP) and ascorbic acid (AA). The SWCNT/CCE displayed excellent electrochemical catalytic activities toward APAP and AA oxidation compared with bare CCE. In the differential pulse voltammetry technique, both AA and APAP gave sensitive oxidation peaks at -62 and 302 mV versus saturated calomel electrode, respectively. Under the optimized experimental conditions, APAP and AA gave linear responses over ranges of 0.2 to 150.0 µM (R(2)=0.998) and 5.0 to 700.0 µM (R(2)=0.992), respectively. The lower detection limits were found to be 0.12 µM for APAP and 3.0 µM for AA. The investigated method showed good stability, reproducibility, and repeatability as well as high recovery in pharmaceutical and biological samples.