Cu-nanoparticles@ graphene nanocomposite: A robust and efficient nanocomposite for micro-solid phase extraction of trace aflatoxins in different foodstuffs.

Cu-nanoparticles-immobilized graphene (Cu@G) nanocomposite was fabricated in this study by reducing Cu(II) ions in the presence of graphene oxide using a simple chemical reduction step. Cu@G nanocomposite was applied as a sorbent for the SPE of four aflatoxins (AFs). A reusable syringe was filled with the fabricated nanocomposite and used as a sorbent for the micro-solid phase extraction of four AFs (AFB1, AFB2, AFG1, AFG2). The impact of different analytical factors was fully investigated and optimized. Excellent recoveries, ranging from 92.0 to 108.5 %, were detected when evaluating target AFs in samples of rice, maize, and pistachio. The LOD, LOQ, and linear ranges were attained under optimal circumstances in the ranges of 0.0062 µg kg-1, 0.0192 µg kg-1, and 0.0-20 µg kg-1, respectively. The discovered approach provided the dual benefits of a high enrichment capability of Cu-nanoparticles via AFs complexation and a huge porosity of graphene sheets.

Facile adsorption-electroflotation method for the removal of heavy metal ions from water using carbon nanomaterials.

Due to the none-biodegradable and carcinogenic nature of toxic metal ions, a novel sorption-electroflotation method was developed using carbon nanomaterials. The metal ions removed were Ni(II), Co(II), Zn(II), Fe(II), and Cu(II) using carbon nanotubes (CNTs) and carbon nanoshells (CNSs). The porous structure, morphology, composition, and surface properties of carbon nanomaterials, viz. the presence and number of functional groups are characterized by methods of low-temperature nitrogen adsorption, scanning electron microscopy, Boem, X-ray photoelectron spectroscopy. The surface of the materials was rough with varied particle sizes. Regardless of the sorbed ion and the nature of the nanomaterial, the Langmuir, Temkin, Dubinin-Radushkevich, and Flory-Higgins models were applied to the data. The maximum sorption removal on CNTs were 15.0-69.0, 36.0-75.0, 33.0-72.0, 18.0-70.0, 29.0-69.0% for Fe(II), Zn(II), Co(II), Cu(II), and Ni(II) while these values on CNSs were 19.0-53, 23.0-58.0, 30.0-79.0, 12.0-46.0, and 41.0-86%. But after simultaneous sorption-electroflotation, the percentage removal was 99.0, 97.0, 95.0, 99.0, and 52% for these metal ions, indicating an excellent combination of sorption-electro flotation. The method is highly beneficial to work in varied pH ranges as sorption and electroflotation gave the best results in acidic and basic mediums. The method is very effective, efficient, and inexpensive and can be used for the removal of the reported metal ions in water.

Seawater Splitting for Hydrogen Generation Using Zirconium and Its Niobium Alloy under Gamma Radiation.

Hydrogen production is produced for future green energy. The radiation-chemical yield for seawater without a catalyst, with Zr, and with Zr1%Nb (Zr = 99% Nb = 1%) were (G(H2) = 0.81, 307.1, and 437.4 molecules/100 eV, respectively. The radiation-thermal water decomposition increased in γ-radiation of the Zr1%Nb + SW system with increasing temperature. At T = 1273 K, it prevails over radiation processes. During the radiation and heat radiation heterogeneous procedures in the Zr1% Nb + SW system, the production of surface energetic sites and secondary electrons accelerated the accumulation of molecular hydrogen and Zr1%Nb oxidation. Thermal radiation and thermal processes caused the metal phase to collect thermal surface energetic sites for water breakdown and Zr 1%Nb oxidation starting at T = 573 K.

An Ionic-Liquid-Imprinted Nanocomposite Adsorbent: Simulation, Kinetics and Thermodynamic Studies of Triclosan Endocrine Disturbing Water Contaminant Removal.

The presence of triclosan in water is toxic to human beings, hazardous to the environment and creates side effects and problems because this is an endocrine-disturbing water pollutant. Therefore, there is a great need for the separation of this notorious water pollutant at an effective, economic and eco-friendly level. The interface sorption was achieved on synthesized ionic liquid-based nanocomposites. An N-methyl butyl imidazolium bromide ionic liquid copper oxide nanocomposite was prepared using green methods and characterized by using proper spectroscopic methods. The nanocomposite was used to remove triclosan in water with the best conditions of time 30 min, concentration 100 µg/L, pH 8.0, dose 1.0 g/L and temperature 25 °C, with 90.2 µg/g removal capacity. The results obeyed Langmuir, Temkin and D-Rs isotherms with a first-order kinetic and liquid-film-diffusion kinetic model. The positive entropy value was 0.47 kJ/mol K, while the negative value of enthalpy was -0.11 kJ/mol. The negative values of free energy were -53.18, -74.17 and -76.14 kJ/mol at 20, 25 and 30 °C. These values confirmed exothermic and spontaneous sorption of triclosan. The combined effects of 3D parameters were also discussed. The supramolecular model was developed by simulation and chemical studies and suggested electrovalent bonding between triclosan and N-methyl butyl imidazolium bromide ionic liquid. Finally, this method is assumed as valuable for the elimination of triclosan in water.

Polyaniline Modified CNTs and Graphene Nanocomposite for Removal of Lead and Zinc Metal Ions: Kinetics, Thermodynamics and Desorption Studies.

A novel polyaniline-modified CNT and graphene-based nanocomposite (2.32-7.34 nm) was prepared and characterized by spectroscopic methods. The specific surface area was 176 m2/g with 0.232 cm3/g as the specific pore volume. The nanocomposite was used to remove zinc and lead metal ions from water; showing a high removal capacity of 346 and 581 mg/g at pH 6.5. The data followed pseudo-second-order, intraparticle diffusion and Elovich models. Besides this, the experimental values obeyed Langmuir and Temkin isotherms. The results confirmed that the removal of lead and zinc ions occurred in a mixed mode, that is, diffusion absorption and ion exchange between the heterogeneous surface of the sorbent containing active adsorption centers and the solution containing metal ions. The enthalpy values were 149.9 and 158.6 J.mol-1K-1 for zinc and lead metal ions. The negative values of free energies were in the range of -4.97 to -26.3 kJ/mol. These values indicated an endothermic spontaneous removal of metal ions from water. The reported method is useful to remove the zinc and lead metal ions in any water body due to the high removal capacity of nanocomposite at natural pH of 6.5. Moreover, a low dose of 0.005 g per 30 mL made this method economical. Furthermore, a low contact time of 15 min made this method applicable to the removal of the reported metal ions from water in a short time. Briefly, the reported method is highly economical, nature-friendly and fast and can be used to remove the reported metal ions from any water resource.

Hydrothermal synthesis of Mn3O4 nanorods modified indium tin oxide electrode as an efficient nanocatalyst towards direct urea electrooxidation.

Control fabrication of metal-oxide nanocatalysts for electrochemical reactions has received considerable research attention. Here, manganese oxide (Mn3O4) nanorods modified indium tin oxide (ITO) electrodes were prepared based on the in-situ one-step hydrothermal methods. The nanorods were well characterized using field emission scanning electron microscopy, Fourier transform infrared, and X-ray diffraction spectroscopy. The results showed the formation of pure crystalline Mn3O4 nanorods with a length of approximately 1.4 µm and a thickness of approximately 100 ± 30 nm. The Mn3O4 nanorod-modified ITO electrodes were used for accelerating urea electrochemical oxidation at room temperature using cyclic and square wave voltammetry techniques. The results indicated that the modified electrode demonstrated excellent electrocatalytic performance toward urea electrooxidation in an alkaline medium over concentrations ranging from 0.2 to 4 mol/L. The modified electrode showed high durability, attaining more than 88% of its baseline performance after 150 cycles; furthermore, the chronoamperometry technique demonstrated high stability. Thus, the Mn3O4 nanorod-modified ITO electrode is a promising anode for direct urea fuel cell applications.

Synthesis of gold nanoparticles@reduced porous graphene-modified ITO electrode for spectroelectrochemical detection of SARS-CoV-2 spike protein.

Here, we reported the synthesis of reduced porous graphene oxide (rPGO) decorated with gold nanoparticles (Au NPs) to modify the ITO electrode. Then we used this highly uniform Au NPs@rPGO modified ITO electrode as a surface-enhanced Raman spectroscopy-active surface and a working electrode. The uses of the Au nanoparticles and porous graphene enhance the Raman signals and the electrochemical conductivity. COVID-19 protein-based biosensor was developed based on immobilization of anti-COVID-19 antibodies onto the modified electrode and its uses as a probe for capturing the COVID-19 protein. The developed biosensor showed the capability of monitoring the COVID-19 protein within a concentration range from 100 nmol/L to 1 pmol/L with a limit of detection (LOD) of 75 fmol/L. Furthermore, COVID-19 protein was detected based on electrochemical techniques within a concentration range from 100 nmol/L to 500 fmol/L that showed a LOD of 39.5 fmol/L. Finally, three concentrations of COVID-19 protein spiked in human serum were investigated. Thus, the present sensor showed high efficiency towards the detection of COVID-19.

Synergistic effect of Cu-nanoparticles and ß-cyclodextrin functionalized reduced graphene oxide nanocomposite on the adsorptive remediation of tetracycline antibiotics.

Pollution by tetracyclines antibiotics has a great potential risk on human and animal health even at trace levels. Copper nanoparticles immobilized-ß-cyclodextrin functionalized reduced graphene oxide (Cu/ß-CD/rGO) were successfully prepared as an efficient extractor of tetracycline (TC), oxytetracycline (OTC) and doxycycline (DC) antibiotics from different environmental water samples. Tetracyclines (TCs) are strongly deposited in the matrix of Cu/ß-CD/rGO nanocomposite via surface complexation with the Cu-nanoparticles besides the formation of inclusion complexes with ß-cyclodextrin and π-π interaction of reduced graphene oxide. The novel nanocomposite was characterized by HRSEM, TEM, TGA, FT-IR, XPS, and XRD. The optimization of variables such as the pH, contact time, ionic strength and TC concentration were successfully analyzed. The maximum adsorption capacity (qm) of Cu/ß-CD/rGO calculated from the Langmuir isotherm was 403.2 mg.g-1 for TC, 476.2 mg.g-1 for OTC and 434.8 mg.g-1 for DC at 298 K. The removal efficiency was decreased by 3.7% after five adsorption-desorption cycles. The Cu/ß-CD/rGO nanocomposite was applied for removing TCs from tap water and the Nile River water samples. The novel nanocomposite demonstrated fast and highly efficient removing performance for different TCs with low levels and large sample volume.

Electrochemical Microbiosensor for Detecting COVID-19 in a Patient Sample Based on Gold Microcuboids Pattern.

As continues increasing the COVID-19 infections, there is an urgent need for developing fast, simple, selective, and accurate COVID-19 biosensors. A highly uniform gold (Au) microcuboid pattern was used as a microelectrode that allowed monitoring a small analyte. The electrochemical biosensor was used to monitor the COVID-19 S protein within a concentration range from 100 to 5 pmol L-1; it showed a lower detection limit of 276 fmol L-1. Finally, the developed COVID-19 sensor was used to detect a positive sample from a human patient obtained through a nasal swab; the results were confirmed using the PCR technique. The results showed that the SWV technique showed high sensitivity towards detecting COVID-19 and good efficiency for detecting COVID-19 in a positive human sample.

A 2D Graphitic-Polytriaminopyrimidine (g-PTAP)/Poly(ether-block-amide) Mixed Matrix Membrane for CO2 Separation.

Poly(ether-block-amide)/g-PTAP mixed matrix membranes (MMMs) were developed by incorporating different wt.% (1-10%) of a novel 2D g-PTAP nanofiller and its effects on membrane structure and gas permeability were studied. The novel 2D material g-PTAP was synthesized and characterized by various analytical techniques including field-emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and Raman spectroscopy. The fabricated MMMs were investigated to study the interaction and compatibility between Pebax and g-PTAP. The MMMs showed an effective integration of g-PTAP nanofiller into the Pebax matrix without affecting its thermal stability. Gas permeation experiments with MMMs showed improved CO2 permeability and selectivity (CO2 /N2 ) upon incorporation of g-PTAP in the Pebax polymer matrix. The maximum CO2 permeability enhancement from 82.3 to 154.6 Barrer with highest CO2 /N2 selectivity from 49.5 to 83.5 were found with 2.5 wt.% of nanofiller compared to neat Pebax membranes.

Layer-by-Layer Motif Heteroarchitecturing of N,S-Codoped Reduced Graphene Oxide-Wrapped Ni/NiS Nanoparticles for the Electrochemical Oxidation of Water.

A new heterostructured material is synthesized with lamellar arrangements in nanoscale precision through an innovative synthetic approach. The self-assembled Ni-based cyano-bridged coordination polymer flakes (Ni-CP) and graphene oxide (GO) nanosheets with a layered morphology (Ni-CP/GO) are used as precursors for the synthesis of multicomponent hybrid materials. Annealing of Ni-CP/GO in nitrogen at 450 °C allows the formation of Ni3 C/rGO nanocomposites. Grinding Ni-CP/GO and thiourea and annealing under the same conditions produces N,S-codoped reduced GO-wrapped NiS2 flakes (NiS2 /NS-rGO). Interestingly, further heating up to 550 °C allows the phase transformation of NiS2 into NiS accompanied by the formation of a face-centered cubic (FCC-Ni) metal phase between NS-rGO layers (FCC-Ni-NiS/NS-rGO). Among all the materials, the resulting FCC-Ni-NiS/NS-rGO exhibits good electrocatalytic activity and stability toward the oxygen evolution reaction (OER) owing to the synergistic effect of multiphases, the well-designed alternating layered structures on the nanoscale with abundant active sites.

Controlled fabrication of gold nanobipyramids/polypyrrole for shell-isolated nanoparticle-enhanced Raman spectroscopy to detect γ-aminobutyric acid.

Shell-isolated nanoparticle-enhanced Raman Spectroscopy (SHINERS) has been a non-destructive, highly sensitive, specific and powerful sensing method. Detection of γ-aminobutyric acid (GABA) and glutamate, main neurotransmitters in the human brain, is important to diagnosis the neurological disorder. The purpose of this study is preparing a simple, rapid and inexpensive fabrication of Au nanobipyramids/polymer core/shell as a SHINERS-based biosensor to detect different neurotransmitters such as GABA and glutamate with high sensitivity and specificity. Au nanobipyramids/polymer core/shell was fabricated by using two steps process. In the first Au nanobipyramids with longitude and latitude axial of about 100 nm and 10 nm, respectively, was prepared based on the chemical reduction of Au ions by using sodium borohydride as a reducing agent. Then a thin layer of polypyrrole was used for decorating the Au nanobipyramids by using direct polymerization in the presence of Au nanobipyramids. The sensor composed Au nanobipyramids with a thin layer of polypyrrole that could measure GABA within a wide range of concentrations in the presence of human serum. And this sensor was used for direct monitoring of GABA and glutamate. The proposed biosensor can be applied to monitor the level of neurotransmitters accurately for the diagnosis of various neurological disorders with optical signal enhancement.

Cyclodextrin-Modified Micellar UPLC for Direct, Sensitive and Selective Determination of Water Soluble Vitamins in Milk.

Cyclodextrin-modified micellar ultra pressure liquid chromatography (CD-MUPLC) was firstly developed and directly applied to the simultaneous determination of water-soluble vitamins thiamine hydrochloride (VB1), pyridoxine hydrochloride (VB6) and ascorbic acid (VC) in milk samples. A hybrid isocratic mobile phase consisting of ß-cyclodextrin (ß-CD, 5.0 mmol L-1) and cetyltrimethylammonium bromide (CTAB, 0.1 mol L-1) in the presence of acetic acid (0.1 mol L-1) at pH 2.9 on a RP-C18 column at 25.0°C was successfully used. The separation of vitamins was achieved in less than 10 min at a 0.2 mL min-1 flow rate showing adequate linearity at 245 nm in the ranges of 5.0-500.0 µg L-1 for VB1, 5.0-1000.0 µg L-1 for VB6 and 5.0-10000.0 µg L-1 for VC with coefficients of variation (r2) of 0.9999, 0.9987 and 0.9971, respectively. In addition, limits of detection obtained were 0.885, 1.352 and 1.358 µg L-1 and limits of quantification were 2.681, 4.096 and 4.115 µg L-1 for VB1, VB6 and VC, respectively. The high sensitivity of the proposed CD-MUPLC-UV method permitted its applications to the determination of water-soluble vitamins VB1 (32-488 µg L-1), VB6 (82-95 µg L-1) and VC (790-45000 µg L-1) in breast and bovine milk samples. The relative standard deviations and recoveries ranged between 0.07 and 2.14% and between 85.27 and 114.8%, respectively, indicating the accurate and precise measurements without any negative impact of matrix. The current analytical method illustrated several advantages including direct, sensitive, selective and non-consuming organic solvents over the hitherto published methods. These features could be attributed to the four-point competitive interactions among analytes, pseudostationary phases and modified C18 stationary phases.

Simple and rapid liquid chromatographic and electrophoretic methods for phenol quantification and its stability in tuberculin purified protein derivative preparations.

Phenol is commonly used as an antimicrobial agent with an initial concentration of 0.35% (w/v) in injectable diluted tuberculin purified protein derivative (TPPD) solution. The anti-microbial action of phenol in TPPD is directly concentration dependent. Furthermore, high phenol content (>0.5%) may have a negative effect on the stability and clinical effectiveness of TPPD solution. Therefore, simple, rapid and reliable reversed phase liquid chromatographic (RPLC) and capillary zone electrophoretic (CZE) methods were firstly developed and validated for phenol quantification in Connaught tuberculin (CT68) PPD diluted preparations at 5 TU per test dose of 0.1 mL. In RPLC, the elution was carried out by 80% (v/v) ACN mixed with 20% (v/v) phosphate buffer containing 0.05% (v/v) triflouroacetic acid (pH 3.2) at 0.2 mL min-1 flow rate and 20.0 °C column temperature. In addition, phenol was separated from tuberculin (CT68) protein with a resolution of (R = 2.81) and was quantified within 3 min. In CZE, the migration of phenol was performed by 50 mmol L-1 borate buffer (pH 9.8) at -20 kV applied voltage and 25.0 °C capillary temperature. Furthermore, excellent linearity was achieved within 0.17-0.53% (w/v) for the phenol content with coefficients of determination (r2) higher than 0.9995. Moreover, the detection and quantification limits were found to be 0.046 & 0.153% and 0.051 & 0.171% (w/v) with RPLC and CZE respectively. Additionally, the intraday precision (RSD%, n = 9) was ranged between 0.18 and 0.39 and 0.33-54 with RPLC and CZE respectively. Moreover, the interday precision (RSD%, n = 27) was varied between 2.06 and 2.99 and 2.25-3.40 by RPLC and CZE, respectively. Furthermore, the obtained mean recoveries were ranged between 91.32 and 107.51% with RPLC and 90.71-108.92% with CZE. In addition, the effect of different storage temperatures at 4, 25 and 37 °C over storage periods of 2, 7, 14, 21 and 30 days was also studied on the TPPD product. The obtained results have revealed that the phenol content was effectively decreased about 37% of its original content after 30 days at storage temperatures of 25 and 37 °C. However, the phenol content did not change and was stable up to 21 days at storage temperature of 4 °C. Therefore, the simple and rapid proposed analytical methods could be used for a rapid expiry investigation of TPPD products based on phenol quantification, as a marker.

Fabrication and evaluation of an organic monolithic column based upon the polymerisation of hexyl methacrylate with 1,6-hexanediol ethoxylate diacrylate for the separation of small molecules by capillary liquid chromatography.

This paper describes the fabrication of a new porous monolith, prepared in 100µm i.d. capillaries by the co-polymerisation of hexyl methacrylate with 1,6-hexanediol ethoxylate diacrylate, poly (HMA-co-1,6 HEDA), in the presence of azobisisobutyronitrile, 1, 4-butanediol and 1-propanol were used as porogens for the monoliths; the monoliths were then used as a stationary phase for capillary liquid chromatography. Two cross linkers namely 1,6 HEDA and EDMA were utilised in order to investigate the effects of cross linker length on the separation efficiency of small molecules, and it was found that the efficiency of the separation improved tenfold when using the longer cross linker, 1,6 HEDA. This improvement is associated with the increase in number of methylene groups which resulted in an increased number of mesopores, less than 50nm. The 1,6 HEDA based monolith showed a high porosity (90%) and no evidence of swelling or shrinking with the use of organic solvents. Moreover, the 1,6 HEDA monolith demonstrated high reproducibility for the separation of the retained compounds anisole and naphthalene; these showed retention time RSDs of 1.79% and 2.74% respectively. The fabricated monolith also demonstrated high selectivity for neutral non-polar molecules, weak acids, and basic molecules. The asymmetry factors for basic molecules (nortriptyline and amitriptyline) were 1.5 and 1.3 respectively, indicating slight tailing, which is often noticeable on silica based phases due to secondary interactions between basic moieties and the hydroxyl groups of the silica.