Amperometric sensing of hydrazine using a magnetic glassy carbon electrode modified with a ternary composite prepared from Prussian blue,Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles,and reduced graphene oxide

A magnetic glassy carbon electrode (mGCE) was modified with a ternary composite prepared from Prussian blue (PB), magnetite (Fe₃O₄) nanoparticles, and reduced graphene oxide (rGO) in order to obtain an amperometric sensor for hydrazine. The utilization of Fe₃O₄ facilitates the magnetic immobilization and separation of sensing material, while the use of rGO enhances sensitivity. The surface coverage and the stability of the PB on the modified electrode were considerably improved. The electro-oxidative response to hydrazine was investigated with this modified mGCE using cyclic voltammetry and amperometric. The sensor, typically operated at a voltage of 0.2 V (vs. SCE), displays superior response hydrazine, with a response time of 4 s, a sensitivity of 97.73 μA μM^?1 cm^?2 and a 13.7 nM detection limit.

Open image in new window

Graphical abstract A magnetic glassy carbon electrode was modified with a ternary composite prepared from Prussian blue, magnetite nanoparticles, and reduced graphene oxide to obtain a selective amperometric sensor for dissolved hydrazine.

     

Electrochemical detection of DNA methylation using a glassy carbon electrode modified with a composite made from carbon nanotubes and β-cyclodextrin

We describe a method for detecting DNA methylation. It is based on direct oxidation of DNA bases at a glassy carbon electrode (GCE) modified with film of a multiwalled carbon nanotube-β-cyclodextrin composite. This nano-structured film causes a strong enhancement on the oxidation current of DNA bases due to its large effective surface area and extraordinary electronic properties. Well-defined peaks were obtained as a result of electro-oxidation of guanine (at 0.67 V), adenine (at 0.92 V), thymine (at 1.11 V), cytosine (at 1.26 V), and 5-methylcytosine (at 1.13 V; all data vs. saturated calomel electrode (SCE)). The potential difference between 5-methylcytosine and cytosine (130 mV) is large enough to enable reliable simultaneous determination and analysis. The interference by thymine can be eliminated by following the principle of complementary pairing between purine and pyrimidine bases in DNA. The modified electrode was successfully applied to the evaluation of 5-methylcytosine in a fish sperm DNA, the methylation level of cytosine was found to be 7.47 %, and the analysis process took less than 1 h.     

Voltammetric determination of the anti-cancer drug nilutamide using a screen-printed carbon electrode modified with a composite prepared from β-cyclodextrin,gold nanoparticles and graphene oxide

The authors describe an electrochemical method for the determination of the anti-cancer drug nilutamide. The method is based on the use of a composite prepared from β-cyclodextrin, gold nanoparticles and graphene oxide (β-CD-AuNP/GO). An alkaline solution of glucose was used as a reducing agent to reduce the gold ions, rather than citric acid and a harmful reducing agent such as hydrazine and sodium borohydride. The structure and surface morphology of the β-CD-AuNP/GO composite was characterized by Raman spectroscopy, transmission electron microscopy and energy-dispersive X-ray spectroscopy. A screen printed carbon electrode was modified with the nanocomposite, and the resulting electrode used as a disposable sensor for the determination of nilutamide by differential pulse voltammetry. Best operated at a working voltage of 0.43 V (vs Ag/AgCl), it exhibits excellent electrocatalytic activity and a detection limit as low as 0.4 nM. The sensor was applied to the determination of nilutamide in (spiked) human serum, as well as in a tablet, where it displays good recovery and accuracy. The sensor is repeatable, reproducible, stable and selective even in the presence of other aromatic nitro compounds.

Open image in new window

Graphical abstract An electrochemical method for the determination of the anti-cancer drug nilutamide is described. A screen printed carbon electrode is modified with the nanocomposite prepared from β-cyclodextrin, gold nanoparticles and graphene oxide (β-CD-AuNP/GO). Best operated at a working voltage of 0.43 V (vs Ag/AgCl), it exhibits excellent electrocatalytic activity and a detection limit as low as 0.4 nM. The sensor was applied to the determination of nilutamide in (spiked) human serum and a tablet where it displays good recovery and accuracy.

     

Electrochemical determination of picric acid based on platinum nanoparticles–reduced graphene oxide composite

Platinum nanoparticles–reduced graphene oxide composite-modified glassy carbon electrode (PtNPs–rGO/GCE) was developed as a simple, selective and sensitive electrochemical sensor for determination of picric acid (PA). Cyclic voltammogram (CV) of PA showed three well-defined irreversible reduction peaks at the potentials of ?0.43, ?0.57 and ?0.66 V versus Ag/AgCl. In this work, the interference effect of other nitrophenol compounds (NPhCs) was significantly reduced by appropriate adjusting of pH. Square wave voltammetry was used for quantification of PA in the range of 5–500 µM (1.15–115 mg L^?1) with practical detection limit of 1 µM (0.23 mg L^?1). The proposed sensor was successfully applied for the determination of PA in two natural water samples.     

Electrochemical chiral recognition of tryptophan using a glassy carbon electrode modified with β-cyclodextrin and graphene

We report on a method for electrochemical enantioselective recognition of tryptophan (Trp) enantiomers. It is based on competitive host-guest interaction between a deoxy-(2-aminoethylamino)-β-cyclodextrin (CD) bound to graphene nanosheets and the Cu(II) complexes of the Trp enantiomers via a ligand exchange mechanism. Chiral recognition was investigated via cyclic voltammetry and electrochemical impedance spectroscopy. The results reveal that the CD bound to graphene displays a stronger interaction with the Cu(II) complex of L-Trp than to that of D-Trp. The method was applied to the determination of the ratio of Trp enantiomers in mixtures.

Non-enzymatic sensing of hydrogen peroxide using a glassy carbon electrode modified with a composite consisting of chitosan‐encapsulated graphite and platinum nanoparticles

We report on a non-enzymatic hydrogen peroxide (H₂O₂) sensor which makes use of a nanocomposite consisting of platinum nanoparticles (PtNPs) and chitosan-encapsulated graphite (graphite-CS). The composite was prepared by sonication of pristine graphite in chitosan (CS) in 5 % acetic acid. The PtNP decorated graphite-CS (graphite-CS/PtNPs) composite was prepared by electrodeposition of PtNPs on the graphite-CS modified glassy carbon electrode. The graphite-CS/PtNP composite was characterized by scanning electron microscopy, elemental analysis and FTIR spectroscopy. The modified electrode displays an enhanced reduction peak current for H₂O₂ when compared with electrodes modified with graphite/PtNPs and PtNPs. The modified electrode exhibits excellent electrocatalytic activity towards the reduction of H₂O₂, and the amperometric response is linear over the concentration range from 0.25 to 2890 μM. The sensitivity and the detection limit are 0.465 μA?μM￣¹ ? cm￣² and 66 nM, respectively. The sensor shows fast response (3 s) in detecting H₂O₂. It is also highly selective in the presence of potentially interfering compounds, and may therefore be used as a feasible platform for sensing H₂O₂ in real samples.

Open image in new window

Graphical abstract Preparation of graphite-CS/PtNP composite, and its application to electrochemical reduction of H₂O₂.

     

Synthesis of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@Au core–shell nanoparticles

A new two-step synthesis of Fe₃O₄@Au core–shell nanoparticles stabilized in polyethylene glycol is described. The nanoparticles were characterized by transmission electron microscopy, X-ray powder diffraction, UV and Mössbauer spectroscopy. Fe₃O₄@Au nanoparticles featured both optical properties (they featured a plasmon resonance band) and magnetic properties (they responded to an external magnetic field), typical of individual gold and magnetite nanoparticles, respectively.     

Direct electron transfer of horseradish peroxidase at Co<Subscript>3</Subscript>O<Subscript>4</Subscript>–graphene nanocomposite modified electrode and electrocatalysis

In this paper, the mixture of Co₃O₄–graphene nanocomposite and horseradish peroxidase (HRP) was spread on the surface of carbon ionic liquid electrode (CILE). Then, Nafion film was used for the immobilization. The results of spectroscopy proved that HRP kept up its native structure in the complex material. Direct electrochemistry of HRP resulted in a couple of quasi-reversible redox waves on cyclic voltammograms, reflecting the realization of direct electron transfer of HRP with electrode. The improvement in electrochemical responses was due to the usage of highly conductive Co₃O₄–graphene nanocomposite with biocompatible interface. Electrochemical parameters such as the electron transfer coefficient (α) was estimated as 0.47, and the apparent heterogeneous electron transfer rate constant (k _s) was calculated as 2.90 s^?1. The HRP modified electrode exhibited good electrochemical catalytic ability toward the reduction of trichloroacetic acid and NaNO₂. As a consequence, an updated third-generation electrochemical HRP biosensor with Co₃O₄–GR/CILE was constructed successfully.     

Study on Bi—Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanocomposite prepared via mechanochemical processing

In this work Bi-Fe₃O₄ nanocomposite was synthesized by room temperature milling of Bi₂O₃ and Fe powders using a planetary ball mill in air. The synthesis reaction proceeds with increase in milling time and is finished by about 4 h. The XRD pattern of the as-milled powder shows that the main phases are Bi and Fe₃O₄ without any extra phases. The average crystallite sizes of the constituents have been determined by Scherrer’s formula and they were 22 and 18 nm for Bi and Fe₃O₄ respectively. This was also confirmed by Transmission Electron Microscopy (TEM). Magnetic hysteresis loops at room temperature were recorded using a vibrating sample magnetometer (VSM). A tow-probe method was used to measure resistivity variation of the nanocomposite as a function of magnetic filed and temperature. We have observed a room temperature magnetoresistance (ρ₀ — ρ _H )/ρ₀ as large as 17% in a magnetic field of 1 T.     

Electrochemical determination of quercetin by self-assembled platinum nanoparticles/poly(hydroxymethylated-3,4-ethylenedioxylthiophene) nanocomposite modified glassy carbon electrode

A simple and sensitive platinum nanoparticles/poly(hydroxymethylated-3,4-ethylenedioxylthiophene)nanocomposite(PtNPs/PEDOT-MeOH) modified glassy carbon electrode(GCE) was successfully developed for the electrochemical determination of quercetin.Scanning electron microscopy and energy dispersive X-ray spectroscopy results indicated that the PtNPs were inserted into the PEDOTMeOH layer.Compared with the bare GCE and poly(3,4-ethylenedioxythiophene)(PEDOT) electrodes,the PtNPs/PEDOT-MeOH/GCE modified electrode exhibited a higher electrocatalytic ability toward the oxidation of quercetin due to the synergic effects of the electrocatalytic activity and strong adsorption ability of PtNPs together with the good water solubility and high conductivity of PEDOT-MeOH.The electrochemical sensor can be applied to the quantification of quercetin with a linear range covering0.04-91 μmol L~(-1) and a low detection limit of 5.2 nmol L~(-1).Furthermore,the modified electrode also exhibited good reproducibility and long-term stability,as well as high selectivity.     

Preparation and adsorption properties of magnetic Co<Subscript>0.5</Subscript>Ni<Subscript>0.5</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript>–chitosan nanoparticles

Magnetic chitosan microspheres were prepared by the emulsification cross-linking technique in the presence of glutaraldehyde as cross-linking agent, liquid paraffin as dispersant, and Span-80 as emulsifier. The optimal cross-linking time and Co_0.5Ni_0.5Fe₂O₄: chitosan ratio were determined. The morphology of particles was studied by different techniques. The adsorption characteristics were studied and the effect exerted by the initial concentration of methyl orange, the time of cross-linking, and the amount of the adsorbent was determined. It is found that the product obtained at the Co_0.5Ni_0.5Fe₂O₄: chitosan ratio 1: 4 and the crosslinking time 5 h has the uniform morphology. At room temperature, the Co_0.5Ni_0.5Fe₂O₄–chitosan magnetic composite has maximal adsorption for methyl orange at the dosage 20 mg.     

Bright blue pigment CoAl<Subscript>2</Subscript>O<Subscript>4</Subscript> nanocrystals prepared by modified sol–gel method

Nanocrystalline films of magnetite have been prepared by a novel sol–gel route in which, a solution of iron (III) nitrate dissolved in ethylene glycol was applied on glass substrates by spin coating. Coating solution showed Newtonian behaviour and viscosity was found as 0.0215 Pa.s. Annealing temperature was selected between 291 and 350 °C by DTA analysis in order to obtain magnetite films. In-plane grazing angle XRD and TEM studies showed that magnetite phase was present upon annealing the films at 300 °C. The films had crack free surfaces and their thicknesses varied between ~10 and 200 nm. UV–Vis spectrum results showed that transmittance of the films increases with decreasing annealing temperature and increasing spinning rate. Up to 96% transmittance was observed between the wavelengths of 900–1,100 nm. Vibrating sample magnetometer measurements indicated that magnetite thin films showed ferromagnetic behavior and the saturation magnetization value was found as ~35 emu/cm³.     

Sol–gel synthesis of iron yttrium garnet Y<Subscript>3</Subscript>Fe<Subscript>5</Subscript>O<Subscript>12</Subscript> using metal acetylacetonates

The synthesis of hydrolytically active heteroligand complexes of the composition [M(O₂C₅H₇)x(ⁱOC₅H₁₁)_y] (M = Fe³⁺ and Y³⁺) using iron and yttrium acetylacetonates was studied. Their reactivity was shown to be dependent on the degree of shielding of iron and yttrium cations in hydrolysis and polycondensation during the formation of a connected dispersion system. The crystallization temperature of iron yttrium garnet Y₃Fe₅O₁₂ upon heating xerogel was determined. It was found that the dispersity, microstructure, and magnetic characteristics of the products depend on the synthesis conditions.     

Silver nanoparticles embedded phosphomolybdate–polyaniline hybrid electrode for electrocatalytic reduction of H<Subscript>2</Subscript>O<Subscript>2</Subscript>

Hybrid silver/phosphophomolybdate/polyaniline (Ag/PMo12/PAni) was obtained through one pot synthesis, and then, it was successfully fabricated on the glassy carbon electrode by simple casting method for electrocatalytic reduction of hydrogen peroxide (H₂O₂). The cyclic voltammetric studies of the Ag/PMo12/PAni hybrid electrode suggest that the electronic properties of the phosphomolybdate are retained even after the formation of hybrid material and in addition effectively electro-catalyzing the reduction of H₂O₂ with a less negative over potential. The Ag/PMo12/PAni-modified electrode showed the lowest detection limit (750 nM) for H₂O₂ reduction among the hybrid-modified electrodes already reported with a sensitivity of 4.398 nA μM⁻¹. The prepared hybrid material was well characterized by using UV, XRD and TEM analysis.     

Organometallic polymer-functionalized Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles as a highly efficient and eco-friendly nanocatalyst for C–C bond formation

A magnetically recoverable biopolymer-based nanocatalyst was prepared through the covalent immobilization of a chitosan-bound 2-hydroxynaphthaldehyde Pd complex on the surface of superparamagnetic nanoparticles. The nanocatalyst was characterized by FTIR, X-ray powder diffraction and scanning electron microscopy, revealing an average particle size of 70 nm. The catalyst shows high thermostability by thermogravimetric analysis. Estimated Pd loading by inductively coupled plasma atomic emission analysis was found to be 0.348 mmol g^?1. The nanocatalyst exhibits excellent catalytic performance in Suzuki couplings of various aryl halides with phenylboronic acid, and Heck reactions of iodo- and bromoarenes with butylacrylate. The catalyst can be easily separated from the reaction mixture with an external magnet and reused consecutively four times without significant loss in activity.     

Thermal behavior of Co<Subscript>x</Subscript>Fe<Subscript>3−x</Subscript>O<Subscript>4</Subscript>/SiO<Subscript>2</Subscript> nanocomposites obtained by a modified sol–gel method

The thermal behavior of Co_xFe_3?xO₄/SiO₂ nanocomposites obtained by direct synthesis starting from nonahydrate ferric nitrate and hexahydrate cobalt nitrate in different ratios with and without the addition of 1,4-butanediol was studied. For the synthesis of Co_xFe_3?xO₄ (x = 0.5–2.5) dispersed in the silica matrix a wide Co/Fe molar ratio was used. The decomposition processes, formation of crystalline phases, gases evolvement and mass changes during gels annealing at different temperatures were assessed by thermal analysis. The absence of succinate precursor and a low mass loss were observed in the case of the gel obtained in the absence of 1,4-butanediol. In case of gels obtained using a stoichiometric ratio of Co/Fe, no clear delimitation between Co and Fe succinates was observed, while for samples with a Fe or Co excess, the formation of the two succinates was observed. The evolution of the crystalline phase after annealing (673, 973 and 1273 K) investigated by X-ray diffraction analysis and Fourier transformed infrared spectrometry revealed that in samples with Fe excess, stoichiometric Fe/Co ratio or low Co excess, the cobalt ferrite (CoFe₂O₄) was obtained as a single phase, while in samples with higher cobalt excess, olivine (Co₂SiO₄) as a main phase, cobalt oxide and CoFe₂O₄ as secondary phases were obtained after annealing at 1273 K. The SEM images confirmed the nanoparticles embedding in the silica matrix, while the TEM and X-ray diffraction data showed that the obtained nanoparticles’ size was below 10 nm in most samples.     

A magnetic CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/SiO<Subscript>2</Subscript> nanocomposite fabricated by the sol-gel method for electrocatalytic oxidation and determination of L-cysteine

Magnetic CoFe₂O₄/SiO₂ spinel-type nanocomposites have been fabricated by a sol-gel method in the presence of various acids. Their structural, morphological and magnetic properties were characterized by XRD, SEM, TEM, FTIR, VSM and EDX which revealed that they are formed in the presence of all precursors. TEM analysis indicates homogeneous and porous spherical morphology with nanosize grains 10–20 nm in diameter in the presence of salicylic acid. Electrochemical sensor application of nanocrystalline CoFe₂O₄/SiO₂ synthesized by salicylic acid for determination of L-cysteine was investigated using differential pulse voltammetry (DPV) and cyclic voltammetry (CV). DPV indicates that the sensor shows remarkable sensitivity for the determination of L-Cys. The response of a glassy carbon electrode modified with CoFe₂O₄/SiO₂ is linear in the 0.02–425 μM L-Cys concentration range, with a 0.20 μM detection limit (at an S/N ratio of 3). The electrode produces a negligible current response for tryptophan, glutamic acid and citric acid at the working potential applied (+0.748 V vs Ag/AgCl). The electrode is reliable, simple, rapidly prepared, precise, and the method does not require extensive sample treatment.

Open image in new window

Graphical abstract A CoFe₂O₄/SiO₂ magnetic nanocomposite was synthesized by a sol-gel auto combustion method in the presence of various acids as precursors. A highly sensitive electrochemical sensor was fabricated for determination of trace amount of L-cysteine using a glassy carbon electrode modified with the nanocomposite.

     

Synthesis of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>—Ag nanocomposites and their application to enzymeless hydrogen peroxide detection

To achieve highly sensitive nonenzymatic detection of H₂O₂, a novel electrochemical sensor based on Fe₃O₄-Ag nanocomposites was developed. Nanocomposites were synthesized by reducing [Ag(NH₃)₂]⁺ at the gas/liquid interface in the presence of silver seeds and confirmed by transmission electron microscopy and X-ray diffractometry. Electrochemical investigations indicate that the sensor is able to detect H₂O₂ within a wide linear range of 0.5 μM to 4.0 mM, sensitivity of 135.4 μA mM^?1 cm^?2 and low detection limit of 0.2 μM (S/N = 3). Additionally, the sensor exhibits good anti-interference ability, stability and repeatability. These results show that the Fe₃O₄-Ag nanocomposite is a promising electrocatalytic material for sensors construction.     

Thermal analysis study of LiFeO<Subscript>2</Subscript> formation from Li<Subscript>2</Subscript>CO<Subscript>3</Subscript>–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> mechanically activated reagents

Series of n-octadecane/expanded graphite composite phase-change materials (PCMs) with different mass ratio were prepared using n-octadecane as PCMs, expanded graphite as multi-porous supporting matrix through vacuum impregnation method. Microstructure, crystallization properties, energy storage behavior, thermal cycling property and intelligent temperature-control performance of the composite PCMs were investigated. Results show that the composite PCMs have a good energy storage property. The melting enthalpy and crystallization enthalpy can reach 164.85 and 176.51 J g^?1, respectively. Furthermore, the good thermal conductivity of expanded graphite reduces the super-cooling degree of n-octadecane and endows the composite PCMs with fast thermal response rate and excellent thermal cycling stability. As a result, the phase-change temperatures and phase-change enthalpy almost have no change after 50 thermal-cooling cycles. The test of intelligent temperature-control performance shows that the electronic radiator filled with the composite PCMs possesses a high intelligent temperature-control performance, and its temperature can sustain in the range of 22–27.5 °C for about 6120 s. These results indicate that the prepared composite PCMs possess good comprehensive property and can be widely used in energy storage and thermal management systems.