Electrochemical determination of sulfite and phenol using a carbon paste electrode modified with ionic liquids and graphene nanosheets: Application to determination of sulfite and phenol in real samples

Benzoylferrocene was used to construct a modified-graphene paste electrode. Also, hydrophilic ionic liquid (n-hexyl-3-methylimidazolium hexafluoro phosphate) was used as a binder to prepare the modified electrode. The electro-oxidation of sulfite at the surface of the modified electrode was studied using electrochemical approaches. This modified electrode offers a considerable improvement in voltammetric sensitivity toward sulfite, compared to the bare electrode. Square wave voltammetry (SWV) exhibits a linear dynamic range from 5.0 × 10⁻⁸ to 2.5 × 10⁻⁴ M and a detection limit of 20.0 nM for sulfite. The diffusion coefficient and kinetic parameters (such as electron transfer coefficient and the heterogeneous rate constant) for sulfite oxidation were also determined. The prepared modified electrode exhibits a very good resolution between the voltammetric peaks of sulfite and phenol that makes it suitable for the detection of sulfite in the presence of phenol in real samples.     

A sensitive nanocomposite-based electrochemical sensor for voltammetric simultaneous determination of isoproterenol,acetaminophen and tryptophan

The electrooxidation of isoproterenol (ISPT), acetaminophen (AC) and tryptophan (Trp) and their mixture has been studied using an 8,9-dihydroxy-7-methyl-12H-benzothiazolo[2,3-b]quinazolin-12-one modified multiwall carbon nanotubes paste electrode (DMBQ-MCNTPE). The novel sensor exhibited potent and persistent electron mediating behavior followed by well separated oxidation peaks towards ISPT, AC and Trp with activation over-potential. The peak currents were linearly dependent on ISPT, AC and Trp concentrations using square wave voltammetry (SWV) method in the range of 0.04–400, 5.0–500, and 10.0–800 μmol L⁻¹, with detection limits of 0.009, 1.0, and 4.0 μmol L⁻¹, respectively. The modified electrode was used for the determination of ISPT, AC and Trp in biological and pharmaceutical samples.     

Rapid and simultaneous determination of tetracycline and cefixime antibiotics by mean of gold nanoparticles-screen printed gold electrode and chemometrics tools

The screen-printed gold electrode (SPGE) modified with the formation of self-assembly monolayer (SAM) of cysteine (Cys) on gold-nanoparticles (Au_nano) was utilized for rapid and simultaneous determination of tetracycline and cefixime antibiotics by square wave voltammetry (SWV). Electrochemical investigation and characterization of the modified electrode was achieved using cyclic voltammetry (CV) and scanning electron microscopy (SEM). A principal component artificial neural network (PCANN) with three layer back-propagation network was utilized for the analysis of the voltammogram data. It is possible to simultaneously determine the tetracycline and cefixime concentrations in the ranges of 10⁻⁵ and 10⁻³ mol L⁻¹, under the optimum conditions. Moreover the SPGE-Au_nano-Cys biosensor together with chemometrics tools was successfully applied to the determination of tetracycline and cefixime in biological fluids, which may provide a promising alternative in routine biosensing applications.     

Nano composite system based on fullerene-functionalized carbon nanotubes for simultaneous determination of levodopa and acetaminophen

In this paper we report an electrochemical sensor based on fullerene (C₆₀)-functionalized carbon nanotubes composite for the sensitive determination of the levodopa (LD) and acetaminophen (AC). A modified electrode by fullerene-functionalized carbon nanotubes (CNTs) composite has been fabricated and its electrochemical behavior was investigated by cyclic voltammetry, chronoamperometry and differential pulse voltammograms. The modified electrode shows electrocatalytic activity toward LD oxidation in phosphate buffer solution (pH 7.0) with a reduction of the overpotential of about 270 mV and an increase in peak current. These conditions are sufficient to allow determination of LD and AC in the samples at fullerene-functionalized carbon nanotubes composite. The differential pulse voltammetry data showed that the obtained anodic peak currents were linearly dependent on the LD concentrations in the range of 0.5–2000 μM, with the detection limit of 0.035 μM. The prepared electrode was successfully applied for the determination of LD and AC in real samples.     

Determination of haloperidol drug in ampoules and in urine samples using a potentiometric modified carbon paste electrode

A modified carbon paste electrode for haloperidol drug based on haloperidol-phosphomolybdate (HP-PM) as an ion-exchanger dissolved in plasticizer DBP and its potentiometric characteristics were discussed. The electrode exhibited a good Nernstian slope of 56.9 ± 0.3 mV/decade with a linear concentration range from 3.2 × 10⁻⁶ to 1.0 × 10⁻² M for the haloperidol ion. The limit of detection (LOD) was 1.5 × 10⁻⁶ M. It had response time of 5–8 seconds (s), useable in pH range of 6.2–8.6 and temperature of 20–60 °C. The electrode shows clear discrimination of haloperidol drug from several inorganic ions, sugars and some common drug excipients. The sensor was applied for determination of haloperidol drug in urine and in pharmaceutical formulations using potentiometric determination, standard addition and the calibration curve methods. The results are satisfactory with excellent percentage recovery comparable or better than those obtained by other routine methods.     

Potential step study of electrooxidation of methanol in 1-butyl-3-methylimidazolium tetrafluoroborate

A potential step method was used to characterize the electrooxidation of methanol on a chemically modified electrode in an ionic liquid solvent. Two major findings were reported from this study. Firstly, the oxidation was dominant 2.2 s after the potential step. Before that, the double layer charging and adsorption were dominant. Therefore, there should be a waiting time of a few seconds if a methanol sensor is developed with a potential step method. Secondly, the oxidation of methanol on the electrode was diffusion controlled. The concentration of methanol affected the diffusion. The diffusion constant D₀ was 8.37 × 10⁻¹⁷ m²/s when the concentration was lower than 0.5 M and was 2.66 × 10⁻¹³ m²/s when the concentration was higher than 1.0 M. This suggests that the methanol concentration should be kept higher than a threshold in an ionic liquid based fuel cell.     

The design of polyaniline based sensor for the qualitative estimation of malonaldehyde

The detection of contaminated food in every stage of processing required new technology for fast identification and isolation of toxicity in food. Since effect of food contaminant are severe to human health, the need of pioneer technologies also increasing over last few decades. In the current study, MDA was prepared by hydrolysis of 1,1,3,3-tetramethoxypropane in HCl media and used in the electrochemical studies. The electrochemical sensor was fabricated with modified glassy carbon electrode with polyaniline. These sensors were used for detection of sodium salt of malonaldehyde and observed that a high sensitivity in the concentration range ∼1 × 10⁻¹ M and 1 × 10⁻² M. Tafel plots show the variation of over potential from − 1.73 V to − 3.74 V up to 10⁻⁵ mol/L indicating the lower limit of detection of the system.     

Application of L-DOPA modified carbon nanotubes as a bifunctional electrocatalyst for simultaneous determination of ascorbic acid,adrenaline, acetaminophen and tyrosine

L-DOPA multi-wall carbon nanotube modified glassy carbon electrode (DOPA-MWCNT-GCE) was used as a bifunctional electrocatalyst for simultaneous quantitative determination of ascorbic acid (AA) and adrenaline (AD). Electrochemical experiments show that the modified electrode plays the role of an excellent bifunctional electrocatalyst for the oxidation of AA and AD in two different potentials. The kinetic parameters such as the electron transfer coefficient, α, and the heterogeneous electron transfer rate constant, k′, for the electrocatalytic oxidation of AA and AD at the DOPA-MWCNT-GCE surface were estimated. Through a different pulse voltammetric (DPV) method, the plot of the electrocatalytic current versus AA and AD concentrations emerged to be constituted of two linear segments with different sensitivities. In addition, detection limits of 1.5 μM for AA and 0.62 μM for AD were obtained. In DPV, the proposed bifunctional electrocatalyst could separate the oxidation peak potentials of AA, AD, acetaminophen (AC) and tyrosine (Tyr) present in a mixture though, at the bare GCE, the peak potentials overlap. Finally, DOPA-MWCNT-GCE was satisfactorily used for the determination of AA, AD, AC and Tyr in pharmaceutical preparations.     

Determination of ganciclovir as an antiviral drug and its interaction with DNA at Fe3O4/carboxylated multi-walled carbon nanotubes modified glassy carbon electrode

The electrochemical oxidation of an antiviral drug, ganciclovir (GCV) at Fe₃O₄/carboxylated multi-walled carbon nanotubes modified glassy carbon electrode (Fe₃O₄/cMWCNTs/GCE) was studied by voltammetric techniques. The influence of the effective parameters on the electrochemical behavior of GCV was investigated. Under optimized conditions, the proposed sensor was applied for low level GCV determination. The relationship between peak current and the concentration of GCV was linear in the range of 80–53,000 nM with a detection limit of 20 nM through square wave voltammetry (SWV). The interaction of GCV with calf thymus DNA was also explored by voltammetric and spectrofluorometric methods. Based on the obtained data the mode of binding of GCV to DNA was intercalative binding. The decrease in the SWV peak current of GCV in the presence of DNA was used for the determination of DNA. The modified electrode exhibited a good sensitivity, stability and pleasant reproducibility, and it was applied for the determination of GCV in spiked serum and urine, with satisfactory results.     

Silver nanoparticles/polymethacrylic acid (AgNPs/PMA) hybrid nanocomposites-modified electrodes for the electrochemical detection of nitrate ions

AgNPs/PMA hybrid nanocomposite materials with different Ag loadings have been synthesized using a simple chemical route assisted by UV irradiation. The hybrid composites were characterized by means of SEM and TEM, UV–vis spectroscopy and XPS. The as synthesized hybrid samples, composed of small Ag nanoparticles (AgNPs) embedded within the PMA (poly-methacrylic-acid) matrix, have been used to modify the working electrode of disposable screen printed carbon electrodes (SPCEs). It has been observed that hybrid composite with the lowest Ag loading forms dendritic silver structures on the surface of working electrode, whereas at higher loadings massive structures were formed. The electrocatalytic properties of the AgNPs/PMA/SPCEs were investigated toward the reduction of nitrate at neutral pH. Based on these modified electrodes, both voltammetric and amperometric sensors were developed for the electrochemical sensing of nitrate. Voltammetric sensor showed a wide linear range (0–20 mM) and high sensitivity (130 μA mM⁻¹ cm⁻²).     

Effect of SiC particles on the friction and wear behavior of Ti3Si(Al)C2-based composites

The non-lubricated, sliding friction and wear behavior of Ti₃Si(Al)C₂ and SiC-reinforced Ti₃Si(Al)C₂ composites against AISI 52100 bearing steel ball were investigated using a ball-on-flat, reciprocating tribometer at room temperature. The contact load was varied from 5 to 20 N. For monolithic Ti₃Si(Al)C₂, high friction coefficients between 0.61 and 0.90 and wear rates between 1.79 × 10⁻³ and 2.68 × 10⁻³ mm³ (N m)⁻¹ were measured. With increasing SiC content in the composites, both the friction coefficients and the wear rates were significantly decreased. The friction coefficients reduced to a value between 0.38 and 0.50, and the wear rates to between 2.64 × 10⁻⁴ and 1.93 × 10⁻⁵ mm³ (N m)⁻¹ when the SiC content ranged from 10 to 30 vol.%. The enhanced wear resistance of Ti₃Si(Al)C₂ is mainly attributed to the facts that the hard SiC particles inhibit the plastic deformation and fracture of the soft matrix, the oxide debris lubricate the counterpair, and the wear mode converts from adhesive wear to abrasive wear during dry sliding.     

Determination of phenyl acetic acid by cyclic voltammetry with electrochemical detection

The phenyl acetic acid (PAA) has been determined by cyclic voltammetry with electrochemical detection using CuGeO₃ nanowires as the glassy carbon electrode (GCE) modified materials. The electrochemical behaviors of the PAA at the CuGeO₃ nanowire modified GCE in neutral solution show that two pairs of electrochemical CV peaks are observed. Two anodic CV peaks are located at 0.31 V and −0.02 V for cv peak 1 and cv peak 2, respectively. The intensities of two anodic peaks vary linearly with the increase of the PAA concentrations from 0.01 to 2 mM. The detection limit is 82.1 μM and 9.1 μM for cv peak 1 and cv peak 2, respectively. The CuGeO₃ nanowire modified GCE exhibits good reproducibility, stability and sensibility.     

Effects of carbon fiber length on the tribological properties of paper-based friction materials

Four kinds of paper-based friction materials reinforced with carbon fibers of 100, 400, 600 and 800 μm were prepared by paper-making processes. Experimental results showed that the friction materials became porous with fiber length increasing. The friction torque curves were flat except the sample with 100 μm fibers. The wear rate of the sample with 100 μm fibers was only 1.40×10⁻⁵ mm³/J. Tiny debris and fine scratches formed in the worn surface were the reason for excellent wear resistance of friction pairs with 100 μm fibers. The friction pairs with 400, 600 and 800 μm fibers showed typically abrasive wear and fatigue wear.     

Development of a simple ‘temperature versus sliding speed’ wear map for the sliding wear behaviour of dissimilar metallic interfaces

The variation in wear behaviour during limited debris retention sliding wear of Nimonic 80A versus Stellite 6 (counterface) between room temperature and 750 °C, at sliding speeds of 0.314, 0.654 and 0.905 m s⁻¹, was investigated. At 0.314 m s⁻¹, mild oxidational wear was observed at all temperatures, due to transfer and oxidation of Stellite 6-sourced debris to the Nimonic 80A and resultant separation of the Nimonic 80A and Stellite 6 wear surfaces. Between room temperature and 450 °C, this debris mostly remained in the form of loose particles (with only limited compaction), whilst between 510 and 750 °C, the particles were compacted and sintered together to form a wear protective ‘glaze’ layer.At 0.654 and 0.905 m s⁻¹, mild oxidational wear due to transfer and oxidation of Stellite 6-sourced debris was only observed at room temperature and 270 °C (also 390 °C at 0.654 m s⁻¹). At 390 °C (450 °C at 0.654 m s⁻¹) and above, this oxide was completely absent and ‘metal-to-metal’ contact resulted in an intermediate temperature severe wear regime—losses in the form of ejected metallic debris were sourced almost completely from the Nimonic 80A. Oxide debris, this time sourced from the Nimonic 80A sample, did not reappear until 570 °C (630 °C at 0.654 m s⁻¹), however, were insufficient to eliminate completely severe wear until 690 and 750 °C. At both 0.654 and 0.905 m s⁻¹, the oxide now preventing severe wear at 690 and 750 °C tended not to form ‘glaze’ layers on the surface of the Nimonic 80A and instead supported continued high wear by abrasion. This abrasive action was attributed to the poor sintering characteristics of the Nimonic 80A-sourced oxide, in combination with the oxides’ increased mobility and decreased residency.The collected data were used to compose a simple wear map detailing the effects of sliding speed and temperature on the wear of Nimonic 80A slid against Stellite 6, at these speeds and temperatures of between room temperature and 750 °C.     

A comparative study on the wear properties of coarse-grained Al6061 alloy and nanostructured Al6061–Al2O3 composites

Wear behavior of nanostructured Al6061 alloy and Al6061–Al₂O₃ nanocomposites produced by milling and hot consolidation were investigated. The samples were characterized by hardness test, pin-on-disk wear test, X-ray diffraction (XRD), and scanning electron microscopy (SEM). Nanocomposites containing 3 vol% Al₂O₃ showed a maximum hardness of 235 HV and optimum wear rate of 4×10⁻³ mg/m. Increasing the amount of Al₂O₃ up to 5 vol% resulted in decrease in hardness values (∼112 HV) and a sharp rise in wear rate (∼18×10⁻³ mg/m).     

Uncertainty evaluation of a 10N·m dead weight torque standard machine and comparison with a 1kN·m dead weight torque standard machine

A 10N·m dead weight torque standard machine (10-N·m-DWTSM) has been developed and evaluated since 2006 at the National Metrology Institute of Japan (NMIJ), a part of the National Institute of Advanced Industrial Science and Technology (AIST). Previously, the lengths of a moment arm, made of a low-thermal-expansion alloy (Super Invar), and the sensitivity limit of the fulcrum were evaluated. However, it is known that mechanical parts made of Super Invar vary in size with time. Therefore, the sensitivity limit of the fulcrum should be investigated under real calibration conditions. In this study, the moment arm lengths and the sensitivity limit of the fulcrum were re-evaluated. The moment arm lengths were found to have increased by an average of 6.3 μm in five years. The relative combined standard uncertainty of the moment arm length, w_arm, was re-evaluated in consideration of the uncertainty of the secular length change and was found to be 1.8 × 10⁻⁵. The sensitivity limit of the fulcrum was investigated by using a highly accurate, small-rated-capacity torque measuring device. The relative combined standard uncertainty due to the sensitivity limit of the fulcrum was 2.5 × 10⁻⁵ in the 0.1–10N·m torque range. The uncertainty budget table of the 10-N·m-DWTSM was completed. The relative expanded uncertainty of torque realized by the 10-N·m-DWTSM, W_tsm, was evaluated in the 0.1–10N·m torque range and was found to be 6.6 × 10⁻⁵, with a coverage factor, k, being equal to 2. In addition, the 10-N·m-DWTSM was compared with the existing 1-kN·m-DWTSM at NMIJ by using small-rated-capacity torque measuring devices at 5N·m and 10N·m torque steps. Two loading conditions were adopted in this comparison. The comparison results showed good agreement within the uncertainties in all cases. Thus, the torque realized by the 10-N·m-DWTSM was shown to be equivalent to that achieved by the 1-kN·m-DWTSM.     

Study of TiAlSiN coatings post-treated with N and C + N ion implantations. Part 2: The tribological analysis

Ion implantation has found to be an effective approach to modify surface properties of materials. The present research investigates the effect of (1) nitrogen (N), and (2) carbon subsequently with nitrogen (C + N) implantations on the mechanical and tribological properties of the titanium–aluminium–silicon–nitride (Ti–Al–Si–N) coatings. Superhard TiAlSiN coatings produced by magnetron sputtering, of approximately 2.5 μm thickness, were post-treated by implantations of N or C + N at an energy level of 50 keV. The dose range was between 5 × 10¹⁶ and 1 × 10¹⁸ ions cm^?2. After implantation, the tribological performance of the coatings was investigated by a ball-on-disk tribometer against WC–6 wt.%Co ball under dry condition in ambient air. The wear performance of the samples was examined by a variety of characterization techniques, such as secondary electron microscopy (SEM), 3D profilometry, atomic force microscopy (AFM), and micro-Raman. The results showed that the wear performance of the samples depended strongly on the implanted elements and doses. There was slight improvement on the samples implanted with N whereas significant improvement was found on the C + N implantations. Particularly, the friction coefficient of the sample with 5 × 10¹⁷ C⁺ cm^?2 and 5 × 10¹⁷ N⁺ cm^?2 could reach 0.1. In addition, the specific wear rate of the sample was extremely low (0.85 × 10^?7 mm³/Nm), which was nearly two orders of magnitude below that of the un-implanted coating. The speculation of the mechanical and tribological analyses of the samples indicates that the improvement of the N implanted and C + N implanted TiAlSiN samples could be due to a combined effect of improved hardness, plus enhanced adhesive and cohesive strength. In addition, the improved performance of the C + N implanted samples could be explained by the formation of lubricating implanted-layer, which existed mostly in sp² C–C and C–N forms. The formation of such implanted layer could lead to a change of wear mode from strong abrasive wear to mostly adhesive wear, and result in a drop of friction coefficient and wear rate.     

Studies of high temperature sliding wear of metallic dissimilar interfaces IV: Nimonic 80A versus Incoloy 800HT

Wear variations of Nimonic 80A slid against Incoloy 800HT between room temperature (RT) and 750 °C, and sliding speeds of 0.314 and 0.905 m s⁻¹ were investigated using a ‘reciprocating-block-on-cylinder’, low debris retention configuration. These were considered alongside previous observations at 0.654 m s⁻¹.Different wear types occurring were mapped, including high transfer ‘severe wear’ (RT and 270 °C, also 0.905 m s⁻¹ at ≤570°C), low transfer ‘severe wear’ (0.314 m s⁻¹ at 390 °C to 510 °C oxide abrasion assisted at 510 °C), and ‘mild wear’ (0.314 m s⁻¹ at ≥570 °C; 0.905 m s⁻¹ at ≥630 °C). Wear surfaces at 750 °C were cross-sectioned and profiled.     

A comparison of tribological properties of evenly distributed and agglomerated diamond nanoparticles in lubricated high-load steel–steel contact

The tribological properties of evenly distributed and agglomerated nanodiamonds on steel contact surfaces were compared in ethylene glycol lubricated tests using a pin-on-disc tribometer with a steel counter ball. The nanodiamond distributions were studied on silicon and steel surfaces using scanning electron microscopy. Friction and wear decreasing effects were observed with both sprayed and agglomerated nanodiamonds. The average friction coefficient with pure ethylene glycol lubricated contacts decreased from 0.16 to 0.12 with agglomerated nanodiamonds when 100 N load was applied. A minimum for both disc wear rate (0.40×10⁻⁶ mm³/Nm) and ball wear rate (0.29×10⁻⁶ mm³/Nm) was observed with agglomerated nanodiamonds. One of the mechanisms of nanodiamond lubrication was observed to be the incorporation of nanodiamond particles in to the tribolayer.     

Adsorption effect of a cationic surfactant at carbon paste electrode as a sensitive sensor for study and detection of folic acid

The present study is the first report on the effect of cetyltrimethylammonium bromide (CTAB) on the electrochemical behavior of folic acid (FA) at the surface of carbon paste electrode (CPE) in real samples. The studies were performed by cyclic voltammetry (CV), chronocoulometry and differential pulse voltammetry (DPV). CTAB, with a hydrophobic C–H chain, could absorb at the CPE surface by hydrophobic interaction and then changed the electrode/solution interface, and eventually affects the electrochemical response of FA, confirming from the remarkable oxidation peak current enhancement. For investigation of the electrode properties, CV technique was used at the various scan rates. Electrochemical parameters including diffusion coefficient (D), electron transfer coefficient (α) and ionic exchanging current density (j_o) were determined for the FA at the surface of the electrode. Under optimized conditions, the proposed method showed acceptable analytical performances for FA in terms of linearity (over the concentration range from 0.01 to 1.5 and 1.5 to 10.0 μM), detection limit (2.89 nM), repeatability (1.37%) and stability (13% reduction in peak current after 60 days). After studying on the effect of probable interferences it was found that the method was free of the interferences. Finally, the proposed method was successfully applied for the determination of FA in real samples.