Electrocatalytic oxidation of quinine sulfate at a multiwall carbon nanotubes-ionic liquid modified glassy carbon electrode and its electrochemical determination

The electrocatalytic oxidation of quinine sulfate (QS) was investigated at a glassy carbon electrode, modified by a gel containing multiwall carbon nanotubes (MWCNTs) and room-temperature ionic liquid of 1-Butyl-3-methylimidazolium hexafluorophate (BMIMPF₆) in 0.10 M of phosphate buffer solution (PBS, pH 6.8). It was found that an irreversible anodic oxidation peak of QS with E _pa as 0.99 V appeared at MWCNTs-RTIL/glassy carbon electrode (GCE). The electrode reaction process was a diffusion-controlled one and the electrochemical oxidation involved two electrons transferring and two protons participation. Furthermore, the charge-transfer coefficient (α), diffusion coefficient (D), and electrode reaction rate constant (k _f) of QS were found to be 0.87, 7.89 × 10⁻³ cm²⋅s⁻¹ and 3.43 × 10⁻² s⁻¹, respectively. Under optimized conditions, linear calibration curves were obtained over the QS concentration range 3.0 × 10⁻⁶ to 1.0 × 10⁻⁴ M by square wave voltammetry, and the detection limit was found to be 0.44 μM based on the signal-to-noise ratio of 3. In addition, the novel MWCNTs-RTIL/GCE was characterized by the electrochemical impedance spectroscopy and the proposed method has been successfully applied in the electrochemical quantitative determination of quinine content in commercial injection samples and the determination results could meet the requirement.     

Electrochemical behaviors of metol on ionic-liquid-modified carbon paste electrode and its analytical application

The electrochemical behaviors of metol on an ionic liquid N-butylpyridinium hexafluorophosphate modified carbon paste electrode (IL-CPE) were studied in this paper. The results indicated that a pair of well-defined quasi-reversible redox peaks of metol appeared with the decrease of overpotential and the increase of redox peak current, which was the characteristics of electrocatalytic oxidation. The electrocatalytic mechanism was discussed and the electrochemical parameters were calculated with results of the charge-transfer coefficient (α) as 0.45, the electrode reaction rate constant (k _s) as 4.02 × 10⁻³ s⁻¹, and the diffusion coefficient (D) as 6.35 × 10⁻⁵ cm²/s. Under the optimal conditions, the anodic peak current was linear with the metol concentration in the range of 5.0 × 10⁻⁶ ∼ 1.0 × 10⁻³ mol/L (n = 11, γ = 0.994) and the detection limit was estimated as 2.33 × 10⁻⁶ mol/L (3σ). The proposed method was successfully applied to determination of metol content in synthetic samples and photographic solutions.     

Electrochemical reduction and kinetics of hydrogen peroxide on the rotating disk palladium-plated aluminum electrode modified by Prussian blue film as an improved electrocatalyst

This paper describes the use of an aluminum electrode plated by metallic palladium and modified by Prussian blue (PB/Pd-Al) in the electrocatalytic reduction of hydrogen peroxide (H₂O₂). The effect of pH on the electroreduction of H₂O₂ on the modified electrode is investigated and a simple irreversible reduction pathway is suggested. The electroreduction kinetics including transfer coefficient α, potential-dependent charge transfer rate constants k _f, and diffusion coefficient D are estimated by means of forced hydrodynamic voltammetry using a rotating disk PB/Pd-Al electrode. The mean values obtained for kinetics are 0.38, 10⁻² cm⁻¹, and 7.6 × 10⁻⁶ cm² s⁻¹, respectively. The long-term stability of the modifying layers on the Al substrate was studied.     

Scale up and Application of Biosurfactant from <Emphasis Type="Italic">Bacillus subtilis</Emphasis> in Enhanced Oil Recovery

There is a lack of fundamental knowledge about the scale up of biosurfactant production. In order to develop suitable technology of commercialization, carrying out tests in shake flasks and bioreactors was essential. A reactor with integrated foam collector was designed for biosurfactant production using Bacillus subtilis isolated from agricultural soil. The yield of biosurfactant on biomass (Y _p/x), biosurfactant on sucrose (Y _p/s), and the volumetric production rate (Y) for shake flask were obtained about 0.45 g g⁻¹, 0.18 g g⁻¹, and 0.03 g l⁻¹ h⁻¹, respectively. The best condition for bioreactor was 300 rpm and 1.5 vvm, giving Y _x/s, Y _p/x, Y _p/s, and Y of 0.42 g g⁻¹, 0.595 g g⁻¹, 0.25 g g⁻¹, and 0.057 g l⁻¹ h⁻¹, respectively. The biosurfactant maximum production, 2.5 g l⁻¹, was reached in 44 h of growth, which was 28% better than the shake flask. The obtained volumetric oxygen transfer coefficient (K _L a) values at optimum conditions in the shake flask and the bioreactor were found to be around 0.01 and 0.0117 s⁻¹, respectively. Comparison of K _L a values at optimum conditions shows that biosurfactant production scaling up from shake flask to bioreactor can be done with K _L a as scale up criterion very accurately. Nearly 8% of original oil in place was recovered using this biosurfactant after water flooding in the sand pack.     

Sequential spectrofluorimetric determination of free and total glycerol in biodiesel in a multicommuted flow system

A new procedure for spectrofluorimetric determination of free and total glycerol in biodiesel samples is presented. It is based on the oxidation of glycerol by periodate, forming formaldehyde, which reacts with acetylacetone, producing the luminescent 3,5-diacetyl-1,4-dihydrolutidine. A flow system with solenoid micro-pumps is proposed for solution handling. Free glycerol was extracted off-line from biodiesel samples with water, and total glycerol was converted to free glycerol by saponification with sodium ethylate under sonication. For free glycerol, a linear response was observed from 5 to 70 mg L⁻¹ with a detection limit of 0.5 mg L⁻¹, which corresponds to 2 mg kg⁻¹ in biodiesel. The coefficient of variation was 0.9% (20 mg L⁻¹, n = 10). For total glycerol, samples were diluted on-line, and the linear response range was 25 to 300 mg L⁻¹. The detection limit was 1.4 mg L⁻¹ (2.8 mg kg⁻¹ in biodiesel) with a coefficient of variation of 1.4% (200 mg L⁻¹, n = 10). The sampling rate was ca. 35 samples h⁻¹ and the procedure was applied to determination of free and total glycerol in biodiesel samples from soybean, cottonseed, and castor beans.     

Electrochemical methods for simultaneous determination of trace amounts of dopamine and uric acid using a carbon paste electrode incorporated with multi-wall carbon nanotubes and modified with α-cyclodextrine

In this work, we investigate the electrochemical activity of dopamine (DA) and uric acid (UA) using both a bare and a modified carbon paste electrode as the working electrode, with a platinum wire as the counter electrode and a silver/silver chloride (Ag/AgCl) as the reference electrode. The modified carbon paste electrode consists of multi-walled carbon nanotubes (>95%) treated with α-cyclodextrine, resulting in an electrode that exhibits a significant catalytic effect toward the electro-chemical oxidation of DA in a 0.2-M Britton–Robinson buffer solution (pH 5.0). The peak current increases linearly with the DA concentration within the molar concentration ranges of 2.0 × 10⁻⁶ to 5.0 × 10⁻⁵ M and 5.0 × 10⁻⁵ to 1.9 × 10⁻⁴ M. The detection limit (signal to noise >3) for DA was found to be 1.34 × 10⁻⁷ M, respectively. In this work, voltammetric methods such as cyclic voltammetry, chronoamperometry, chronocuolometry, differential pulse and square wave voltammetry, and linear sweep and hydrodynamic voltammetry were used. Cyclic voltammetry was used to investigate the redox properties of the modified electrode at various scan rates. The diffusion coefficient (D, cm² s⁻¹ = 3.05 × 10⁻⁵) and the kinetic parameters such as the electron transfer coefficient (α = 0.51) and the rate constant (k, cm³ mol⁻¹ s⁻¹ = 1.8 × 10³) for DA were determined using electrochemical approaches. By using differential pulse voltammetry for simultaneous measurements, we obtained two peaks for DA and UA in the same solution, with the peak separation approximately 136 mV. The average recovery was measured at 102.45% for DA injection.     

Electrocatalytic oxidation of aspirin and acetaminophen on a cobalt hydroxide nanoparticles modified glassy carbon electrode

The electrocatalytic oxidation of aspirin and acetaminophen on nanoparticles of cobalt hydroxide electrodeposited on the surface of a glassy carbon electrode in alkaline solution was investigated. The process of oxidation and the kinetics have been investigated using cyclic voltammetry, chronoamperometry, and steady-state polarization measurements. Voltammetric studies have indicated that in the presence of drugs, the anodic peak current of low valence cobalt species increases, followed by a decrease in the corresponding cathodic current. This indicates that drugs are oxidized on the redox mediator which is immobilized on the electrode surface via an electrocatalytic mechanism. With the use of Laviron’s equation, the values of anodic and cathodic electron-transfer coefficients and charge-transfer rate constant for the immobilized redox species were determined as α _s,a = 0.72, α _s,c = 0.30, and k _s = 0.22 s⁻¹. The rate constant, the electron transfer coefficient, and the diffusion coefficient involved in the electrocatalytic oxidation of drugs were reported. It was shown that by using the modified electrode, aspirin and acetaminophen can be determined by amperometric technique with detection limits of 1.88 × 10⁻⁶ and 1.83 × 10⁻⁶ M, respectively. By analyzing the content of acetaminophen and aspirin in bulk forms using chronoamperometric and amperometric techniques, the analytical utility of the modified electrode was achieved. The method was also proven to be valid for analyzing these drugs in urine samples.     

Simultaneous determination of catechol and hydroquinone based on poly (diallyldimethylammonium chloride) functionalized graphene-modified glassy carbon electrode

Simultaneous determination of catechol (CC) and hydroquinone (HQ) were investigated by voltammetry based on glassy carbon electrode (GCE) modified by poly (diallyldimethylammonium chloride) (PDDA) functionalized graphene (PDDA-G). The modified electrode showed excellent sensitivity and selectivity properties for the two dihydroxybenzene isomers. In 0.1 mol/L phosphate buffer solution (PBS, pH 7.0), the oxidation peak potential difference between CC and HQ was 108 mV, and the peaks on the PDDA-G/GCE were three times as high as the ones on graphene-modified glass carbon electrode. Under optimized conditions, the PDDA-G/GCE showed wide linear behaviors in the range of 1 × 10⁻⁶−4 × 10⁻⁴ mol/L for CC and 1 × 10⁻⁶−5 × 10⁻⁴ mol/L for HQ, with the detection limits 2.0 × 10⁻⁷ mol/L for CC and 2.5 × 10⁻⁷ mol/L for HQ (S/N = 3) in mixture, respectively. Some kinetic parameters, such as the electron transfer number (n), charge transfer coefficient (α), and the apparent heterogeneous electron transfer rate constant (k _s), were calculated. The proposed method was applied to simultaneous determine CC and HQ in real water samples of Yellow River with satisfactory results.     

Electrocatalytic oxidation of pyridoxine (vitamin B<Subscript>6</Subscript>) on aluminum electrode modified by metallic palladium particles/iron (III) hexacyanoferrate (II) film

The electrocatalytic activity of a Prussian blue (PB) film on the aluminum electrode by taking advantage of the metallic palladium characteristic as an electron-transfer bridge (PB/Pd–Al) for electrooxidation of 2-methyl-3-hydroxy-4,5-bis (hydroxyl–methyl) pyridine (pyridoxine) is described. The catalytic activity of PB was explored in terms of Fe^III [Fe^III (CN)₆]/Fe^III [Fe^II (CN)₆]¹⁻ system. The best mediated oxidation of pyridoxine (PN) on the PB/Pd–Al-modified electrode was achieved in 0.5 M KNO₃ + 0.2 M potassium acetate of pH 6 at scan rate of 20 mV s⁻¹. The mechanism and kinetics of the catalytic oxidation reaction of PN were monitored by cyclic voltammetry and chronoamperometry. The results were explained using the theory of electrocatalytic reactions at chemically modified electrodes. The charge transfer-rate limiting reaction step is found to be a one-electron abstraction, whereas a two-electron charge transfer reaction is the overall oxidation reaction of PN by forming pyridoxal. The value of α, k, and D are 0.5, 1.2 × 10² M⁻¹ s⁻¹, and 1.4 × 10⁻⁵ cm² s⁻¹, respectively. Further examination of the modified electrodes shows that the modifying layers (PB) on the Pd–Al substrate have reproducible behavior and a high level of stability after posing it in the electrolyte or Pyridoxine solutions for a long time.     

Effect of cooling rate on the crystal/mesophase polymorphism of polyamide 6

The solidification of the quiescent polyamide 6 (PA 6) melt has been analyzed as a function of the cooling rate in a wide range between 1.67 × 10⁻² and close to 2 × 10² K s⁻¹, by means of differential scanning calorimetry at a low cooling rate of up to about 1 K s⁻¹, and by the recording of continuous cooling curves and time-resolved X-ray diffraction on cooling at a higher rate. The performed experiments allowed for the first time to establish the relationship between the cooling rate, the crystallization temperature, and the X-ray structure of PA 6. The exclusive formation of monoclinic α-crystals is only detected if the crystallization temperature is higher than about 430 K or if the cooling rate is slower than about 5 K s⁻¹, respectively. The formation of α-crystals is increasingly replaced by the development of mesophase with increasing cooling rate, accompanied with a decrease of the temperature of crystallization/ordering. Finally, completely amorphous samples were obtained on cooling faster than about 10² K s⁻¹. The continuous decrease of the temperature of crystallization with increasing cooling rate, regardless of the specific structure formed, precludes a primary effect of the nucleation mechanism on the α-crystal/mesophase polymorphism of PA 6. A preliminary discussion of the effect of molar mass of PA 6 on the cooling rate-dependent polymorphism is also included.     

Electrocatalytic oxidation of nitrite at a terpyridine manganese(II) complex modified carbon past electrode

A carbon past electrode modified with [Mn(H₂O)(N₃)(NO₃)(pyterpy)], ( \textpyterpy = 4￠- ( 4 - \textpyridyl ) - 2,2￠:\text6￠,\text2￠￠- \textterpyridine ) \left( {{\text{pyterpy}} = 4\prime - \left( {4 - {\text{pyridyl}}} \right) - 2,2\prime:{\text{6}}\prime,{\text{2}}\prime\prime - {\text{terpyridine}}} \right) complex have been applied to the electrocatalytic oxidation of nitrite which reduced the overpotential by about 120 mV with obviously increasing the current response. Relative standard deviations for nitrite determination was less than 2.0%, and nitrite can be determined in the ranges of 5.00 × 10⁻⁶ to 1.55 × 10⁻² mol L⁻¹, with a detection limit of 8 × 10⁻⁷ mol L⁻¹. The treatment of the voltammetric data showed that it is a pure diffusion-controlled reaction, which involves one electron in the rate-determining step. The rate constant k′, transfer coefficient α for the catalytic reaction, and diffusion coefficient of nitrite in the solution, D, were found to be 1.4 × 10⁻², 0.56× 10⁻⁶, and 7.99 × 10⁻⁶ cm² s⁻¹, respectively. The mechanism for the interaction of nitrite with the Mn(II) complex modified carbon past electrode is proposed. This work provides a simple and easy approach to detection of nitrite ion. The modified electrode indicated reproducible behavior, anti-fouling properties, and stability during electrochemical experiments, making it particularly suitable for the analytical purposes.     

Voltammetric sensor for nitrite determination based on its electrocatalytic reduction at the surface of p-duroquinone modified carbon paste electrode

A p-duroquinone (tetramethyl-p-benzoquinone) modified carbon paste electrode (DMCPE) was employed to study the electrocatalytic reduction of nitrite in aqueous solutions using cyclic voltammetry (CV), double potential-step chronoamperometry, and differential pulse voltammetry (DPV). It has found that under an optimum condition (pH 1.00), the reduction of nitrite at the surface of DMCPE occurs at a potential of about 660 mV less negative than that of an unmodified carbon paste electrode (CPE). The catalytic rate constant, k′_h, based on Andrieux and Saveant theoretical model was calculated as for scan rate 10 mV s^-1. Also, the apparent diffusion coefficient, D _app, was found as 2.5 × 10^–10 and 3.61 × 10^–5 cm² s^-1 for p-duroquinone in carbon paste matrix and nitrite in aqueous buffered solution, respectively. The values for αn_α were estimated to be −0.65 and −0.19 for the reduction of nitrite at the surface of DMCPE and CPE, respectively. The electrocatalytic reduction peak currents showed a linear dependence on the nitrite concentration, and a linear analytical curve was obtained in the ranges of 5.0 × 10^–5 M to 8.0 × 10^–3 M and 6.0 × 10^–6 M to 8.0 × 10^–4 M of nitrite concentration with CV and DPV methods, respectively. The detection limits (2σ) were determined as 2.5 × 10^–5 M and 4.3 × 10^–6 M by CV and DPV methods. This method was also applied as a simple, selective and precise method for determination of nitrite in real samples (the weak liquor from the wood and paper factory of Mazandaran province in Iran) by using a standard addition method.     

Fabrication of gold nanoparticles/polypyrrole composite-modified electrode for sensitive hydroxylamine sensor design

A highly sensitive hydroxylamine (HA) electrochemical sensor is developed based on electrodeposition of gold nanoparticles with diameter of 8 nm on the pre-synthesized polypyrrole matrix and formed gold nanoparticles/polypyrrole (GNPs/PPy) composite on glassy carbon electrode. The electrochemical behavior and electrocatalytic activity of the composite-modified electrode are investigated. The GNPs/PPy composite exhibits a distinctly higher electrocatalytic activity for the oxidation of HA than GNPs with twofold enhancement of peak current. The enhanced electrocatalytic activity is attributed to the synergic effect of the highly dispersed gold metal particles and PPy matrix. The overall numbers of electrons involved in HA oxidation, the electron transfer coefficient, catalytic rate constant, and diffusion coefficient are investigated by chronoamperometry. The sensor presents two wide linear ranges of 4.5 × 10⁻⁷–1.2 × 10⁻³ M and 1.2 × 10⁻³–19 × 10⁻³ M with the detection limit of 4.5 × 10⁻⁸ M (s/n = 3). In addition, the proposed electrode shows excellent sensitivity, selectivity, reproducibility, and stability properties.     

Characterization of a Thermostable Family 1 Glycosyl Hydrolase Enzyme from <Emphasis Type="Italic">Putranjiva roxburghii</Emphasis> Seeds

A 66-kDa thermostable family 1 Glycosyl Hydrolase (GH1) enzyme with β-glucosidase and β-galactosidase activities was purified to homogeneity from the seeds of Putranjiva roxburghii belonging to Euphorbiaceae family. N-terminal and partial internal amino acid sequences showed significant resemblance to plant GH1 enzymes. Kinetic studies showed that enzyme hydrolyzed p-nitrophenyl β-d-glucopyranoside (pNP-Glc) with higher efficiency (K _cat/K _m = 2.27 × 10⁴ M⁻¹ s⁻¹) as compared to p-nitrophenyl β-d-galactopyranoside (pNP-Gal; K _cat/K _m = 1.15 × 10⁴ M⁻¹ s⁻¹). The optimum pH for β-galactosidase activity was 4.8 and 4.4 in citrate phosphate and acetate buffers respectively, while for β-glucosidase it was 4.6 in both buffers. The activation energy was found to be 10.6 kcal/mol in the temperature range 30–65 °C. The enzyme showed maximum activity at 65 °C with half life of ~40 min and first-order rate constant of 0.0172 min⁻¹. Far-UV CD spectra of enzyme exhibited α, β pattern at room temperature at pH 8.0. This thermostable enzyme with dual specificity and higher catalytic efficiency can be utilized for different commercial applications.     

Ultra-trace level determination of nitrite in human saliva by spectrofluorimetry using 1,3,5,7-tetramethyl-8-(3,4-diaminophenyl)-difluoroboradiaza-s-indacene

A rapid, highly sensitive and selective fluorogenic method for the determination of traces of nitrite is described. It is based on the reaction of weakly fluorescent 1,3,5,7-tetramethyl-8-(3,4-diaminophenyl)-difluoroboradiaza-s-indacence (DAMBO) and nitrite in acidic aqueous solution to give 1,3,5,7-tetramethyl-8-(5-benzotriazolyl)-difluoroboradiaza-s-indacene (DAMBO-T), which is highly fluorescent. The optimum reaction conditions and other analytical parameters are investigated to enhance the sensitivity of the method. The fluorescence enhancement at 507 nm is linearly related to the concentration of nitrite in the range of 6.0 × 10⁻⁹–5.0 × 10⁻⁷ mol L⁻¹ with a correlation coefficient of R = 0.9995 (n = 10) and a detection limit of 1.0 × 10⁻¹⁰ mol L⁻¹. The R.S.D. is 1.12% (n = 10). The method is applied to the determination of nitrite in human saliva samples with the recoveries of 96. 24–105.30%. Correspondence: Ke-Jing Huang, Department of Chemistry, Wuhan University, Wuhan 430072, P.R. China     

Analysis of domperidone in pharmaceutical formulations and wastewater by differential pulse voltammetry at a glassy-carbon electrode

The redox characteristics of the drug domperidone at a glassy-carbon electrode (GCE) in aqueous media were critically investigated by differential-pulse voltammetry (DPV) and cyclic voltammetry (CV). In Britton–Robinson (BR) buffer of pH 2.6–10.3, an irreversible and diffusion-controlled oxidation wave was developed. The dependence of the CV response of the developed anodic peak on the sweep rate (ν) and on depolizer concentration was typical of an electrode-coupled chemical reaction mechanism (EC) in which an irreversible first-order reaction is interposed between the charges. The values of the electron-transfer coefficient (α) involved in the rate-determining step calculated from the linear plots of E _p,a against ln (ν) in the pH range investigated were in the range 0.64 ± 0.05 confirming the irreversible nature of the oxidation peak. In BR buffer of pH 7.6–8.4, a well defined oxidation wave was developed and the plot of peak current height of the DPV against domperidone concentration at this peak potential was linear in the range 5.20 × 10⁻⁶ to 2.40 × 10⁻⁵ mol L⁻¹ with lower limits of detection (LOD) and quantitation (LOQ) of 6.1 × 10⁻⁷ and 9.1 × 10⁻⁷ mol L⁻¹, respectively. A relative standard deviation of 2.39% (n = 5) was obtained for 8.5 × 10⁻⁶ mol L⁻¹ of the drug. These DPV procedures were successfully used for analysis of domperidone in the pure form (98.2 ± 3.1%), dosage form (98.35 ± 2.9%), and in tap (97.0 ± 3.6%) and wastewater (95.0 ± 2.9%) samples. The method was validated by comparison with standard titrimetric and HPLC methods. Acceptable error of less than 3.3 % was also achieved. Figure In aqueous media at pH 7.6- 8.4, the DPV and cyclic voltammetry of the drug domperidone (I) at GCE showed an irreversible and diffusion controlled oxidation wave. The values of the electron transfer coefficient (α) involved in the rate determining step were found in the range 0.64± 0.05 confirming the irreversible nature of the peak. The analysis of the drug in pure form and in wastewater samples was successfully achieved     

Simultaneous and sensitive determination of procaine and its metabolite for pharmaceutical quality control and pharmacokinetic research by using a graphite paste electrode

A simple, rapid, sensitive, and accurate method for simultaneous electrochemical determination of procaine and its metabolite (p-aminobenzoic acid, PABA) for pharmaceutical quality control and pharmacokinetic research was developed using a graphite paste electrode. The differential pulse voltammetric results revealed that procaine and p-aminobenzoic acid, respectively, showed well-defined anodic oxidation peaks on a carbon paste electrode with a current peak separation of 155 mV at a scan rate of 100 mV s⁻¹. This well separation of the current peaks for these two compounds in voltammetry enables us to simultaneously determine them. Good linearity (r > 0.998) between oxidation peak current and concentration was obtained in the range of 5.0 × 10⁻⁷–5.0 × 10⁻⁵ M for procaine and 5.0 × 10⁻⁷–2.0 × 10⁻⁵ M for PABA in pH 4.50 acetate buffer solution. The detection limit for both analytes is 5 × 10⁻⁸ M (S/N = 3:1). The present voltammetric method has been successfully used to determine trace p-aminobenzoic acid in procaine hydrochloride injection and procaine in plasma with a linear relationship of current to its concentration ranging from 1.0 × 10⁻⁶ to 5.0 × 10⁻⁵ M (correlation coefficient of 0.9981) with a low detection limit of 5.0 × 10⁻⁷ M (S/N = 3:1). This validated method is promising to the study of pharmacokinetics in Sprague–Dawley rat and rabbit plasma after an intravenous administration of procaine hydrochloride injection.     

Thermochemistry of Microhydration of Sodiated and Potassiated Monosaccharides

The thermochemical properties ΔH ^o _n , ΔS ^o _n , and ΔG ^o _n for the hydration of sodiated and potassiated monosaccharides (Ara = arabinose, Xyl = xylose, Rib = ribose, Glc = glucose, and Gal = galactose) have been experimentally studied in the gas phase at 10 mbar by equilibria measurements using an electrospray high-pressure mass spectrometer equipped with a pulsed ion beam reaction chamber. The hydration enthalpies for sodiated complexes were found to be between −46.4 and −57.7 kJ/mol for the first, and −42.7 and −52.3 kJ/mol for the second water molecule. For potassiated complexes, the water binding enthalpies were similar for all studied systems and varied between −48.5 and −52.7 kJ/mol. The thermochemical values for each system correspond to a mixture of the α and β anomeric forms of monosaccharide structures involved in their cationized complexes.     

Tetracyanoquinodimethanide adsorbed on a silica gel modified with titanium oxide for electrocatalytic oxidation of hydrazine

The electrocatalytical oxidation of hydrazine at low potential using tetracyanoquinodimethanide adsorbed on silica modified with titanium oxide was investigated by cyclic voltammetry and amperometry. The modified electrode was prepared modifying a carbon paste electrode employing lithium tetracyanoquinodimethanide adsorbed onto silica gel modified with titanium oxide. This electrode showed an excellent catalytic activity and stability for hydrazine oxidation. With this modified electrode, the oxidation potential of hydrazine was shifted toward less positive value, presenting a peak current much higher than those observed on a bare GC electrode. The linear response range, sensitivity and detection limit were, respectively, 2 up to 100 μmol l⁻¹, 0.36 μA l μmol⁻¹, and 0.60 μmol l⁻¹. The repeatability of the modified electrode evaluated in term of relative standard deviation was 4.2% for 10 measurements of 100 μmol l⁻¹ hydrazine solution. The number of electrons involved in hydrazine oxidation (4), the heterogenous electron transfer rate constant (1.08 × 10³ mol⁻¹ l s⁻¹), and diffusion coefficient (5.9 × 10⁻⁶ cm² s⁻¹) were evaluated with a rotating disk electrode.     

Synthesis and characterization of mesoporous Mn–Ni oxides for supercapacitors

Mesoporous Mn–Ni oxides with the chemical compositions of Mn_1-x Ni _x O _δ (x = 0, 0.2, and 0.4) were prepared by a solid-state reaction route, using manganese sulfate, nickel chloride, and potassium hydroxide as starting materials. The obtained Mn–Ni oxides, mainly consisting of the phases of α- and γ-MnO₂, presented irregular mesoporous agglomerates built from ultra-fine particles. Specific surface area of Mn_1–x Ni _x O _δ was 42.8, 59.6, and 84.5 m² g⁻¹ for x = 0, 0.2, and 0.4, respectively. Electrochemical properties were investigated by cyclic voltammetry and galvanostatic charge/discharge in 6 mol L⁻¹ KOH electrolyte. Specific capacitances of Mn_1-x Ni _x O _δ were 343, 528, and 411 F g⁻¹ at a scan rate of 2 mV s⁻¹ for x = 0, 0.2, and 0.4, respectively, and decreased to 157, 183, and 130 F g⁻¹ with increasing scan rate to 100 mV s⁻¹, respectively. After 500 cycles at a current density of 1.24 A g⁻¹, the symmetrical Mn_1–x Ni _x O _δ capacitors delivered specific capacitances of 160, 250, and 132 F g⁻¹ for x = 0, 0.2, and 0.4, respectively, retaining about 82%, 89%, and 75% of their respective initial capacitances. The Mn_0.8Ni_0.2O _δ material showed better supercapacitive performance, which was promising for supercapacitor applications.