Electrochemical behaviour of N-acetyl-l-cysteine on gold electrode—A tentative reaction mechanism

The electrochemical behaviour of N-acetyl-l-cysteine (NAC) has been investigated by linear and cyclic voltammetry on gold electrode at room temperature. The results showed two oxidation peaks under acid and neutral conditions and only one in basic medium. For each oxidation, as many electron was exchanged as proton. The influence of both the concentration and the potential scan rate on the peak currents highlighted a diffusion-controlled phenomenon for the first peak and an adsorption-limited reaction rate for the second one. The diffusion coefficient of NAC in solution and the surface concentration of the adsorbed species at pH 3 and 7 were close to 2 × 10⁻⁴ to 2 × 10⁻⁵ cm² s⁻¹ and 6 × 10⁻⁹ to 6 × 10⁻¹⁰ mol cm⁻², respectively. Film transfer experiments resulted in an irreversible adsorption of NAC on gold electrode, and the formation of a self-assembled monolayer (SAM).     

Solubilities of actinides in a domestic groundwater and a bentonite porewater calculated by using PHREEQC

This study presents the solubilities and speciations of actinides, calculated by the PHREEQC (V.2) code in a granitic groundwater and a Ca-bentonite porewater under a reducing condition. The respective solubilities for the amorphous U, Am, Th, Np and Pu compounds in the groundwater were 2.2 × 10⁻⁵, 1.2 × 10⁻⁷, 3.1 × 10⁻⁹, 3.4 × 10⁻⁹ and 6.3 × 10⁻¹¹ mole/L, and these values are comparable to the results calculated by the MUGREM and EQ3/6 codes. The major dissolved species for U, Am, Th, Np and Pu were UO₂(OH)₃⁻, Am(OH)₂⁺, Th(OH)₄(aq), Np(OH)₃CO₃⁻ and Pu(OH)₃CO₃⁻, respectively. However, carbonate complex ions were anticipated as the major species in the porewater except for thorium due to an increase of the carbonate concentration and a decrease of the pH.     

Voltammetric measurements of aminosalicylate drugs using bismuth film electrode

A bismuth film electrode (BiFE) prepared ex-situ on a supporting glassy carbon electrode exhibited convenient electroanalytical performance for voltammetric measurement of selected aminosalycilate drugs. The reduction behaviour of aminosalycilate drugs was studied in aqueous solutions within the pH range of 4–6. The voltammetric responses were compared with those obtained at the bare glassy carbon electrode under identical conditions. In the square-wave voltammetric operation mode the BiFE showed a linear response in the concentration range of 5 × 10⁻⁶ to 3.5 × 10⁻⁴ and 1 × 10⁻⁶ to 5 × 10⁻⁴ M for sulfasalazine and olsalazine, respectively. Its electrode surface revealed auspiciously high stability and remarkable reproducibility in the rapid analysis of aminosalycilate drugs. Finally, the BiFE was satisfactorily applied for direct quantitation of azo prodrugs in real pharmaceutical samples.     

Application of silica gel as an effective modifier for the voltammetric determination of dopamine in the presence of ascorbic acid and uric acid

Amorphous silica gel modified carbon paste electrode (CPE) offers substantial improvements in voltammetric sensitivity and selectivity towards determination of dopamine (DA). Cyclic voltammetry of Fe(CN)₆^3−/4− as a negatively charged probe revealed that the surface of the silica gel modified carbon paste electrode had a high density of negative charge at pH 8.0. Therefore, the modified electrode adsorbed DA (pK_a = 8.9) and enhanced its voltammetric response while repulsed ascorbic acid (AA) (pK_a = 4.2) and uric acid (UA) (pK_a = 5.4) and inhibited their interfering effects. The influence of various experimental parameters including percent of silica gel in the CPE, pH of solution, and accumulation time and potentials, on the voltammetric response of DA was investigated. At the optimum conditions, the analytical curve was linear for dopamine concentrations from 2.0 × 10⁻⁷ to 1.0 × 10⁻⁶ mol L⁻¹ and 2.0 × 10⁻⁶ to 1.5 × 10⁻⁴ mol L⁻¹ with a detection limit (3σ) of 4.8 × 10⁻⁸ mol L⁻¹. The prepared electrode was used for determination of DA spiked into DA injection and human serum samples, and very good recovery results were obtained over a wide concentration range of DA.     

Usage of solar-assisted spouted bed drier in drying of pea

The main objective of this study is to evaluate the effects of solar-assisted spouted bed and open sun drying on the drying rate and quality parameters of pea. Color, shrinkage, bulk and apparent densities, internal and bulk porosities, rehydration capacity and microstructure were the quality parameters investigated in dried product.Drying rate for solar-assisted spouted bed was about 3.5 times of drying rate for open sun drying. Air temperature changed between 20 °C and 27.4 °C during open sun drying while temperature of air at the inlet of solar-assisted spouted bed dryer varied between 35.3 °C and 65.5 °C during the experiments. Effective diffusivities were found to be 0.64 × 10^?10 and 3.27 × 10^?10 m²/s for open sun and solar-assisted spouted bed drying of pea, respectively. In color analysis, it was observed that a* value increased while b* value decreased for both drying methods. Bulk density and apparent density of peas dried under open sun was higher than that in solar-assisted spouted bed drier. In both drying methods, internal and bulk porosities decreased. Shrinkage was more for open sun dried samples. Rehydration capacity for solar-assisted spouted bed dried sample was higher than the one for open sun dried.     

Spouted bed and microwave-assisted spouted bed drying of parboiled wheat

The effect of spouted bed and microwave-assisted spouted bed drying on drying rates of parboiled wheat was investigated. In addition, the effective moisture diffusivities of parboiled wheat were calculated. The drying experiments were performed using 200 g of parboiled wheat, at three different air temperatures (50, 70, 90 °C) and at two different microwave powers (3.5 W/g (db), 7.5 W/g (db)). Microwave-assisted spouted bed drying at microwave power of 3.5 W/g and 7.5 W/g reduced drying time by at least 60% and 85%, respectively compared to spouted bed drying. The effective diffusivity values were in the range of 1.44 × 10^?10–3.32 × 10^?10 in spouted bed drying while they were between 5.06 × 10^?10 and 11.3 × 10^?10 in microwave-assisted spouted bed drying at different experimental conditions.     

Immobilization of horseradish peroxidase on self-assembled (3-mercaptopropyl)trimethoxysilane film: Characterization, direct electrochemistry, redox thermodynamics and biosensing

Highly organized (3-mercaptopropyl)trimethoxysilane (3-MPT) films have been prepared via self-assembled coupled with sol–gel linking technology. Horseradish peroxidase (HRP) is successfully immobilized onto the densely packed three-dimensional (3D) 3-MPT network and the direct electrochemistry of HRP is achieved without any electron mediators or promoters. Redox thermodynamics of HRP on the 3-MPT films, which is obtained from the temperature dependence of the reduction potential, suggests that the positive shift of redox potentials of HRP at the interface of 3-MPT originates from the solvent reorganization effects and conformational change of the polypeptide chain of HRP. Based on the direct electrochemistry and electrocatalytic ability of HRP, a sensitive third-generation amperometric H₂O₂ biosensor is developed with two linear dependence ranges of 5.0 × 10⁻⁷ to 1.0 × 10⁻⁴ and 1.0 × 10⁻⁴ to 2.0 × 10⁻² mol L⁻¹.     

Poly (acridine orange) film modified electrode for the determination 1-naphthol in the presence of 2-naphthol

The voltammetric behavior of 1-naphthol was studied with a poly (acridine orange) (PAO) film modified glass carbon electrode (GCE). The electrooxidation of 1-naphthol was an irreversible process with its oxidation overpotential at the PAO electrode 180 mV lower than that on the GCE. PAO electrode demonstrated electrocatalytic activity to the electrooxidation of 1-naphthol giving a greatly improved detection limit down to 8 × 10⁻⁸ mol L⁻¹(S/N = 3). At the optimal experimental condition, the oxidation peak current from the PAO electrode was linearly proportional to the concentration of 1-naphthol in the range of 2 × 10⁻⁷ to 3.2 × 10⁻⁶ mol L⁻¹ and 5.2 × 10⁻⁶ to 1.2 × 10⁻⁴ mol L⁻¹. The differences of the oxidation peak potentials between 1-naphthol and the coexisted 2-naphthol was 170 mV allowing the selective detection of 1-naphthol in a mixed solution with 2-naphthol. The detection of 1-naphthol in tap water and river water was carried out with satisfactory results.     

Development and applications of quaternary ammonium (QA) membrane electrodes in pharmaceutical preparation and in bioavailability of Prostaglandin E1 and Deoxycholate

The two novel ion-pairs (PB-TPB and NB-TPB) of quaternary ammonium drugs; propantheline bromide (PB), N,N-Diisopropyl-N-methyl-N-[2-(xanthen-9ylcarbonyloxy)ethyl] ammonium bromide and neostigmine bromide (NB), 3-(dimethylcarbamoyloxy) phenyl]-trimethylazanium have been synthesized, respectively and incorporated in poly (vinyl chloride)-based membrane electrodes for the quantification of propantheline bromide and neostigmine bromide in different pharmaceutical preparations. The influences of membrane compositions on the potentiometric responses of membrane electrodes have been found to substantially improve the performance characteristics. The best performance was reported with membranes having composition (w/w) of PB-TPB or NB-TPB (6%): PVC (34%): o-NPOE (60%). The proposed electrodes exhibit nernstian response in the concentration ranges of 2.1 × 10⁻⁷ M to 1.0 × 10⁻² M and 4.4 × 10⁻⁷ M to 1.0 × 10⁻² M with detection limit of 1.5 × 10⁻⁷ M and 3.3 × 10⁻⁷ M, respectively. Both the membrane electrodes perform satisfactorily over pH ranges of (3.5–7.5 and 4.0–7.0) with fast response times (11 s and 13 s), respectively. These drugs (PB and NB) were further utilized as different ion-pairs of Prostaglandin E₁ (PGE₁) and Deoxycholate (DOC) in poly (vinyl chloride)-based membrane electrodes for the determination of bioavailability of Prostaglandin E₁ and Deoxycholate in plasma of different patients.     

Thermal stability of Mesoporous SBA-15 and Sn-SBA-15 Molecular Sieves: An in situ HTXRD study

Highly ordered SBA-15 and Sn-SBA-15 mesoporous molecular sieves with Si/Sn = 80, 60, 40 and 10 have been prepared through direct synthesis route under milder acidic conditions, which were used for the in situ high temperature X-ray diffraction (HTXRD) studies in the temperature range 298–1573 K for the first time in the literature. SBA-15 is found to be thermally stable up to 1473 K and appearance of α-cristobalite was observed at 1573 K also supported by the thermogravimetric (TG) data. A strong negative thermal expansion was observed on heating from 298 to 1573 K (α_a = −4.3 × 10⁻⁶ K⁻¹). Sn containing samples (Si/Sn = 80 and 60) showed a positive thermal expansion (6.75 × 10⁻⁶ K⁻¹ and 9.04 × 10⁻⁶ K⁻¹, respectively). On the other hand, the samples with Si/Sn = 40 and 10 showed a strong negative thermal expansion (−4.12 × 10⁻⁶ K⁻¹ and −7.56 × 10⁻⁶ K⁻¹) similar to SBA-15. The linear thermal expansion coefficient varied in the order: Si/Sn = 60 > 80 > 40 > 0 > 10. Sn⁴⁺ ions exhibit both tetrahedral and octahedral coordination depending upon the location of these ions either on the walls of the silica (Si/Sn = 80 and 60) or in the corona region of the structure (Si/Sn = 40 and 10), respectively. The thermal decomposition of the samples (TG data) is correlated to the thermal expansion behavior (HTXRD data). The decomposition behavior of template ions located within the pores is strongly influenced by the presence of Sn in the framework and a ‘soft’ interaction probably exists between the template ions and the Sn sites.     

Photodegradation of tetrahalobisphenol-A (X = Cl, Br) flame retardants and delineation of factors affecting the process

The photoassisted degradation (HPLC-UV absorption), dehalogenation (HPLC-IC) and mineralization (TOC decay) of the flame retardants tetrabromobisphenol-A (TBBPA) and tetrachlorobisphenol-A (TCBPA) were examined in UV-irradiated alkaline aqueous TiO₂ dispersions (pH 12), and for comparison the parent bisphenol-A (BPA, an endocrine disruptor) in pH 4–12 aqueous media to assess which factor impact most on the photodegradative process. Complete degradation (2.7–2.8 × 10⁻² min⁻¹) and dehalogenation (1.8 × 10⁻² min⁻¹) of TBBPA and TCBPA occurred within 2 h of UV irradiation, whereas only 45–60% mineralization (2.3–2.7 × 10⁻³ min⁻¹) was complete within 5 h for the flame retardants at pH 12 and ca. 80% for the parent BPA. Factors examined in the pH range 4–12 that impact the degradation of BPA were the point of zero charge of TiO₂ particles (pH_pzc; electrophoretic method), particle or aggregate sizes of TiO₂ (light scattering), and the relative number of OH radicals (as DMPO–OH adducts; ESR spectroscopy) produced in the UV-irradiated dispersion. Dynamics of BPA degradation (2.0–2.4 × 10⁻² min⁻¹) were pH-independent and independent of particle/aggregate size, but did correlate with the number of OH radicals, at least at pHs 4 to 8–9, after which the rates decreased somewhat at pH > 9 with decreasing adsorption owing to Coulombic repulsive forces between the very negative TiO₂ surface and the anionic forms of BPA (pK_as ca. 9.6–11.3), even though the number of OH radicals continued to increase at the higher pHs.     

Electrodeposition of silver from the system AgNO3—ethyleneglycol—water. Effect of temperature ( −30°C) on the smoothness of silver deposits

The electrodeposition of silver from a nitrate bath can be improved by lowering the temperature and by the addition of ethyleneglycol as anti-freeze. When the bath temperature is lowered below 0°C, the dendritic silver deposition is suppressed and a smooth surface is obtained; at −30°C a very finegrained deposit results. The dendritic growth is supposedly prohibited partly by the lowering of temperature and to a less extent by the adsorption of ethyleneglycol at the surface both of which might enhance the activation overvoltage of silver deposition. From the polarisation measurement in, 0·25 M AgNO₃ electrolytes, the exchange current density of Ag deposition was evaluated as 1·70 × 10⁻² A/cm²(25°C) and with 50 vol. per cent ethyleneglycol, 9·72 × 10⁻⁴ A/cm² (25°C) and 1·22 × 10⁻⁵ A/cm² (−32°C). Adsorption of ethyleneglycol on Ag cathode was discussed by differential capacitance change.     

Electrochemical behaviour of uranium (IV) in DMF at vitreous carbon

The electrochemical behaviour of UCl₄ (0.01 mol L⁻¹ up to 0.05 mol L⁻¹) in 0.1 mol L⁻¹ TBAPF₆/DMF solution at vitreous carbon was studied, at room temperature, by cyclic voltammetry and potentiostatic techniques. The electrolytic solutions were analyzed by UV spectroscopy (UV), and the electrodeposited films were characterized by Rutherford Backscattering Spectroscopy (RBS) and X-ray diffraction (XRD). The cyclic voltammetric results, at low UCl₄ concentrations (0.01 mol L⁻¹), point that the reduction of U(IV) to U(0) occurs in two steps involving mainly U(IV) and U(III) species. The first electron transfer reaction is quasi-reversible and the second irreversible. The diffusion coefficient of U(IV) in DMF and the charge rate constant were determined to be 4.78 × 10⁻⁷ cm² s⁻¹ and 1.93 × 10⁻³ cm s⁻¹ (at 0.02 V s⁻¹), respectively.RBS data obtained from samples prepared at constant potential (−3.10 V) during 3 h at room temperature, indicated the presence of uranium particles deposited all over the vitreous carbon surface with aggregates in some places, confirming that the second reduction step corresponds to uranium electrodeposition. No crystallographic ordering could be seen by XRD, pointing to an amorphous character of the uranium films.     

Pt recovery using Cyphos IL-101 immobilized in biopolymer capsules

Cyphos^® IL-101, a tetraalkylphosphonium chloride salt (ionic liquid, IL) has been immobilized in capsules prepared by ionotropic gelation in calcium chloride solutions. The IL content was varied in the resin between 0.29 and 1.28 mmol IL g⁻¹. These resins have been tested for Pt recovery from HCl solutions. The equilibrium was very slightly affected by the concentration of HCl and chloride ions. The sorption isotherms were modeled using the Langmuir equation: the maximum sorption capacity was influenced by the drying of the resin but remained close to 177 mg Pt g⁻¹ for wet resin (i.e. 0.9 mmol Pt g⁻¹, dry weight basis, or 0.7 mol Pt mol⁻¹ Cyphos) and 142 mg Pt g⁻¹ for dry resin (i.e. 0.73 mmol Pt g⁻¹, or 0.57 mol Pt mol⁻¹ Cyphos). The presence of nitrates, nickel or copper ions (added under the form of chloride salts) did not significantly decrease sorption capacity even at concentrations as high as 5 g L⁻¹. Conversely, zinc at the concentration of 5 g L⁻¹, significantly decreased Pt sorption, probably due to the competition effect of chloro-anionic Zn species. This is another evidence of the ion exchange mechanism involved in the binding of hexachloroplatinate species. The kinetics are weakly affected by the agitation speed (in the range 150–350 rpm) indicating that the resistance to film diffusion is not the limiting step. The kinetics are affected by the IL content, metal concentration and more specifically the drying of the resin: intraparticle diffusion sounds to be the controlling kinetic step: the intraparticle diffusion coefficient varied between 2 × 10⁻¹² and 18 × 10⁻¹¹ m² min⁻¹, depending on experimental conditions. Platinum can be desorbed from loaded resin using either nitric acid (5 M) or thiourea (0.1 M in 0.1 M HCl acid solution). The resin was efficiently used for three sorption/desorption cycles using nitric acid: a decrease in sorption capacity and desorption efficiency was observed beginning with the third cycle, probably due to a progressive degradation of the resin.     

Gasification of charcoal using supercritical CO2 at high pressures

A novel one-shell high temperature and high pressure semi-continuous reactor has been developed for the study of the Boudouard reaction at temperatures up to 820 °C and pressures up to 32.5 MPa. Semicontinuous gasification of charcoal using supercritical CO₂ has been achieved at conversions up to 90.8% (w/w) at LSHV between 20 and 30 h⁻¹ after 5–9 h. A gasification model is proposed and validated. Effective rates of gasification (1.32 ± 0.12) × 10⁻⁶ to (6.10 ± 2.03) × 10⁻⁵ s⁻¹ were obtained. The results indicated that this method is technically feasible for the on-line production of high pressures streams of CO/CO₂ in the lab for carrying out further chemistries, avoiding the use of CO high pressure bottles.     

Highly conductive ionic liquid based ternary polymer electrolytes obtained by in situ photopolymerisation

New ternary polymer electrolytes based on a commercial cross-linking resin dianol diacrylate (DDA), tetramethylene sulphone (TMS) as a compatibilizing solvent and ionic liquids (ILs) were prepared by in situ photopolymerisation. The electrolytes containing two polymer-to-TMS-to-IL ratios, 20:30:50 and 20:20:60 by weight, respectively and six various ILs were investigated. The obtained materials were flexible, self-standing with good mechanical properties and a long-term stability. They showed high ionic conductivities, in the range of ca. 7 × 10⁻³ to 3 × 10⁻² S cm⁻¹ at 25 °C. A very important result is that the conductivities of all the prepared polymer electrolytes exceeded the conductivities of the corresponding neat ILs by 2–3.5 times. The temperature dependence of the ionic conductivity correlates with VTF equation. All the materials prepared were characterized by a broad electrochemical stability window (3.3–3.7 V).     

Multi-walled carbon nanotubes (MWCNTs) and room temperature ionic liquids (RTILs) carbon paste Er(III) sensor based on a new derivative of dansyl chloride

Solution studies showed the strong interaction of [5-(dimethylamino) naphthalene-1-sulfonyl 4-phenylsemicarbazide] (NSP) with Er(III) ions. NSP was used as a sensing material during construction of carbon paste Er(III) sensors. The electrodes were modified with 1-n-butyl-3-methylimidazolium tetrafluoroborate, [bmim]BF₄, as room temperature ionic liquid (RTIL) and multi-walled carbon nanotube (MWCNT). Potentiometric sensors constructed with [bmim]BF₄ and MWCNTs show better sensitivity, selectivity, response time, and response stability compared to Er(III) carbon paste sensors. The best performance for the modified sensor was obtained with an electrode composition of 20% [bmim]BF₄, 20% NSP, 45% graphite powder and 15% MWCNT. This particular sensor formulation exhibits a Nernstian response (19.8 ± 0.3 mV decade⁻¹) toward Er(III) ions in the range of 1.0 × 10⁻⁷ to 1.0 × 10⁻¹ mol L⁻¹ with a detection limit of 5.0 × 10⁻⁸ mol L⁻¹. The proposed modified Er(III) sensor can be used over the pH range from 3.5 to 9.0.     

Magnetic properties of CNX whiskers

Carbon–nitrogen whiskers have been prepared by pyrolysis of 1,2-diaminopropane at 950 °C or of allylamine at 900 °C followed by quenching. They are scrolls of carbon film typically 250 nm thick and up to 1 mm long with about five layers in a structure like a “cigare russe” or “brandy snap”, about 50 μm in diameter. Approximately 8 wt% of nitrogen is incorporated into the carbon films, which are practically amorphous, exhibiting a broad diffraction peak at d = 0.34 nm. The whiskers are on the border of metallic conductivity with a resistivity of about 10⁻⁶ Ωm, and they may show either a positive or a negative temperature coefficient of resistance. The pyrolysis produces either whiskers, soot or both. Magnetization measurements of the whiskers made from 1,2-diaminopropane reveal a large diamagnetic susceptibility of χ = −170 × 10⁻⁹ m³  kg⁻¹ and a small ferromagnetic component of unknown origin with σ_S of up to 0.2 A m² kg⁻¹, whereas the soot shows a purely diamagnetic signal, with χ ≈ −40 × 10⁻⁹ m³ kg⁻¹.     

Uptake-curves for the determination of diffusion coefficients and sorption equilibria for n-alkanes on zeolites

Sorption capacities and diffusion coefficients were measured for n-alkanes on a 5A-zeolite and ZSM-5 with a gravimetric setup. Significant heat effects were observed during the experimental determination of diffusion coefficients, which complicate the interpretation and the analysis of the experimental Uptake-curves. This effect depends significantly of the sorption rate, heat of adsorption and dissipation of heat. Taking into account these heat effects, reliable transport coefficients can be extracted. These agree well with diffusion coefficients obtained from other techniques, like PFG–NMR or ZLC. With the carbon chain-length the measured diffusivities decrease from 1.6 × 10⁻¹² to 0.5 × 10⁻¹² m²/s for propane to n-hexane for 5A-zeolite at 473 K. For n-butane and n-hexane values about 8 × 10⁻¹¹ and 4.6 × 10⁻¹¹ m²/s on MFI-type zeolites at 303 K are measured.From the equilibrium data, heats of adsorption were calculated and compared with literature data. The heat of adsorption for 5A-zeolite changes with the carbon chain-length from 32 to 44 kJ/mol for n-butane to n-octane, respectively. The heats of adsorption of alkanes on ZSM-5 were 60 kJ/mol for n-butane and 57 kJ/mol for hexane. Due to different adsorption sites in MFI-type zeolites two heats of adsorption were calculated for each alkane.     

Low-temperature thermionic emission from nitrogen-doped nanocrystalline diamond films on n-type Si grown by MPCVD

Temperature-dependent emission current–voltage measurements were carried out for nitrogen (N)-doped nanocrystalline diamond (NCD) films grown on n-type Si substrates by microwave plasma-assisted chemical vapor deposition (MP-CVD). Low threshold temperature (~ 260 °C) and low threshold electric field (~ 5 × 10^− 5 V/µm) were observed. Both the temperature dependence and the electric field dependence have shown that the obtained emission current was based on electron thermionic emission from N-doped NCD films. We have also studied the relation between nitrogen concentration and the saturation emission current. The saturation current obtained was as high as 1.4 mA at 5.6 × 10^− 3 V/µm at 670 °C when the nitrogen concentration was 2.4 × 10²⁰ cm^− 3. Low value of effective work function (1.99 eV) and relatively high value of Richardson constant (~ 70) were estimated by well fitting to Richardson–Dushman equation. The results of smaller φ and larger A′ suggest that N-doped NCD has great possibility of being a highly efficient thermionic emitter material.