Effect of pH and temperature on the formation of volatile compounds in cysteine/reducing sugar/starch mixtures during extrusion cooking

Mixtures of cysteine, reducing sugar (xylose or glucose), and starch were extrusion cooked using feed pH values of 5.5, 6.5, and 7.5 and target die temperatures of 120, 150, and 180 degreesC. Volatile compounds were isolated by headspace trapping onto Tenax and analyzed by gas chromatography-mass spectrometry. Eighty and 38 compounds, respectively, were identified from extrudates prepared using glucose and xylose. Amounts of most compounds increased with temperature and pH. Aliphatic sulfur compounds, thiophenes, pyrazines, and thiazoles were the most abundant chemical classes for the glucose samples, whereas for xylose extrudates highest levels were obtained for non-sulfur-containing furans, thiophenes, sulfur-containing furans, and pyrazines. 2-Furanmethanethiol and 2-methyl-3-furanthiol were present in extrudates prepared using both sugars, but levels were higher in xylose samples. The profiles of reaction products were different from those obtained from aqueous or reduced-moisture systems based on cysteine and either glucose or ribose.

The electrochemical oxidation of hydrogen at activated platinum electrodes in room temperature ionic liquids as solvents

The oxidation of hydrogen was studied at an activated platinum micro-electrode by cyclic voltammetry in the following ionic liquids: [C(2)mim][NTf2], [C(4)mim][NTf2], [N-6.2.2.2][NTf2], [P-14.6.6.6][NTf2], [C(4)mim][OTf], [C(4)mim][BF4] [C(4)mim][PF6], [C(4)mim][NO3], [C(6)mim]Cl and [C(6)mim][FAP] (where [C(n)mim](+) = 1-alkyl-3-methylimidazolium, [N-6,N-2,N-2,N-2](+) = n-hexyltriethylammonium, [P-14,P-6,P-6,P-6](+) = tris(n-hexyltetradecyl) phosphonium, [NTf2](-) = bis(trifluoromethylsulfonyl)amide, [OTf] = trifluoromethlysulfonate and [FAP](-) = tris(perfluoroethyl)trifluorophosphate). Activation of the Pt electrode was necessary to obtain reliable and reproducible voltammetry. After activation of the electrode, the H-2 oxidation waves were nearly electrochemically and chemically reversible in [C(n)mim][NTf2] ionic liquids, chemically irreversible in [C(6)mim]Cl and [C(4)mim][NO3], and showed intermediate characteristics in OTf-, [BF4](-), [PF6](-), [FAP](-) and other [NTf2](-)-based ionic liquids. These differences reflect the contrasting interactions of protons with the respective RTIL anions. The oxidation peaks are reported relative to the half-wave potential of the cobaltocenium/cobaltocene redox couple in all ionic liquids studied, giving an indication of the relative proton interactions of each ionic liquid. A preliminary temperature study (ca. 298-333 K) has also been carried out in some of the ionic liquids. Diffusion coefficients and solubilities of hydrogen at 298 K were obtained from potential-step chronoamperometry, and there was no relationship found between the diffusion coefficients and solvent viscosity. RTILs possessing [NTf2](-) and [FAP](-) anions showed the highest micro-electrode peak currents for the oxidation in H-2 saturated solutions, with[C(4)mim][NTf2] toeing the most sensitive. The large number of available RTIL anion/cation pairs allows scope for the possible electrochemical detection of hydrogen gas for use in gas sensor technology. (c) 2008 Elsevier B.V. All rights reserved.

Electrochemical kinetics of Ag vertical bar Ag+ and TMPD vertical bar TMPD+center dot in the room-temperature ionic liquid [C(4)mpyrr][NTf2]; toward optimizing reference electrodes for voltammetry in RTILs

The voltammetry and kinetics of the Ag vertical bar Ag+ system (commonly used as a reference electrode material in both protic/aprotic and RTIL solvents) was studied in the room-temperature ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [C(4)mpyrr][NTf2] on a 10 mu m diameter Pt electrode. For the three silver salts investigated (AgOTf, AgNTf2, and AgNO3, where OTf- = trifluoromethanesulfonate, NTf2- = bis(trifluoromethylsulfonyl)imide, and NO3- = nitrate), the voltammetry gave rise to a redox couple characteristic of a

An electrochemical study of the oxidation of hydrogen at platinum electrodes in several room temperature ionic liquids

The electrochemical oxidation of dissolved hydrogen gas has been studied in a range of room-temperature ionic liquids (RTILs), namely [C(2)mim][NTf2], [C(4)mim][NTf2], [N-6,N-2,N-2,N-2][NTf2], [P-14,P-6,P-6,P-6][NTf2], [C(4)mpyrr][NTf2], [C(4)mim][BF4], [C(4)mim][PF6], [C(4)mim][OTf], and [C(6)mim]Cl on a platinum microdisk electrode of diameter 10 mu m. In all cases, except [C(6)mim]Cl, a broad quasi-electrochemically reversible oxidation peak between 0.3 to 1.3 V vs Ag was seen prior to electrode activation ([C(6)mim]Cl showed an almost irreversible wave). When the electrode was pre-anodized (

A mechanistic study of the electro-oxidation of bromide in acetonitrile and the room temperature ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide at platinum electrodes

The oxidation of bromide has been investigated by linear sweep and cyclic voltammetry at platinum electrodes in the room temperature ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide, ([C(4)mim][NTf2]), and the conventional aprotic solvent. acetonitrile, (MeCN). Similar voltammetry was observed in both solvents, despite their viscosities differing by more than an order of magnitude. DigiSim(R) was employed to simulate the voltammetric response. The mechanism is believed to involve the direct oxidation of bromide to bromine in a heterogeneous step, followed by a homogenous reaction to form the tribromide anion: 2Br(-) --> Br-2 + 2e(-)

Double potential step chronoamperometry at microdisk electrodes: simulating the case of unequal diffusion coefficients

An efficient approach to the simulation of the double potential step chronoamperometry at a microdisk electrode based on an exponentially expanding time grid and conformal mapping of the space is presented. The dimensionless second potential step flux data are included as a function of the first potential step duration and the ratio of the diffusion coefficients of the reacting species allowing instant analysis of the experimental double potential step chronoamperograms without a need for simulation. The values of the diffusion coefficients are determined for several test systems and found to be in good agreement with existing literature data. (C) 2004 Elsevier B.V. All rights reserved.

Electroreduction of Chlorine Gas at Platinum Electrodes in Several Room Temperature Ionic Liquids: Evidence of Strong Adsorption on the Electrode Surface Revealed by Unusual Voltammetry in Which Currents Decrease with Increasing Voltage Scan Rates

Voltammetry is reported for chlorine, Cl-2, dissolved in various room temperature ionic liquids using platinum microdisk electrodes. A single reductive voltammetric wave is seen and attributed to the two-electron reduction of chlorine to chloride. Studies of the effect of voltage scan rate reveal uniquely unusual behavior in which the magnitude of the currents decrease with increasing scan rates. A model for this is proposed and shown to indicate the presence of strongly adsorbed species in the electrode reaction mechanism, most likely chlorine atoms, Cl*((ads)).

Investigating the Mechanism and Electrode Kinetics of the Oxygen vertical bar Superoxide (O-2 vertical bar O-2(center dot-)) Couple in Various Room-Temperature Ionic Liquids at Gold and Platinum Electrodes in the Temperature Range 298-318 K

The reduction of oxygen was studied over a range of temperatures (298-318 K) in n-hexyltriethylammonium bis(trifluoromethanesulfonyl)imide, [N-6,N-2,N-2,N-2][NTf2], and 1-butyl-2,3-methylimidazolium bis(trifluoromethanesulfonyl)imide, [C(4)dmim][NTf2] on both gold and platinum microdisk electrodes, and the mechanism and electrode kinetics of the reaction investigated. Three different models were used to simulate the CVs, based on a simple electron transfer ('E'), an electron transfer coupled with a reversible homogeneous chemical step ('ECrev') and an electron transfer followed by adsorption of the reduction product ('EC(ads)'), and where appropriate, best fit parameters deduced, including the heterogeneous rate constant, formal electrode potential, transfer coefficient, and homogeneous rate constants for the ECrev mechanism, and adsorption/desorption rate constants for the EC(ads) mechanism. It was concluded from the good simulation fits on gold that a simple E process operates for the reduction of oxygen in [N-6,N-2,N-2,N-2][NTf2], and an ECrev process for [C(4)dmim][NTf2], with the chemical step involving the reversible formation of the O-2(center dot-)center dot center dot center dot [C(4)dmim](+) ion-pair. The E mechanism was found to loosely describe the reduction of oxygen in [N-6,N-2,N-2,N-2][NTf2] on platinum as the simulation fits were reasonable although not perfect, especially for the reverse wave. The electrochemical kinetics are slower on Pt, and observed broadening of the oxidation peak is likely due to the adsorption of superoxide on the electrode surface in a process more complex than simple Langmuirian. In [C(4)dmim][NTf2] the O-2(center dot-) predominantly ion-pairs with the solvent rather than adsorbs on the surface, and an ECrev quantitatively describes the reduction of oxygen on Pt also.

Electrochemistry in Room-Temperature Ionic Liquids: Potential Windows at Mercury Electrodes

The cathodic and anodic: potential limit of eleven different ionic liquids were determined at a mercury hemisphere electrode. Ionic liquids containing the phosphonium cation (tri(n-hexyl)tetradecylphosphonium, [P-14.6,P-6.6](+)) give the largest potential window, especially When Coupled to a trifluorotris(pentafluoroethyl)- [FAP](-). or bis(trifluoromethanesulfonyl)imide, [NTf2](-), anion.

Electrochemical Oxidation of Hydrogen Sulfide at Platinum Electrodes in Room Temperature Ionic Liquids: Evidence for Significant Accumulation of H2S at the Pt/1-Butyl-3-methylimidazolium Trifluoromethylsulfonate Interface

Electrochemical oxidation of hydrogen sulfide gas (H2S) has been studied at a platinum microelectrode (10 mu m diameter) in five room temperature ionic liquids (RTILs): [C(4)mim][OTf], [C(4)dmim][NTf2], [C(4)mim][PF6],. [C(6)mim][FAP], and [P-14,P-6,P-6,P-6][FAP] (where [C-n mim](+) = 1-alkyl-3-methylimidazolium, [C(n)dmim](+) = 1-alkyl-2,3-dimethylimidazolium, [P-14,P-6,P-6,P-6](+) = tris(p-hexyl)-tetradecylphosphonium, [OTf](-) = trifluoromethlysulfonate, [NTf2](-) = bis(trifluoromethylsulfonyl)imide, [PF6](-) = hexafluorophosphate, and [FAP](-) = trifluorotris(pentafluoroethyl)phosphate). In four of the RTILs ([C(4)dmim][NTf2], [C(4)mim][PF6], [C(6)mim][FAP], and [P-14,P-6,P-6,P-6][FAP]), no clear oxidative signal was observed. In [C(4)mim][OTf], a chemically irreversible oxidation peak was observed on the oxidative sweep with no signal seen on the reverse scan. The oxidative signal showed an adsorptive stripping peak type followed by near steady-state limiting current behavior. Potential step chronoamperometry was carried out on the reductive wave, giving a diffusion coefficient and solubility of 1.6 x 10(-11) m(2) s(-1) and 7 mM, respectively (at 25 degrees C). Using these data, we modeled the oxidation signal kinetically, assuming adsorption preceded oxidation and that adsorption was approximately Langmuirian. The oxidation step was described by an electrochemically fully irreversible Tafel law/Butler-Volmer formalism. Modeling indicated a substantial buildup of H2S in the double layer in excess of the coverage that would be expected for a monolayer of chemisorbed H2S, reflecting high solubility of the gas in [C(4)mim][OTf] and possible attractive interactions with the [OTf](-) anions accumulated at the electrode at potentials positive of the potential of zero charge. Solute enrichment of the double layer in the solution adjacent to the electrode appears a novel feature of RTIL electrochemistry.

Effect of solution pH, ionic strength, and temperature on adsorption behavior of reactive dyes on activated carbon

The adsorption behavior of C.I. Reactive Blue 2, C.I. Reactive Red 4, and C.I. Reactive Yellow 2 from aqueous solution onto activated carbon was investigated under various experimental conditions. The adsorption capacity of activated carbon for reactive dyes was found to be relatively high. At pH 7.0 and 298 K, the maximum adsorption capacity for C.I. Reactive Blue 2, C.I. Reactive Yellow 2 and C.I. Reactive Red 4 dyes was found to be 0.27, 0.24, and 0.11 mmol/g, respectively. The shape of the adsorption isotherms indicated an L2-type isotherm according to the Giles and Smith classification. The experimental adsorption data showed good correlation with the Langmuir and Ferundlich isotherm models. Further analysis indicated that the formation of a complete monolayer was not achieved, with the fraction of surface coverage found to be 0.45, 0.42, and 0.22 for C.I. Reactive Blue 2, C.I. Reactive Yellow 2 and C.I. Reactive Red 4 dyes, respectively. Experimental data indicated that the adsorption capacity of activated carbon for the dyes was higher in acidic rather than in basic solutions, and further indicated that the removal of dye increased with increase in the ionic strength of solution, this was attributed to aggregation of reactive dyes in solution. Thermodynamic studies indicated that the adsorption of reactive dyes onto activated carbon was an endothermic process. The adsorption enthalpy (?H) for C.I. Reactive Blue 2 and C.I. Reactive Yellow 2 dyes were calculated at 42.2 and 36.2 kJ/mol, respectively. The negative values of free energy (?G) determined for these systems indicated that adsorption of reactive dyes was spontaneous at the temperatures under investigation (298-328 K). © 2007 Elsevier Ltd. All rights reserved.