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1.
Mathebe NG  Morrin A  Iwuoha EI 《Talanta》2004,64(1):115-120
An amperometric biosensor was prepared by in situ deposition of horseradish peroxidase (HRP) enzyme on a polyaniline (PANI)-doped platinum disk electrode. The PANI film was electrochemically deposited on the electrode at 100 mV s−1/Ag-AgCl. Cyclic voltammetric characterization of the PANI film in 1 M HCl showed two distinct redox peaks, which prove that the PANI film was electroactive and exhibited fast reversible electrochemistry. The surface concentration and film thickness of the adsorbed electroactive species was estimated to be 1.85×10−7 mol cm−2 and approximately 16 nm, respectively. HRP was electrostatically immobilized onto the surface of the PANI film, and voltammetry was used to monitor the electrocatalytic reduction of hydrogen peroxide under diffusion-controlled conditions. Linear responses over the concentration range 2.5×10−4 to 5×10−3 M were observed. Spectroelectrochemistry was used to monitor the changes in UV-vis properties of HRP, before and after the catalysis of H2O2. The biosensor surface morphology was characterized by scanning electron microscopy (SEM) using PANI-doped screen-printed carbon electrodes (SPCEs) in the presence and absence of (i) peroxidase and (ii) peroxide. The SEM images showed clear modifications of the conducting film surface structure when doped with HRP, as well as the effect of hydrogen peroxide on the morphology of biosensor.  相似文献   

2.
A new synthetic method of szaibelyite (2MgO·B2O3·H2O) has been reported. The enthalpy of solution of 2MgO·B2O3·H2O in 2.9842 mol dm−3 HCl (aq) was determined. From a combination of this result with measured enthalpies of solution of H3BO3 in 2.9842 mol dm−3 HCl (aq) and of MgO in (HCl+H3BO3) solution, together with the standard molar enthalpies of formation of MgO (s), H3BO3 (s), and H2O (l), the standard molar enthalpy of formation of −(2884.36±1.82) kJ mol−1 of 2MgO·B2O3·H2O was obtained.  相似文献   

3.
Polyaniline base has been exposed to various temperatures between 100 °C and 1000 °C for 2 h in air. The mass loss has increased with increasing temperature. FTIR and Raman spectroscopies show the gradual destruction of the PANI structure, the possible formation of intermediate oxime and nitrile groups, and the final conversion to graphitic material. The elemental analysis confirmed the dehydrogenation while the content of nitrogen was nearly constant even after treatment at 800 °C. The conductivity of PANI base, 10−8 S cm−1, increased to ∼10−4 S cm−1 after treatment at 1000 °C; most of the products, however, were non-conducting. Another series of experiments involved the polyaniline base heated at 500 °C for 1-8 h. The studies were performed in connection with the potential flame-retardant application of polyaniline.  相似文献   

4.
Gold nanoparticles (Au nps) have been synthesized in aqueous solution of polyvinyl pyrrolidone (PVP) by gamma radiolysis from HAuCl4·3H2O precursor and in presence of small concentrations of Ag+, 2-propanol and acetone. The effect of different experimental parameters, such as concentration of reactant, molecular weight of PVP on nanoparticle formation was studied. TEM image confirmed that spherical Au nps were formed when PVP of molecular weight 360,000 Da was used as capping agent. H2O2 is a reactant in the enzyme catalyzed reaction of o-phenylene diamine (o-PDA). The reaction product has a weak absorption in the yellow region of the spectrum. When this product interacts with Au nps, it leads to enhancement of the absorption peak. The nanoparticles synthesized by radiation method were used for estimation of H2O2. The absorbance value of this peak at λmax was observed to change with H2O2 concentration, which was monitored for estimation of H2O2. The response is linear in the range of 2.5×10−6 mol dm−3 to 2×10−4 mol dm−3 and 1×10−7 mol dm−3 to 3×10−6 mol dm−3 H2O2 in two separate sets of experimental parameters with detection limit 1×10−7 mol dm−3.  相似文献   

5.
With an average diameter of 100-150 nm, composite nanotubes of polyaniline (PANI)/multiwalled carbon nanotubes (MWNTs) containing Fe3O4 nanoparticles (NPs) were synthesized by a two-step method. First, we synthesized monodispersed Fe3O4 NPs (d=17.6 nm, σ=1.92 nm) on the surface of MWNTs and then decorated the nanocomposites with a PANI layer via a self-assembly method. SEM and TEM images indicated that the obtained samples had the morphologies of nanotubes. The molecular structure and composition of MWNTs/Fe3O4 NPs/PANI nanotubes were characterized by Fourier transform infrared spectra (FTIR), energy dispersive X-ray spectrometry (EDX), X-ray photoelectron spectra (XPS), X-ray diffraction (XRD) and Raman spectra. UV-vis spectra confirmed the existence of PANI and its response to acid and alkali. As a multifunctional material, the conductivity and magnetic properties of MWNTs/Fe3O4 NPs/PANI composites nanotubes were also investigated.  相似文献   

6.
This paper describes a procedure for the speciation of antimony by UV-vis spectroscopy using pyrogallol as complexing agent. A partial least squares (PLS) regression was performed to resolve highly overlapping spectrophotometric signals obtained from mixtures of Sb(III) and Sb(V). The relative error in absolute value was less than 5% when concentrations of several mixtures were calculated. The minimum concentration determined was 3.96 × 10−5 mol dm−3 and 3.98 × 10−5 mol dm−3 for Sb(V) and Sb(III), respectively. The analysis of the possible effect of the presence of foreign ions in the solution was performed and the procedure was successfully applied to the speciation of antimony in pharmaceutical preparations and aqueous samples.  相似文献   

7.
Two pure strontium borates SrB2O4·4H2O and SrB2O4 have been synthesized and characterized by means of chemical analysis and XRD, FT-IR, DTA-TG techniques. The molar enthalpies of solution of SrB2O4·4H2O and SrB2O4 in 1 mol dm−3 HCl(aq) were measured to be −(9.92 ± 0.20) kJ mol−1 and −(81.27 ± 0.30) kJ mol−1, respectively. The molar enthalpy of solution of Sr(OH)2·8H2O in (HCl + H3BO3)(aq) were determined to be −(51.69 ± 0.15) kJ mol−1. With the use of the enthalpy of solution of H3BO3 in 1 mol dm−3 HCl(aq), and the standard molar enthalpies of formation for Sr(OH)2·8H2O(s), H3BO3(s), and H2O(l), the standard molar enthalpies of formation of −(3253.1 ± 1.7) kJ mol−1 for SrB2O4·4H2O, and of −(2038.4 ± 1.7) kJ mol−1 for SrB2O4 were obtained.  相似文献   

8.
The polyamines, octyl-[2-(2-octylamino-ethylamino)-ethyl]-amine (L1) and octyl-{2-[2-(2-octylamino-ethylamino)-ethylamino]-ethyl}-amine (L2), have been used as anion ionophores in PVC-based membrane ion-selective electrodes. Different electrodes were prepared containing L1, or L2, and o-nitrophenyl octyl ether (NPOE) or bis(2-ethylhexyl)sebacate (DOS) as plasticizers. The response of the electrodes was tested in two different buffers, HEPES-KOH (pH 7) and MES-KOH (pH 5.6). Electrodes containing L1 and L2 with NPOE (E1 and E2, respectively) showed a Nernstian response for thiocyanate with a good response time. The detection limit, linear range and slope for electrode E1 were 3.8 × 10−6 mol dm−3, 1 × 10−5 to 1 × 10−1 mol dm−3 and −57.2 mV decade−1 at pH 5.6 and 4.47 × 10−6 mol dm−3, 1.95 × 10−5 to 1 × 10−1 mol dm−3 and −58.1 mV decade−1 at pH 7.0. For electrode E2 the detection limit, linear range and slope found were 2.63 × 10−6 mol dm−3, 7.94 × 10−6 to 1 × 10−1 mol dm−3 and −58.5 mV decade−1 at pH 5.6 and 1.23 × 10−5 mol dm−3, 7.95 × 10−5 to 1 × 10−1 mol dm−3 and −46.0 mV decade−1 at pH 7. In contrast, electrodes containing DOS as plasticizers gave only response at pH 5.6 (detection limit, linear range and slope at pH 5.6 were 3.16 × 10−5 mol dm−3, 1 × 10−4 to 1 × 10−1 mol dm−3 and −52.6 mV decade−1). Selectivity coefficients for different anions with respect to thiocyanate were calculated. The electrode E2 at pH 5.6 was also used for the determination of SCN by potentiometric titrations with Ag+ ions with good results. The electrode E2 was also used to determine concentrations of thiocyanate in biological samples.  相似文献   

9.
A procedure for the determination of gallium by differential pulse adsorptive stripping voltammetry (DPADSV), using different complexing agents (ammonium pyrrolidine dithiocarbamate (APDC), pyrocatechol violet (PCV) and diethyldithiocarbamate (DDTC)), has been optimized. The selection of the experimental conditions was made using experimental design methodology. Under these conditions, the calibration was made and the detection limit was determined for each gallium-ligand complex. A robust regression method was applied which allowed the elimination of anomalous points. The detection limit, with α=β=0.05, for gallium-APDC complex was 5.0×10−8 mol dm−3, for gallium-PCV complex was 9.9×10−9 mol dm−3, and the lowest detection limit (1.3×10−9 mol dm−3) was obtained with DDTC. For this reason, DDTC was selected for the determination of the gallium concentration in a certificate sample and in a spiked tap water sample. The linear dynamic range for gallium-APDC complex was from 5.0×10−8 to 2.7×10−7 mol dm−3, for gallium-PCV complex was from 5.0×10−9 to 4.8×10−7 mol dm−3, and for gallium-DDTC complex was from 1.0×10−9 to 2.1×10−7 mol dm−3.  相似文献   

10.
Sérgio M. Santos 《Talanta》2007,72(1):165-171
An efficient methodology for the determination of carbohydrate content in soils, employing acid hydrolysis and subsequent capillary electrophoresis analysis (CE), is here described. Polysaccharides present in soil samples were hydrolyzed, at 100 °C during 4 h, to their monosaccharide form, by addition of 2 mol dm−3 trifluoroacetic acid (TFA) directly to soil. The resulting monosaccharides were then quantitatively derivatized with 4-aminobenzoic acid ethyl ester, via reductive amination with sodium cyanoborohydride, and separated by CE, coupled to an UV-vis diode array set at 300 nm. Separation electrolyte consisted of 5.0 × 10−2 mol dm−3 sodium tetraborate buffer (pH 10.2) and 6 × 10−3 mol dm−3 sodium dodecylsulphate. A 78 cm long capillary with an internal and external diameter of 75 and 375 μm, respectively, was used and separation performed at 16 °C, with an applied voltage of 30 kV. Quantification was undertaken using ribose as the internal standard. As an application example, carbohydrate composition (w/w) of a farmyard manure fertilized soil was found to vary between 0.0045 ± 0.0003% (glucose) and 0.0267 ± 0.0002% (arabinose) of the total soil content. Xylose, rhamnose, mannose, fucose and galactose content were also studied in the present work.  相似文献   

11.
Polyaniline (PANI) base has been suspended in 9 M potassium hydroxide at 20 °C or 90 °C for various time intervals extending to 4 months. The fraction of acetone-soluble material increased from 1.2 wt.% to 4.5 wt.% after exposure to an alkaline medium for 60 days at 20 °C. Gel-permeation chromatography indicates that the aggregation of PANI is reduced, while the chain degradation itself is negligible. FTIR spectroscopy confirms this trend and the absence of hydrolytic changes in the PANI structure. Polyaniline retains the ability to be reprotonated with a 1 M sulfuric acid to a conducting form. No marked changes in the molecular structure have been found, even after suspension of PANI in 9 M KOH at 90 °C for 60 days.Similar immersion of PANI salt in 5 M sulfuric acid at 20 °C was responsible for changes in the protonation, and the mass increased by 11 wt.%. This was explained by the exchange of the original sulfate or chloride counter-ions for hydrogen sulfate anions or by the protonation of secondary amine sites in PANI in addition to imine ones. The changes in the molecular structure are discussed on the basis of FTIR spectra. The conductivity decreased from 1.2 S cm−1 to ∼10−3 S cm−1 but no time-dependence of conductivity was observed. There was no fraction of PANI soluble in acetone. PANI in the protonated state is thus stable also in the strongly acidic medium.The study is supplemented by the assessment of the thermal stability of PANI base, which is of importance for the processing of PANI. Loss of moisture has been observed after exposure to 250 °C for 10 h in both nitrogen atmosphere and in air. Good stability was found at 350 °C only in the nitrogen atmosphere, while a marked mass loss in weight was registered in air.  相似文献   

12.
A series of polyurethane/polyaniline/silica organic/inorganic hybrids were synthesized via the conventional polyurethane (PU) prepolymer technique. Amine-endcapped polyaniline (PANI) with low molecular weight and higher solubility was firstly synthesized. This PANI oligomer was then used together with nano-silica bearing silanol groups as chain extenders to prepare the conducting polyurethane hybrids. The polyurethane hybrids were designated as PU-xPANI-ySiO2 (x + y = 1). For comparison, the urethane-aniline block copolymer and the PU/silica hybrid were designated as PU-PANI and PU-SiO2, respectively.The structures of PU-PANI, PU-SiO2 and conducting polyurethane hybrids were confirmed by FT-IR, solid-state 13C, and 29Si NMR spectra. In nano-silica containing organic/inorganic conducting polyurethane hybrids, UV-vis spectra revealed the maximum absorption bands similar to that of PU-PANI. X-ray diffraction patterns indicated that these samples are typical of semicrystalline/amorphous materials. SEM image of PU-0.5PANI-0.5SiO2 showed that PANI was dispersed homogeneously and interconnected continuously in the insulating PU-silica matrix. TGA results of the polymer hybrids exhibited higher thermal stabilities and lower decomposition rates than that of PU-PANI both in nitrogen and air. Differential scanning calorimetry (DSC) studies indicated that the polyurethane hybrids had higher glass-transition temperatures (Tg) with the increase of PANI, but lower than that of PU-PANI. Stress-strain curves for all of the polyurethane hybrids showed the elastomeric behavior of typical polyurethanes. The surface resistivity values of all hybrids were about 108 ∼ 1010 Ω/sq. and might meet the requirement of the anti-electrostatic materials.  相似文献   

13.
Microscopic information on the complexation of Be2+ with cyclo-tri-μ-imidotriphosphate anions in aqueous solution has been gained by both 9Be and 31P NMR techniques at −2.3 °C. Separate NMR signals corresponding to free and complexed species have been observed in both spectra. Based on an empirical additivity rule, i.e., proportionality observed between the 9Be NMR chemical shift values and the number of coordinating atoms of ligand molecules, the 9Be NMR spectra have been deconvoluted. By precise equilibrium analyses, the formation of [BeX(H2O)3]+ and [BeX2(H2O)2]0 (X = non-bridging oxygen donor as a coordination atom in the phosphate groups) has been verified, and the formation of complexes coordinating with the nitrogen atoms of the cyclic framework in the ligand molecule has been excluded. Instead, the formation of one-to-one (ML) complexes, one-to-two (ML2), together with two-to-one (M2L) complexes (L = cP3O6(NH)3) has been disclosed, the stability constants of which have been evaluated as log KML = 3.87 ± 0.03 (mol dm−3)−1, log KML2 = 2.43 ± 0.03 (mol dm−3)−2 and log KM2L = 1.30 ± 0.02 (mol dm−3)−2, respectively. 31P NMR spectra measured concurrently have verified the formation of the complexes estimated by the 9Be NMR measurement. Intrinsic 31P NMR chemical shift values of the phosphorus atoms belonging to ligand molecules complexed with Be2+, together with the 31P-31P spin-spin coupling constants have been determined.  相似文献   

14.
The physical and electrolytic properties of difluorinated dimethyl carbonate (DFDMC) synthesized using F2 gas (direct fluorination) were examined. The dielectric constant and viscosity of DFDMC are higher than those of monofluorinated dimethyl carbonate (MFDMC) and dimethyl carbonate (DMC). The oxidative decomposition voltage of DFDMC is higher than those of DMC and MFDMC. The specific conductivity in DFDMC solution is considerably lower than those in MFDMC and DMC solutions. The ethylene carbonate (EC)-DFDMC equimolar binary solution containing 1 mol dm−3 LiPF6 shows a moderate conductivity of 6.91 mS cm−1 at 25 °C. The lithium electrode cycling efficiency (charge-discharge coulombic cycling efficiency of lithium electrode) in EC-DFDMC equimolar binary solution containing 1 mol dm−3 LiPF6 is higher than 80%. The EC-DFDMC solution is a good electrolyte for rechargeable lithium batteries.  相似文献   

15.
A hyphenated ion-pair (tetrabutylammonium chloride—TBACl) reversed phase (C18) HPLC-ICP-MS method (High Performance Liquid Chromatography Inductively Coupled Plasma Mass Spectroscopy) for anionic Rh(III) aqua chlorido-complexes present in an HCl matrix has been developed. Under optimum chromatographic conditions it was possible to separate and quantify cationic Rh(III) complexes (eluted as a single band), [RhCl3(H2O)3], cis-[RhCl4(H2O)2], trans-[RhCl4(H2O)2] and [RhCln(H2O)6−n]3−n (n = 5, 6) species. The [RhCln(H2O)6−n]3−n (n = 5, 6) complex anions eluted as a single band due to the relatively fast aquation of [RhCl6]3− in a 0.1 mol L−1 TBACl ionic strength mobile phase matrix. Moreover, the calculated t1/2 of 1.3 min for [RhCl6]3− aquation at 0.1 mol kg−1 HCl ionic strength is significantly lower than the reported t1/2 of 6.3 min at 4.0 mol kg−1 HClO4 ionic strength. Ionic strength or the activity of water in this context is a key parameter that determines whether [RhCln(H2O)6−n]3−n (n = 5, 6) species can be chromatographically separated. In addition, aquation/anation rate constants were determined for [RhCln(H2O)6−n]3−n (n = 3-6) complexes at low ionic strength (0.1 mol kg−1 HCl) by means of spectrophotometry and independently with the developed ion-pair HPLC-ICP-MS technique for species assignment validation. The Rh(III) samples that was equilibrated in differing HCl concentrations for 2.8 years at 298 K was analyzed with the ion-pair HPLC method. This analysis yielded a partial Rh(III) aqua chlorido-complex species distribution diagram as a function of HCl concentration. For the first time the distribution of the cis- and trans-[RhCl4(H2O)2] stereoisomers have been obtained. Furthermore, it was found that relatively large amounts of ‘highly’ aquated [RhCln(H2O)6−n]3−n (n = 0-4) species persist in up to 2.8 mol L−1 HCl and in 1.0 mol L−1 HCl the abundance of the [RhCl5(H2O)]2− species is only 8-10% of the total, far from the 70-80% as previously proposed. A 95% abundance of the [RhCl6]3− complex anion occurs only when the HCl concentration is above 6 mol L−1. The detection limit for a Rh(III) species eluted from the column is below 0.147 mg L−1.  相似文献   

16.
Electrocodepositions were conducted in solutions of aniline and MnSO4 through potential cycling to afford hybrid films of polyaniline (PANI) and manganese dioxide (PANI/MnO2). The films obtained displayed characteristic redox peaks of PANI on cyclic voltammograms in acidic aqueous solution. While in 1.0 M NaNO3 at pH 1, the films showed pseudocapacitive behaviors from 0 to 0.65 V vs. SCE. MnO2 was detected through XRD and XPS measurements on the films. The codeposition of PANI with MnO2 had dramatic effects on morphologies of the obtained hybrid films that displayed fibrous morphologies instead of granular one of PANI. Hybrid film PM50 obtained in the presence of 50 mM Mn2+ displayed a specific capacitance of 532 F g−1 at 2.4 mA cm−2 discharging current, 26% higher than that of similarly prepared PANI. It showed a coulombic efficiency (η) of 97.5% over 1200 cycles with 76% specific capacitance maintained.  相似文献   

17.
The enthalpies of solution of NaRb[B4O5(OH)4]·4H2O in approximately 1 mol dm−3 aqueous hydrochloric acid and of RbCl in aqueous (hydrochloric acid + boric acid + sodium chloride) were determined. From these results and the enthalpy of solution of H3BO3 in approximately 1 mol dm−3 HCl(aq) and of sodium chloride in aqueous (hydrochloric acid + boric acid), the standard molar enthalpy of formation of −(5128.02 ± 1.94) kJ mol−1 for NaRb[B4O5(OH)4]·4H2O was obtained from the standard molar enthalpies of formation of NaCl(s), RbCl(s), H3BO3(s) and H2O(l). The standard molar entropy of formation of NaRb[B4O5(OH)4]·4H2O was calculated from the Gibbs free energy of formation of NaRb[B4O5(OH)4]·4H2O computed from a group contribution method.  相似文献   

18.
Polyaniline (PANI) nanofibers with interconnected network-like structures were electropolymerized on stainless steel substrates by galvanostatic electrolysis. The samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-visible spectroscopy (UV-vis) and Fourier transform infrared spectroscopy (FTIR). The results show that PANI and gels (mixtures of oligomer, dopant and aniline) form simultaneously during the electrochemical deposition. The gels play an important role in the formation of PANI nanofibers. The PANI formed in the early stage of polymerization is subject to secondary growth along one dimension, since the nucleation sites are suppressed by the wrapped gels. The dendritic degree of PANI nanofibers is related to dopants, and the order is as follows: PANI-H3PO4 > PANI-H2SO4 > PANI-HNO3. No nanofibers are obtained using CH3COOH as dopants due to the high solubility of PANI-CH3COOH.  相似文献   

19.
New types of conducting composites using red mud as an inorganic substrate and polyaniline as the conducting phase were prepared. Red mud/polyaniline (RM/PANI) composites were synthesized in acidic aqueous solution by the chemical oxidative polymerization of aniline using ammonium peroxydisulfate as the oxidant. The composites exhibit conductivities in the 0.42-5.2 S cm−1 range, depending on the amount of polyaniline. They were characterized by infrared and UV-vis spectroscopy, scanning electron microscopy and X-ray diffraction. The IR and X-ray results show that PANI is deposited on the RM surface. The composites have a globular structure and the PANI globules synthesized on the surface of RM are smaller than those prepared under the same conditions without the substrate. Thermogravimetric analysis was used for investigation of the thermal stability of the composites. The thermal stability of the conductivity of RM/PANI composites was studied by ageing at 125 °C, the conductivity being measured in situ during this process.  相似文献   

20.
New polyesters having azomethine and phenylthiourea groups in the polymer backbone were synthesized by interfacial polycondensation method. The dihydroxy monomer N-(4-hydroxy-3-methoxybenzal) N′-(4′-hydroxyphenyl)thiourea was condensed with six diacid chlorides: terephthaloyl, isophthaloyl, azeloyl, suberoyl, pimeloyl and adipolyl chlorides. The resulting polyesters were characterized by viscosity, IR, NMR and TGA analysis. The wholly aromatic poly(azomethine ester) derived from terephthaloyl chloride when blended with polyaniline/NH4OH, polyaniline/HCl and pure polyaniline shows conductance in the range 3.2 × 10−3-0.91 × 10−1 S cm−1.  相似文献   

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