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1.
The permeability of polymers, electrosynthesized at neutral pH on Pt-Ir cylinders from each of the three isomers of phenylenediamine (oPD, mPD and pPD), to H2O2 (signal transduction molecule in many oxidase-based biosensors) and ascorbic acid (AA, archetypal interference species in biological applications of biosensors) was measured, and used to determine the permselectivity of the three polymers. PmPD was the coating with the greatest permselectivity for H2O2 over AA, for low concentrations of AA. For AA levels greater than 200 μM, however, poly-ortho-phenylenediamine (PoPD) was superior. Furthermore, stability studies indicated that the permselectivity of PmPD degraded rapidly, even after 1 day, supporting the choice of PoPD as the permselective membrane for biosensor implantation where AA levels are high, such as in brain monitoring. A variety of techniques were used to gain further insight into the PPD layers, specifically electrochemical quartz crystal microbalance, mass spectrometry and scanning electron microscopy. Together these studies indicate that PmPD forms the thickest layer (∼15 nm) and is the least soluble of the polymers, that the PoPD layer is ∼4 nm thick and may consist mostly of tetramers, while PpPD is the thinnest (∼3 nm) and appears to consist of trimers.  相似文献   

2.
Aromatic diamine monomers, including o‐phenylenediamine (oPD), 4‐methyl‐o‐phenylenediamine (4Me‐oPD), 4,5‐dimethyl‐o‐phenylenediamine (dMe‐oPD) and 4‐(tert‐butyl)‐o‐phenylenediamine (tBu‐oPD), were polymerized by chemical oxidation using ammonium persulfate as an oxidant. Aluminium triflate (Al(OTf)3) was also used for the first time as a co‐catalyst under various reaction conditions for the polymerization of oPD derivatives. The polymerization yield was improved when Al(OTf)3 was introduced to the polymerization reaction for most polymers. The solubility of poly(4‐methyl‐o‐phenylenediamine) (P(4Me‐oPD)), poly(4,5‐dimethyl‐o‐phenylenediamine) (P(dMe‐oPD)) and poly(4‐(tert‐butyl)‐o‐phenylenediamine) (P(tBu‐oPD)) polymers was improved compared with the poly(o‐phenylenediamine) (P(oPD)) polymers in most common solvents. The homopolymers obtained were characterized by Fourier transform IR spectroscopy, UV?visible spectroscopy, 1H and 13C NMR, wide‐angle X‐ray diffraction, DSC and TGA. The results showed that the yield, solubility and structure of the polymers are significantly dependent on the polymerization conditions. DSC measurements indicated that the polymers exhibited melting and crystallization transitions. The polymers also showed good thermal stability and decompose above 400 °C in nitrogen. © 2013 Society of Chemical Industry  相似文献   

3.
N,N‐Diallyl nicotinamide (DANA) and acrylic acid (AA) were used to react with acrylamide (AM) and synthesize a novel nicotinic acid functionalized water‐soluble copolymer AM/AA/DANA by redox free‐radical polymerization. Then, the acrylamide/sodium acrylamido methanesulfonate/acrylic acid/N,N‐diallyl nicotinamide (AM/AMS/AA/DANA) was obtained by the introduction of the ? SO3? group into AM/AA/DANA after sulfomethylation. The optimal reaction conditions, such as the monomer ratio, initiator concentration, reaction temperature, and pH of the copolymerization or sulfomethylation, were investigated. Both AM/AA/DANA and AM/AMS/AA/DANA were characterized by IR spectroscopy, 1H‐NMR, scanning electron microscopy, and intrinsic viscosity testing. We found that the AM/AMS/AA/DANA had a remarkable temperature tolerance (120°C, viscosity retention rate = 39.8%), shear tolerance (1000 s?1, viscosity retention rate = 23.3%), and salt tolerance (10 g/L NaCl, 1.5 g/L MgCl2, 1.5 g/L CaCl2, viscosity retention rates = 37.4, 27.5, and 21.6%). In addition, the result of the core flood test showed that the about 13.1% oil recovery could be enhanced by 2.0 g/L AM/AMS/AA/DANA at 70°C. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40165.  相似文献   

4.
Poly(o‐phenylenediamine) (PoPD) film has been electrochemically prepared on Pt electrode in an acetonitrile–water medium containing o‐phenylenediamine (oPD) monomer and (±)‐10‐camphorsulfonic acid (HCSA) by using the cyclic voltammetry (CV). The PoPD film (PoPD–CSA) has been characterized by FTIR, CV, EIS, FESEM, and conductivity measurement. The glucose biosensor (Pt/PoPD–CSA/GOx) has been prepared from the PoPD coated electrode by immobilizing glucose oxidase (GOx) enzyme using glutaraldehyde. The biosensor shows a low detection limit and wide linear working range, a good reusability, long‐term stability, and anti‐interference ability. The Pt/PoPD–CSA/GOx has possesses higher sensitivity (2.05 μA/mmol L?1) and affinity to glucose due to the use of CSA ion as dopant. The linear concentration ranges of Pt/PoPD–CSA/GOx have been found to be 9.6 × 10?3 to 8.2 mmol L?1 from calibration curve and 4.6 × 10?2 to 100 mmol L?1 from the relationship between the (1/glucose concentration) and (1/current difference). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39864.  相似文献   

5.
Novel cadmium selective coated graphite electrodes were prepared using three different ionophores N1, N2-dicyanoethyl-N1, N2-bis(pyridin-2-ylmethyl)benzene-1, 2-diamine [L1], N1, N2-dicyanoethyl-N1, N2-bis(thiophen-2-ylmethyl) benzene-1, 2-diamine [L2] and N1, N2-dicyanoethyl-N1, N2-bis(furan-2-ylmethyl)benzene-1, 2-diamine [L3], and their potentiometric characteristics were determined. Membranes having different compositions of poly(vinylchloride) (PVC), the plasticizer o-nitrophenyloctylether (o-NPOE), sodium tetraphenylborate (NaTPB) as an anionic additive and ionophores were coated onto the graphite surface. The potential response measurements showed that the best performance was exhibited by the electrodes with membranes having the composition L1: o-NPOE:NaTPB:PVC as 4:51:2.5:42.5 (wt.%), L2: o-NPOE:NaTPB:PVC as 3:52.5:1.5:43 (wt.%) and L3: o-NPOE:NaTPB:PVC as 7:49:3.5:40.5 (wt.%). These electrodes had the widest working concentration range, Nernstian slope and fast response times of 12 s, 7 s and 17 s for L1, L2 and L3, respectively. The selectivity studies showed that these electrodes have higher selectivity towards Cd2+ over a large number of cations and could tolerate up to 20 vol.% non-aqueous impurities. Furthermore, the electrodes generated constant potentials in the pH range 2.0–8.0, with a shelf life of approximately four to six weeks. The high selectivity of these electrodes permits their use in the detection of the Cd2+ content in some medicinal plants, soil and industrial wastewater samples. The electrodes could also be used as an indicator electrode in the potentiometric titration of Cd2+ with EDTA.  相似文献   

6.
When the flax fibers (machine tow) were treated with KMnO4 solution, MnO2 was deposited over‐all the fiber surface. The amount of MnO2 deposited relied on the KMnO4 concentration. Subjecting the flax‐containing MnO2 to a solution consisting of monomer (acrylic acid, AA) and citric acid, CA (or any acid used in this work) resulted in formation of poly(AA)‐flax graft copolymer. Dependence of the polymer criteria, namely, the total percentage conversion (%TC) and the carboxyl content of the grafted flax fibers on various grafting parameters, viz., concentrations of the redox pair as well as AA, material‐to‐liquor ratio (M/R), duration and temperature of polymerization, kind of the acid and kind of the flax fibers pretreatment was studied systematically. The results indicated that the polymerizability of AA molecules, expressed as %TC (i.e., counting both grafting and homopolymerization) and thence the carboxyl content (i.e., evaluating the extent of AA grafting along the flax backbone) was optimized with the following conditions: [AA], 100% (based on weight of flax fibers, owf); [CA], 0.4 meq/1 g flax; [MnO2], 0.4 meq/1 g flax; polymerization temperature, 40°C; polymerization time, 30 min; and the M/R, 1 : 50. A tentative mechanism for grafting of flax fibers with AA using MnO2‐acid redox system was elucidated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3028–3036, 2006  相似文献   

7.
o‐Xylene combustion in air over a Pt/γ‐Al2O3 catalyst was investigated in a laboratory reactor at low concentrations typical for depollution applications. The results evidenced a slightly negative influence of o‐xylene concentration on combustion rate. A kinetic model of the combustion process was developed by using the Langmuir‐Hinshelwood mechanism, assuming the surface reaction between adsorbed oxygen atoms and adsorbed o‐xylene molecules as controlling step. The rate expression includes the influences of o‐xylene and water adsorption on the active centers of the catalyst. The estimation of rate expression parameters is based on o‐xylene conversion measurements obtained under conditions free of influences of physical steps.  相似文献   

8.
BACKGROUND: Synergistic extraction has been proven to enhance extractability and selectivity. Numerous types of synergistic extraction systems have been applied to rare earth elements, among which sec‐nonylphenoxyacetic acid (CA100) has proved to be an excellent synergistic extractant. In this study, the synergistic enhancement of the extraction of holmium(III) from nitrate medium by mixtures of CA100 (H2A2) with 2,2′‐bipyridyl (bipy, B) in n‐heptane has been investigated. The extraction of all other lanthanides (except polonium) and yttrium by the mixtures in n‐heptane has also been studied. RESULTS: Mixtures of CA100 and bipy have significant synergistic effects on all rare earth elements, for example holmium(III) is extracted as Ho(NO3)2HA2B with the mixture instead of HoH2A5, which is extracted by CA100 alone. The thermodynamic functions, ΔHo, ΔGo, and ΔSo have been calculated as 2.96 kJ mol?1, ? 6.23 kJ mol?1, and 31.34 J mol?1 K?1, respectively. CONCLUSION: Methods of slope analysis and constant molar ratio have been successfully applied to study the synergistic extraction stoichiometries of holmium(III) by mixtures of CA100 and bipy. Mixtures of these extractants have also shown various synergistic effects with other rare earth elements, making it possible to separate them. Thus CA100 + bipy may be used to separate yttrium from other lanthanides at appropriate ratios of the extractants. Copyright © 2011 Society of Chemical Industry  相似文献   

9.
The dehydrocyclisation of n-octane to iso-octane, ethylbenzene and o-, m- and p-xylene was investigated on monofunctional (non-acidic) and bifunctional (acidic) Pt/Al2O3 catalyst in a microcatalytic reactor with hydrogen as carrier at 1.8 atm and 563–673 K. On bifunctional Pt/Al2O3, the total conversion of n-octane started from a high value and decreased with increasing temperature for all pulse sizes investigated. The primary product of n-octane conversion on acidic Pt/Al2O3 was iso-octane. The product yield-temperature profiles showed a large initial production of iso-octane which decreased to a minimum as the catalyst temperature increased due to its conversion to ethylbenzene and o-xylene. On non-acidic Pt/Al2O3, the total conversion of n-octane increased initially and then went through a maximum as the catalyst temperature increased. The primary products of the reaction were found to be ethylbenzene and o-xylene, indicative of the activity of the metal to effect these ring closure reactions.  相似文献   

10.
The kinetics of oxidation of thiourea and N-substituted thioureas namely: N-methylthiourea, N-allylthiourea N-phenylthiourea and N-tolylthiourea to the corresponding formamidine disulfides by sodium N-chloro-p-toluenesulfonamide or chloramine-T (CAT) in the presence of HClO4 has been investigated at 278 K. The reactions follow identical kinetics for all thioureas, being first order each with respect to [CAT]o, [Thiourea]o and [H+]. Ionic strength of the medium and addition of p-toluenesulfonamide or halide ions have negligible influence on the rate. The solvent isotope effect has been studied using D2O in the case of the oxidation of thiourea. Decrease in the dielectric constant of the medium by adding methanol decreases the rate. The reactions were studied at different temperatures, and the composite activation parameters have been computed. An isokinetic relationship was observed with β=314 K, indicating that enthalpy factors control the reaction rate. Under comparable experimental conditions, the rate of oxidation of thioureas increases in the order: N-allylthiourea>N-phenylthiourea>N-methylthiourea>thiourea>N-tolylthiourea. A mechanism involving the interaction of conjugate acid (CH3C6H4SO2NHCl) and substrate giving an intermediate complex, in a slow step, has been suggested. The derived rate law is in agreement with the observed kinetics.  相似文献   

11.
Cellulose acetate (CA) is well known glassy polymer used in the fabrication of gas‐separation membranes. In this study, 5,11,17,23‐tetrakis(N‐morpholinomethyl)‐25,26,27,28‐tetrahydroxycalix[4]arene (CL) was blended with CA to study the gas‐permeation behavior for CO2, N2, and CH4 gases. We prepared the pure CA and CA/CL blended membranes by following a diffusion‐induced phase‐separation method. Three different concentrations of CL (3, 10, and 30 wt %) were selected for membrane preparation. The CA/CL blended membranes were then characterized via Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), and X‐ray diffraction analysis. The homogeneous blending of CL and CA was confirmed in the CA/CL blended membranes by both SEM and AFM analysis. In addition to this, the surface roughness of the CA/CL blended membranes also increased with increasing CL concentration. FTIR analysis described the structural modification in the CA polymer after it was blended with CL too. Furthermore, CL improved the tensile strength of the CA membrane appreciably from 0.160 to 1.28 MPa, but this trend was not linear with the increase in the CL concentration. CO2, CH4, and N2 gases were used for gas‐permeation experiments at 4 bars. With the permeation experiments, we concluded that permeability of N2 was higher in comparison to those of CO2 and CH4 through the CA/CL blended membranes. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 39985.  相似文献   

12.
The reaction between Ru2(OAc)4Cl and di(o-methoxyphenyl)formamidine led to the unexpected products trans-Ru2(O2CCH3)2(μ-N,N′-η2-N,O-o-MeOForm)(μ-N,N′-η2-N,O-o-MeOForm′) (1) and Ru2(O2CCH3)(μ-N,N′-o-MeOForm)(μ-N,N′-η2-N,O-o-MeOForm)(μ-N,N′-η2-N,O-o-MeOForm′) (2), where o-MeOForm is di(o-methoxyphenyl)formamidinate, and o-MeOForm′ is the O-demethylation derivative of o-MeOForm, (o-methoxyphenyl)(o-oxyphenyl)formamidinate. Both compounds 1 and 2 were structurally characterized by X-ray diffraction analysis, and are isoelectronic with the previously studied chloro-tetracarboxylatodiruthenium(II,III) and chlorotetrakis(diarylformamidinato)diruthenium(II,III) on the basis of structural and magnetic data.  相似文献   

13.
To optimize the experimental conditions for the recycling of plastic wastes, we modeled the thermal degradation process of a standard polystyrene, having a low polydispersity index. The number of initial ruptures, No, in the macromolecular chain during the pyrolysis at 350°C under nitrogen pressure is determined from the gel permeation chromatography results from the experiments with tetralin as the hydrogen donor solvent, assuming that all radicals have been stabilized by this solvent. The calculation shows that there are 23 depropagation reactions, 40 intramolecular transfers, and for n intermolecular transfers, n – 2 recombinations, and Non + 2 dismutations. © 1996 John Wiley & Sons, Inc.  相似文献   

14.
This article exploits a new approach for synthesis of acrylic acid/carboxymethyl cellulose (AA/CMC) superabsorbent hydrogel in aqueous solution by a simple one‐step using glow‐discharge electrolysis plasma, in which N,N′‐methylenebisacrylamide (MBA) was used as a crosslinking agent. The reaction parameters affecting the equilibrium swelling, that is, discharge voltage, discharge time, mass ratio of AA to CMC, content of crosslinker, and degree of neutralization, were systematically optimized to achieve a superabsorbent hydrogel with a maximum equilibrium swelling. The structure, thermal stability, and morphology of AA/CMC superabsorbent hydrogel were characterized by Fourier transform infrared spectroscopy, X‐ray diffraction analysis, thermogravimetric analysis, and scanning electron microscopy. The swelling kinetics in distilled water and swelling behaviors in various pH solutions and salts solutions (NaCl, KCl, MgCl2, CaCl2, AlCl3, and FeCl3) were investigated in detail. The effect of six cationic salt solutions on the equilibrium swelling had the following order K+ > Na+ > Mg2+ > Ca2+ > Al3+ > Fe3+. In addition, the pH‐reversibility was preliminarily investigated with alternating pH between 6.5 and 2.0. The results showed that the equilibrium swelling of AA/CMC was achieved in 90 min. The hydrogel was responsive to the pH and salts, and was reversible swelling and deswelling behavior. POLYM. ENG. SCI., 54:2310–2320, 2014. © 2013 Society of Plastics Engineers  相似文献   

15.
Cassava (Manihot esculenta Crantz) is an important starch‐rich crop, but the storage roots only have a short shelf‐life due to post‐harvest physiological deterioration (PPD), which includes the over‐production and polymerisation of hydroxycoumarins. Key aspects of coumarin secondary‐metabolite biosynthesis remain unresolved. Here we exploit the accumulation of hydroxycoumarins to test alternative pathways for their biosynthesis. Using isotopically labelled intermediates (p‐coumarate‐2‐13C, caffeate‐2‐13C, ferulate‐2‐13C, umbelliferone‐2‐18O and esculetin‐2‐18O), we show that the major biosynthetic pathway to scopoletin and its glucoside, scopolin, in cassava roots during PPD is through p‐coumaric, caffeic and then ferulic acids. An alternate pathway through 2′,4′‐dihydroxycinnamate and umbelliferone leads to esculetin and esculin. We have used C18O2‐carboxylate‐labelled cinnamic and ferulic acids, and feeding experiments under an atmosphere of 18O2, to investigate the o‐hydroxylation and cyclisation steps. We demonstrate that the major pathway is through o‐hydroxylation and not via a proposed spirolactone‐dienone intermediate.  相似文献   

16.
The electrocatalytic oxidative polymerization of o-phenylenediamine (o-PD) was performed on a reduced graphene oxide (RGO)/glassy carbon (GC) electrode. The electrolysis of o-PD was carried out using cyclic voltammetry and potentiostatic and galvanostatic methods. The experimental results demonstrated that the reduced graphene oxide (RGO) has a pronounced catalytic ability for the electrochemical oxidative polymerization of o-PD in a 0.60 M H2SO4 solution compared to the bare GC electrode; however, graphene oxide has only a slight catalytic ability for the electrochemical oxidative polymerization of o-PD. The above three electrochemical techniques confirmed that there is a considerable discrepancy between the characteristics of the electrocatalytic oxidation of a species and the characteristics of the electrocatalytic oxidative polymerization of o-PD. This effect occurs because the charges passed during the electrolysis of o-PD on the bare GC electrode were mainly consumed for the formation of the soluble oligomer; however, RGO plays an important role in suppressing the formation of the soluble oligomer. An unexpected result was obtained: two or three pairs of the redox peaks of poly(o-phenylenediamine) (PoPD), synthesized using RGO as a catalyst, occur on the cyclic voltammogram in a wider potential range, depending on the polymerization conditions; however, only one pair of redox peaks occurs on the cyclic voltammogram of the conventional PoPD in a narrow potential range under exactly the same experimental conditions. The NMR and ESR spectra of the PoPD polymerized on the RGO/GC electrode are presented in this paper.  相似文献   

17.
Titanium oxy-nitride was developed for the first time as Pt electrocatalyst support for the ORR in PEM fuel applications. The conditions of the support preparation and the Pt/TiO x N y -based electrodes’ elaboration by chemical reduction method were determined. Comparison of the polarization curves of the carbon and the TiO x N y supported how clearly TiO x N y was more stable than the Vulcan XC-72R. It was found that the 40 wt% Pt/TiO x N y -based electrocatalyst is active for the ORR in acid medium, but the activity was less than that of Pt/C. The normalized electrochemical surface area degradation of Pt/TiO x N y was significantly less than that of Pt/C. The kinetics of the ORR on Pt/TiO x N y proceeded through a four-electron transfer process. The single-cell hydrogen/oxygen PEM fuel cell performances based on Pt/TiO x N y cathode electrocatalyst exhibited the same range of characteristics as those based on Pt/C.  相似文献   

18.
The effect of catalyst film thickness on the magnitude of the effect of electrochemical promotion was investigated for the model catalytic reaction of C2H4 oxidation on porous Pt paste catalyst-electrodes deposited on YSZ. It was found that the catalytic rate enhancement ρ is up to 400 for thinner (0.2 μm) Pt films (40,000% rate enhancement) and gradually decreases to 50 for thicker (1 μm) films. The Faradaic efficiency Λ was found to increase moderately with increasing film thickness and to be described semiquantitatively by the ratio 2Fr o/I 0, where r o is the unpromoted rate and I 0 is the exchange current of the catalyst–electrolyte interface. The results are in good qualitative agreement with model predictions describing the diffusion and reaction of the backspillover O2- species, which causes electrochemical promotion.  相似文献   

19.
The monomers containing phenylsulfonamide N-allyl-4-methylbenzenesulfonamide (TCAP) and N,N-diallyl-4-methyl benzenesulfonamide (TCDAP) were copolymerized with acrylamide (AM), acrylic acid (AA), and 3-(3-methacrylamidopropyl-dimethylammonio)-propane-1-sulfonate (MDPS), respectively, through free-radical micellar copolymerization in deionized water for enhanced oil recovery (EOR). Then, the effect of the synthesis conditions was investigated simultaneously; the copolymers were characterized by Fourier transform infraredFTIR, nuclear magnetic resonance, scanning electron microscopy, and thermogravimetric analysis. It was found that the thickening function, high-temperature resistance (120 °C), and anti-shear ability were improved significantly. It was also found that the copolymers had excellent viscoelasticity at the lower shear frequencies. When the copolymers were dissolved in 10,000 mg L−1 NaCl, 2000 mg L−1 CaCl2, and 2000 mg L−1 MgCl2 solutions, the viscosity retention rates of AM/AA/TCAP/MDPS and AM/AA/TCDAP/MDPS were 13.3, 11.1, 10.6% and 18.6, 15.2, 11.7%, respectively. In addition, the copolymers for EOR at 60 °C were 11.4 and 13.8%, respectively, which demonstrated that the copolymers possessed excellent performance for potential application in EOR. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47971.  相似文献   

20.
This research is aimed to improve the activity and stability of ternary alloy Pt–Ru–Ni/C catalyst. A novel anodic catalyst for direct methanol fuel cell (DMFC), carbon supported Pt–Ru–Ni–P nanoparticles, has been prepared by chemical reduction method by using NaH2PO2 as a reducing agent. One glassy carbon disc working electrode is used to test the catalytic performances of the homemade catalysts by cyclic voltammetric (CV), chronoamperometric (CA) and amperometric it measurements in a solution of 0.5 mol L–1 H2SO4 and 0.5 mol L–1 CH3OH. The compositions, particle sizes and morphology of home‐made catalysts are evaluated by means of energy dispersive analysis of X‐ray (EDAX), X‐ray diffraction (XRD) and transmission electron micrographs (TEM), respectively. TEM images show that Pt–Ru–Ni–P nanoparticles have an even size distribution with an average diameter of less than 2 nm. The results of CV, CA and it curves indicate that the Pt–Ru–Ni–P/C catalyst shows significantly higher activity and stability for methanol electrooxidation due to the presence of non‐metal phosphorus in comparison to Pt–Ru–Ni/C one. All experimental results indicate that the addition of non‐metallic phosphorus into the Pt–Ru–Ni/C catalyst has definite value of research and practical application for enhancing the performance of DMFC.  相似文献   

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