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1.
Summary LDPE/P4VP films synthesized by in situ sorption and thermal polymerization of 4-vinylpyridine, (4VP), were used for conductivity investigations. The conductivities of swollen films varied from 7×10−6 to 1.21×10−3 S.cm−1 at room temperature depending on P4VP mass increase in the host matrix. For the temperature range of 303–333K the conductivity varied from 7×10−6 to 2.66×10−3 S.cm−1. A comparison between Arrhenius and VTF plots for conductivity measurements showed a best fit for temperature dependence according Arrhenius modified equation. The materials are stable for temperatures below 645 K. Received: 8 June 2001/ Revised version: 14 January 2002/ Accepted: 15 January 2002  相似文献   

2.
An oxetane-derived monomer, 3-acryloyloxy-methyl-3′-methyloxetane (AMO) was prepared from the reaction of 3-hydromethyl-3-methyloxetane with acryloyl chloride. The cationic ring-opening copolymerization of AMO with another oxetane-derived monomer, 3-(2-(2-(2-methoxyethylenoxy)ethylenoxy)ethylenoxy)-3′-methyloxetane (MEMO) was conducted in CH2Cl2 solution using BF3 · OEt2/1,4-butanediol as a co-initiator. The resulting copolymers were characterized by FTIR, 1H NMR and Gel Permeation Chromatography (GPC) analyses, and it was found that the enchained ratio of AMO in the copolymers is far lower than its feed ratio. They were crosslinked in situ via the radical polymerization of the vinyl group initiated by BPO after doping with lithium trifluoromethanesulfonimide (LiTFSI) to give rise to tough polymeric electrolyte films. The ionic conductivity was measured at varying content of AMO and different concentration of lithium salt LiTFSI by AC impedance, and a maximum ion conductivity of 1.44 × 10−5 S/cm at 30°C or 1.25 × 10−4 S/cm at 80°C was attained in the sample PAM 33 at the mole ratio of O: Li = 20. The DSC results indicated that T g decreases with the increase of the proportion of AMO in the copolymer, well consistent with the ion conductivity trend. The TGA (thermogravimetric analysis) measurement revealed that this kind of copolymer electrolytes is more thermostable than their liquid counterparts. __________ Translated from Transactions of Beijing Institute of Technology, 2006, 26(12): 1098–1103 [译自: 北京理工大学学报]  相似文献   

3.
Summary   A new class of lithium salt with single-ionic characteristics, lithium sulfonated styrene oligomer (LiSSO) [(CH2CHC6H5)7-(CH2CHC6H4SO3 Li+)2], was synthesized and its complex with poly(ethylene oxide) (PEO) was prepared. The maximum ionic conductivity of the PEO/LiSSO complex at 65°C was 2.1×10−4S/cm at a salt concentration of [Li+]/[EO] = 0.20. The lithium cationic transference number (t +) of the PEO/LiSSO complex was found to be 0.95, and the polymer electrolyte was electrochemically stable up to 6.2V. Received: 2 April 2001/Revised version: 30 July 2001/Accepted: 30 July 2001  相似文献   

4.
Kazuo Mukai  Yuji Okauchi 《Lipids》1989,24(11):936-939
A kinetic study of the reaction between a tocopheroxyl radical and unsaturated fatty acid esters has been undertaken. The rates of allylic hydrogen abstraction from various unsaturated fatty acid esters (ethyl oleate2, ethyl linoleate3, ethyl linolenate4, and ethyl arachidonate5) by the tocopheroxyl radical (5,7-diisopropyltocopheroxyl6) in benzene have been determined spectrophotometrically. The second-order rate constants, k3, obtained are 1.04×10−5 M−1s−1 for2, 1.82×10−2 M−1s−1 for3, 3.84×10−2 M−1s−1 for4, and 4.83×10−2 M−1s−1 for5 at 25.0°C. Thus, the rate constants, kabstr/H, given on an available hydrogen basis are k3/4=2.60×10−6 M−1s−1 for2, k3/2=9.10×10−3 M−1s−1 for3, k3/4=9.60×10−3 M−1s−1 for4, and k3/6=8.05×10−3 M−1s−1 for5. The kabstr/H values obtained for the polyunsaturated fatty acid esters3,4, and5 containing H-atoms activated by two π-electron systems are similar to each other, and are about three orders of magnitude higher than that for the ethyl oleate2 containing H-atoms activated by a single π-system. From these results, it is suggested that the prooxidant effect of α-tocopherol in edible oils and fats may be induced by the above hydrogen abstraction reaction.  相似文献   

5.
Dichlorodicarbonylbis (triphenylphosphine) ruthenium (II), RuCl2 (CO)2 (PPh3)2, was investigated as a catalyst for edible oil hydrogenation in a preliminary screening of potential catalysts for producing partially hydrogenated fats with lowtrans-isomer content. Refined, bleached and deodorized canola oil was hydrogenated using 1.77 × 10−5 − 6.64 × 10−4 mol/kg-oil of ruthenium catalyst equivalent to 1.79 × 10−4 − 6.71 × 10−3 wt% Ru. The effects of temperature (50–180 C) and pressure (50–750 psig) on reaction rate,trans-isomer content and fatty acid composition were examined. The activities of RuCl2 (CO)2 (PPh3)2 and nickel (Nysel HK-4 and AOCS standard nickel catalyst) were compared on a molar basis. At 4.40 × 10−4 mol/kg-oil (0.0026 wt/Ni or 0.0044 wt% Ru), 140 C and 50 psig, the nickel catalysts were completely inactive, but the ruthenium catalyst produced an IV drop of 40 units in 60 min. At 110 C, 750 psig and 1.34 × 10−4 mol/kg-oil (1.35 × 10−3 wt% Ru), a hydrogenation rate of 0.89 ΔIV/min and a maximumtrans-isomer content of 10.4% (IV=45.0) was obtained with the ruthenium catalyst.  相似文献   

6.
Well-defined star shaped polymers with α-Cyclodextrin (α-CD) core linking PMMA-block arms were synthesized by atom transfer radical polymerization (ATRP). Gel polymer electrolytes (GPEs) were prepared by encapsulating electrolyte solution of 1 mol L−1 of LiClO4/EC-PC (volume 1:1) into the obtained star shaped polymer host. The ionic conductivity of the GPEs and the cycling characteristics of LiCoO2/GPEs/Graphite cell were studied by electrochemical impedance spectroscopy and charge-discharge testing, respectively. The results indicate that the GPEs have a high ionic conductivity up to 1.63 × 10−3 S cm−1 at room temperature and exhibit a high electrochemical stability potential of 4.5 V (vs. Li/Li+). The discharge capacity of LiCoO2/GPEs/Graphite cell is about 98% of its initial discharge capacity after 20 cycles at 0.1 C rate. Discharge capacity of the model cell with GPEs is stable with charge-discharge cycling.  相似文献   

7.
Chia seeds as a source of natural lipid antioxidants   总被引:8,自引:0,他引:8  
Chia (Salvia sp) seeds were investigated as a source of natural lipid antioxidants. Methanolic and aqueous extracts of defatted chia seeds possessed potent antioxidant activity. Analysis of 2 batches of chia-seed oils demonstrated marked difference in the fatty acid composition of the oils. In both batches, the oils had high concentrations of polyunsaturated fatty acids. The major antioxidant activity in the nonhydrolyzed extract was caused by flavonol glycosides, chlorogenic acid (7.1 × 10−4 mol/kg of seed) and caffeic acid (6.6 × 10−3 m/kg). Major antioxidants of the hydrolyzed extracts were flavonol aglycones/kaempferol (1.1 × 10−3 m/kg), quercetin (2.0 × 10−4 m/kg) and myricetin (3.1 × 10−3 m/kg); and caffeic acid (1.35 × 10−2 m/kg). Two methods were used to measure antioxidant activities. Both were based on measuring bleaching ofβ-carotene in the coupled oxidation ofβ-carotene and linoleic acid in the presence of added antioxidants.  相似文献   

8.
Free radical solution polymerization of heptadecafluorodecyl acrylate (HDFDA) and heptadecafluorodecyl methacrylate (HDFDMA) was carried out by using 2,2′-azobisisobutyronitrile (AIBN) as the initiator in supercritical carbon dioxide (scCO2). We performed solution polymerization with changing initiator concentration, temperature and polymerization time to study the polymerization kinetics. A nonlinear least square method and dead-end theory were used to determine the constant, K (K=(k p √f)/√k d k d ) and initiator decomposition rate constant (k d ) from experimental data. k d was measured as 3.77 × 10−5 s−1 at 62.7°C for poly(HDFDA) and 2.71 × 10−5 s−1 at 62.5 °C for poly(HDFDMA), respectively, by nonlinear least square method.  相似文献   

9.
In order to obtain efficient microwave absorbers that possess high conductivity, dielectric and magnetic properties, hexanoic acid doped polyaniline (PAni) nanocomposites which contain different ratios of ferum (II) oxide (Fe3O4) and titanium dioxide (TiO2) nanoparticles were successfully prepared by in situ chemical polymerization through template free method. Chemical structure, conductivity, morphology, thermal stability, magnetic properties, and amorphous/crystalline behavior of PAni nanocomposites were characterized by Fourier transform infrared spectrometer (FTIR), four point probe, field emission scanning electron microscope (FESEM), thermal gravimetric analysis (TGA), vibrating samples magnetometer (VSM), and X‐ray diffractometer (XRD), respectively. From this study, conductivity was significantly improved from 8.48 × 10−4−1.23 × 10−2 S/cm for PAni nanocomposites without any chemical treatment (during addition of Fe3O4) to 3.58 × 10−2−4.77 × 10−2 S/cm for those with chemical treatment. PAni nanocomposites with chemical treatment show a narrow sharp reflection loss (RL) peak with high absorption (−48.9 dB) at lower frequency due to the limited individual Fe3O4 nanoparticles outside the nanorods/nanotubes as proved by the new proposed mechanism (Fig. 5 ), while it shows a broad RL peak with poor absorption (−13 dB) at higher frequency for those without chemical treatment. The novelty of this research has been focused on PAni with chemical treatment which yield better microwave absorption property (99.999% absorption), combination of high conductivity (3.58 × 10−2−4.77 × 10−2 S/cm), high heterogeneity and moderate magnetization (Ms = 8.87–28.49 emu/g) compare to the PAni without chemical treatment. POLYM. COMPOS., 34:1186–1194, 2013. © 2013 Society of Plastics Engineers  相似文献   

10.
A kinetic study of the prooxidant effect of α-tocopherol was performed. The rates of allylic hydrogen abstraction from various unsaturated fatty acid esters (ethyl stearate 1, ethyl oleate 2, ethyl linoleate 3, ethyl linolenate 4, and ethyl arachidonate 5) by α-tocopheroxyl radical in toluene were determined, using a double-mixing stopped-flow spectrophotometer. The second-order rate constants (k p) obtained are <1 × 10−2 M−1 s−1 for 1, 1.90 × 10−2 M−1 s−1 for 2, 8.33 × 10−2 M−1 s−1 for 3, 1.92 × 10−1 M−1 s−1 for 4, and 2.43 × 10−1 M−1 s−1 for 5 at 25.0 °C. Fatty acid esters 3, 4, and 5 contain two, four, and six –CH2– hydrogen atoms activated by two π-electron systems (–C=C–CH2–C=C–). On the other hand, fatty acid ester 2 has four –CH2– hydrogen atoms activated by a single π-electron system (–CH2–C=C–CH2–). Thus, the rate constants, k abstr/H, given on an available hydrogen basis are k p/4 = 4.75 × 10−3 M−1 s−1 for 2, k p/2 = 4.16 × 10−2 M−1 s−1 for 3, k p/4 = 4.79 × 10−2 M−1 s−1 for 4, and k p/6 = 4.05 × 10−2 M−1 s−1 for 5. The k abstr/H values obtained for 3, 4, and 5 are similar to each other, and are by about one order of magnitude higher than that for 2. From these results, it is suggested that the prooxidant effect of α-tocopherol in edible oils, fats, and low-density lipoproteins may be induced by the above hydrogen abstraction reaction.  相似文献   

11.
The present study was designed to examine the effects of EFA deficiency (EFAD) on biochemical, functional, and structural aspects of the kidney in growing and adult rats fed a normal or EFAD diet for 9 wk after weaning. Food and fluid intake (FI), urine volume, and Na+ and K+ excretions were measured weekly from weeks 4 to 8 by placing the rats in individual metabolic cages for 24 h. At week 9, Li+ and a 5% water load, respectively, were administered at 14 and 1.5 h prior to glomerular and proximal tubular function studies, as assessed by 3-h creatinine (CCr) and Li+ (CLi+) clearances. Hematocrit and urine volume; serum and urine [Cr], [Li+], [Na+], and [K+]; and renal FA distribution were also measured. Data [corrected to 100 g/body weight (bw) and presented as means ±SEM] were significant, at P<-0.05. Despite a similar ingestion of solids from weeks 4 to 7 (weeks 7 to 10 of life), the rats on the EFAD diet showed a decreased body weight from week 5. From weeks 4 to 8, Fl and urine volume were similar for both groups, but the Fl increased at week 6 in the EFAD group; 24-h Na+ and K+ excretions were similar at all weeks, except for an increase in the EFAD group for both ions at week 7. In the EFAD group, CCr and CLi+ decreased by 27 and 56.3%, respectively (385.7±33.4 vs. 280±21.1, and 21.0±2.1 vs. 9.2±1.1 μL/min/100 g; n=9 vs. 10), the latter result suggesting increased proximal reabsorption. The 3-h Na+ and K+ excretions were similar, but the Li+ decreased (0.78±0.06×10−2 vs. 0.32±0.03×10−2 μeq/min/100 g) in the EFAD group, giving additional support to the suggestion. Renal structure was normal and similar for both groups, but the EFAD group showed a more prominent proximal tubule brush border, together with heavier periodic acid-Schiff staining in all specimens from weeks 5 to 9. In the EFAD group, FA of the n−9 and n−7 series were higher, but most of the n−6 series were lower as a percentage of total lipids in the medulla and cortex. Medullary levels of 20∶4n−6 were maintained, 22∶4n−6 declined twice, arachidonic acid was maintained, and 20∶5n−3 was lower. The EFAD diet affected glomerular function, proximal tubular structure and function, and FA distribution in the rat kidney.  相似文献   

12.
In a study of stable emulsions of linoleic acid in 0.1M-KH2PO4/Na2HPO4 buffer solutions prepared by sonic vibrations, the influence of linoleic acid on pH was manifested in buffer solutions of pH 8.00 and decreased gradually till it became negligible in pH 4.50. This change in pH values was due to differences in solubility of linoleic acid in the buffer solutions. Ultraviolet spectra of soluble linoleic acid in buffer solutions indicated the presence of conjugated dienes, which increased with the increasing of the pH of the system. Unbuffered aqueous emulsions of linoleic acid had a pH value which ranged between 4.69 and 5.10. Saturated aqueous solutions, obtained by high-speed centrifugation, had concentrations of 15.80 to 16.00 mg. linoleic acid per 100 ml. of D.I. water. From the solubility data and conductivity values of linoleic acid the apparent classic and thermodynamic ionization constants were calculated to be 6.974±0.023×10−6 and 6.905±0.017×10−6 at 0.7°C. and 1.730±0.009×10−5 and 1.689±0.007×10−5 at 25°C., respectively. The result of the chemical interaction of linoleic acid and water is a saturated hydroxy fatty acid. This acid gave a positive test for glycol groups with periodic acid oxidation test and appeared to be a tetrahydroxy compound with the exact structure unknown. Presented at the 51st Annual Meeting, American Oil Chemists' Society at Dallas, Tex., April 4–6, 1960. American Meat Institute Foundation Journal Paper No.204.  相似文献   

13.
Separation of As(III) and As(V) ions from sulphate media by hollow fiber supported liquid membrane has been examined. Cyanex 923 was diluted in toluene and used as an extractant. Water was used as a stripping solution. The extractability of As(V) was higher than As(III). When the concentration of sulphuric acid in feed solution and Cyanex 923 in liquid membrane increased, more arsenic ions were extracted into liquid membrane and recovered into the stripping solution. The mathematical model was focused on the extraction side of the liquid membrane system. The mass transfer coefficients of the aqueous phase (k i ) and organic phase (k m ) are 7.15×10−3 and 3.45×10−2 cm/s for As(III), and 1.07×10−2 and 1.79×10−2 cm/s for As(V). Therefore, the rate-controlling step for As(III) and As(V) in liquid membrane process is the mass transfer in the aqueous film between the feed solution and liquid membrane. The calculated mass transfer coefficients agree with the experimental results.  相似文献   

14.
With TiCl4/MgCl2 (Ti) and Al(i-Bu)3 (Al) as catalysts, the thermoplastic copolymer of 1-butene(Bt) and 1-hexene(He) was synthesized successfully. The effects of Bt/He, Ti/(He+Bt), Al/Ti, temperature and reaction time on conversion, catalyst efficiency(CE), intrinsic viscosity([η]) and insoluble content were studied. The copolymer was analyzed with Fourier transform-infrared (FTIR) and nuclear magnetic resonance (1H-NMR). Results showed that the optimal polymerization conditions were: He/Bt = 0.25, temperature 40°C−50°C, Al/Ti = 400−500, Ti/(Bt+He) = 3 × 10−5 − 4 × 10−5, time 4 h. Intrinsic viscosity was found to increase with increasing Ti/(Bt+He) and decreasing Al/Ti and polymerization temperature. When the molar content of He, Al/Ti and polymerization temperature increased, the insoluble content in CH2Cl2 of copolymers decreased. When Ti/(Bt+He) and reaction time increased, the insoluble content in CH2Cl2 of copolymers also increased. The crystallization and stereoregularity of poly(1-butene) decreased with the addition of He. Translated from China Synthetic Rubber Industry, 2006, 29(6): 429–434 [译自: 合成橡胶工业]  相似文献   

15.
H3PO4-doped proton-exchange membranes based on benzimidazole-2-yl-substituted polybenzimidazoles have been obtained and studied. Attempts have been made to stabilize the mechanical properties of doped membranes by crosslinking of the initial polymers. The treatment with sulfuric acid is selected as the most efficient crosslinking method. Target characteristics (proton conductivity and performance in the fuel cell) of a membrane based on crosslinked benzimidazole-2-yl-substituted polybenzimidazole have been investigated. The proton conductivity of the membrane is estimated as 5.2 × 10−2 S/cm at 160°C. The current density in a hydrogen—air fuel cell based on the developed membrane is found to be 0.21 A/cm2 at 160°C, 0.6 V, with a total platinum content on electrodes of 1 mg/cm2.  相似文献   

16.
The electrocatalytic behavior of uric acid has been investigated with a glassy carbon electrode modified with p-aminobenzene sulfonic acid through electrochemical polymerization. This resulting electrode shows an excellent electrocatalytic response to uric acid and ascorbic acid, with a peak-to-peak separation of 0.267 V in a 0.1 mol L−1 phosphate buffer solution (PBS) at pH 7.0. These results indicate that the proposed electrode can eliminate the serious interference of ascorbic acid, which coexists with uric acid in body fluids. Differential pulse voltammetry (DPV) was used for detecting uric acid with selectivity and sensitivity. The anodic peak current of uric acid was proportional to its concentration in the range of 1.2 × 10−7–8.0 × 10−4 mol L−1, with a detection limit of 4.0 × 10−8 mol L−1. The proposed method has been applied with satisfactory results to the determination of uric acid in human urine without any pretreatment.  相似文献   

17.
Summary Influence of some aromatic amino acids (histidine, phenylalanine and tryptophan) on the swelling behavior of acrylamide/maleic acid hydrogel (AAm/MA) prepared by γ-radiation was investigated. Swelling tests of AAm/MA hydrogel were made in buffer solutions and amino acid solutions at various pH at 37°C. The pH values are ionization of α-carboxyl groups (pK'1), α-amino groups (pK'2) and, isoelectric points (pI) of amino acids. The swelling of AAm/MA hydrogel increased when pH values of solutions were increased. The value of equilibrium swelling of AAm/MA hydrogel was 1035% at pH 10 buffer, while it was 880% at pH 2 buffer. The values of equilibrium swelling of AAm/MA hydrogel in phenylalanine, tryptophan and histidine solutions varied among 1130–1245% at pH 10, while they were among 790–975% at pH 2. The rate constant of swelling, diffusional exponent, network parameter and, diffusion and intrinsic diffusion coefficient were calculated by swelling kinetics. Diffusion of the penetrants into the hydrogel was found to be non-Fickian character. The diffusion coefficients of the hydrogel varied between 3.33×10−6– 7.71×10−6 cm 2s−1, while the intrinsic diffusion coefficients waried between 4.03×10−6– 8.48×10−6 cm 2s−1. Received: 22 December 1997/Revised version: 3 March 1998/Accepted: 5 March 1998  相似文献   

18.
The influence of sodium fluoride additives on the physicochemical properties of glasses in the Na2O-B2O3 systems is investigated. The introduction of sodium fluoride into the Na2O · 2B2O3 and Na2O · 3B2O3 glasses leads to an increase in the electric conductivity. The temperature-concentration dependence of the electric conductivity has been investigated. It is shown that, in glasses of the NaF-Na2O · 2B2O3 system, an increase in the volume concentration of sodium ions from 2.4 × 10−2 to ∼3 × 10−2 mol/cm3 is accompanied by an insignificant decrease in the activation energy Eσ from 1.44 to 1.38 eV and a sharp (by a factor of ∼30) increase in the electric conductivity. In glasses of the NaF-Na2O · 3B2O3 system, an increase in the concentration of sodium ions from 1.8 × 10−2 to ∼2.3 × 10−2 mol/cm3 brings about an increase in the electric conductivity by a factor of approximately 100 and an increase in Eσ from 1.6 to 1.83 eV. A further increase in the concentration of sodium ions (up to 2.5 × 10−2 mol/cm3) virtually does not affect the electric conductivity and Eσ. At the same concentration of sodium ions (∼2.46 × 10−2 mol/cm3) in the 9.8NaF · 90.2[Na2O · 2B2O3] and 57.1NaF · 42.9[Na2O · 3B2O3] glasses, the electric conductivity and the activation energy are considerably higher in the glass with a larger fluorine content. The regularities revealed are interpreted in the framework of the microinhomogeneous glass structure.  相似文献   

19.
Three conjugated ethynylene-carbazole polymers with Tetrathiafulvalene (TTF) as pendant group (P1–P3) were synthesized by using sonogashira coupling reaction and characterized by 1H NMR, GPC, CV, UV–Vis, FL, and TGA. CV and UV–Vis spectra showed that an intramoleular interaction existed between the electron-rich moiety TTF and electron-deficient moiety polyethynylcarbazole of the polymers. A strong fluorescence quench (ca. 99%) could be observed, compared to the polyethynylene-carbazole without TTF units, which could be ascribed to the photo-induced electron transfer (PET) interaction from TTF moiety to the polyethynylene-carbazole backbone. The observed onset decomposition temperatures (T d) for P1–P3 varied from 256 to 298 °C. The polymers mentioned above exhibited good thermal properties and higher conductivity (neutral conductivity ~7–11 × 10−7 S cm−1; doped conductivity ~6–11 × 10−4 S cm−1).  相似文献   

20.
The influence of sodium fluoride additives on the physicochemical properties of glasses in the Na2O-B2O3 systems is investigated. The introduction of sodium fluoride into the Na2O · 2B2O3 and Na2O · 3B2O3 glasses leads to an increase in the electric conductivity. The temperature-concentration dependence of the electric conductivity has been investigated. It is shown that, in glasses of the NaF-Na2O · 2B2O3 system, an increase in the volume concentration of sodium ions from 2.4 × 10−2 to ∼3 × 10−2 mol/cm3 is accompanied by an insignificant decrease in the activation energy Eσ from 1.44 to 1.38 eV and a sharp (by a factor of ∼30) increase in the electric conductivity. In glasses of the NaF-Na2O · 3B2O3 system, an increase in the concentration of sodium ions from 1.8 × 10−2 to ∼2.3 × 10−2 mol/cm3 brings about an increase in the electric conductivity by a factor of approximately 100 and an increase in Eσ from 1.6 to 1.83 eV. A further increase in the concentration of sodium ions (up to 2.5 × 10−2 mol/cm3) virtually does not affect the electric conductivity and Eσ. At the same concentration of sodium ions (∼2.46 × 10−2 mol/cm3) in the 9.8NaF · 90.2[Na2O · 2B2O3] and 57.1NaF · 42.9[Na2O · 3B2O3] glasses, the electric conductivity and the activation energy are considerably higher in the glass with a larger fluorine content. The regularities revealed are interpreted in the framework of the microinhomogeneous glass structure.  相似文献   

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