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1.
The in vitro effect of technical grade malathion was assessed via the kinetic parameters of human plasma butyrylcholinesterase (BChE) using N-methylindoxyl acetate as a substrate for BChE. An inhibitor kinetics study demonstrated the existence of a biphasic inhibition curve, indicating high-and low-affinity binding sites of malathion. The IC 50 values as calculated from the experimental inhibition curves were 1.33 × 10−9 and 1.48 × 10−5 M for the high-and low-affinity binding sites, respectively; Hill’s analysis gave 1.29 × 10−9 and 1.38 × 10−6 M. The Cornish-Bowden plots and their secondary plots indicated that the nature of inhibition was of mixed type with the predominant competitive character of both affinity binding sites. The article is published in the original.  相似文献   

2.
Amperometric acetylcholinesterase biosensors have been developed for quantification of the pesticides carbofuran, carbaryl, methylparaoxon, and dichlorvos in phosphate buffer containing 5% acetonitrile. Three different biosensors were built using three different acetylcholinesterase (AChE) enzymes—AChE from electric eel, and genetically engineered (B394) and wild-type (B1) AChE from Drosophila melanogaster. Enzymes were immobilized on cobalt(II) phthalocyanine-modified electrodes by entrapment in a photocrosslinkable polymer (PVA-AWP). Each biosensor was tested against the four pesticides. Good operational stability, immobilisation reproducibility, and storage stability were obtained for each biosensor. The best detection limits were obtained with the B394 enzyme for dichlorvos and methylparaoxon (9.6 × 10−11 and 2.7 × 10−9 mol L−1, respectively), the B1 enzyme for carbofuran (4.5 × 10−9 mol L−1), and both the B1 enzyme and the AChE from electric eel for carbaryl (1.6 × 10−7 mol L−1). Finally, the biosensors were used for the direct detection of the pesticides in spiked apple samples.  相似文献   

3.
The construction and performance characteristics of phenytoin sodium selective electrodes are detailed. Two types of electrodes: plastic membrane I and coated wire II, were constructed based on the incorporation of phenytoin sodium with tungstosilicic acid. The influence of membrane composition, kind of plasticizer, pH of the test solution, soaking time and the electrodes’ foreign ions were investigated. The electrodes showed a Nernstian response with a mean calibration graph slope of 30.9±0.1 and 28.9±0.1 mV decade−1 at 25°C for electrode I and II respectively, over a phenytoin sodium concentration range of 5×10−3−5×10−6 M and 1×10−3−1×10−6 M with a detection limit 1.3×10−6 M and 2.5×10−7 M for electrode I and II, respectively. The electrodes gave average selective precision and were usable within the pH range 6–10. Interference studies from common cations, alkaloids, sugars, amino acids and drug excipients are reported. The results obtained by the proposed electrodes were also applied successfully for the determination of the drug in pharmaceutical preparations and biological fluids.  相似文献   

4.
A simple and new reagentless phenolic compound biosensor was constructed with tyrosinase immobilized in the gelatine matrix cross-linked with formaldehyde. The morphologies of gelatine and gelatine/tryosinase were characterized by SEM. The tyrosinase retains its bioactivity when being immobilized by the gelatine film. Phenolic compounds were determined by the direct reduction of biocatalytically liberated quinone at -0.1 V vs SCE. The process parameters for the fabrication of the enzyme electrode were studied. Optimization of the experimental parameters has been performed with regard to pH, operating potential, temperature and storage stability. This biosensor exhibits a fast amperometric response to phenolic compounds. The linear range for catechol, phenol, and p-Cresol determination was from 5×10−8 to 1.4×10−4 M, 5×10−8 to 7.1×10−5 M, and 1×10−7 to 3.6×10−5 M, with a detection limit of 2.1×10−8 M, 1.5×10−8 M, and 7.1×10−8 M, respectively. The enzyme electrode retained ca.77% of its activity after 7 days of storage at 4°C in a dry state. The proposed sensor presented good repeatability, evaluated in terms of relative standard deviation (R.S.D.=8.6%) for eight different biosensors and was applied for determination in water sample. The recovery for the sample was from 99.0% to 99.8%.  相似文献   

5.
The chemical effects of self-sustained spark discharge with an energy per pulse of 5.9 × 10−2 J, a pulse repetition frequency of 10 Hz, and a spark-gap breakdown voltage of 6 kV have been studied. The discharge generated a UV photon flux of (2.5 ± 0.3) × 1015 cm−2 s−1 with an energy density of (2 ± 0.3) × 10−3 J cm−1 s−1 and the emission spectrum maximum at 220 nm. The action of the discharge on water samples leads to a decrease in pH and to buildup of oxidizing and reducing species. The formation of HO2· radicals with an initial yield of (1.2 ± 0.3) × 10−6 mol L−1 s−1 has been detected in the liquid. The initial yields of acid residues (increment in [H+]), oxidants, and reducing agents are (5.8 ± 1.6) × 10−7, (3.3 ± 1) × 10−6, and (4.2 ± 1) × 10−7 mol equiv L−1s−1, respectively. The formation of NO3 and NO4+ ions, nitrosamines, and organic compounds has been established.  相似文献   

6.
A new high α1A adrenoreceptor (α1AAR) expression cell membrane chromatography (CMC) method was developed for characterization of α1AAR binding interactions. HEK293 α1A cell line, which expresses stably high levels of α1AAR, was used to prepare the stationary phase in the CMC model. The HEK293 α1A/CMC-offline-HPLC system was applied to specifically recognize the ligands which interact with the α1AAR, and the dissociation equilibrium constants (K D) obtained from the model were (1.87 ± 0.13) × 10−6 M for tamsulosin, (2.86 ± 0.20) × 10−6 M for 5-methylurapidil, (3.01 ± 0.19) × 10−6 M for doxazosin, (3.44 ± 0.19) × 10−6 M for terazosin, (3.50 ± 0.21) × 10−6 M for alfuzosin, and (7.57 ± 0.31) × 10−6 M for phentolamine, respectively. The competitive binding study between tamsulosin and terazosin indicated that the two drugs interacted at the common binding site of α1AAR. However, that was not the case between tamsulosin and oxymetazoline. The results had a positive correlation with those from radioligand binding assay and indicated that the CMC method combined modified competitive binding could be a quick and efficient way for characterizing the drug–receptor interactions.  相似文献   

7.
An in-capillary derivatization of amino acids and peptides with 4-fluoro-7-nitro-2,1,3-benzoxadiazole (NBD-F) was developed for their subsequent capillary electrophoretic analysis with laser-induced fluorescence detection (λ ex=488 nm). The in-capillary derivatization was achieved in zone-passing mode by introducing successive plugs of sample and NBD-F into a fused silica capillary previously equilibrated with an alkaline borate buffer. To prevent NBD-F hydrolysis and to achieve a reliable derivatization, NBD-F was prepared daily in absolute ethanol and a plug of absolute ethanol was introduced between the sample and NBD-F reagent plugs. Various parameters influencing the derivatization efficiency were investigated and the optimum conditions were as follows: background electrolyte (BGE), 20 mM borate buffer (pH 8.8); introduction time, 4 s for sample and 2 s for NBD-F; molar ratio of NBD-F/sample, above 215; temperature, 45 °C for amino acids and 35 °C for peptides; applied voltage, +15 kV. The validation of the in-capillary derivatization method under optimal conditions showed a good linearity between the heights of the derivative peaks and the concentrations of the amino acids. The intra-day relative standard deviations of the migration times and the peak heights were less than 1.3% and 4.6%, respectively. The efficient derivatization and separation of a mixture of valine, alanine, glutamic acid and aspartic acid were achieved using this technique. Peptides such as buccaline and β-protein fragment 1–42 could also be derivatized using the developed in-capillary derivatization procedure. In‑capillary derivatization and separation of amino acids with different concentrations. From the top to bottom the concentrations are 1.11×10−5 M, 5.55×10−6 M, 2.78×10−6 M, 6.95×10−7 M. for valine; 1.26×10−5 M, 6.30×10−6 M, 3.15×10−6 M, 7.88×10−7 M for alanine; 3.78×10−5 M, 1.89×10−5 M, 9.45×10−6 M, 2.36×10−6 M for glutamic acid;, 4.27×10−5 M, 2.14×10−5 M, 1.07×10−5 M, 2.68×10−6 M for aspartic acid. Experiment conditions: injection order: 4s for sample, 1s for absolute ethanol, and then 2s for 5.24×10−2 M NBD‑F; BGE: 20 mM borate pH 8.77; Applied voltage: 15 kV.  相似文献   

8.
Three methods were used to immobilize myoglobin (Mb) on chitosan/single-wall carbon nanotubes (SWNTs) film, and direct electrochemistry of the immobilized Mb was extensively investigated. Immobilized Mb displayed a couple of stable and well-defined redox peaks with the formal potential (E’) is at about −0.27 V (vs. SCE) in 0.1 M phosphate buffer solution (pH 7.0). The E′ was shifted linearly with pH in the range of 3.0 to 9.0 with a slope of −54.1 mV pH−1, denoting that one-electron accompanies with one-proton transfer in electrode reaction process. The FT-IR spectroscopy and UV-vis spectroscopy showed that Mb on the film retained its secondary structure similar to its native state. The experimental results demonstrated that the immobilized Mb exhibited excellent electrocatalytic activity to reduction of cimetidine with a significant lowering of overpotential. The electrocatalytic current was proportional to the concentration of cimetidine over the range from 9.80 × 10−6 to 1.1 × 10−4 M; the detection limit is 8.40 × 10−6 M (signal-to-noise ratio of 3). The proposed method exhibits good sensitivity, stability and reproducibility. Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 2, pp. 235–243. The text was submitted by the authors in English  相似文献   

9.
Quartz crystal microbalance (QCM) was used to study the self-assembly of per-6-thio-β-cyclodextrin (t7-βCD) on gold surfaces, and the subsequent inclusion interactions of immobilized βCD with adamantane-poly(ethylene glycol) (5,000 MW, AD-PEG), 1-adamantanecarboxylic acid (AD-C) and 1-adamantylamine (AD-A). From a 50 μM solution of t7-βCD in 60:40 DMSO:H2O, a t7-βCD layer was formed on gold with surface density of 71.7 ± 2.7 pmol/cm2, corresponding to 80 ± 3% of close-packed monolayer coverage. Gold sensors with immobilized t7-βCD were then exposed alternately to six different concentrations of AD-PEG, 500 μM AD-C or 500 μM AD-A aqueous solutions for association, and water for dissociation. Association of AD-PEG conformed to a Langmuir isotherm, with a best fit equilibrium constant K = 125,000 ± 18,000 M−1. For AD-C and AD-A, association (k a ) and dissociation (k d ) rate constants were extracted from kinetic profiles by fitting to the Langmuir model, and equilibrium constants were calculated. The parameters for AD-C were found to be: k a = 100 ± 5 M−1 s−1, k d = 110 (±18) × 10−4 s−1, and K = 9,400 ± 1,700 M−1. For AD-A, k a = 58 ± 6 M−1 s−1, k d = 154 (±7) × 10−4 s−1, and K = 3,800 ± 400 M−1. The results demonstrate the utility of QCM as a tool for studying small molecule surface adsorption and guest–host interactions on surfaces. More specifically, the kinetic and thermodynamic data of AD-C, AD-A, and AD-PEG inclusion with immobilized t7-βCD form a basis for further surface association studies of AD-X conjugates to advance surface sensory and coupling applications.  相似文献   

10.
Summary A simple, selective and sensitive ion-chromatography method was investigated for simultaneously determining silicic acid, Ca2+, Mg2+, Al3+ and anions (Cl and NO 3 ) in real samples. It involved a single-column ion-chromatograph with sodium hydroxide-methanol-water eluent and conductometric detection. Cations were converted to complex anions by adding EDTA to the sample solution. A set of well-defined peaks of silicic acid, Ca2+, Mg2+, Al3+, Cl and NO 3 were obtained. Detection limits using 3.3σ (σ=standard deviation of blank solution) were 1.25×10−6 M for H3SiO 4 , 1.32×10−6 M for Ca2+, 1.28×10−6 M for Mg2+, 1.33×10−6 M for Al3+, 1.31×10−6 M for Cl and 1.24×10−6 M for NO 3 . The method was successfully applied to analysis of mineral water and composite tablets.  相似文献   

11.
A trazodone-selective electrode for application in pharmaceutical quality control and urine analysis was developed. The electrode is based on incorporation of a trazodone-tetraphenylborate ion exchanger in a poly(vinyl chloride) membrane. The electrode showed a fast, stable and Nernstian response over a wide trazodone concentration range (5 × 10−5−1 × 10−2 M) with a mean slope of 59.3 ± 0.9 mV/dec of concentration, a mean detection limit of 1.8 × 10−5 ± 2.2 × 10−6 M, a wide working pH range (5–7.5) and a fast response time (less than 20 s). The electrode also showed good accuracy, repeatability, reproducibility and selectivity with respect to some inorganic and organic compounds, including the main trazodone metabolite. The electrode provided good analytical results in the determination of trazodone in pharmaceuticals and spiked urine samples; no extraction steps were necessary. Dissolution testing of trazodone tablets, in different conditions of pH and particle size, based on a direct potentiometric determination with the new selective electrode is presented as well.  相似文献   

12.
A new p-tetra-butyl calix [6] arene-L-Histidine chemically modified glassy carbon electrode (BCH/GCE) has been proposed for simultaneous investigation and determination of epinephrine (Ep) and serotonin (5-HT) by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). In potassium dihydrogen phosphate-borax (PDPB) buffer solution (pH 5.8), the anodic peaks of Ep and 5-HT were observed at 0.27 and 0.45 V, respectively, with E up to 180 mV. The peak currents on the DP voltammogram are in a linear relationship with the concentrations of Ep in the range of 1.0 × 10−6−1.30 × 10−4 M in the presence of 1.0 × 10−4 M 5-HT. A linear relationship was similarly found for 5-HT in the range 1.0 × 10−6− 1.40 × 10−4 M in the presence of 1.0 × 10−4 M Ep. It is found that Ep and 5-HT could be simultaneously determined with good sensitivity in the presence of 1.0 × 10−3 M ascorbic acid (AA). The developed method has been applied to the determination of Ep and 5-HT in synthetic samples with satisfactory results. The text was submitted by the authors in English.  相似文献   

13.
A new modified carbon paste electrode based on a recently synthesized mercury (II) complex of a pyridine containing proton transfer compound as a suitable carrier for Br ion is described. The electrode has a linear dynamic range between 3.00×10−2 and 1.0×10−5 M with a near-Nernastian slope of 61.0±0.9 mV per decade and a detection limit of 4.0×10−6 M (0.32 ppm). The potentiometric response is independent of the pH of the solution in the pH range 4.0–8.3. The electrode possesses the advantages of low resistance, fast response and good over a variety of other anions. It was applied as an indicator electrode in potentiometric titration of bromide ions and for the recovery of Br from tap water.  相似文献   

14.
Iodide ion selective poly(aniline) solid contact electrode based on quinine-Cu ionophore as a sensing material has been successfully developed. The electrode exhibits good linear response of 52.0 mV/decade (at 20 ± 0.2°C, r 2 = 0.9998) within the concentration range of 1 × 10−6.4–1 × 10−1.0 M KI. The composition of this electrode was quinine-Cu 2.0: PVC 30.0: bis(2-ethylhexyl)sebacate 68.0 (mass). This plasticizer provides the best response characteristics. The electrode shows good selectivity for iodide ion in comparison with any other anions and is suitable for use with aqueous solutions of pH 3.3–9.4. The standard deviations of the measured EMF difference were ±1.4 and ±1.3 mV for iodide sample solutions of 1.0 × 10−2 M and 1.0 × 10−3 M, respectively. The stabilization time was less than 10 min and response time was less than 15 sec.  相似文献   

15.
 The second derivative spectrophotometric method has been developed as a procedure for the determination of neodymium, holmium and erbium in mixed rare earths. It was found that the 1-ethyl-6, 8-difluoro-7-(3-methyl-1-piperazinyl)-4-oxo-1,4- dihydro-3-quinoline carboxylic acid forms stable complexes with neodymium, holmium and erbium ions in the pH 9.2–10.5 range. In the second derivative spectra the optimum analytical signals for neodymium, holmium and erbium are at 576.2 (+)−574.5 (−)nm, 444.2 (+) −447.8 (−)nm and 516.0 (+) −517.2(−)nm, respectively. Beer’s law is obeyed from 5.0×10−5 M to 2.5×10−4 M of neodymium, holmium and erbium. The quantification limits (10 Sb) were 1.2×10−5 M for Nd, 9.7×10−5 M for Ho and 3.0×10−6 M for Er. Received April 22, 1998. Revision March 8, 1999.  相似文献   

16.
Lactate oxidase from the species Pediococcus is immobilized in a conducting polymer film on the surface of planar electrodes modified with Prussian blue. Polypyrrole ammonium is electropolymerized to obtain the conducting polymer. The analytical characteristics of the resulting biosensor are as follows: a sensitivity of 190 ± 14 mA M−1 cm−2, a linear dynamic range of 5 × 10−7 to 5 × l0−4 M, and high operational stability. The applicability of a lactate biosensor for food quality control (for example, quality control of kvass) is shown. Effective and inexpensive biosensors for lactate analysis may be applied in clinical diagnostics, sports medicine, quality control of food and farm products, as well as for biotechnology processes.  相似文献   

17.
Direct electrochemistry of hemoglobin (Hb) immobilized on the dihexadecyl hydrogen phosphate (DHP)/single-wall carbon nanotubes (SWNTs) film modified Au electrode is investigated. The immobilized Hb displays a couple of stable and well-defined redox peaks, whose formal potential (E 0) is −0.434 V (SCE) in a phosphate buffer solution of pH 7.0. The formal potential of the heme Fe(III)/Fe(II) couple shifts negatively linearly with increased pH with a slope of −42.3 mV/pH, denoting that one electron transfer accompanies single proton transportation. Both SWNTs and DHP can accelerate the electron transfer between Hb and the electrode. Using DHP/Hb/SWNTs-film-modified Au electrode, the interaction between Hb and taxol is investigated. The voltammetric response of Hb decreases with increasing concentration of taxol. The peak currents decreases proportionally to the taxol concentration at 1.4 × 10−5 to 1.3 × 10−4 M, the linear regression equation being Δi (A) = 2.9603 − 0.4225 ctaxol (M), with a correlation coefficient (r) 0.9985, and the detection limit 6.95 × 10−6 M (signal-to-noise ratio of three). Published in Russian in Elektrokhimiya, 2007, Vol. 43, No. 7, pp. 801–807. The text was submitted by the authors in English.  相似文献   

18.
A simple capillary electrophoresis partial-filling technique for the enantioseparation of pheniramine is presented. Phosphate buffer and hydroxypropyl-β-cyclodextrin (HP-β-CD) were used as the electrolyte and chiral selector, respectively. Several experimental parameters such as HP-β-CD concentration, HP-β-CD plug length, CE temperature and applied voltage were studied. Under the selected conditions, pheniramine enantiomers can be separated within less than 14 min. The assay was validated for linearity (5.0 × 10−6–5.0 × 10−4 M; R 2 = 0.9987), limit of detection (5.0 × 10−7 M), limit of quantitation (5.0 × 10−6 M), analytical precision (%RSD ≤ 9.8) and accuracy (%recovery = 101 ± 3). The proposed methodology was then applied to the analysis of a commercially available pharmaceutical eye drop preparation. The results are in good agreement with that declared by the manufacturer. The proposed methodology provides adequate results in terms of simplicity, cost, sample throughput, repeatability and accuracy for quality control of pheniramine enantiomers in pharmaceutical preparations.  相似文献   

19.
A kinetic method for the determination of organosulfur compounds by UV spectrophotometry is described. Organosulfur compounds have been shown to inhibit the Hg(II)-catalyzed substitution of cyanide in hexacyanoferrate(II) by 2-methylpyrazine (2-Mepz). The inhibitory effect is proportional to the concentration of inhibitor and can be used as the basis for the determination of trace amounts of organosulfur compounds such as cysteine, 2,3-dimercaptopropanol (DMP) and thioglycolic acid (TGA). Both the influence of the reaction variables and interference of a variety of ions have been studied. A mechanism for the inhibition process is proposed. The determination range depends on the amount of Hg(II) added and stability of the Hg(II)–ligand complex. Kinetic parameters were determined from Lineweaver–Burk plots, obtained in the absence and presence of the inhibitor. Excellent linearity is observed for all analytes over their respective concentration ranges with correlation coefficient >0.9. The condition calibration curves were linear in the range of 5 × 10−6–15 × 10−6 M for cysteine, 1 × 10−7–7 × 10−7 M for DMP and 1 × 10−6–10 × 10−6 M for TGA. The detection limits were 1.18 × 10−7 M for cysteine, 4.16 × 10−8 M for DMP and 1.30 × 10−7 M for TGA. The effects of amino acids that can interfere in the determination of cysteine were studied.  相似文献   

20.
Summary A capillary electrophoretic method for the determination of lansoprazole in pharmaceutical preparations is described. The analysis was performed in a fused silica capillary using 20 mM borate buffer at pH 8.7 as a background electrolyte. The best resolution was obtained by applying a potential of 30 kV and vacuum injection of 1 s. Detection was made at 200 nm. Phenobarbital sodium was a good internal standard and the migration times were 4.1±0.2 min (lansoprazole) and 5.7±0.2 min (phenobarbital sodium). A well-correlated calibration equation was found in the range of 1.12×10−5 and 2.24×10−4 M. Limit of detection (LOD) and limit of quantitation (LOQ) were 1.4×10−6 M (RSD 1.44%) and 4.42×10−6 M (RSD 1.49%), respectively. The method was validated and applied to the capsules containing enteric coated pellets of lansoprazole. The results of the proposed method were compared those of UV spectrophotometry. Insignificant differences were found between the two methods at the 95% probability level. The described CE method is selective, rapid, sensitive and accurate for the analysis of lansoprazole in quality control laboratories.  相似文献   

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