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1.
Zhao YD  Bi YH  Zhang WD  Luo QM 《Talanta》2005,65(2):489-494
Direct electrochemistry of hemoglobin (Hb) is observed at carbon nanotube (CNT) interface. The adsorbing Hb can transfer electron directly at CNT interface compared with common carbon material. The heterogeneous electron transfer rate constant k of Hb can be calculated as 0.062 s−1, the transfer coefficient α is 0.21 and the average surface coverage of Hb on CNT surface is 3.58 × 10−9 ± 2.7 × 10−10 mol/cm2. It is found that the adsorbing Hb still keeps its catalytic activity to H2O2. This sensor was used to detect H2O2. The apparent Michaelis-Menten constant is calculated as 6.75 × 10−4 mol L−1.  相似文献   

2.
Takamoto M  Himeno S 《Talanta》2003,59(3):637-642
On the basis of the formation and pre-concentration of an α-Keggin-type [PMo12O40]3− complex, a novel voltammetric method was developed for the determination of trace levels of P(V). The α-[PMo12O40]3− complex was formed by heating a 5×10−4 M Mo(VI)-0.2 M HCl-40% (v/v) CH3CN system containing a trace amount of P(V) at 70 °C for 30 min. During the electrochemical polymerization of pyrrole in the α-[PMo12O40]3− solution, the α-[PMo12O40]3− complex was accumulated into the polypyrrole film on a glassy carbon electrode. The differential pulse voltammetric peak current due to the α-[PMo12O40]3− complex incorporated in the polypyrrole film was linearly dependent on the P(V) concentration in the range of 5×10−9-5×10−7 M; a detection limit of 2×10−9 M was achieved.  相似文献   

3.
In this article a new coated platinum Cu2+ ion selective electrode based on 2-((2-(2-(2-(2-hydroxy-5-methoxybenzylideneamino)phenyl)disufanyl)phenylimino) methyl)-4-methoxyphenol Schiff base (L1) as a new ionophore is described. This sensor has a wide linear range of concentration (1.2 × 10−7-1.0 × 10−1 mol L−1) and a low detection limit of 9.8 × 10−8 mol L−1of Cu(NO3)2. It has a Nernstian response with slope of 29.54 ± 1.62 mV decade−1 and it is applicable in the pH range of 4.0-6.0 without any divergence in potentioal. The coated electrode has a short response time of approximately 9 s and is stable at least for 3.5 months. The electrode shows a good selectivity for Cu2+ ion toward a wide variety of metal ions. The proposed sensor was successfully applied for the determination of Cu2+ ion in different real and environmental samples and as indicator electrode for potentiometric titration of Cu2+ ion with EDTA.  相似文献   

4.
The water exchange reaction of [Be(H2O)2(1H‐imidazole‐4,5‐dicarboxylate)] and [Be(H2O)2(1H‐imidazol‐3‐ium‐4,5‐dicarboxylate)]+ in water was studied by DFT calculations (RB3LYP/6‐311+G**) and identified as an associative interchange mechanism. The activation barriers for [Be(H2O)2(1H‐imidazole‐4,5‐dicarboxylate)] (16.6 kcal/mol) and [Be(H2O)2(1H‐imidazol‐3‐ium‐4,5‐dicarboxylate)]+ (13.8 kcal/mol) are similar to the barrier for [Be(H2O)4)]2+ and independent of the overall charge. NICS calculations show no indication that the aromaticity of the imidazole ring is affected during the water exchange process.  相似文献   

5.
Li B  Wang D  Lv J  Zhang Z 《Talanta》2006,69(1):160-165
A flow-injection chemiluminescence (CL) system is proposed for simultaneous determination of Co2+ and Cu2+ using partial least squares (PLS) calibration. This method is based on the fact that both Co2+ and Cu2+ catalyse the CL reaction of luminol-H2O2, and that their kinetic characteristics of Co2+ and Cu2+ are significantly different in the luminol-H2O2 system. The CL intensity was measured and recorder at different reaction times of luminol-H2O2Co2+Cu2+, and the obtained data were processed by the chemometric approach of partial least squares. The experimental calibration set was composed of 16 sample solutions using an orthogonal calibration design for two component mixtures. The proposed method offers the potential advantages of high sensitivity, simplicity and rapidity for Co2+ and Cu2+ determination, and was successfully applied to the simultaneous determination of both analytes in real water sample. The present paper demonstrated that the simultaneous determination of two metal ions without any prior separation has been possible using flow-injection CL system.  相似文献   

6.
A novel in-capillary reduction and capillary electrophoretic (CE)-chemiluminescence (CL) method was developed for the sensitive and selective determination of chromium(III) and chromium(VI). The proposed method was based on the in-capillary reduction of Cr(VI) with acidic H2O2 to form Cr(III) using the zone-passing technique and chemiluminescence detection of Cr(III). The sample [Cr3+ and CrO42−], hydrochloric acid, and H2O2 (reductant) solution segments were injected for specified periods of time in this order from the anodic end of a capillary, followed by application of an appropriate running voltage between both ends. As both chromium species have opposite charges, Cr3+ migrates to the cathode while CrO42− ion, moving oppositely to the anode, reacts with acidic H2O2, resulted in formation of Cr3+. Based on the migration time difference of both Cr3+ ions, they were separated by zone electrophoresis. Running buffer was composed of 0.02 mol l−1 HAc-NaAc (pH 4.7) with 1×10−3 mol l−1 EDTA. Parameters affecting CE-CL separation and detection, such as reductant concentration, mixing mode of the analytes with CL reagent, CL reaction reagent pH and concentration, stability of luminol-hydrogen peroxide mixed solution were optimized. The limits of detection for chromium(III) and chromium(VI) (3σ) were 6×10−13 mol l−1 (mass concentration 12 zmol) and 8×10−12 mol l−1 (160 zmol), respectively. This method offered potential advantages of simplicity, sensitivity, selectivity and applicability to the determination of Cr(III) and Cr(VI) in environmental water.  相似文献   

7.
The octahedral complex, [CoIII(HL)]·9H2O (H4L = (1,8)-bis(2-hydroxybenzamido)-3,6-diazaoctane) incorporating bis carboxamido-N-, bis sec-NH, phenolate, and phenol coordination has been synthesized and characterized by analytical, NMR (1H, 13C), e.s.i.-Mass, UV–vis, i.r., and Raman spectroscopy. The formation of the complex has also been confirmed by its single crystal X-ray structure. The cyclic voltammetry of the sample in DMF ([TEAP] = 0.1 mol dm−3, TEAP = tetraethylammonium perchlorate) displayed irreversible redox processes, [CoIII(HL)] → [CoIV(HL)]+ and [CoIII(HL)] → [CoII(HL)] at 0.41 and −1.09 V (versus SCE), respectively. A slow and H+ mediated isomerisation was observed for the protonated complex, [CoIII(H2L)]+ (pK = 3.5, 25 °C, I = 0.5 mol dm−3). H2Asc was an efficient reductant for the complex and the reaction involved outer sphere mechanism; the propensity of different species for intra molecular reduction followed the sequence: [{[CoIII(HL)],(H2Asc)}–H] <<< {[CoIII(H2L)],(H2Asc)}+ < {[CoIII(HL)],(H2Asc)}. A low value (ca. 3.7 × 10−10 dm3 mol−1 s−1, 25 °C, I = 0.5 mol dm−3) for the self exchange rate constant of the couple [CoIII(HL)]/[CoII(HL)] indicated that the ligand HL3− with amido (N-) donor offers substantial stability to the CoIII state. HSO3 and [CoIII(HL)] formed an outer sphere complex {[CoIII(HL)],(HSO3)}, which was slowly transformed to an inner sphere S-bonded sulfito complex, [CoIII(H2L)(HSO3)] and the latter was inert to reduction by external sulfite but underwent intramolecular SIV → CoIII electron transfer very slowly. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

8.
In this study, a series of 1-R1-2-R-4,5-di(furan-2-yl)-1H-imidazole derivatives were synthesized in better yield 59.0%∼89.8% by the treatment of purified imidazole compounds with benzyl chloride or allyl chloride in the presence of sodium hydride, and were characterized by FT–IR, HRMS, 1H NMR and 13C NMR spectroscopy. Furthermore, the luminescence properties of the synthesized products were investigated. It was found that N-substituted groups of imidazole have little influence on the absorption bands in a 0.1 N H2SO4 aqueous solution containing 0.5 mL of dissolved CH3OH. However, the emission of some compounds in solution was sensitive to the polarity of the solvents.  相似文献   

9.
Catalytic effect of metal ions on luminol chemiluminescence (CL) was investigated by sequential injection analysis (SIA). The SIA system was set up with two solenoid micropumps, an eight-port selection valve, and a photosensor module with a fountain-type chemiluminescence cell. The SIA system was controlled and the CL signals were collected by a LabVIEW program. Aqueous solutions of luminol, H2O2, and a sample solution containing metal ion were sequentially aspirated to the holding coil, and the zones were immediately propelled to the detection cell. After optimizing the parameters using 1 × 10−5 M Fe3+ solution, catalytic effect of some metal species was compared. Among 16 metal species examined, relatively strong CL responses were obtained with Fe3+, Fe2+, VO2+, VO3, MnO4, Co2+, and Cu2+. The limits of detection by the present SIA system were comparable to FIA systems. Permanganate ion showed the highest CL sensitivity among the metal species examined; the calibration graph for MnO4 was linear at the concentration level of 10−8 M and the limit of detection for MnO4 was 4.0 × 10−10 M (S/N = 3).  相似文献   

10.
Gao Y  Wang G  Huang H  Hu J  Shah SM  Su X 《Talanta》2011,85(2):1075-1080
In this paper, we utilized the instinct peroxidase-like property of Fe3O4 magnetic nanoparticles (MNPs) to establish a new fluorometric method for determination of hydrogen peroxide and glucose. In the presence of Fe3O4 MNPs as peroxidase mimetic catalyst, H2O2 was decomposed into radical that could quench the fluorescence of CdTe QDs more efficiently and rapidly. Then the oxidization of glucose by glucose oxidase was coupled with the fluorescence quenching of CdTe QDs by H2O2 producer with Fe3O4 MNPs catalyst, which can be used to detect glucose. Under the optimal reaction conditions, a linear correlation was established between fluorescence intensity ratio I0/I and concentration of H2O2 from 1.8 × 10−7 to 9 × 10−4 mol/L with a detection limit of 1.8 × 10−8 mol/L. And a linear correlation was established between fluorescence intensity ratio I0/I and concentration of glucose from 1.6 × 10−6 to 1.6 × 10−4 mol/L with a detection limit of 1.0 × 10−6 mol/L. The proposed method was applied to the determination of glucose in human serum samples with satisfactory results.  相似文献   

11.
A series of spinel-type CoxNi1−xFe2O4 (x = 0, 0.2, 0.4, 0.5, 0.6, 0.8, 1.0) magnetic nanomaterials were solvothermally synthesized as enzyme mimics for the eletroctrocatalytic oxidation of H2O2. X-ray diffraction and scanning electron microscope were employed to characterize the composition, structure and morphology of the material. The electrochemical properties of spinel-type CoxNi1−xFe2O4 with different (Co/Ni) molar ratio toward H2O2 oxidation were investigated, and the results demonstrated that Co0.5Ni0.5Fe2O4 modified carbon paste electrode (Co0.5Ni0.5Fe2O4/CPE) possessed the best electrocatalytic activity for H2O2 oxidation. Under optimum conditions, the calibration curve for H2O2 determination on Co0.5Ni0.5Fe2O4/CPE was linear in a wide range of 1.0 × 10−8–1.0 × 10−3 M with low detection limit of 3.0 × 10−9 M (S/N = 3). The proposed Co0.5Ni0.5Fe2O4/CPE was also applied to the determination of H2O2 in commercial toothpastes with satisfactory results, indicating that CoxNi1−xFe2O4 is a promising hydrogen peroxidase mimics for the detection of H2O2.  相似文献   

12.
Cathodic reductions of 2,2′-furils in the presence of N-arylcarbonimidoyl dichlorides lead to 2-arylimino-4,5-di(2-furyl)-1,3-dioxoles in high yields, along with minor amounts of (E)-1,2-di(2-furyl)vinylene bis(N-arylchloroformimidates). HF and B3LYP density functional theory methods have been applied to the determination of molecular geometries and to study the topomerization mechanism of aryliminodioxoles. The molecular structure of (E)-1,2-di(2-furyl)vinylene bis[N-(2-chloro-4-methylphenyl)chloroformimidate] has been determined by X-ray crystallography and compared with the calculated structure.  相似文献   

13.
Liu H  Yuan R  Chai Y  Mao L  Yang X  Zhuo Y  Yuan Y 《Talanta》2011,84(2):387-392
A new electrochemiluminescence (ECL) detector for capillary electrophoresis (CE) based on tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)32+) immobilized in Nafion/PTC-NH2 (an ammonolysis product of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA)) composite film was presented for the first time. The Nafion/PTC-NH2 composite film could effectively immobilize tris(2,2′-bipyridyl)ruthenium(II) via ion-exchange and electrostatic interaction. Cyclic voltammetric and ECL behavior of Nafion/PTC-NH2/Ru composite film was investigated compared to Nafion/Ru composite. The Nafion/PTC-NH2/Ru composite film exhibited good ECL stability and simple operability. Then the CE with solid-state ECL detector system was successfully used to detect sophora - a quinolizidine type - alkaloids as sophoridine (SR) and matrine (MT). The CE-ECL parameters that affected separation and detection were optimized. Under the optimized conditions, the linear range was from 2.5 × 10−8 to 2 × 10−6 mol/L for SR, 1.0 × 10−8 to 1.0 × 10−6 mol/L for MT. The detection limit (S/N = 3) was estimated to be 5 × 10−9 and 10−9 mol/L for SR and MT, respectively. It was shown that the CE coupling with solid-state ECL detector system exhibited satisfying sensitivity of analysis.  相似文献   

14.
Two novel light-emitting materials bis-[2′-2″-(9H-fluoren-2-yl)-vinyl-8-hydroxyquinoline] zinc(II) (3) and bis-[2′-4″-(4,5-diphenyl-1H-imidazol-2-yl)styryl-8-hydroxyquinoline] zinc(II) (4) containting 8-hydroxyquinoline and fluorene or imidazole moieties have been synthesized. The optical properties of these complexes were influenced by the styryl substituents, and exhibited orange-emission. They have higher fluorescence quantum yields than Alq3, and good stabilities with thermal decomposition temperatures 395 °C and 435 °C. The single-layer OLED fabricated by 3 emitted lemon-yellow, and exhibited good device performance with a maximum luminance of 489 cd m−2, and luminance efficiency of up to 0.41 cd A−1. The single-layer OLED fabricated by 4 emitted yellow-green, and exhibited good device performance with a maximum luminance of 323 cd m−2, and luminance efficiency of up to 0.54 cd A−1.  相似文献   

15.
Compounds [HQ]2[Hg(L)2] and [HQ][PhHg(L)] [where HQ = diisopropylammonium cation; L = pspa, fspa, tspa, where p = 3-(phenyl), f = 3-(2-furyl), t = 3-(2-thienyl), and spa = 2-sulfanylpropenoato] have been prepared by the reaction of mercury(II) acetate or phenylmercury(II) acetate with the corresponding acid in the presence of diisopropylamine in ethanol. The compounds have been characterized by elemental analysis, FAB mass spectrometry and IR and NMR (1H, 13C) spectroscopy. The crystal structures of the [HQ]2[Hg(L)2] compounds show the presence of diisopropylammonium cations and [Hg(L)2]2− anions. In each anion the Hg atom is in an HgO2S2 environment and this can be described as nido-tbp. The crystal structures of the [HQ][PhHg(L)] compounds show the presence of diisopropylammonium cations and [PhHg(L)] anions in which the Hg atom adopts an HgCOS distorted T-environment. The NMR data suggest that the coordination mode of the ligand L2− determined by X-ray diffractometry in the solid remains in solution.  相似文献   

16.
The direct electron transfer of myoglobin (Mb) was achieved based on the immobilization of Mb/Silver nanoparticles (AgNPs) on glassy carbon electrode by multi-wall carbon nanotubes (MWNTs)-chitosan(Chit) film. The immobilized Mb displayed a pair of well-defined and reversible redox peaks with a formal potential (Eθ′) of − 24 mV (vs. Ag/AgCl) in 0.1 M pH 7.0 phosphate buffer solution. The apparent heterogeneous electron transfer rate constants (ks) of Mb confined to Chit-MWNTs film was evaluated as 5.47 s− 1 according to Laviron's equation. The surface concentration (Γ?) of the electroactive Mb in the Chit-MWNTs film was estimated to be (4.16 ± 0.35) × 10− 9 mol cm− 2. Meanwhile, the catalytic ability of Mb toward the reduction of H2O2 was studied. Its apparent Michaelis–Menten constant for H2O2 was 0.024 mM, showing a good affinity. The linear range for H2O2 determination was from 2.5 × 10− 5 M to 2.0 × 10− 4 M with a detection limit of 1.02 × 10− 6 M (S/N = 3). Moreover, the biosensor displays rapid response to H2O2 and good stability and reproducibility.  相似文献   

17.
Du J  Hao L  Li Y  Lu J 《Analytica chimica acta》2007,582(1):98-102
A simple flow injection chemiluminescence (FI-CL) method was proposed for the determination of nitrofurazone. Strong CL signal was generated during the reaction of nitrofurazone with H2O2 and N-bromosuccinimide (NBS) in alkaline condition. The CL signal was proportional to the nitrofurazone concentration in the range 1.0 × 10−7 to 1.0 × 10−5 g mL−1. The detection limit was 2 × 10−8 g mL−1 nitrofurazone and the relative standard deviation was less than 4% (6.0 × 10−6 g mL−1 nitrofurazone, n = 11). The proposed method was successfully applied to the determination of nitrofurazone in compound furacillin nasal drops, human plasma and urine samples. The CL reaction mechanism was also discussed briefly. Singlet oxygen generated in the reaction between H2O2 and NBS was suggested to be participated in the CL reaction.  相似文献   

18.
JingJing Xu  Yuan Tian  Litong Jin 《Talanta》2010,82(4):1511-1515
A highly soluble poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid)/Au (PEDOT-PSS/Au) nanocomposite was prepared via one-step chemical synthesis and the matrix was characterized by UV-vis spectroscopy (UV-vis), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM) and transmission electron microscope (TEM). Due to the excellent aqueous compatibility and biocompatibility, the PEDOT/PSS-Au nanocomposite can be used as biomaterial for enzymes immobilization. In this system, redox enzyme, horseradish peroxidase (HRP) was integrated with PEDOT/PSS-Au nanocomposite and the direct electron transfer of HRP was observed. Moreover, we find that the HRP/PEDOT-PSS/Au modified electrode shows excellent electrocatalytic ability for H2O2 and the formal Michaelis-Menten constant was 0.78 mmol/L. The response currents have good linear relation with the concentrations of H2O2 with a linear range from 2.0 × 10−7 to 3.8 × 10−4 mol/L.  相似文献   

19.
In order to evaluate the chemiluminescence (CL) reagents for selective detection of reactive oxygen species (ROS), we comprehensively measured the CL responses of 20 CL reagents (three luminol derivatives, two imidazopyrazinone derivatives, eight lophine derivatives, six acridinium ester derivatives and lucigenin) against six types of ROS (superoxide anion: O2, hydroxyl radical: OH, hydrogen peroxide: H2O2, hypochlorite anion: ClO, singlet oxygen: 1O2, and nitric oxide: NO). As a result of the screening, it was found that nine CL reagents selectively detected O2 while one CL reagent selectively detected OH. However, no CL reagent had selectivity on the detection of H2O2, ClO, 1O2 and NO. Our screening results could help to select the most suitable CL reagent for selective determination of different ROS.As an application study, 4-methoxyphenyl-10-methylacridinium-9-carboxylate (MMAC), one of the acridinium ester derivatives, showed high selectivity on the detection of O2, and thus was applied to the assay of superoxide dismutase (SOD) activity. The dynamic range and detection limit of the developed CL assay were 0.1-10 and 0.06 U mL−1, respectively. Significant correlation (r = 0.997) was observed between the results by the CL assay using MMAC and the spectrophotometric assay using 2-(4-iodophenyl)-3-(4-nitrophenyl)-5-(2,4-disulfophenyl)-2H-tetrazolium monosodium salt.  相似文献   

20.
《Comptes Rendus Chimie》2016,19(5):604-613
A series of 1-(2,6-dimethyl-4-fluorenylphenylimino)-2-aryliminoacenaphthylene compounds (aryl = 2,6-di(Me)Ph (L1), 2,6-di(Et)Ph (L2), 2,6-di(i-Pr)Ph (L3), 2,4,6-tri(Me)Ph (L4), 2,6-di(Et)-4-MePh (L5)) was prepared and used to form their corresponding dibromonickel complexes (D1D5). Both L1–L5 and D1–D5 were fully characterized by FT-IR and elemental analysis as well as NMR measurements in the case of ligands L1L5. The molecular structure of the representative complex D5 was confirmed by single crystal X-ray diffraction revealing a distorted trigonal bipyramidal geometry around the nickel center. On activation with either ethylaluminium sesquichloride (Et3Al2Cl3, EASC) or methylaluminoxane (MAO), all nickel complexes exhibited high activities up to 9.82 × 106 g of PE (mol of Ni)−1 h−1 for ethylene polymerization. In comparison with the polyethylenes obtained with related Ni pre-catalysts, the polyethylenes obtained in this work possessed relatively higher molecular weights and lower levels of branching, highlighting the significant influence of the remote fluorenyl substituent.  相似文献   

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