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1.
过氧化物模拟酶在介体型生物传感器方面应用初探   总被引:2,自引:0,他引:2  
奚星林  章咏华 《分析化学》1993,21(7):838-841
meso-四(4-磺基苯)卟啉锰(Ⅲ)作为过氧化物模拟酶可催化H_2O_2与K_4Fe(CN)_6反应。电流响应与H_2O_2浓度在3.0×10~(-4)~1.0×10~(-3)mol/L范围内呈线性关系。重现性和回收率良好。抗坏血酸和DL-半胱氨酸干扰严重。  相似文献   
2.
In this work, two well known polymers, carboxymethyl dextran and poly(ethyleneglycol), are used for easily producing a platform for electrochemical affinity assays, avoiding nonspecific adsorption of proteins. In this way, modified electrode surfaces able to bind a recognition agent are constructed through simple and reliable reactions.  相似文献   
3.
A detection scheme for the simultaneous evaluation of two bioassays based on fluorescence spectroscopy is presented. For the determination of hydrogen peroxide-generating enzymes or peroxidases, the non-fluorescent 4-(N-methylhydrazino)-7-nitro-2,1,3-benzooxadiazole (MNBDH) is converted to the strongly fluorescent 4-(N-methylamino)-7-nitro-2,1,3-benzooxadiazole (MNBDA). Phosphatases are detected based on the cleavage of the non-fluorescent 5-fluorosalicyl phosphate (5-FSAP) under formation of the fluorescent 5-fluorosalicylic acid (5-FSA). While excitation of the fluorophores may be carried out at the same wavelength, their emission spectra differ significantly. This allows the read-out of both assays using commercially available microplate readers without additional chemometric tools. Compared with individual assays, limits of detection are similar, and linearity of the calibration functions for both enzymes is observed over 2-3 concentration decades starting at the limit of quantification. The simultaneous determination of glucose oxidase and acid phosphatase in honey is presented as example for the application of the detection scheme.  相似文献   
4.
DFT method (B3LYP) with 6-31G* basis set was utilized in the computation of a fully optimized structure, net atomic charges and spin densities of the intermediate of cytochrome P-450-oxoiron(IV) porphyrin cation radical, compound I – in the presence of axial ligand such as thiolate (SMe) imidazole (IM), phenoxide (OPh), methoxide (OMe) and chloride (Cl). The results show doublet states in compound I are about 2–4 kcal/mol more stable than quartet states for all aforementioned ligands, and the doublet state is the ground state in all cases. However, electron donor ability of the ligands are in the order of SMe− > IM > OMe− > OPh− > Cl. Also the active oxidant intermediate of cytochrome P-450 between different mesomeric structures select sulfur oxygen radical type structure and can be viewed as (RS)Fe(IV)(O)(Por). In horseraddish peroxidase (HRP) and peroxidase with histidine axial ligand π cation radical character of porphyrin ring is preferred (Im)Fe(IV)(O)(Por). For the ligands such as OMe, OPh and Cl oxidation mainly took place on the iron and the active intermediate can be viewed as (L)Fe(V)(O)(Por) with one unpaired electron localized on the iron.  相似文献   
5.
Polypeptides with two histidines and an iron porphyrin (1H40-7H46) were synthesized with a variety of positions of a histidine. In 4H43, histidine (H43) was in the hydrophobic region of an α-helix. The other polypeptides were of slightly or substantially distorted conformation. In the pH 7.2 buffer solution, two histidines of the polypeptide coordinated the iron porphyrin regardless of their positions. Some polypeptides (1H40, 3H42, and 5H44) showed an enhanced catalytic activity in the peroxidase reaction using cumene hydroperoxide compared to that of 4H43, whereas some polypeptides (2H41 and 6H45) were ineffective catalysts. The distortion of the peptide conformation by the addition of MeOH was also effective for the peroxidase reaction.  相似文献   
6.
The properties of porphyrinogen as a new chromogenic reagent were examined. 5,10,15,20-Tetrahydro-tetraphenylporphyrinogen (TPPN) is changed to 5,10,15,20-tetraphenylporphine (TPP) by the oxidative reaction involving six electrons, and its formation of the porphine ring significantly increased the absorbance in the Soret band.The horseradish peroxidase (HRP) accelerated the oxidative reaction as a catalyst and the increment of absorbance depended upon the increase in the concentration of HRP. The reaction proceeded in the presence of dissolved oxygen and in the neighborhood of pH 7. Based on these findings, a chemical analysis by catalytic action using HRP was developed.In the procedure for this determination, the difference in absorbance at 419 nm (ΔA419=AsAb, where As and Ab are the absorbances of the sample solution containing HRP and the blank solution without HRP after 30 min, respectively), was measured. The determination range of HRP, which was obtained from the ΔA419—HRP concentration curve, was 0.05-1.0 mg/l. The relative standard deviation in the median of the calibration curve was 3.19% (seven determinations), and the detection limit (S/N=3) was 29 ng/l. Furthermore, when the proposed method was applied to the enzyme immunoassay, bisphenol A (BPA) was selectively and sensitivity determined.  相似文献   
7.
Colloidal noble metal-based nanoparticles are able to catalyze oxidation of chromogenic substrates by H2O2, similarly to peroxidases, even in basic media. However, lack of robust chromogens, which work in high pH impedes their real applications. Herein we demonstrate the applicability of selected catechol derivatives: bromopyrogallol red (BPR) and pyrogallol (PG) as chromogenic substrates for peroxidase-like activity assays, which are capable of working over wide range of pH, covering also basic values. Hyperbranched polyglycidol-stabilized gold nanoparticles (HBPG@AuNPs) were used as model enzyme mimetics. Efficiency of several methods of improving stability of substrates in alkaline media by means of selective suppression of their autoxidation by molecular oxygen was evaluated. In a framework of presented studies the impact of borate anion, applied as complexing agent for PG and BPR, on their stability and reactivity towards oxidation mediated by catalytic AuNPs was investigated. The key role of high concentration of hydrogen peroxide in elimination of non-catalytic oxidation of PG and improvement of optical properties of BPR in alkaline media containing borate was underlined. Described methods of peroxidase-like activity characterization with the use of BPR and PG can become universal tools for characterization of nanozymes, which gain various applications, among others, they are used as catalytic labels in bioassays and biosensors.  相似文献   
8.
Pentacyanoferrate-bound poly(1-vinylimidazole) (PVI[Fe(CN)5]) was selected as a mediator for amperometric creatinine determination based on the reductive H2O2 detection. Creatinine amidohydrolase (CNH), creatine amidohydrolase (CRH), sarcosine oxidase (SOD), peroxidase (POD), and PVI[Fe(CN)5] were crosslinked with poly(ethylene glycol) diglycidyl ether (PEGDGE) on a glassy carbon (GC) electrode for a creatinine biosensor fabrication. Reduction current was monitored at −0.1 V in the presence of creatinine and O2. It is revealed that PVI[Fe(CN)5] is suitable as a mediator for a bioelectrocatalytic reaction of POD, since PVI[Fe(CN)5] neither reacts with reactants nor works as an electron acceptor of SOD. The amounts of PVI[Fe(CN)5], PEGDGE, and enzymes were optimized toward creatinine detection. Nafion as a protecting film successfully prevented the enzyme layer from interferences. The detection limit and linear range in creatinine determination were 12 μM and 12–500 μM (R2 = 0.993), respectively, and the sensitivity was 11 mA cm−2 M−1, which is applicable for urine creatinine tests. The results of the creatinine determination for four urine samples measured with this proposed method were compared with Jaffe method, and a good correlation was obtained between the results.  相似文献   
9.
Selenium has been identified as an essential dietary trace e1ementQ)which is a component of glutathione peroxidase (GSH-Px)(2)and a cytochrome C-like protein(3), The enzyme,the four subunits of which each contain one atom of selenium in the form of selenocysteine, the selenium containing active centre being amenable to chemical modification, catalyses the reduction of H,O,and organic hydroperoxides to water.In this way GSH-Px plays an important role in the protection of the cell from oxidative stresses such as the superoxide anion,organic hydroperoxides and H2O2  相似文献   
10.
Horseradish peroxidase-, hematin- and pegylated-hematin mediated polymerization of sodium styrene sulfonate and sodium acrylate in water is reported. Molecular weight and yields were influenced by the concentrations of hydrogen peroxide and initiator, 2,4-pentanedione. Hematin and pegylated-hematin were studied in lieu of peroxidase at pH 11.0 and 7.0 in aqueous solution, respectively. Polymer with a high molecular weight (Mn = 223,520) was formed when the pegylated-hematin was used as the catalyst. The results demonstrate vinyl polymerizations in an all aqueous process in high yield and molecular weight catalyzed by peroxidase as well as biomimetic catalysts.  相似文献   
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