CN116493043A - Spindle-shaped Cu-Ru bimetallic mesoporous nano-mimic enzyme and preparation method and application thereof - Google Patents
Spindle-shaped Cu-Ru bimetallic mesoporous nano-mimic enzyme and preparation method and application thereof Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
The invention relates to the field of nanometer enzyme-like catalytic materials, and particularly provides spindle-shaped Cu-Ru bimetallic mesoporous nanometer mimic enzyme, and a preparation method and application thereof. The material has good nano-simulated oxidase activity and simulated peroxidase activity, and can play a role of double-function nano-enzyme. The material is guided downwards by a positive Cetyl Trimethyl Ammonium Bromide (CTAB) template, and the copper-ruthenium bimetallic base nanometer mimic enzyme (CTAB@Cu-Ru) is prepared by a one-pot reduction method, so that the strong interaction between copper and ruthenium metals is further promoted, the charge transfer between the copper and ruthenium metals is further promoted, and the catalytic activity of the CTAB@Cu-Ru mimic oxidase/peroxidase is synergistically enhanced. In detection application, the CTAB@Cu-Ru nanometer mimic enzyme has the characteristics of excellent specificity and selectivity on o-aminophenol and m-aminophenol, good anti-interference performance, convenience and rapidness, high sensitivity, accurate detection result, strong visibility and the like, and can effectively detect ultra-trace o-AP and m-AP in an environmental sample.
Description
Technical Field
The invention belongs to the field of nano materials, and particularly relates to spindle-shaped Cu-Ru bimetallic mesoporous nano-mimic enzyme, and a preparation method and application thereof.
Background
Ortho-aminophenol and meta-aminophenol are two important contaminants. This compound is very slowly degraded in the environment and is easily absorbed by skin or mucous tissues, causing methemoglobin and asthma. Common methods for detecting aminophenol isomers (o-aminophenol, m-aminophenol, p-aminophenol) at present include high performance liquid chromatography, fluorescence spectroscopy, capillary electrophoresis, gas chromatography, electrochemistry, microfluidic devices, and the like. Although effective detection effect can be achieved, the required instrument is expensive, the pretreatment of the sample is complicated, and the interference of the coexistence of the aminophenol isomers is easy to occur; the traditional colorimetric analysis method is convenient and quick, but has lower detection limit and poor selectivity, and can not meet the high-sensitivity selective colorimetric detection of the p-aminophenol, the m-aminophenol and the p-aminophenol. Therefore, the development of a convenient, efficient and sensitive colorimetric detection method for amplifying the catalysis signals of the o-aminophenol and the m-aminophenol has important significance.
The nanometer mimic enzyme is used as a high-efficiency bionic catalyst, has low cost and high stability, can catalyze various reactions under mild conditions, has higher substrate specificity, selectivity and catalytic efficiency, and has been widely applied to the fields of anticancer, photodynamic therapy, bionic catalysis, biosensing, environmental analysis and detection and the like.
Disclosure of Invention
In order to solve the problems of high analysis price, complex sample processing, low sensitivity, poor selectivity and the like of the traditional colorimetric detection of conventional instruments and solve the environmental pollution caused by o-aminophenol, m-aminophenol and p-aminophenol, the invention aims to provide spindle-shaped Cu-Ru bimetallic mesoporous nano-mimic enzyme and a preparation method thereof, and application of the nano-mimic enzyme in catalytic visual detection of o-aminophenol and m-aminophenol. Based on good synergistic enhancement between copper and ruthenium bimetallic, a spindle-shaped Cu-Ru bimetallic-based nano-mimic enzyme (CTAB@Cu-Ru) is successfully prepared by adopting a surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) to assist in one-pot reduction; through researches, CTAB@Cu-Ru mimic enzyme is applied to simultaneous colorimetric detection of o-aminophenol (o-AP) and m-aminophenol (m-AP), and has the advantages of strong visibility, simplicity and convenience in operation, good selectivity and high sensitivity.
In order to achieve the above purpose, the invention adopts the following technical scheme:
according to a first aspect of the invention, a spindle-shaped Cu-Ru bimetallic mesoporous nano-mimic enzyme (CTAB@Cu-Ru) is provided, and comprises Cu nanoparticles and Ru nanoparticles, wherein the nano Cu and Ru are connected through metal bond interaction.
Further, during the formation of the nano-mimic enzyme, the CTAB solution easily forms a double-atomic layer micelle, and the surface of the double-atomic layer micelle is hydrolyzed with a hydrolysate OH of a reducing agent - After ion exchange, OH on CTAB micelle surface - Based on strong electrostatic action and Cu 2+ 、Ru 3 + And combining, quickly reducing by a reducing agent, and assembling on CTAB to finally obtain the spinning cone-shaped nano material.
Further, the particle size of the nano mimic enzyme is 150-250 nm; the nanometer mimic enzyme has uniform particle size, good dispersibility and good stability.
The invention provides a preparation method of CTAB@Cu-Ru nanometer mimic enzyme, which comprises the following steps:
(1) Will contain Cu 2+ Ion, ru 3+ Adding the ionic raw materials into the dispersion liquid of the cetyl trimethyl ammonium bromide to be mixed, so as to obtain a precursor mixed liquid;
(2) Adding a reducing agent into the precursor mixed solution, stirring for 0.5-3 h at room temperature, and centrifugally separating to obtain a solid product, thus obtaining the nano mimic enzyme CTAB@Cu-Ru.
Further, the Cu 2+ The ion source is selected from Cu (NO) 3 ) 2 、CuSO 4 、CuCl 2 At least one of them.
Further, the Ru 3+ The ion source is selected from RuCl 3 Hydrate, ruthenium acetate,Anhydrous RuCl 3 At least one of them.
Further, cu described in the step (1) 2+ Ions and Ru 3+ The mole ratio of the ions is 0.1-0.4: 0.02 to 0.06.
Further, cu described in the step (1) 2+ The feeding ratio of the sodium dodecyl sulfate and hexadecyl trimethyl ammonium bromide is 0.1-0.4: 100-300 parts; cu (Cu) 2+ Cetyltrimethylammonium bromide in mg in mol.
Further, cu is dispersed in an ultrasonic manner in the step (1) 2+ Ion source, ru 3+ The ion source was dispersed in a positive cetyltrimethylammonium bromide solution.
Further, the reducing agent in step (2) is selected from NaBH 4 、LiAlH 4 At least one of hydrazine hydrate and vitamin C; OH through CTAB micelle surface - Based on strong electrostatic action and Cu 2+ 、Ru 3+ And combining, quickly reducing by a reducing agent, and assembling on CTAB to finally obtain the spinning cone-shaped nano material.
And (3) after the solid product is centrifugally separated in the step (2), centrifugally washing the solid product by ethanol and water, and then vacuum drying the solid product to obtain the target product CTAB@Cu-Ru nanometer mimic enzyme.
The invention provides an application of the CTAB@Cu-Ru nano mimic enzyme in the fields of environmental water, biology, medicine and the like.
Further, the application is to detect the o-aminophenol by using CTAB@Cu-Ru nano mimic enzyme, and the method comprises the following steps of:
s1, adding colorimetric substrate 3,3', 5' -tetramethyl benzidine (TMB), disodium hydrogen phosphate-citric acid buffer solution and sample liquid to be detected into CTAB@Cu-Ru standard solution to obtain liquid to be detected;
s2, observing the color change of the liquid to be detected.
Still further, the standard solution in step S1 is CTAB@Cu-Ru solution with a concentration of 0.1 mg/mL.
Further, the 3,3', 5' -Tetramethylbenzidine (TMB) and the disodium hydrogen phosphate-citric acid buffer solution in the step S1 are added in the following amounts: 20-200 mu L of 1.5mM TMB, 50-200 mu L of disodium hydrogen phosphate-citric acid buffer solution with pH of 3.5.
Further, in step S2, the color change is a blue to colorless visual color change, which means that the sample solution to be tested contains o-aminophenol.
Further, the application is to detect the m-aminophenol by using the CTAB@Cu-Ru nano mimic enzyme, and the method comprises the following steps of:
s3, adding colorimetric substrate ABTS, disodium hydrogen phosphate-citric acid buffer solution and H into the CTAB@Cu-Ru standard solution 2 O 2 Obtaining a sample liquid to be detected;
and S4, observing the color change of the liquid to be detected.
Further, in the step S3, the standard solution is CTAB@Cu-Ru solution with the concentration of 0.1 mg/mL.
Further, in step S3, the above-mentioned ABTS, disodium hydrogen phosphate-citric acid buffer solution and H 2 O 2 The addition amounts of (1) 5mM ABTS and (50) 5.0mM H are respectively 20-280 mu L and 50-500 mu L 2 O 2 50-200 mu L of disodium hydrogen phosphate-citric acid buffer solution with the pH value of 3.0.
Further, in step S4, the color change from blue-green to pink is a visual color change, which indicates that the sample solution to be measured contains meta-aminophenol.
Further, the application is that the CTAB@Cu-Ru nanometer mimic enzyme can be used for carrying out double-mode colorimetric detection on the o-aminophenol and the m-aminophenol, and the method comprises the following steps of:
s1, adding colorimetric substrate 3,3', 5' -tetramethyl benzidine (TMB), disodium hydrogen phosphate-citric acid buffer solution and sample liquid to be detected into CTAB@Cu-Ru standard solution to obtain liquid to be detected;
s2, observing the color change of the liquid to be detected;
s3, adding colorimetric substrate ABTS, disodium hydrogen phosphate-citric acid buffer solution and H into the CTAB@Cu-Ru standard solution 2 O 2 Obtaining a sample liquid to be detected;
and S4, observing the color change of the liquid to be detected.
Still further, the standard solution in step S1 is CTAB@Cu-Ru solution with a concentration of 0.1 mg/mL.
Further, the 3,3', 5' -Tetramethylbenzidine (TMB) and disodium hydrogen phosphate-citric acid buffer solution described in the step S1 are added in the following amounts:
further, in step S2, the color change is a blue to colorless visual color change, which means that the sample solution to be tested contains o-aminophenol.
Further, in the step S3, the standard solution is CTAB@Cu-Ru solution with the concentration of 0.1 mg/mL.
Further, in step S3, the above-mentioned ABTS, disodium hydrogen phosphate-citric acid buffer solution and H 2 O 2 The addition amount of (2) is as follows:
further, in step S4, the color change from blue-green to pink is a visual color change, which indicates that the sample solution to be measured contains meta-aminophenol.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides spindle-shaped Cu-Ru bimetal mesoporous nano-mimic enzyme (CTAB@Cu-Ru), which has good nano-mimic oxidase activity and simulated peroxidase activity and can play a role of double-function nano-enzyme. Under the conditions of room temperature and air, 3', 5' -tetramethyl benzidine (TMB) can be rapidly catalyzed and oxidized to generate blue oxTMB, and the characteristic absorption peak position is 653nm; CTAB@Cu-Ru-TMB has stronger visual colorimetric recognition capability on o-AP, and the characteristic absorption intensity at 653nm is gradually reduced and is accompanied with visual blue-light blue-colorless change; at room temperature and H 2 O 2 Under the condition, the ABTS can be rapidly catalyzed and oxidized to generate the blue-green oxABTS, and the characteristic absorption peak position is 727nm; CTAB@Cu-Ru-TMB-H 2 O 2 The fluorescent dye has stronger visual colorimetric recognition capability on m-AP, the characteristic absorption intensity at 727nm is gradually reduced, a new characteristic absorption peak appears at 513nm, and the absorption intensity is gradually increased with the change of visual blue-pink purple-pink. Is convenient for highThe method can effectively and conveniently visually detect the ultra-trace o-AP and m-AP in environmental water, commercial fruit juice beverage and the like, and has high sensitivity and accurate detection result.
(2) The invention provides a preparation method of the CTAB@Cu-Ru nano mimic enzyme, which is characterized in that a positive cetyltrimethylammonium bromide (CTAB) template is used for guiding, and a one-pot reduction method is used for preparing copper-ruthenium bimetallic base nano mimic enzyme (CTAB@Cu-Ru), wherein: the empty d orbit on the Cu and Ru atoms and the coordination bond of the CTAB rich electrons are loaded on the CTAB template, and can be conveniently removed in the process of water centrifugal washing after synthesis due to the solubility of the CTAB template, and the CTAB template can form a double micelle surface and form a strong electrostatic effect with Cu 2+ 、Ru 3+ Bonding, avoiding the formation of random nanoparticles. Meanwhile, copper and ruthenium interact to further promote charge transfer among the copper and ruthenium, and synergistically enhance the catalytic activity of CTAB@Cu-Ru mimic oxidase/peroxidase.
(3) The application of the CTAB@Cu-Ru nanometer mimic enzyme shows excellent specificity and selectivity to o-aminophenol and m-aminophenol in detection samples of environmental water, commercial fruit juice beverage and the like; the CTAB@Cu-Ru nanometer mimic enzyme has the characteristics of good anti-interference performance, convenience and rapidness in detection application, high sensitivity, accurate detection result and the like, and can effectively detect ultra-trace o-AP and m-AP in a sample.
Drawings
FIG. 1 is a TEM image of CTAB@Cu-Ru nano-mimic enzyme prepared in example one.
FIG. 2 elemental analysis EDS (panel a) HR-TEM (panel b) of CTAB@Cu-Ru nanomesh enzyme prepared in example one.
FIG. 3 XPS spectrum (panel a) and XRD spectrum (panel b) of CTAB@Cu-Ru nano-mimic enzyme prepared in example I.
FIG. 4. CTAB@Cu-Ru nanomechanical enzyme prepared in example one optimizes surfactant usage (panel a), cu and Ru ratio (panel b); graph of enzyme activity simulated under conditions of different pH systems (graph c), TMB concentration (graph d) and reaction time (graph e) of CTAB@Cu-Ru nanometer simulated enzyme.
FIG. 5. Example 1 preparationCTAB@Cu-Ru nano-mimic enzyme at different system pH (FIG. a), ABTS concentration (FIG. b), H 2 O 2 Concentration (panel c) and reaction time (panel d).
FIG. 6. Kinetic curves of CTAB@Cu-Ru nano-mimic enzyme prepared in example one when the catalytic substrate is TMB (FIG. a); graph b is a double reciprocal plot.
FIG. 7A CTAB@Cu-Ru nano-mimic enzyme prepared according to example one shows the concentration of ABTS, H 2 O 2 Kinetic profile of change (figures a, c); graph b is a double reciprocal plot of ABTS concentration change, graph d is H 2 O 2 Double reciprocal plot of concentration change.
FIG. 8. FIG. a is a graph showing the effect of different interfering ions on the spectral properties of CTAB@Cu-Ru nanomorphic enzymes prepared in example one (inset: color comparison graph); FIG. b is a graph showing the effect of interfering ions on spectral properties of CTAB@Cu-Ru nano-mimic enzyme prepared in example one.
FIG. 9. FIG. a is a graph showing the effect of different interfering ions on the spectral properties of CTAB@Cu-Ru nanoenzyme prepared in example one (inset: color comparison graph); FIG. b is a graph showing the effect of interfering ions on spectral properties of CTAB@Cu-Ru nano-imitation enzymes prepared in example I when the interfering ions coexist with m-AP.
FIG. 10A shows a spectral titration curve (inset: color change picture; and b shows absorbance intensity (A) 653 ) And o-aminophenol concentration (c) o-AP ) Linear relationship between the two.
FIG. 11, panel a is a spectral titration curve (inset: color change panel) of a colorimetric sensor m-AP; panel b shows lg (A 513 /A 727 ) Or lg (A) 513 /A 415 ) With m-aminophenol concentration (c) m-AP ) Linear relationship between the two.
Detailed Description
The present application will be described in further detail below by way of examples to enable those skilled in the art to practice the present application. It is to be understood that other embodiments may be utilized and that appropriate changes may be made without departing from the spirit or scope of the present application. To avoid detail not necessary to enable those skilled in the art to practice the application, the description may omit certain information known to those skilled in the art. The following detailed description is, therefore, not to be taken in a limiting sense, and the scope of the present invention is defined only by the appended claims. The following examples facilitate a better understanding of the present application, but are not intended to limit the scope of the present application.
Example 1
(1) Accurately weigh 0.1180g (0.4 mmol) Cu (NO) 3 ) 2 ·3H 2 O and 0.0108g (0.05 mmol) anhydrous RuCl 3 Dissolving in 25mL of 10mg/mL CTAB dispersion liquid, and uniformly stirring to obtain a precursor mixed liquid;
(2) Adding 5.0mL (0.2M) of freshly prepared NaBH into the precursor mixed solution obtained in the step (1) 4 After stirring the solution for 1h, centrifugally separating, washing 3 times by using ethanol and water for centrifugation (the rotating speed is 7000 rpm), removing the template CTAB, and then carrying out vacuum drying at 60 ℃ to obtain the CTAB@Cu-Ru nano-imitation enzyme.
Example two
(1) Accurately weigh 0.0635g (0.4 mmol) CuSO 4 And 0.0139g (0.05 mmol) of ruthenium acetate are dissolved in 25mL of 10mg/mL CTAB dispersion, and the precursor mixed solution is obtained after uniform stirring;
(2) And (3) adding 5.0mL of freshly prepared hydrazine hydrate solution (0.2M) into the precursor mixed solution obtained in the step (1), stirring for 1h, centrifuging with ethanol and water respectively (the rotating speed is 7000 rpm), washing for 3 times, removing the template CTAB, and then carrying out vacuum drying on a solid product obtained by centrifugation at 60 ℃ to obtain the CTAB@Cu-Ru nano-imitation enzyme.
Example III
(1) Accurately weigh 0.0682g (0.4 mmol) CuCl 2 ·2H 2 O and 0.0139g (0.05 mmol) of ruthenium acetate are dissolved in 25mL of 10mg/mL CTAB dispersion, and precursor mixed solution is obtained after uniform stirring;
(2) Adding 5.0mL of 0.2M LiAlH into the precursor mixed solution obtained in the step (1) 4 Stirring for 1h, centrifuging with ethanol and water (with the rotation speed of 7000 rpm) for 3 times, removing the template CTAB, and then vacuum drying the solid product obtained by centrifugation at 60 ℃ to obtain the CTAB@Cu-Ru nano-imitation enzyme.
Performance characterization, testing:
1. microscopic observation and component detection are carried out on the spindle-shaped Cu-Ru bimetallic mesoporous nano-mimic enzyme prepared in the first embodiment by adopting a transmission electron microscope, and the results are shown in figures 1 to 3. FIG. 1 is a microscopic view of the CTAB@Cu-Ru under a transmission electron microscope, and shows that the prepared CTAB@Cu-Ru nanometer mimic enzyme is of a multi-spinning cone-shaped structure, is uniformly dispersed, has a particle size of about 150-250 nm, can provide a larger surface area, has more active sites, and improves the detection capability of organic amino phenols. Further, it is apparent from FIG. 2b that the three lattice spacings of 0.234nm, 0.255nm and 0.263nm are attributed to the (111) and (002) crystal planes of Cu and the crystal lattice of copper-ruthenium alloy, respectively. As can be seen from fig. 3a, the XPS spectrum contains all elements of Cu, ru, O; fig. 3b shows the characteristic crystal diffraction signals of Cu (2θ=32.7 °, 35.9 °, 38.7 °, 48.8 °, 54.1 °, 58.2 °, 61.5 °, 66.7 ° and 68.1 °) and Ru (2θ=26.7 °, 35.4 °, 42.5 °, 53.4 ° and 57.5 °).
2. Testing the detection capability of spindle-shaped Cu-Ru bimetallic mesoporous nanometer mimic enzyme on o-AP and m-AP:
(1) Preparation of 0.1mg/mL CTAB@Cu-Ru standard solution: 0.01g of CTAB@Cu-Ru sample is weighed, dispersed into 100mL of purified water under ultrasonic conditions, and prepared into a CTAB@Cu-Ru standard solution with the concentration of 0.1mg/mL, and the CTAB@Cu-Ru standard solution is preserved in a dark place at room temperature for standby.
(2) Preparation of o-AP standard solution: 0.01091g of o-aminophenol is added into a 100mL volumetric flask, and after complete dissolution, ethanol is used for fixing the volume to 100mL to prepare the water-soluble phenol with the concentration of 1.0X10 -3 mol/L, and storing at room temperature for standby.
Preparation of m-AP standard solution: 0.01091g of o-aminophenol is added into a 100mL volumetric flask, and after complete dissolution, ethanol is used for fixing the volume to 100mL to prepare the water-soluble phenol with the concentration of 1.0X10 -3 mol/L, and storing at room temperature for standby.
(3) Preparing an actual sample to be tested:
(i) Randomly weighing 1 part of each of 50.0mL of environmental water samples (such as Yi river water, polygonum river water, apartment tap water and the like), filtering three times by a 4 mu m microporous filter membrane, concentrating by distillation to 10.0mL, and storing the sample to be detected in a refrigerator (4 ℃) for later use.
(ii) 50.0mg of Gankang tablet is weighed, dissolved in 50.0mL of solution with pH=3.5, filtered three times by a micro-pore filter membrane with the thickness of 4 mu m, and a sample to be tested is placed in a refrigerator (4 ℃) for storage for standby.
(4) Test of CTAB@Cu-Ru mimic oxidase catalytic activity: measuring 500 μl (0.1 mg/mL) of CTAB@Cu-Ru standard solution and 160 μl (1.5 mM) of TMB, placing into a biological centrifuge tube with a volume of 5mL, mixing thoroughly, metering to 3.0mL with disodium hydrogen phosphate-citric acid buffer solution (pH=3.5), aging at room temperature for 45min, measuring ultraviolet-visible absorption spectrum in the range of 300-800 nm, and making the system have strong absorption peak (A at 653nm 653 =0.532), the color of the solution changes from colorless to blue.
(5) Test of CTAB@Cu-Ru mimic peroxidase catalytic activity: 200. Mu.L of the CTAB@Cu-Ru standard solution, 220. Mu.L (1.5 mM) of ABTS and 400. Mu.L (5.0 mM) of H are measured 2 O 2 Placing the materials into a 5mL biological centrifuge tube, fully mixing, fixing the volume to 3.0mL by using disodium hydrogen phosphate-citric acid buffer solution (pH=3.0), aging for 75min at room temperature, measuring ultraviolet-visible absorption spectrum in the range of 300-800 nm, and obtaining a system with two stronger absorption peaks (A) at 415nm and 727nm 415 ＝2.01，A 727 =0.83) with a color change of "colorless-bluish green".
(6) Optimization of enzyme-like catalysis experimental conditions: in order to obtain the optimal CTAB@Cu-Ru nano enzyme-like catalytic activity, firstly taking a TMB colorimetric substrate as an example, discussing the influence of the dosage of a surfactant and the molar ratio of material components; on the basis, the pH, the reaction temperature, the TMB concentration, the ABTS concentration and the H of the system are discussed 2 O 2 The effects of factors such as the concentration and reaction time, namely, the pH (2.5 to 7.0), cu to Ru molar ratio (20:1 to 7:1), reaction temperature (20 to 90 ℃ C.), TMB content (0.01 to 0.15 mM), ABTS content (0.01 to 0.14 mM) or H were investigated in accordance with the methods of (4) and (5) above 2 O 2 (0.083-0.83 mM) on the catalytic activity of CTAB@Cu-Ru nano-imitation enzyme.
As can be seen from FIG. 4, the optimized conditions of the CTAB@Cu-Ru mimetic oxidaseThe method comprises the following steps: ph=3.5, 0.08mm TMB, aged at 30 ℃ for 45min; the optimized conditions for the simulated peroxidase are as follows from fig. 5: ph=3.0, 0.11mM ABTS,0.67mM H 2 O 2 Aging at 30deg.C for 75min. Namely, the CTAB@Cu-Ru nano-mimic enzyme has good nano-mimic oxidase activity or mimic peroxidase activity.
As can be seen from fig. 6 and 7: the Mie constant Km of the CTAB@Cu-Ru nano enzyme-like catalytic TMB is 0.0072mM, and the maximum initial rate Vmax is 6.33 multiplied by 10 -8 M·s -1 The method comprises the steps of carrying out a first treatment on the surface of the CTAB@Cu-Ru nano enzyme-like catalysis ABTS and H 2 O 2 Miq constants (Km) of 0.017mM and 3.81mM, respectively, and maximum initiation rates (Vmax) of 6.47×10, respectively -8 M·s -1 And 8.23×10 -8 M·s -1 The method comprises the steps of carrying out a first treatment on the surface of the This means that CTAB@Cu-Ru nano-imitation enzyme has good imitation enzyme catalytic activity and catalytic rate, and can rapidly catalyze TMB, ABTS and H 2 O 2 And (3) completely reacting the substrate to realize detection of the target object to be detected.
(7) FIGS. 8 and 9 show the activity selectivity of common interfering ions on CTAB@Cu-Ru nano-scale enzyme, and as can be seen from FIGS. 8 and 9, common coexisting ions in the samples are detected: ba (Ba) 2+ 、Mg 2+ 、K + 、Hg 2+ CTAB@Cu-Ru-TMB System having a variation in absorption intensity at 653nm in the Co-existence of o-AP, phenylalanine, glycine, threonine, alanine, glucose, aniline, urea, phenol, acetone, meta-aminophenol and para-aminophenol (FIG. 8 a), and CTAB@Cu-Ru-TMB-H in the co-existence of m-AP 2 O 2 The system has an absorption intensity variation at 727nm (FIG. 9 a) of less than 5% in the analysis error range. The CTAB@Cu-Ru-TMB system has specific selective colorimetric response to o-AP and is accompanied by color change from blue to colorless; CTAB@Cu-Ru-TMB-H 2 O 2 The system has good visual colorimetric response to the m-AP and is accompanied with visual blue-green-pink change, so that the CTAB@Cu-Ru nanometer imitation enzyme can be used for detecting o-AP and m-AP in a sample quickly and efficiently by naked eyes without using other observation instruments.
(8) The method for detecting the o-AP content by enzyme catalysis and colorimetry comprises the following steps: taking out500. Mu.L (0.1 mg/mL) of the CTAB@Cu-Ru standard solution is added into a 5mL biological centrifuge tube, 160. Mu.L (1.5 mM) of TMB and 200. Mu.L of disodium hydrogen phosphate-citric acid buffer solution with pH=3.5 are added, uniformly mixed, and the mixture is subjected to constant volume to 2.8mL by using three distilled water, and is aged for 45min at room temperature, 200. Mu.L of o-AP standard solution with different concentrations is added, and is aged for 3min, UV-vis absorption spectrum and color change within the range of 300-800 nm are measured, and A is found out 653 Linear relationship with o-AP concentration (co-AP). As shown in fig. 10: as the o-AP concentration gradually increased (the o-AP concentrations represented by the curves from top to bottom are, in order, 0, 0.33, 0.67, 1.00, 1.67, 2.67, 4.3, 5.00, 5.67, 6.67, 8.00, 9.33, 10.67, 11.67. Mu.M), the absorption intensity (A) at 653nm of the CTAB@Cu-Ru-TMB system 653 ) Gradually decrease, the color of the material is gradually changed from blue to colorless, and the material is 0 to 11.67 multiplied by 10 -6 The mol/L range shows good linear relation, and the linear regression equation is as follows: a is that 653 ＝0.52776-0.02955c o-Ap (R 2 = 0.9981), the detection limit is 1.60×10 -8 mol/L(S/N＝3)。
(9) The method for detecting the m-AP content by enzyme catalysis and colorimetry comprises the following steps: 200. Mu.L (0.1 mg/mL) of the CTAB@Cu-Ru standard solution was taken in a 5mL bioaugtube and 220. Mu.L (1.5 mM) of ABTS, 200. Mu.L of disodium hydrogen phosphate-citric acid buffer solution with pH=3.5, and 400. Mu. L H were added 2 O 2 (5.0 mM) and then three distilled water is used for constant volume to 2.8mL, the mixture is aged for 75min at room temperature, 200 mu L of m-AP standard solution with different concentrations is added, the mixture is aged for 30min, and the UV-vis absorption spectrum and the color change within the range of 300-800 nm are measured. As shown in FIG. 11, CTAB@Cu-Ru-ABTS-H 2 O 2 The system showed a new characteristic peak at 513nm, with increasing M-AP concentration (0, 0.667, 1.33, 2, 2.67, 3.33, 5, 6.67, 8.33, 10, 11.67, 13.33, 15, 16.67, 18.33, 21.67. Mu.M in the order of o-AP concentration represented by the curves from top to bottom), absorption intensity at 513nm (A 513 ) Gradually rising with a color change of "bluish green-pink purple-pink", and lg (a 513 /A 727 ) Or lg (A) 513 /A 415 ) With m-aminophenol concentration (c) m-AP ) At 0 to 21.67 multiplied by 10 -6 There are good multiple ratios in the mol/L rangeLinear relationship. The linear regression equation is lg (A 513 /A 727 )＝0.07187c m-AP -0.60598(R 2 = 0.9979) or lg (a 513 /A 415 )＝0.06315c m-AP -0.97034(R 2 =0.9987). The detection limit was 3.25X10 -8 mol/L(S/N＝3)。
(10) The o-AP and m-AP content of environmental water, commercial juice beverages and pharmaceutical samples were measured colorimetrically for trace amounts of o-AP and m-AP according to the methods of (8) and (9) above, and the results are shown in tables 1 and 2.
Table 1 trace o-AP detection results in sample (n=5) a
a PB,pH＝3.5,c CTAB@Cu-Ru-TMB ＝0.1mg/mL
Table 2 results of trace m-AP detection in sample (n=5) a
a PB,pH＝3.5,c CTAB@Cu-Ru-TMB ＝0.1mg/mL
As can be seen from Table 1, the o-AP recovery rate in the samples is between 97.2% and 103.5%, and the relative error (RSD) is less than 4.58%; as can be seen from Table 2, the recovery of m-AP in the samples was between 96.6% and 102.27%, with a relative error (RSD) of less than 3.34%. The CTAB@Cu-Ru nanometer mimic enzyme has the characteristics of convenience, rapidness, high sensitivity, accurate detection result and the like when being applied to trace o-AP and m-AP in environmental water, commercial fruit juice beverage and medicament samples, and can effectively detect ultra-trace o-AP and m-AP in the samples.
The foregoing is illustrative of only a few embodiments of the present invention and is not to be construed as limiting the scope of the invention. It should be noted that modifications, substitutions, improvements, etc. can be made by others skilled in the art without departing from the spirit and scope of the present invention. The scope of the invention should, therefore, be determined with reference to the appended claims.
Claims (10)
1. The spindle-shaped Cu-Ru bimetallic mesoporous nano-mimic enzyme is characterized by comprising Cu nanoparticles and Ru nanoparticles, wherein the nano Cu and Ru are connected through metal bond interaction.
2. The nano-mimetic enzyme of claim 1, wherein the particle size of the nano-mimetic enzyme is 150-250 nm.
3. The preparation method of the spindle-shaped Cu-Ru bimetallic mesoporous nano-mimic enzyme is characterized by comprising the following steps of:
(1) Will contain Cu 2+ Ion, ru 3+ Adding the ionic raw materials into the dispersion liquid of the cetyl trimethyl ammonium bromide to be mixed, so as to obtain a precursor mixed liquid;
(2) And adding a reducing agent into the precursor mixed solution, and separating out a solid product after the reaction is completed to obtain the nano mimic enzyme CTAB@Cu-Ru.
4. The method according to claim 1, wherein the Cu 2+ The ion source is selected from Cu (NO) 3 ) 2 、CuSO 4 、CuCl 2 At least one of them.
5. The method according to claim 1, wherein the Ru 3+ The ion source is selected from RuCl 3 Hydrate, ruthenium acetate and anhydrous RuCl 3 At least one of them.
6. The method of claim 1, wherein the steps areCu described in step (1) 2+ Ions and Ru 3+ The molar ratio of the ions is 0.1-0.4: 0.02 to 0.06.
7. The method according to claim 1, wherein the Cu in the step (1) 2+ The feeding ratio of the cetyl trimethyl ammonium bromide to the cetyl trimethyl ammonium bromide is 0.1-0.4: 100-300 parts; cu (Cu) 2+ Cetyltrimethylammonium bromide in mg in mol.
8. The process according to claim 1, wherein the reducing agent in step (2) is selected from NaBH 4 、LiAlH 4 At least one of hydrazine hydrate and vitamin C.
9. Use of a ctab@cu-Ru nano-mimic enzyme according to claims 1-2 or prepared according to claims 3-8 in the fields of environmental water, biology, medicine, etc.
10. The use according to claim 9, characterized in that detection of o-aminophenol and/or m-aminophenol is performed using ctab@cu-Ru nanomechanical enzyme:
the detection process of the o-aminophenol comprises the following steps: s1, adding colorimetric substrate 3,3', 5' -tetramethyl benzidine (TMB), disodium hydrogen phosphate-citric acid buffer solution and sample liquid to be detected into CTAB@Cu-Ru standard solution to obtain liquid to be detected;
s2, observing the color change of the liquid to be detected;
the detection process of the m-aminophenol comprises the following steps: s3, adding colorimetric substrate ABTS, disodium hydrogen phosphate-citric acid buffer solution and H into the CTAB@Cu-Ru standard solution 2 O 2 Obtaining a sample liquid to be detected;
and S4, observing the color change of the liquid to be detected.
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| CN117664887B (en) * | 2024-01-29 | 2024-04-12 | 云南伦扬科技有限公司 | Method for rapidly detecting lead and zearalenone by using phenolic coordination polymer nano enzyme group |
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