Dual-core phthalocyanine modified iron molybdate composite material, preparation, detection method and sensor

Abstract

The present invention belongs to the technical field of preparation of new materials, and discloses a binuclear phthalocyanine modified iron molybdate composite material, preparation, detection method and sensor. The preparation method comprises: modifying the binuclear phthalocyanine on the prepared iron molybdate by a two-step hydrothermal method, and preparing a binuclear phthalocyanine modified iron molybdate composite material as a peroxidase mimetic enzyme for rapid colorimetric sensing of adrenaline. The iron molybdate in the present invention is easy to prepare, quick and easy to obtain. The present invention uses the prepared binuclear phthalocyanine modified iron molybdate composite material for rapid colorimetric detection of adrenaline. The binuclear phthalocyanine modified iron molybdate composite material prepared by the present invention is used for rapid colorimetric detection of adrenaline, and the detection limit can be as low as micromolar level, the detection speed is fast, and the operation is simple.

Description

Technical Field

[0001] The invention belongs to the technical field of new material preparation, and in particular relates to a binuclear phthalocyanine modified iron molybdate composite material, a preparation method, a detection method and a sensor. Background Art

[0002] Adrenaline is a very important hormone secreted by the human body. Disorders in the adrenaline content in the human body may lead to a series of serious diseases, including Parkinson's disease, Alzheimer's disease and schizophrenia. The concentration of adrenaline in the human body is closely related to many physiological phenomena, such as accelerated heart rate, increased blood pressure, bronchial dilation, and mydriasis. The side effects of adrenaline are generally caused by excessive or unintentional vascular injection, leading to palpitations, dizziness, hypertension, cerebral hemorrhage and acute pulmonary edema. Therefore, the accurate determination of adrenaline concentration is not only important for the diagnosis of neurological diseases, but also for the development of new drugs closely related to demand. Colorimetry is a detection technology with fast response, fast analysis, low cost and sensitive detection. The effect of pure iron molybdate material on peroxidase mimicking enzyme is not obvious. After the iron molybdate is modified with binuclear phthalocyanine, the effect of binuclear phthalocyanine modified iron molybdate composite material is more obvious than the peroxidase mimicking enzyme of pure iron molybdate. Therefore, binuclear phthalocyanine modified iron molybdate composites can be prepared for sensitive colorimetric detection of adrenaline by peroxidase mimetic enzymes.

[0003] Iron molybdate has been widely used in the fields of optics, catalysis, magnetism and electrochemistry, and has therefore attracted the attention of researchers. The patented technology of "An in-situ core-shell structure iron molybdate powder and its preparation method" (CN109574082A) produces a core-shell structure iron molybdate with a particle size of 10 to 100 μm, but the preparation process of this method is complicated and the required reaction time is long. The patented technology of "An iron molybdate carbon composite nanosphere, preparation method and its application as an electrode material" (CN110492070A) produces an iron molybdate carbon composite nanosphere with a particle size of 100 to 200 nm, but requires inert gas protection and high-temperature calcination to prepare the iron molybdate carbon composite nanosphere, which has high equipment requirements and preparation energy consumption.

[0004] The patented technology of "binuclear / trinuclear phthalocyanine cobalt carboxylate oxidative desulfurization catalyst and its preparation method" (CN101525337A) produces binuclear / trinuclear phthalocyanine cobalt carboxylate, which is used as an oxidative desulfurization catalyst, but the reaction takes a long time and the preparation process is relatively complicated. It is a new and effective method to use binuclear phthalocyanine to modify and enhance the peroxidase mimicking activity of ferric molybdate to prepare a composite material for rapid colorimetric detection of adrenaline at the micromolar level.

[0005] Through the above analysis, the problems and defects of the prior art are as follows:

[0006] (1) The prior art preparation of iron molybdate is complicated, the reaction route is long, and the cost is high.

[0007] (2) The rapid colorimetric detection limit of adrenaline in the existing technology is easily affected by external interference, and the detection level cannot reach the micromolar level, which limits its practicality;

[0008] (3) The existing technology for rapid colorimetric detection of adrenaline is slow and complex to operate, and has poor selectivity for colorimetric detection of adrenaline. Summary of the invention

[0009] In order to overcome the existing technical defects in the related art, the disclosed embodiments of the present invention provide a binuclear phthalocyanine modified iron molybdate composite material, preparation, detection method and sensor. Specifically, it relates to a binuclear phthalocyanine modified iron molybdate composite material preparation and its peroxidase mimetic enzyme activity for rapid colorimetric detection of adrenaline.

[0010] The preparation method of the invention is a two-step hydrothermal method, the preparation method is simple, and the prepared binuclear phthalocyanine modified iron molybdate composite material is used for rapid colorimetric detection of adrenaline, and the detection limit can reach the micromole level.

[0011] The technical scheme is as follows: A method for preparing a binuclear phthalocyanine modified iron molybdate composite material comprises:

[0012] Through a two-step hydrothermal method, binuclear phthalocyanine was modified on the prepared iron molybdate to prepare a binuclear phthalocyanine-modified iron molybdate composite material that can be used as a peroxidase mimetic for rapid colorimetric sensing of adrenaline.

[0013] In one embodiment, the preparation of a binuclear phthalocyanine-modified iron molybdate composite material as a peroxidase mimetic enzyme for rapid colorimetric sensing of adrenaline comprises the following steps:

[0014] The binuclear phthalocyanine is dissolved in a chloroform solution, and the prepared iron molybdate is added into the chloroform solution containing the binuclear phthalocyanine. The formed mixed solution is ultrasonically treated, and then transferred into a polytetrafluoroethylene-lined reactor, reacted in an oven, washed with water and ethanol, and dried to obtain a binuclear phthalocyanine-modified iron molybdate composite material.

[0015] In one embodiment, the mass ratio of the iron molybdate to the binuclear phthalocyanine is (10-50):1.

[0016] In one embodiment, the iron molybdate comprises: α-FeMoO4 (monoclinic phase, unit cell constant is β=114.05°, space group C2 / m, JCPDS number: 22-1115), β-FeMoO4 (monoclinic phase, unit cell parameters are β=106.31°, space group C2 / m, JCPDS number: 22-0628).

[0017] In one embodiment, the method for preparing iron molybdate comprises:

[0018] FeSO4·7H2O and Na2MoO4·2H2O are added into a hydrochloric acid solution with a pH value of 2 at a molar ratio of 1:1, and after dissolution, a brown mixed solution of iron salt and molybdenum salt dissolved in hydrochloric acid is obtained;

[0019] The reaction solution after mixing evenly is transferred to a polytetrafluoroethylene-lined reactor and kept in an oven at 160°C-200°C for 2 hours to 6 hours. After the reaction is completed and cooled to room temperature, it is centrifugally washed several times with deionized water and ethanol, placed in an oven at 60°C-80°C and dried overnight, and the product is collected to prepare FeMoO4 solid.

[0020] In one embodiment, the process of modifying the dinuclear phthalocyanine on the prepared iron molybdate by a two-step hydrothermal method comprises the following steps:

[0021] Dissolve binuclear phthalocyanine in chloroform, add the prepared iron molybdate after dissolution, and perform ultrasonic treatment for 1 hour, so that the prepared iron molybdate and binuclear phthalocyanine are evenly dispersed in the chloroform solution;

[0022] The mixed solution was transferred to a polytetrafluoroethylene-lined reactor, reacted at 100°C-120°C for 1 hour-3 hours, cooled, centrifuged and washed several times with deionized water and anhydrous ethanol, and dried overnight in an oven at 60°C-80°C to prepare a binuclear phthalocyanine-modified iron molybdate composite material.

[0023] Another object of the present invention is to provide a binuclear phthalocyanine modified ferric molybdate composite material, wherein the binuclear phthalocyanine modified ferric molybdate composite material is prepared by using the preparation method of the binuclear phthalocyanine modified ferric molybdate composite material.

[0024] Another object of the present invention is to provide a method for rapid colorimetric detection of adrenaline using a binuclear phthalocyanine-modified iron molybdate composite material, the method for rapid colorimetric detection of adrenaline comprising the following steps:

[0025] The binuclear phthalocyanine modified iron molybdate composite material is added to a buffer solution, hydrogen peroxide is added, and then a TMB solution is added. The binuclear phthalocyanine modified iron molybdate composite material catalyzes hydrogen peroxide to produce active free radicals and catalyzes TMB to ox-TMB. Then adrenaline is added to reduce ox-TMB to TMB.

[0026] After the binuclear phthalocyanine-modified iron molybdate composite material catalyzes hydrogen peroxide in a buffer solution for 3 minutes and generates a certain amount of active free radicals that catalyze the oxidation of TMB into ox-TMB in a short period of time, adrenaline is added to reduce ox-TMB to TMB.

[0027] Another object of the present invention is to provide a sensor for rapid colorimetric detection of adrenaline, wherein the sensor for rapid colorimetric detection of adrenaline comprises the binuclear phthalocyanine modified iron molybdate composite material and acts as a peroxidase mimetic enzyme for rapid colorimetric detection of adrenaline, and the minimum detection limit of the sensor for rapid colorimetric detection of adrenaline is 0.23 μM.

[0028] The rapid colorimetric detection of adrenaline as a peroxidase mimetic enzyme comprises:

[0029] (1) Based on the data obtained from the above-mentioned colorimetric detection of adrenaline at 652 nm, a linear equation was determined: y = 0.04502x - 0.07273.

[0030] (2) Add 200 μL of binuclear phthalocyanine-modified iron molybdate composite material, 200 μL of H2O2, and 200 μL of TMB to 1200 μL of buffer solution; add 200 μL of adrenaline solution of unknown concentration respectively, incubate the mixed solution at room temperature for 3 min, record the absorbance change at 652 nm, and calculate the concentration of adrenaline according to the linear equation obtained in (1).

[0031] The pH value of the buffer solution is 4;

[0032] The concentration of adrenaline is 2 μM-8 μM;

[0033] The concentration of the binuclear phthalocyanine modified iron molybdate composite material is 0.3 mg / mL, the molar concentration of H2O2 is 240 mM, and the molar concentration of TMB is 1 mM.

[0034] Combining all the above technical solutions, the advantages and positive effects of the present invention are as follows:

[0035] First, in view of the technical problems existing in the above-mentioned prior art and the difficulty of solving the problems, the technical solutions to be protected by the present invention and the results and data during the research and development process are closely combined to analyze in detail and deeply how the technical solutions of the present invention solve the technical problems, and some creative technical effects brought about after solving the problems. The specific description is as follows:

[0036] The iron molybdate of the present invention is easy to prepare, quick and easy to obtain. Iron molybdate itself has a certain activity of peroxide mimicking enzyme, and can catalyze hydrogen peroxide to produce active free radicals to turn colorless TMB blue. Iron molybdate is modified with binuclear phthalocyanine to prepare a binuclear phthalocyanine-modified iron molybdate composite material, which improves the hydrogen peroxide mimicking enzyme activity of iron molybdate. In view of this, the present invention adopts the prepared binuclear phthalocyanine-modified iron molybdate composite material for rapid colorimetric detection of adrenaline.

[0037] The binuclear phthalocyanine modified iron molybdate composite material prepared by the present invention is used for rapid colorimetric detection of adrenaline, and the detection limit can be as low as micromolar level, the detection speed is fast, and the operation is simple. The binuclear phthalocyanine modified iron molybdate composite material prepared by the present invention has good selectivity for colorimetric detection of adrenaline.

[0038] Second, the present invention provides a method of using iron molybdate (FeMoO4) and binuclear phthalocyanine (BiPc (OC8H9) 12 ) as raw materials, a simple two-step hydrothermal method was used to prepare a binuclear phthalocyanine-modified iron molybdate composite material, which was applied as a peroxidase and used for rapid colorimetric sensing of adrenaline. First, the raw materials FeSO4·7H2O and Na2MoO4·2H2O were used to prepare iron molybdate nanorods. Then, the binuclear phthalocyanine was modified on the iron molybdate using hydrothermal technology, and the preparation process was simple and fast.

[0039] Third, as auxiliary evidence of the inventiveness of the claims of the present invention, it is also reflected in the following important aspects:

[0040] (1) The technical solution of the present invention solves a technical problem that people have been eager to solve but have never been able to solve successfully: the detection limit of the binuclear phthalocyanine-modified iron molybdate composite material synthesized by the present invention for adrenaline is 0.23 micromoles, and it has good selectivity in the presence of various metal ions, amino acids, and sugars. It was applied to the detection of adrenaline concentration in human serum and achieved satisfactory results.

[0041] (2) Whether the technical solution of the present invention overcomes technical bias: The preparation method of the present invention has the advantages of simplicity, low cost, low detection limit, good selectivity and reliability, and has certain guiding significance for the detection of adrenaline. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present disclosure and, together with the description, serve to explain the principles of the present disclosure.

[0043] Figure 1 This is a flow chart of a method for preparing a binuclear phthalocyanine-modified iron molybdate composite material provided by an embodiment of the present invention;

[0044] Figure 2This is a flow chart of a method for using a binuclear phthalocyanine-modified iron molybdate composite material provided by an embodiment of the present invention for rapid colorimetric detection of adrenaline;

[0045] Figure 3 is an X-ray diffraction pattern of a binuclear phthalocyanine-modified iron molybdate composite material prepared by a hydrothermal method using iron molybdate and binuclear phthalocyanine as raw materials provided in an embodiment of the present invention;

[0046] FIG4( a ) is a scanning electron microscope morphology and structure diagram of a binuclear phthalocyanine-modified iron molybdate composite material prepared by a hydrothermal method using iron molybdate and binuclear phthalocyanine as raw materials, provided in an embodiment of the present invention;

[0047] FIG4( b ) is an X-ray photoelectron spectrum of a binuclear phthalocyanine-modified iron molybdate composite material prepared by a hydrothermal method using iron molybdate and binuclear phthalocyanine as raw materials according to an embodiment of the present invention;

[0048] FIG5(a) is a linear response curve of the binuclear phthalocyanine modified iron molybdate composite material prepared as a peroxidase mimic provided in an embodiment of the present invention for detecting the relationship between absorbance and adrenaline concentration. Figure 1 ;

[0049] FIG5( b ) is a linear fitting curve relationship between absorbance and adrenaline concentration of the binuclear phthalocyanine-modified iron molybdate composite material prepared as a peroxidase mimic provided in an embodiment of the present invention. Figure 2 ;

[0050] Figure 6 This is a graph showing the selectivity of the binuclear phthalocyanine-modified ferric molybdate composite material for adrenaline detection under the condition that the concentration of the interfering substance is 20 times that of the detected substance. DETAILED DESCRIPTION

[0051] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific embodiments of the present invention are described in detail below in conjunction with the accompanying drawings. In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without violating the connotation of the present invention, so the present invention is not limited by the specific implementation disclosed below.

[0052] 1. Explanation of the embodiment:

[0053] The preparation method of the binuclear phthalocyanine modified iron molybdate composite material provided in the embodiment of the present invention comprises:

[0054] The binuclear phthalocyanine was modified on the prepared iron molybdate by a two-step hydrothermal method to prepare a binuclear phthalocyanine-modified iron molybdate composite material as a peroxidase mimetic enzyme for rapid colorimetric sensing of adrenaline, which specifically includes the following steps:

[0055] BiPc(OC8H9) 12 Dissolve in chloroform (CHCl3) solution, add the prepared FeMoO4 into BiPc (OC8H9) solution 12 The resulting mixed solution was ultrasonically treated for one hour and then transferred into a polytetrafluoroethylene-lined reactor and kept at a reaction temperature of 100°C in an oven for 2 hours. The product was washed several times with water and ethanol and dried in an oven to obtain a binuclear phthalocyanine-modified iron molybdate composite material.

[0056] In the embodiment of the present invention, the iron molybdate used is α-FeMoO4 (monoclinic phase, unit cell constant is β=114.05°, space group C2 / m, JCPDS number: 22-1115), β-FeMoO4 (monoclinic phase, unit cell parameters are β=106.31°, space group C2 / m, JCPDS number: 22-0628).

[0057] In an embodiment of the present invention, the mass ratio of iron molybdate to binuclear phthalocyanine is (10-50): 1. Preferably, the mass ratio of iron molybdate to binuclear phthalocyanine is 30:1.

[0058] Example 1

[0059] like Figure 1 As shown, the preparation method of the binuclear phthalocyanine modified iron molybdate composite material provided in the embodiment of the present invention comprises the following steps:

[0060] S101, adding FeSO4·7H2O and Na2MoO4·2H2O in a molar ratio of 1:1 into 51 mL of a hydrochloric acid solution having a pH value of 2, and dissolving them to obtain a brown mixed solution of iron salt and molybdenum salt dissolved in hydrochloric acid;

[0061] S102, transferring the mixed reaction solution to a polytetrafluoroethylene-lined reactor, keeping it in an oven at 160-200° C. for 2-6 hours, cooling it to room temperature after the reaction is completed, washing it several times by centrifugation with deionized water and ethanol, drying it in an oven at 60-80° C. overnight, collecting the product, and preparing FeMoO4 solid;

[0062] S103, dissolving binuclear phthalocyanine in chloroform, adding the prepared iron molybdate after dissolution, and ultrasonically treating for 1 hour, so that the prepared iron molybdate and binuclear phthalocyanine are uniformly dispersed in the chloroform solution;

[0063] S104, the mixed solution is transferred to a polytetrafluoroethylene-lined reactor, reacted at 80-120°C for 1-3 hours, cooled, centrifuged and washed several times with deionized water and anhydrous ethanol, and dried overnight in an oven at 60-80°C to prepare a binuclear phthalocyanine modified iron molybdate composite material (FeMoO4 / BiPc(OC8H9) 12 ).

[0064] Preferably, step S102 comprises: transferring the uniformly mixed reaction solution to a 100 mL polytetrafluoroethylene-lined reactor, keeping it in an oven at 180° C. for 4 hours, cooling it to room temperature after the reaction is completed, washing it several times by centrifugation with deionized water and ethanol, drying it in an oven at 60° C. overnight, collecting the product, and preparing a FeMoO4 black solid.

[0065] Preferably, step S103 comprises: dissolving 6 mg of binuclear phthalocyanine in 60 mL of chloroform, and after dissolution, adding 180 mg of the iron molybdate prepared in step S102, and ultrasonically treating for 1 hour, so that the prepared iron molybdate and binuclear phthalocyanine are uniformly dispersed in the chloroform solution;

[0066] Preferably, step S104 comprises: transferring the mixed solution to a 100 mL polytetrafluoroethylene-lined reactor, reacting at 100° C. for 2 hours, cooling and washing several times by centrifugation with deionized water and anhydrous ethanol, and drying in an oven at 60° C. overnight to prepare a binuclear phthalocyanine-modified iron molybdate composite material (FeMoO4 / BiPc(OC8H9) 12 ).

[0067] Example 2

[0068] The method for preparing the binuclear phthalocyanine modified iron molybdate composite material provided in the embodiment of the present invention comprises the following steps:

[0069] S1, adding FeSO4·7H2O and Na2MoO4·2H2O in a molar ratio of 1:1 into 51 mL of hydrochloric acid solution with a pH value of 2, and dissolving them to obtain a brown mixed solution of iron salt and molybdenum salt dissolved in hydrochloric acid;

[0070] S2, transfer the mixed reaction solution to a polytetrafluoroethylene-lined reactor, keep it in an oven at 160°C for 2 hours, cool it to room temperature after the reaction is completed, wash it several times with deionized water and ethanol by centrifugation, dry it in an oven at 60°C overnight, collect the product, and prepare FeMoO4 solid;

[0071] S3, dissolving binuclear phthalocyanine in chloroform, adding the prepared iron molybdate after dissolution, and ultrasonically treating for 1 hour, so that the prepared iron molybdate and binuclear phthalocyanine are uniformly dispersed in the chloroform solution;

[0072] S4, the mixed solution was transferred to a polytetrafluoroethylene-lined reactor, reacted at 80°C for 1 hour, cooled, centrifuged and washed several times with deionized water and anhydrous ethanol, and dried overnight in an oven at 65°C to prepare a binuclear phthalocyanine-modified iron molybdate composite material (FeMoO4 / BiPc(OC8H9) 12 ).

[0073] Example 3

[0074] The method for preparing the binuclear phthalocyanine modified iron molybdate composite material provided in the embodiment of the present invention comprises the following steps:

[0075] S1, adding FeSO4·7H2O and Na2MoO4·2H2O in a molar ratio of 1:1 into 51 mL of hydrochloric acid solution with a pH value of 2, and dissolving them to obtain a brown mixed solution of iron salt and molybdenum salt dissolved in hydrochloric acid;

[0076] S2, transfer the mixed reaction solution to a polytetrafluoroethylene-lined reactor, keep it in an oven at 200°C for 6 hours, cool it to room temperature after the reaction is completed, wash it several times with deionized water and ethanol by centrifugation, dry it in an oven at 80°C overnight, collect the product, and prepare FeMoO4 solid;

[0077] S3, dissolving binuclear phthalocyanine in chloroform, adding the prepared iron molybdate after dissolution, and ultrasonically treating for 1 hour, so that the prepared iron molybdate and binuclear phthalocyanine are uniformly dispersed in the chloroform solution;

[0078] S4, the mixed solution was transferred to a polytetrafluoroethylene-lined reactor, reacted at 120°C for 3 hours, cooled, centrifuged and washed several times with deionized water and anhydrous ethanol, and dried overnight in an oven at 80°C to prepare a binuclear phthalocyanine-modified iron molybdate composite material (FeMoO4 / BiPc(OC8H9) 12 ).

[0079] Example 4

[0080] The method for preparing the binuclear phthalocyanine modified iron molybdate composite material provided in the embodiment of the present invention comprises the following steps:

[0081] S1, adding FeSO4·7H2O and Na2MoO4·2H2O in a molar ratio of 1:1 into 51 mL of hydrochloric acid solution with a pH value of 2, and dissolving them to obtain a brown mixed solution of iron salt and molybdenum salt dissolved in hydrochloric acid;

[0082] S2, transfer the mixed reaction solution to a polytetrafluoroethylene-lined reactor, keep it in an oven at 180°C for 4 hours, cool it to room temperature after the reaction is completed, wash it several times with deionized water and ethanol by centrifugation, dry it in an oven at 70°C overnight, collect the product, and prepare FeMoO4 solid;

[0083] S3, dissolving binuclear phthalocyanine in chloroform, adding the prepared iron molybdate after dissolution, and ultrasonically treating for 1 hour, so that the prepared iron molybdate and binuclear phthalocyanine are uniformly dispersed in the chloroform solution;

[0084] S4, the mixed solution was transferred to a polytetrafluoroethylene-lined reactor, reacted at 90°C for 2 hours, cooled, centrifuged and washed several times with deionized water and anhydrous ethanol, and dried overnight in an oven at 70°C to prepare a binuclear phthalocyanine-modified iron molybdate composite material (FeMoO4 / BiPc(OC8H9) 12 ).

[0085] Example 5

[0086] A binuclear phthalocyanine modified iron molybdate composite material was prepared according to the preparation method provided in Example 1 of the present invention.

[0087] Example 6

[0088] like Figure 2 As shown, the method for rapid colorimetric detection of adrenaline using the binuclear phthalocyanine modified iron molybdate composite material provided in Example 5 of the present invention specifically comprises the following steps:

[0089] S201, adding a binuclear phthalocyanine-modified iron molybdate composite material to a buffer solution, adding hydrogen peroxide, then adding a colorless TMB solution, and finally adding adrenaline. The binuclear phthalocyanine-modified iron molybdate composite material catalyzes hydrogen peroxide to produce active free radicals, and the active free radicals catalyze the colorless TMB to become blue ox-TMB (oxidized 3,3',5,5'-tetramethylbenzidine). After adding adrenaline, the blue color disappears rapidly.

[0090] S202, after the binuclear phthalocyanine modified iron molybdate composite material catalyzes hydrogen peroxide in a buffer solution for 3 minutes, a certain amount of active free radicals are generated, which catalyze the oxidation of colorless TMB into visible blue ox-TMB in a short time, and then adrenaline is added to quickly reduce the blue ox-TMB to colorless TMB.

[0091] Example 7

[0092] The method for preparing the binuclear phthalocyanine modified iron molybdate composite material provided in the embodiment of the present invention comprises the following steps:

[0093] Step 1, after weighing 3mmol FeSO4·7H2O and 3mmol Na2MoO4·2H2O, add 51mL hydrochloric acid solution with a pH value of 2 to prepare a brown mixed solution;

[0094] Step 2, transfer the mixed reaction solution to a 100 mL polytetrafluoroethylene-lined reactor, keep it in an oven at 180° C. for 4 hours, cool it to room temperature after the reaction is completed, wash it several times by centrifugation with deionized water and ethanol, dry it in an oven at 60° C. overnight, collect the product, and prepare a FeMoO4 black solid product.

[0095] Step 3: Add the prepared iron molybdate and binuclear phthalocyanine to 60 mL of chloroform solution containing 6 mg of binuclear phthalocyanine in a mass ratio of 1:30, wherein the ratio of binuclear phthalocyanine to chloroform is 1:10. Then, the mixed solution is ultrasonically treated for 60 minutes to uniformly disperse the binuclear phthalocyanine and iron molybdate in the chloroform solution.

[0096] Step 4: The mixed solution was transferred to a 100 mL stainless steel autoclave lined with polytetrafluoroethylene, and then sealed in a drying oven at 100°C and heated for 2 hours. After that, the autoclave was cooled to room temperature, the product was centrifuged, washed several times with deionized water and ethanol, and dried at 60°C for 12 hours to obtain the target product, binuclear phthalocyanine modified iron molybdate composite material.

[0097] In the above embodiments, the description of each embodiment has its own emphasis. For parts that are not described or recorded in detail in a certain embodiment, reference can be made to the relevant descriptions of other embodiments.

[0098] 2. Application examples:

[0099] The binuclear phthalocyanine modified iron molybdate composite material is applied to the rapid colorimetric detection of adrenaline.

[0100] The rapid colorimetric detection of adrenaline as a peroxidase mimetic enzyme comprises:

[0101] (1) Based on the data obtained from the above-mentioned colorimetric detection of adrenaline at 652 nm, a linear equation was determined: y = 0.04502x - 0.07273.

[0102] (2) Add 200 μL of binuclear phthalocyanine-modified iron molybdate composite material, 200 μL of H2O2, and 200 μL of TMB to 1200 μL of buffer solution; add 200 μL of adrenaline solution of unknown concentration respectively, incubate the mixed solution at room temperature for 3 min, record the absorbance change at 652 nm, and calculate the concentration of adrenaline according to the linear equation obtained in (1).

[0103] The pH value of the buffer solution is 4;

[0104] The concentration of adrenaline is 2 μM-8 μM;

[0105] The concentration of the binuclear phthalocyanine modified iron molybdate composite material is 0.3 mg / mL, the molar concentration of H2O2 is 240 mM, and the molar concentration of TMB is 1 mM.

[0106] III. Evidence of the relevant effects of the embodiments:

[0107] like Figure 3 As shown in the figure, the X-ray diffraction test of the composite material of iron molybdate and binuclear phthalocyanine modified iron molybdate shows that the composite diffraction peak has no obvious change, which is basically consistent with the diffraction peak of the standard card, and no other impurity peaks appear. These results show that iron molybdate has been successfully synthesized, and even after modification with binuclear phthalocyanine, the diffraction peaks are still basically consistent with those of iron molybdate. This shows that the iron molybdate of this structure has basically no effect even after modification with binuclear phthalocyanine.

[0108] As shown in FIG4( a ), the morphology and structure of the binuclear phthalocyanine modified iron molybdate composite material is a rod-like morphology with a length of about 500 nm and a width of about 200 nm.

[0109] As shown in Figure 4(b), the surface atomic composition of the sample was further determined by X-ray photoelectron spectroscopy analysis. The XPS total spectrum of the binuclear phthalocyanine modified iron molybdate composite material shows that the material contains Fe, Mo, O, C, and N elements, and the nitrogen element exists in the binuclear phthalocyanine. Therefore, the XPS total spectrum of the binuclear phthalocyanine modified iron molybdate composite material shows that the binuclear phthalocyanine has been successfully modified on the surface of pure iron molybdate.

[0110] In the present embodiment, the peroxidase mimicking activity of the binuclear phthalocyanine modified iron molybdate composite material was tested using an ultraviolet-visible absorption spectrometer UV-1810PC, and the results were as follows:

[0111] In order to quantitatively detect adrenaline, a sensitive and effective colorimetric sensor was constructed based on a binuclear phthalocyanine-modified iron molybdate composite material with enhanced peroxidase-like activity. The prepared binuclear phthalocyanine-modified iron molybdate composite material was added to a buffer solution, hydrogen peroxide was added, and then colorless TMB was added. The prepared binuclear phthalocyanine-modified iron molybdate composite material catalyzed hydrogen peroxide to produce active free radicals, and the active free radicals catalyzed the oxidation of colorless TMB to generate blue ox-TMB. Three minutes later, adrenaline was added to quickly reduce the blue ox-TMB to colorless TMB, and its absorbance at 652nm was measured using a UV-visible absorption spectrometer.

[0112] As shown in FIG5 , there is a linear relationship between absorbance and adrenaline concentration.

[0113] FIG5(a) is a linear response curve of the binuclear phthalocyanine modified iron molybdate composite material prepared as a peroxidase mimic provided in an embodiment of the present invention for detecting the relationship between absorbance and adrenaline concentration. Figure 1 ;

[0114] FIG5( b ) is a linear fitting curve relationship between absorbance and adrenaline concentration of the binuclear phthalocyanine-modified iron molybdate composite material prepared as a peroxidase mimic provided in an embodiment of the present invention. Figure 2 ; It can be seen that the detection range of the sensor is between 2-8μM, and the detection limit is as low as 0.23μM.

[0115] Detection of adrenaline concentration in human serum

[0116] The three groups of actual adrenaline samples 1, 2, and 3 were dissolved in diluted human serum to the detection range. 200 μL of binuclear phthalocyanine-modified iron molybdate composite material (0.3 mg / mL, dissolved in human serum diluent), 200 μL of H2O2 (240 mM, dissolved in human serum diluent), and 200 μL of TMB (1 mM, dissolved in human serum diluent) were added to 1400 μL of buffer solution (pH = 4.0); the mixed solution was incubated at room temperature for 3 minutes, the absorbance change at 652 nm was recorded, and the absorbance value was substituted into the linear relationship in Figure 5 (b) to calculate the concentration of adrenaline in the actual serum, and compared with the sample labeled content data. The results are shown in Table 1.

[0117] Table 1 Detection results of adrenaline in human serum samples

[0118]

[0119] As shown in Table 1, the relative deviation of the proposed method for colorimetric detection of adrenaline using binuclear phthalocyanine modified iron molybdate composite material and the labeled content data of the sample is less than 5%, which proves that the proposed method for detecting adrenaline has good reliability.

[0120] like Figure 6 As shown, in order to analyze the selectivity of the colorimetric method for detecting adrenaline, the present invention selects some metal ion reducing substances, sugars and amino acids as interfering substances. The concentration of the interfering substance is 100μM, while the concentration of adrenaline is only 5μM. Even if the concentration of the interfering substance is 20 times higher than that of adrenaline, the detection of adrenaline is still much more obvious than the presence of the interfering substance, which indicates that these interfering substances have little effect on the determination of adrenaline. In other words, the colorimetric method constructed using the binuclear phthalocyanine modified iron molybdate composite material shows good selectivity for the detection of adrenaline.

[0121] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any modifications, equivalent substitutions and improvements made by any technician familiar with the technical field within the technical scope disclosed by the present invention and within the spirit and principles of the present invention should be covered within the protection scope of the present invention.

Claims

1. A method for preparing a binuclear phthalocyanine modified iron molybdate composite material, characterized in that: The preparation method of the binuclear phthalocyanine modified iron molybdate composite material comprises: The prepared iron molybdate was modified with binuclear phthalocyanine by a two-step hydrothermal method to prepare a binuclear phthalocyanine-modified iron molybdate composite material as a peroxidase mimetic for rapid colorimetric sensing of adrenaline. The preparation method of ferric molybdate comprises: FeSO4·7H2O and Na2MoO4·2H2O are added into a hydrochloric acid solution with a pH value of 2 at a molar ratio of 1:1, and after dissolution, a brown mixed solution of iron salt and molybdenum salt dissolved in hydrochloric acid is obtained; The mixed reaction solution was transferred to a polytetrafluoroethylene-lined reactor and kept in an oven at 160°C-200°C for 2 hours to 6 hours. After the reaction was completed and cooled to room temperature, it was washed several times by centrifugation with deionized water and ethanol, and dried overnight in an oven at 60°C-80°C. The product was collected to prepare FeMoO4 solid; The method of modifying the binuclear phthalocyanine on the prepared iron molybdate by a two-step hydrothermal method comprises the following steps: Dissolve binuclear phthalocyanine in chloroform, add the prepared iron molybdate after dissolution, and perform ultrasonic treatment for 1 hour to make the prepared iron molybdate and binuclear phthalocyanine evenly dispersed in the chloroform solution; The mixed solution was transferred to a polytetrafluoroethylene-lined reactor, reacted at 80°C-120°C for 1 hour-3 hours, cooled and washed several times by centrifugation with deionized water and anhydrous ethanol, and dried overnight in an oven at 60°C-80°C to prepare a binuclear phthalocyanine-modified iron molybdate composite material.

2. The method for preparing the binuclear phthalocyanine modified iron molybdate composite material according to claim 1, characterized in that: The mass ratio of the iron molybdate to the binuclear phthalocyanine is (10-50):

1.

3. The method for preparing the binuclear phthalocyanine modified iron molybdate composite material according to claim 1, characterized in that: The iron molybdate includes: α-FeMoO4 and β-FeMoO4.

4. A binuclear phthalocyanine modified iron molybdate composite material, characterized in that: The binuclear phthalocyanine modified iron molybdate composite material is prepared by the preparation method of the binuclear phthalocyanine modified iron molybdate composite material according to any one of claims 1 to 3.

5. A method for rapid colorimetric detection of adrenaline using the binuclear phthalocyanine modified iron molybdate composite material as claimed in claim 4, characterized in that: The method for rapid colorimetric detection of adrenaline comprises the following steps: The binuclear phthalocyanine modified iron molybdate composite material is added to a buffer solution, hydrogen peroxide is added, and then a TMB solution is added. The binuclear phthalocyanine modified iron molybdate composite material catalyzes hydrogen peroxide to produce active free radicals and catalyzes TMB to ox-TMB. Then adrenaline is added to reduce ox-TMB to TMB.

6. The method for rapid colorimetric detection of adrenaline according to claim 5, characterized in that: After the binuclear phthalocyanine-modified iron molybdate composite material catalyzes hydrogen peroxide in a buffer solution for 3 minutes and generates a certain amount of active free radicals that catalyze the oxidation of TMB into ox-TMB in a short period of time, adrenaline is added to reduce ox-TMB to TMB.

7. A sensor for rapid colorimetric detection of adrenaline, characterized in that: The sensor for rapid colorimetric detection of adrenaline comprises the binuclear phthalocyanine modified iron molybdate composite material of claim 4, and is used as a peroxidase mimetic enzyme for rapid colorimetric detection of adrenaline, and the minimum detection limit of the sensor for rapid colorimetric detection of adrenaline is 0.23 µM; The rapid colorimetric detection of adrenaline as a peroxidase mimetic enzyme comprises: (1) Based on the data obtained from the absorbance change of adrenaline colorimetric detection at 652 nm, the linear equation was determined: y=0.04502x-0.07273; (2) Add 200 μL of binuclear phthalocyanine-modified iron molybdate composite material, 200 μL of H2O2, and 200 μL of TMB to 1200 μL of buffer solution; add 200 μL of adrenaline solution of unknown concentration respectively, incubate the mixed solution at room temperature for 3 min, record the absorbance change at 652 nm, and calculate the concentration of adrenaline according to the linear equation obtained in (1); The pH value of the buffer solution is 4; The concentration of adrenaline is 2 μM-8 μM; The concentration of the binuclear phthalocyanine modified iron molybdate composite material is 0.3 mg / mL, the molar concentration of H2O2 is 240 mM, and the molar concentration of TMB is 1 mM.

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