CN111257311B - Folic acid modified molybdenum vanadium polyacid/C3N4Composite material and preparation method and application thereof - Google Patents
Folic acid modified molybdenum vanadium polyacid/C3N4Composite material and preparation method and application thereof Download PDFInfo
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- OVBPIULPVIDEAO-LBPRGKRZSA-N Folic acid Natural products C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 title claims abstract description 120
- 239000011724 folic acid Substances 0.000 title claims abstract description 77
- OVBPIULPVIDEAO-UHFFFAOYSA-N N-Pteroyl-L-glutaminsaeure Natural products C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229960000304 folic acid Drugs 0.000 title claims abstract description 67
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- -1 Folic acid modified molybdenum vanadium Chemical class 0.000 title claims abstract description 14
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- 239000000463 material Substances 0.000 title claims description 5
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 claims abstract description 90
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- 108010077895 Sarcosine Proteins 0.000 claims abstract description 45
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- 238000006555 catalytic reaction Methods 0.000 claims description 3
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- 238000004519 manufacturing process Methods 0.000 claims description 3
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
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- WUJISAYEUPRJOG-UHFFFAOYSA-N molybdenum vanadium Chemical compound [V].[Mo] WUJISAYEUPRJOG-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
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- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910020881 PMo12O40 Inorganic materials 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
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- FRYOUKNFWFXASU-UHFFFAOYSA-N 2-(methylamino)acetic acid Chemical compound CNCC(O)=O.CNCC(O)=O FRYOUKNFWFXASU-UHFFFAOYSA-N 0.000 description 1
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- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- CADZRPOVAQTAME-UHFFFAOYSA-L calcium;hydroxy phosphate Chemical compound [Ca+2].OOP([O-])([O-])=O CADZRPOVAQTAME-UHFFFAOYSA-L 0.000 description 1
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- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
- G01N21/78—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 producing a change of colour
-
- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
Abstract
The invention discloses folic acid modified molybdenum vanadium polyacid/C3N4Composite material of the general Formula (FA)6(NH4)5PMo4V8O40/C3N4(nwt%), wherein FA is folic acid molecule, n represents the loading of polyacid, and the value is 5, 10, 15, 20, 25, 30; and a preparation method of the composite material and a method for rapidly detecting the prostate cancer marker by using the composite material. Prepared by the invention (FA)6(NH4)5PMo4V8O40/C3N4(nwt%) the composite material has mild condition, high sensitivity and quick color reaction, and can simultaneously react with H in the presence of color developing agent 3,3-, 5, 5-tetramethyl benzidine2O2And sarcosine for color development detection, the method can replace the currently used horseradish peroxidase and sarcosine oxidase to complete the targeted detection of tumor cells.
Description
Technical Field
The invention relates to the technical field of biomedicine and clinical diagnosis, in particular to a vanadium-molybdenum-containing heteropoly acid folic acid compound loaded on C3N4Formed (FA) above6(NH4)5PMo4V8O40 /C3N4(nwt%) Synthesis method of Complex-substituted sarcosine oxidase/hydrogen peroxide oxidase Dual mimic and Simultaneous color development detection H2O2And sarcosine.
Background
Prostate cancer (PCa) seriously troubles male patients, and the common methods in the initial detection include digital rectal examination, rectal ultrasound, prostate biopsy, Computerized Tomography (CT), Multiple Internal Reflection (MIR), etc., and these detection means are expensive and complex to operate, and cause great psychological burden and physiological damage to patients, and also cause misjudgment or over treatment of the disease condition, and it is urgent to develop an efficient, convenient, and rapid method with human care. As the Sreekumar group discovers that sarcosine (N-methylglycine) can effectively sense the invasion of PCa cancer cells at the earliest time, the growth behavior of the cancer cells can be determined. By analyzing the change of the concentration of sarcosine in the blood and urine of a patient, the growth stage of the PCa cancer cells can be accurately judged. Therefore, sarcosine is an effective and accurate biomarker for clinical diagnosis of PCa, and can be used as a basis for early diagnosis of PCa when the concentration of sarcosine in blood or urine is higher than 5 μ M (0.17 ppm).
At present, sarcosine detection methods including spectrometry, isotope internal standard method, fluorescence time decay spectrometry and the like all have the problems of difficult operation, time consumption, high test cost and the like. As an analysis method, the chromogenic immunoassay has the advantages of simple and rapid analysis process, low cost, intuitive phenomenon and easy judgment, and the like. The principle is to detect various substances (such as drugs, hormones, proteins, microorganisms, cancer cells, etc.) by using a specific binding reaction of an antigen and an antibody and by a change in color. The chromogenic immunoassay has the advantages of simple and rapid analysis process, strong practicability, high sensitivity, low cost, direct detection through color change in the reaction process and the like, has attracted wide attention in various fields, and develops an enzyme-linked immunosorbent assay (ELISA), chemiluminescence immunoassay, an immuno-chip method and a colloidal gold chromatography. The ELISA method is to determine the content of the detected object by the oxidation and color development reaction (colorless to blue) of the enzyme-labeled 3,3-, 5, 5-Tetramethylbenzidine (TMB) catalyzed by enzyme, the commonly used labeled enzymes are horseradish peroxidase (HRP), Alkaline Phosphatase (AP) and beta-D galactosidase (Gal), and the adopted oxidants comprise air and hydrogen peroxide. The ELISA method has the advantages of convenient operation, rapid detection, large sample amount for one-time detection and low cost. However, the biological enzyme is easily denatured by the influence of external temperature and system pH value, and the preparation, purification and storage takes long time, the price is high, the process is complex, and simultaneously, the sample treatment is complex and the interference is serious. Therefore, the synthesis of high-efficiency HRP mimic enzyme is more and more concerned and replacedGeneration H2O2The use of more environmentally friendly oxidants such as oxygen is more challenging and practical.
Polyacids (HPAs) are a class of polynuclear metal-oxygen clusters with strong oxidative properties. HPAs exhibit strong oxidative catalytic activity in catalyzing O2、H2O2And the like, have important application in reactions in which oxidizing agents oxidize organic substrates. The earliest polyacid used for detection was the synthesis of 12-phosphomolybdic heteropolyacid salt by Osmond in 1887 (H)3PMo12O40) And measuring PO by spectrophotometry4 3-The content of (A) is based on the principle of formation of yellow H3PMo12O40There is an absorption peak in the visible region. Subsequently, the molybdenum-containing 12-silicomolybdic acid, 12-germanomolybdic acid and 12-arsenomolybdic acid are used for spectrophotometric detection of inorganic nonmetallic elements, metal ions, drug molecules, proteins and the like, and few reports are currently reported on detection of substances by using the redox catalytic performance of polyacids.
Therefore, it is an urgent problem for those skilled in the art to provide a material for rapidly detecting a prostate cancer marker with mild conditions and excellent sensitivity and stability.
Disclosure of Invention
In view of the above, the invention provides a vanadium molybdenum heteropoly acid folic acid compound loaded on C3N4Formed (FA) above6(NH4)5PMo4V8O40/C3N4(nwt%) composite material and its synthesis method, and substitute sarcosine oxidase/hydrogen peroxide oxidase double simulacrum for simultaneous color development detection H2O2And sarcosine.
In order to achieve the purpose, the invention adopts the following technical scheme:
folic acid modified molybdenum vanadium polyacid/C3N4The composite material is a composite material containing folic acid, vanadium and molybdenum polyacid/graphene oxide, and the general formula of the composite material is as follows:
(FA)6(NH4)5PMo4V8O40/C3N4(nwt％)
wherein FA is folic acid molecule, n represents the loading of polyacid and is a value larger than zero arbitrarily.
Preferably, in one of the above folic acid modified molybdovanado-polyacids/C3N4In a composite material, the composite material is selected from
(FA)6(NH4)5PMo4V8O40/C3N4(5wt％)
(FA)6(NH4)5PMo4V8O40/C3N4(10wt％)
(FA)6(NH4)5PMo4V8O40/C3N4(15wt％)
(FA)6(NH4)5PMo4V8O40/C3N4(20wt％)
(FA)6(NH4)5PMo4V8O40/C3N4(25wt％)
(FA)6(NH4)5PMo4V8O40/C3N4(30 wt.%).
The beneficial effects of the above technical scheme are: in the specific operation process, the amount of the composite material used in the detection can be determined according to the loading amount of the polyacid.
The invention also discloses the folic acid modified molybdenum vanadium polyacid/C3N4The preparation method of the composite material comprises the following steps:
(1) will be (NH)4)5H6PMo4V8O40And folic acid are respectively dissolved in distilled water to obtain a polyacid solution and a folic acid solution;
(2) stirring the mixture C3N4Adding the mixture into a polyacid solution, and then dropwise adding a folic acid solution to obtain a mixed solution;
(3) and (3) carrying out ultrasonic treatment on the mixed liquid obtained in the step (2), carrying out high-speed centrifugal separation to obtain a solid, and washing the solid for 3-6 times by using distilled water until no free polyacid and folic acid exist, thus obtaining the composite material.
Preferably, in one of the above folic acid modified molybdovanado-polyacids/C3N4In the preparation method of the composite material, (NH)4)5H6PMo4V8O40Folic acid and C3N4The mass ratio of (1: 6): (4-25), more preferably 1:6: 20.
The beneficial effects of the above technical scheme are: the ratio can ensure that the molybdenum vanadium polyacid/C modified by folic acid3N4The composite material ensures that folic acid and molybdenum vanadium polyacid exist in the form of one molecule and are efficiently loaded on C3N4The above.
Preferably, in one of the above folic acid modified molybdovanado-polyacids/C3N4In the preparation method of the composite material, in the step (1), (NH)4)5H6PMo4V8O40And distilled water in a mass ratio of 1: (30-40), more preferably 1: 30; the mass ratio of the folic acid to the distilled water is 1: (30-40), more preferably 1: 30.
The beneficial effects of the above technical scheme are: the above ratio is effective in ensuring that folic acid and polyacid exist in the form of one molecule at appropriate concentrations and are efficiently supported on C3N4The above.
Preferably, in one of the above folic acid modified molybdovanado-polyacids/C3N4In the method for producing a composite material, in the step (2), the stirring speed is 50 to 200rpt, and more preferably 50 rpt.
The beneficial effects of the above technical scheme are: the stirring speed has an influence on the loading amount of polyacid in the synthesis process of the compound, and if the stirring speed is too slow and the loading amount of polyacid is small, C can be damaged too fast3N4The sheet structure of (1).
Preferably, in one of the above folic acid modified molybdovanado-polyacids/C3N4In the preparation method of the composite material, the dripping speed of the folic acid solution is 10 drops/min;
the beneficial effects of the above technical scheme are: if the dripping speed of the folic acid solution is too high, the compound of the polyacid and the folic acid can not be deposited on the C3N4The above step (1); too slow will cause the reaction between polyacid and folic acid, resulting in the direct loading of polyacid on C3N4Above, folic acid modified composites could not be formed.
Preferably, in one of the above folic acid modified molybdovanado-polyacids/C3N4In the preparation method of the composite material, in the step (3), the ultrasonic time is 6-24h, more preferably 24h, and the ultrasonic frequency is 20-40 kHz.
The beneficial effects of the above technical scheme are: if the ultrasonic frequency is more than 40kHz or the ultrasonic time is too long, C can be damaged3N4The lamellar structure of (a); while a lower frequency than 20kHz will lower the polyacid concentration at C3N4The loading capacity of the upper layer.
The invention also discloses application of the folic acid modified molybdenum vanadium polyacid/C3N 4 composite material in rapid detection of prostatic cancer markers, and the composite material catalyzes sarcosine to generate H2O2Simultaneous catalysis of 3,3-, 5, 5-tetramethylbenzidine synchronous color development for H detection2O2And sarcosine.
Preferably, in one of the above folic acid modified molybdovanado-polyacids/C3N4The application of the composite material in the rapid detection of the prostatic cancer marker, wherein the detection method comprises the following steps:
(1) filtering urine of prostate cancer patient, adding color-developing agent 3,3-, 5, 5-tetramethylbenzidine solution, distilled water and molybdovanado polyacid/C3N4Compounding the materials to obtain a mixed solution;
(2) culturing the mixed solution obtained in the step (1) at room temperature for 4min, measuring absorbance, and determining sarcosine and H2O2The concentration of (c).
Preferably, in one of the above folic acid modified molybdovanado-polyacids/C3N4In the application of the composite material in the rapid detection of the prostatic cancer marker, 1mL of urine of a prostatic cancer patient is taken in the step (1), and 0.8mM of developing agent is added after the urine is filtered100 muL of 3,3-, 5, 5-tetramethylbenzidine solution, 100 muL of distilled water and molybdovanado-polyacid/C3N40.02-0.100mg of composite material to obtain a mixed solution.
Preferably, in one of the above folic acid modified molybdovanado-polyacids/C3N4Use of a composite material for the rapid detection of prostate cancer markers, said composite material being directed against H2O2The detection linear range of (2) is 0.007-17ppm, and the lowest detection limit is 0.01 ppm; the linear range of sarcosine detection is 0.0002-0.136ppm, the lowest detection limit is 0.0004 ppm.
According to the technical scheme, compared with the prior art, the invention discloses and provides folic acid modified molybdenum vanadium polyacid/C3N4The composite material has the following advantages:
(1) the folic acid modified molybdenum vanadium polyacid/C obtained by the invention3N4Composite material pair H2O2The reagent and sarcosine are subjected to color development immunoassay at the same time, the condition is mild, the sensitivity is high, the color development reaction is fast, the activity is higher than that of biological enzyme, the stability is high, the reagent can be stored for a long time, and the reagent has excellent performance;
(2) the folic acid modified molybdenum vanadium polyacid/C obtained by the invention3N4The composite material is an inorganic polyacid nanoenzyme, can simultaneously substitute catalase and sarcosine oxidase to complete the targeted detection of tumor cells, reduces the detection cost, and has simple preparation method and lower cost than biological enzyme.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 shows (FA)6(NH4)5PMo4V8O40/C3N4(10 wt%) assay H2O2A concentration range standard curve;
FIG. 2 is a drawing (FA)6(NH4)5PMo4V8O40/C3N4(10 wt%) standard curve for sarcosine concentration range;
FIG. 3 is a drawing of the present invention (FA)6(NH4)5PMo4V8O40/C3N4(10 wt%) effect of composite on color development absorbance;
FIG. 4 is a drawing showing (FA) of the present invention6(NH4)5PMo4V8O40/C3N4(n wt%) the composite catalyzes the color development of sarcosine to oxyhydrogen peroxide in the presence of TMB.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a vanadium-molybdenum-containing heteropoly acid folic acid compound loaded on C3N4Formed (FA) above6(NH4)5PMo4V8O40/C3N4(nwt%) composite material and its synthesis method, and substitute sarcosine oxidase/hydrogen peroxide oxidase double simulacrum for simultaneous color development detection H2O2And sarcosine.
The vanadium-molybdenum-containing heteropoly acid folic acid compound provided by the invention is loaded on C3N4Formed (FA) above6(NH4)5PMo4V8O40/C3N4(nwt%) the synthesis of the complex is as follows:
according to the mass ratio of 1:6: 4-25 weighing (NH)4)5H6PMo4V8O40Folic acid and C3N4Will (NH)4)5H6PMo4V8O40And folic acid are respectively dissolved in a mixture with the mass ratio of 1: 30-40 parts of distilled water, stirring at 50-200rpt to obtain C3N4Adding into polyacid solution, and dripping folic acid solution at the speed of 10 drops/min; subjecting the obtained mixture to ultrasonic treatment for 6-24 hr at 20-40kHz, centrifuging at high speed to separate solid, washing with distilled water for 3-6 times to ensure that there is no free polyacid and folic acid to obtain (FA)6(NH4)5PMo4V8O40/C3N4(nwt%) composite material.
The polyacid mimic (FA) capable of developing immune detection provided by the invention6(NH4)5PMo4V8O40/C3N4(nwt%) composite, catalyzing the production of H from sarcosine2O2Simultaneous catalysis of 3,3-, 5, 5-Tetramethylbenzidine (TMB) for synchronous color development and H detection2O2And sarcosine as follows:
1000 μ L of a simulant solution comprising 0.8mM TMB and 0.02-0.1mg (FA)6(NH4)5PMo4V8O40/C3N4(nwt%) composite material catalyst, adding sarcosine with a certain concentration, incubating the mixed solution at room temperature (25 ℃) for 4min, performing ultraviolet detection, and generating a characteristic peak of TMB oxidation product at 625 nm.
See fig. 1 and 2 for (FA)6(NH4)5PMo4V8O40/C3N4(10 wt%) composite catalyst for example, look for the corresponding sarcosine and H on the standard line2O2Concentration, H is finally obtained2O2The detection linear range of (2) is 0.007-17ppm, and the lowest detection limit is 0.01 ppm; the linear range of sarcosine detection was 0.0002-0.136ppm with a minimum detection limit of 0.0004 ppm.
Detection of sarcosine in simulated urine:
a certain amount of water 95%, urea 1.8%, uric acid 0.05%, and inorganic salt 1.1% (including sodium chloride, potassium chloride, magnesium chloride and calcium hydroxy phosphate account for 1.1%) are taken to prepare 10mL of simulated urine. 100 μ L of the simulated urine was taken and 100 μ L of LTMB (0.8mM) solution and 100 μ L of distilled water and 0.02-0.1mg of (FA) were added6(NH4)5PMo4V8O40/C3N4(nwt%) composite catalyst, adding 0.0002-0.136ppm sarcosine, incubating at room temperature (25 ℃) for 4min, measuring the absorbance, and determining the concentration of sarcosine.
Detection of actual urine:
urine from hospital patients with prostate cancer was filtered and 100. mu.L of LTMB (0.8mM) solution and 100. mu.L of distilled water and 0.02-0.1mg of (FA) were added6(NH4)5PMo4V8O40/C3N4(nwt%) of the composite catalyst, incubated at room temperature (25 ℃) for 4min, the absorbance of the resultant was measured, and H was determined2O2And the concentration of sarcosine.
The above-described technical means of the present invention will be described below by way of specific examples.
Example 1
According to the mass ratio of 1:6:20 weigh (NH)4)5H6PMo4V8O40Folic acid and C3N4Will be (NH)4)5H6PMo4V8O40And folic acid are respectively dissolved in a mixture with the mass ratio of 1:30 parts of distilled water, under stirring at 50rpt3N4Added to the polyacid solution and then the folic acid solution was added dropwise at a rate of 10 drops/min. Subjecting the obtained mixture to ultrasonic treatment at 30kHz for 24h, centrifuging at high speed to separate solid, washing with distilled water for 3 times to ensure that there is no free polyacid and folic acid to obtain solid (FA)6(NH4)5PMo4V8O40/C3N4(10 wt%), the yield of the composite material was 80%.
Prepared in example 1 (FA)6(NH4)5PMo4V8O40/C3N4(10 wt%) the composite was used to measure the concentration of sarcosine in the urine of a patient as follows:
urine from a hospital patient with prostate cancer was filtered and 100. mu.L of TMB (0.8mM) solution and 100. mu.L of distilled water and 0.04mg of (FA) were added6(NH4)5PMo4V8O40/C3N4(10 wt%) of the composite catalyst, and the concentration of sarcosine was determined by measuring the absorbance of the composite catalyst after incubation for 4min at room temperature (25 ℃). The urine was found to contain 19.7. + -. 0.523. mu.M sarcosine.
Specifically, (FA)6(NH4)5PMo4V8O40/C3N4(10 wt%) Effect of the composite on absorbance see FIG. 3, at (FA)6(NH4)5PMo4V8O40/C3N4(10 wt%) when the using amount of the composite material catalyst is increased from 0.01mg to 0.12mg, the ultraviolet absorbance is continuously increased, a good test result can be obtained when the using amount of the composite material catalyst is increased to 0.04mg, the influence of the continuously increased using amount on the activity is not large, and 0.04mg is selected as the optimal adding amount of the composite material from the economic perspective.
Example 2
According to the mass ratio of 1:6: 25 weighing (NH)4)5H6PMo4V8O40Folic acid and C3N4Will (NH)4)5H6PMo4V8O40And folic acid are respectively dissolved in a mixture with the mass ratio of 1:30 parts of distilled water, under stirring at 100rpt3N4Added to the polyacid solution and then the folic acid solution was added dropwise at a rate of 10 drops/min. Subjecting the obtained mixture to ultrasonic treatment at 20kHz for 6h, centrifuging at high speed to separate solid, washing with distilled water for 3 times to ensure no free polyacid and folic acid to obtain solid (FA)6(NH4)5PMo4V8O40/C3N4(5 wt%), the yield of the composite material was 84%.
Prepared in example 2 (FA)6(NH4)5PMo4V8O40/C3N4(5 wt%) the composite was used to measure the concentration of sarcosine in the urine of a patient as follows:
urine from a patient suffering from prostate cancer in a hospital was collected, filtered, added with 100. mu.L of TMB (0.8mM) solution and 100. mu.L of distilled water together with 0.10mg of (FA)6(NH4)5PMo4V8O40/C3N4(5 wt%) composite catalyst, and incubated at room temperature (25 ℃) for 4min, followed by measurement of absorbance to determine the concentration of sarcosine. The urine was found to contain 19.7. + -. 0.437. mu.M sarcosine.
Example 3
According to the mass ratio of 1:6: 17 weighing (NH)4)5H6PMo4V8O40Folic acid and C3N4Will (NH)4)5H6PMo4V8O40And folic acid are respectively dissolved in a mixture with the mass ratio of 1:30 parts of distilled water, under stirring at 150rpt3N4Adding into the polyacid solution, and adding dropwise the folic acid solution at a speed of 10 drops/min. Subjecting the obtained mixture to ultrasonic treatment at frequency of 25kHz for 10h, centrifuging at high speed to separate solid, washing with distilled water for 3 times to ensure that there is no free polyacid and folic acid to obtain solid (FA)6(NH4)5PMo4V8O40/C3N4(15 wt%), the yield of the composite material was 80%.
Prepared in example 3 (FA)6(NH4)5PMo4V8O40/C3N4(15 wt%) the composite was used to measure the concentration of sarcosine in the urine of a patient as follows:
urine from a patient with prostate cancer in a hospital was collected, filtered, and added with 100. mu.L of TMB (0.8mM) solution, 100. mu.L of distilled water, and 0.06mg of (FA)6(NH4)5PMo4V8O40/C3N4(15 wt%) of the composite catalyst, and the concentration of sarcosine was determined by measuring the absorbance of the composite catalyst after incubation for 4min at room temperature (25 ℃). It is found thatThe urine contained 19.6. + -. 0.496. mu.M sarcosine.
Example 4
According to the mass ratio of 1:6: 14 weighing (NH)4)5H6PMo4V8O40Folic acid and C3N4Will (NH)4)5H6PMo4V8O40And folic acid are respectively dissolved in a mixture with the mass ratio of 1: 40 of distilled water, under stirring at 200rpt3N4Adding into the polyacid solution, and adding dropwise the folic acid solution at a speed of 10 drops/min. Subjecting the obtained mixture to ultrasonic treatment at frequency of 35kHz for 15h, centrifuging at high speed to separate solid, washing with distilled water for 3 times to ensure that there is no free polyacid and folic acid to obtain solid (FA)6(NH4)5PMo4V8O40/C3N4(20 wt%), the yield of the composite material was 78%.
Prepared in example 4 (FA)6(NH4)5PMo4V8O40/C3N4(20 wt%) of the composite material was used to measure the concentration of sarcosine in the urine of a patient by the following method:
urine from a hospital patient with prostate cancer was filtered and 100. mu.L of TMB (0.8mM) solution, 100. mu.L of distilled water, and 0.05mg of (FA) were added6(NH4)5PMo4V8O40/C3N4(20 wt%) of the composite catalyst, and the concentration of sarcosine was determined by measuring the absorbance of the composite catalyst after incubation for 4min at room temperature (25 ℃). The urine was found to contain 19.9. + -. 0.398. mu.M sarcosine.
Example 5
According to the mass ratio of 1:6: 10 weighing (NH)4)5H6PMo4V8O40Folic acid and C3N4Will (NH)4)5H6PMo4V8O40And folic acid are respectively dissolved in a mixture with the mass ratio of 1: 40 of distilled water, under stirring at 150rpt3N4Adding into the polyacid solution, and then adding 10 dropsThe folic acid solution was added dropwise at a rate of/min. Subjecting the obtained mixture to ultrasonic treatment at frequency of 20kHz for 20h, centrifuging at high speed to separate solid, washing with distilled water for 3 times to ensure that there is no free polyacid and folic acid to obtain solid (FA)6(NH4)5PMo4V8O40/C3N4(25 wt%) the yield of the composite material was 78%.
Prepared in example 5 (FA)6(NH4)5PMo4V8O40/C3N4(25 wt%) the composite was used to measure the concentration of sarcosine in the urine of a patient as follows:
urine from a patient with prostate cancer in a hospital was collected, filtered, and added with 100. mu.L of TMB (0.8mM) solution, 100. mu.L of distilled water, and 0.03mg of (FA)6(NH4)5PMo4V8O40/C3N4(25 wt%) of the composite catalyst, and the concentration of sarcosine was determined by measuring the absorbance of the composite catalyst after incubation for 4min at room temperature (25 ℃). The urine was found to contain 19.5. + -. 0.614. mu.M sarcosine.
Example 6
According to the mass ratio of 1:6: 4 weighing (NH)4)5H6PMo4V8O40Folic acid and C3N4Will be (NH)4)5H6PMo4V8O40And folic acid are respectively dissolved in a mixture with the mass ratio of 1: 40 of distilled water, stirring at 200rpt3N4Adding into the polyacid solution, and adding dropwise the folic acid solution at a speed of 10 drops/min. Subjecting the obtained mixture to ultrasonic treatment at 40kHz for 23h, centrifuging at high speed to separate solid, washing with distilled water for 3 times to ensure that there is no free polyacid and folic acid to obtain solid (FA)6(NH4)5PMo4V8O40/C3N4(30 wt%) the yield of the composite material was 84%.
Prepared in example 6 (FA)6(NH4)5PMo4V8O40/C3N4(30 wt%) of the composite material was used to measure the concentration of sarcosine in the urine of a patient by the following method:
urine from a patient with prostate cancer in a hospital was collected, filtered, and added with 100. mu.L of TMB (0.8mM) solution, 100. mu.L of distilled water, and 0.02mg of (FA)6(NH4)5PMo4V8O40/C3N4(30 wt%) of the composite catalyst, and the concentration of sarcosine was determined by measuring the absorbance of the composite catalyst after incubation for 4min at room temperature (25 ℃). The urine was found to contain 19.9. + -. 0.458. mu.M sarcosine.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A folic acid modified molybdenum vanadium polyacid/C3N 4 composite material is characterized in that the composite material is a composite material containing folic acid, vanadium and molybdenum polyacid/graphene oxide, and the general formula of the composite material is as follows:
(FA)6(NH4)5PMo4V8O40/C3N4(nwt％)
wherein FA is folic acid molecule, and n represents the loading amount of polyacid.
2. The folate-modified molybdovanado-polyacid/C3N 4 composite material of claim 1, wherein said composite material is selected from the group consisting of
(FA)6(NH4)5PMo4V8O40/C3N4(5wt％)
(FA)6(NH4)5PMo4V8O40/C3N4(10wt％)
(FA)6(NH4)5PMo4V8O40/C3N4(15wt％)
(FA)6(NH4)5PMo4V8O40/C3N4(20wt％)
(FA)6(NH4)5PMo4V8O40/C3N4(25wt％)
(FA)6(NH4)5PMo4V8O40/C3N4(30 wt.%).
3. A folate-modified molybdovanado-polyacid/C as claimed in any one of claims 1-23N4The preparation method of the composite material is characterized by comprising the following steps:
(1) will be (NH)4)5H6PMo4V8O40And folic acid are respectively dissolved in distilled water to obtain a polyacid solution and a folic acid solution;
(2) stirring C3N4Adding the mixture into a polyacid solution, and then dropwise adding a folic acid solution to obtain a mixed solution;
(3) and (3) carrying out ultrasonic treatment on the mixed liquid obtained in the step (2), carrying out high-speed centrifugal separation to obtain a solid, and washing with distilled water until no free polyacid and folic acid exist, thus obtaining the composite material.
4. A folate-modified molybdovanado polyacid/C according to claim 33N4A method for producing a composite material, characterized in that (NH)4)5H6PMo4V8O40Folic acid and C3N4The mass ratio of (1): 6: (4-25).
5. A folate-modified molybdovanado polyacid/C according to claim 33N4The preparation method of the composite material is characterized in that in the step (1), (NH)4)5H6PMo4V8O40And distilled water in a mass ratio of 1: (30-40); the mass ratio of the folic acid to the distilled water is 1: (30-40).
6. A folate-modified molybdovanado polyacid/C according to claim 33N4The preparation method of the composite material is characterized in that in the step (2), the stirring speed is 50-200 rpt; the dripping speed of the folic acid solution is 10 drops/min;
in the step (3), the ultrasonic time is 6-24h, and the ultrasonic frequency is 20-40 kHz.
7. A folate-modified Mo-V-polyacid/C of any one of claims 1-23N4The application of the composite material in preparing the prostate cancer marker rapid detector is characterized in that the composite material catalyzes sarcosine to generate H2O2Simultaneous catalysis of 3,3-, 5, 5-tetramethylbenzidine synchronous color development for H detection2O2And sarcosine.
8. A folate-modified molybdovanado polyacid/C according to claim 73N4The application of the composite material in preparing a prostate cancer marker rapid detector is characterized in that the detection method comprises the following steps:
(1) filtering urine of prostate cancer patient, adding color-developing agent 3,3-, 5, 5-tetramethylbenzidine solution, distilled water and molybdovanado polyacid/C3N4Compounding the materials to obtain a mixed solution;
(2) and (2) incubating the mixed solution obtained in the step (1) at room temperature for 4min, measuring the absorbance, and determining the concentration of sarcosine.
9. The folate-modified molybdovanado polyacid/C of claim 83N4The application of the composite material in preparing the prostate cancer marker rapid detector is characterized in that 1mL of urine of a prostate cancer patient is taken in the step (1), 0.8mM of color developing agent 3,3-, 5, 5-tetramethylbenzidine solution 100 mu L, distilled water 100 mu L and molybdovanadophoric acid/C are added after filtration3N40.02-0.100mg of composite material to obtain a mixed solution.
10. A folate-modified molybdovanado polyacid/C according to claim 73N4The application of the composite material in the preparation of the prostate cancer marker rapid detector is characterized in that the composite material is used for detecting H2O2The detection linear range of (2) is 0.007-17ppm, and the lowest detection limit is 0.01 ppm; the linear range of sarcosine detection is 0.0002-0.136ppm, the lowest detection limit is 0.0004 ppm.
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| 氨基酸功能化多钼酸盐[(Gly)_2(H_2O)_2Cu]K_3[Al(OH)_6Mo_6O_(18)]7H_2O的合成及表征;刘丁等;《分子科学学报》;20090615;第25卷(第03期);第163-167页 * |
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