CN114280015A - Application of graphdiyne/heme composite material and method for detecting reduced small molecules by using graphdiyne/heme composite material - Google Patents
Application of graphdiyne/heme composite material and method for detecting reduced small molecules by using graphdiyne/heme composite material Download PDFInfo
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- CN114280015A CN114280015A CN202111450765.1A CN202111450765A CN114280015A CN 114280015 A CN114280015 A CN 114280015A CN 202111450765 A CN202111450765 A CN 202111450765A CN 114280015 A CN114280015 A CN 114280015A
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Abstract
The invention relates to application of a graphite alkyne/heme composite material and a detection method of reduced small molecules.A graphite alkyne/heme composite material is placed in an alkaline environment under aerobic conditions, a detection auxiliary substance and the reduced small molecules are added, detection is realized through fluorescence intensity, the detection auxiliary substance can generate fluorescence after being oxidized, and the reduced small molecules can inhibit the oxidation of the detection auxiliary substance; or placing the graphdiyne/heme composite material in an acid environment, adding hydrogen peroxide, detection auxiliary substances and reduced small molecules, and obtaining the content of the reduced small molecules in the sample to be detected according to the absorbance value of the mixed solution at the maximum absorption wavelength. The method takes the graphdiyne/heme composite material as a superoxide radical or hydroxyl radical source, and realizes the quantitative detection of the reduced micromolecules by detecting whether the auxiliary material is oxidized to generate fluorescence and detecting whether the reduced micromolecules inhibit the fluorescence intensity change caused by oxidation.
Description
Technical Field
The invention relates to the technical field of substance detection, in particular to application of a graphdiyne/heme composite material and a method for detecting reduced small molecules by using the graphdiyne/heme composite material.
Background
The active oxygen comprises free radicals and non-free radical molecules, the main types of the active oxygen comprise superoxide anions, hydroxyl free radicals, hydrogen peroxide, singlet oxygen and the like, and the active oxygen plays an important role in cell regulation, apoptosis, angiogenesis, disease generation and treatment. When the content is low, the free radicals are favorable for promoting tumor promotion gene signals and improving the cell growth activity; when the content is higher, the cell growth can be inhibited, and even the cell apoptosis can be caused. These multiple actions make reactive oxygen species ideal materials for disease treatment and other biomedical applications. At present, in the fields of treatment and other application, researchers can utilize exogenous or endogenous factors such as ultraviolet-visible light, near infrared light, x-ray and Fenton reactions to stimulate the nano material so as to realize the mass preparation of active oxygen. However, the photoinitiated method has the problems of limited tissue penetration depth, body damage of different degrees and the like, and the fenton reagent generally has low reaction rate and strict requirements on reaction conditions, so that the application of the fenton reagent is limited to a certain extent. Therefore, the development of a method for preparing active oxygen free radicals, which is not light-dependent and has mild reaction conditions, has great clinical significance.
Meanwhile, biomolecules in a human body participate in a plurality of important life activities, particularly some biological small molecules with reducibility play an important role in maintaining the health of the human body and resisting diseases, so that the simple, convenient, rapid and accurate detection of the biological small molecules with reducibility has important significance. Currently, for reduced molecules such as reduced glutathione, ascorbic acid, etc., a common detection method is a carbon quantum dot detection method, such as zhanghao morning, etc. (research progress of detecting reduced biological small molecules based on fluorescence start of carbon quantum dots. analytical chemistry, 49(1),10.) detection of reduced small molecules is performed by using carbon quantum dots; for example, chinese patent CN110736724A discloses a novel method for detecting reduced glutathione by using a bifunctional small organic molecule-modified nanogold probe, which uses a synthesized bifunctional small organic molecule containing a disulfide bond as a linker molecule to construct a nanogold probe with a surface-modified fluorescent molecule, and combines Fluorescence Resonance Energy Transfer (FRET) technology and the property that reduced glutathione can reduce disulfide bonds to realize the detection of reduced glutathione; such as Caoyuhua, and the like, and adopts a palladium-zinc oxide nanotube modified electrode to detect ascorbic acid and the like by a capillary electrophoresis-electrochemical method, a Thaun and the like. However, the above detection methods still have problems, such as the fluorescence of CQDs is mostly concentrated in the blue-green band and is easily affected by the conditions such as excitation wavelength, and besides, the sensitivity and selectivity of some detection methods are not high, which limits the application thereof. Therefore, a simple and accurate method for detecting reduced small molecules is still needed.
Disclosure of Invention
In order to solve the technical problems, the invention discloses a new application of a graphdiyne/heme composite material, and provides a detection method of a reduced small molecule based on the application.
The invention provides a method for detecting reduced small molecules, which is based on a graphite alkyne/heme composite material rich in free radicals, the graphite alkyne/heme composite material is placed in an alkaline environment under aerobic conditions, mixed with detection auxiliary substances and reduced small molecules with different known concentrations, the fluorescence intensity of a mixed solution is detected, and the fluorescence intensity and the reduced small molecule concentration are establishedAnd (3) replacing reduced small molecules with different concentrations with a sample to be detected, determining the fluorescence intensity of the sample to be detected according to the same method, and substituting the fluorescence intensity into the standard curve to obtain the content of the reduced small molecules. In the invention, the composite material can generate superoxide radical (O) in the presence of oxygen2 ·-) The detection auxiliary substance generates fluorescence through oxidation (for example, vitamin B1 is oxidized to form dehydrothiamine capable of emitting fluorescence), and the oxidation of the detection auxiliary substance can be inhibited when the reductive small molecule exists (for example, glutathione can inhibit the oxidation of vitamin B1), so that the fluorescence intensity is changed, and a method for quantitatively detecting the reductive small molecule is established by utilizing the competitive relationship between the reductive small molecule and the oxidation of the detection auxiliary substance;
or placing the graphite alkyne/heme composite material in an acid environment, adding hydrogen peroxide, detection auxiliary substances and reduced small molecules with different concentrations, detecting the absorbance value of the mixed solution at the maximum absorption wavelength, establishing a standard curve of the absorbance value and the reduced small molecule concentration, replacing the reduced small molecules with different concentrations with samples to be detected, determining the absorbance value of the samples to be detected according to the same method, and obtaining the content of the reduced small molecules in the samples to be detected according to the absorbance value of the samples to be detected. The composite material retains the efficient catalytic performance of heme, can catalyze hydrogen peroxide to generate a large number of hydroxyl radicals under an acidic condition, a detection auxiliary substance generates fluorescence through oxidation, and the oxidation of the detection auxiliary substance can be inhibited in the presence of a reductive micromolecule, so that the fluorescence intensity is changed, and another method for quantitatively detecting the reductive micromolecule is established.
The graphoyne is a substituted one of sp2And sp hybridized carbon atoms, and the graphdiyne structure not only contains benzene ring, but also contains large triangle ring with 10 carbon atoms formed by benzene ring and carbon-carbon triple bond. The carbon-carbon triple bond formed by sp hybridized carbon atoms has the advantages of linearity, no cis-trans isomerism, high conjugation and the like, so that the graphyne has a plurality of excellent physicochemical properties, and the graphyne and the derived materials thereof are widely applied to batteries, catalysis and biosensing so farAnd in medical treatment. Especially, the larger sparse horizontal surface network, the specific surface area and the binding energy make the catalyst become an excellent substrate for depositing signal atoms or signal site chemistry, which is very important for preparing a monatomic catalyst and realizing high catalytic performance. For example, the use of graphdine to deposit single atoms of nickel and iron has high catalytic activity and material stability, and has great advantages in hydrogen evolution compared with conventional materials. The material synthesized by dispersing platinum monoatomic particles into graphdiyne has extremely high catalytic activity, which is 26.9 times higher than the current most advanced commercial platinum/carbon catalyst in terms of mass activity. Controlling the size of the metal nanoparticles can not only increase the utilization of single atoms, but also increase the selectivity of catalysis, however, the development of graphdine-derived materials for generating superoxide radicals is still in the blank state at present. The application of the graphdiyne/heme composite material is expanded, and the graphdiyne/heme composite material has great potential in the aspect of producing superoxide radicals.
Further, the reduced micromolecules are one or more of glutathione, ascorbic acid, mercaptan, uric acid, catechol, reduced coenzyme I, epicatechin, glucose and dopamine, and the detection auxiliary substances are vitamin B1 and/or 3,3',5,5' -tetramethyl benzidine.
The graphite alkyne/heme composite material is prepared by mixing a graphite alkyne solution and a heme solution and carrying out self-assembly. After many attempts, the composite material has better dispersibility in isopropanol and ethanol compared with the pure heme. Therefore, in the embodiment of the invention, isopropanol or ethanol solution of graphyne is mixed with NMP solution of heme, fully reacted at 20-40 ℃, and then centrifuged, washed by isopropanol or ethanol, and freeze-dried to obtain the graphyne/heme composite material.
In the composite material, the graphite alkyne with good water solubility is adopted to load the heme molecule or the derivative thereof, so that the problem of poor water solubility of the heme is solved, and the composite material has good dispersibility in an alkaline environment and is not easy to aggregate. Graphene has a large specific surface area and an excellent porous structure, and is used as a substrate of single-site chemistry to synthesize a metal atom catalytic material based on graphyne for efficiently generating active oxygen. The compound takes the graphyne as a substrate, is compounded with the heme or the derivative thereof as a free radical generator based on iron atoms, and is synthesized by a wet method, the heme in a monomolecular state or the derivative thereof is successfully compounded on the surface of the graphyne to form the graphyne/heme monomolecular compound.
Further, the hemoglobin solution is obtained by dissolving hemoglobin or its derivative in an alkaline solution, preferably N-methylpyrrolidone.
Furthermore, the concentration of the isopropanol or ethanol solution of the graphdine is 0.5-1.5mg/mL, and the concentration of the NMP solution of the heme or the derivative thereof is 0.5-1.5 mg/mL.
Further, the graphdiyne solution and the heme solution were mixed in a volume ratio of 4: 3.
Further reacting for 20-30 h.
Further, the buffer condition of the reaction at the time of detection was PBS buffer, and the pH was 12 to 14. Specifically, a graphdine/heme complex solution is added into a PBS buffer solution, then a vitamin B1 solution and glutathione solutions with different concentrations are added, the mixture is shaken uniformly and then placed at the temperature of 30-50 ℃ for reaction for 20-60min, and the fluorescence emission spectrum of the obtained solution is measured when the solution is excited at 445 nm.
By the scheme, the invention at least has the following advantages:
the invention discloses a new application of a graphyne/heme composite material in producing superoxide radical, has mild reaction conditions, does not need light source stimulation, widens the downstream application of the new material graphyne/heme composite material, and provides a new reduced small molecule quantitative detection method based on the application, wherein the method is simple, convenient and efficient, and has high sensitivity (detection limit of 0.7nM), high accuracy and good specificity.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following description is made with reference to the preferred embodiments of the present invention and the accompanying detailed drawings.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference will now be made in detail to the present disclosure, examples of which are illustrated in the accompanying drawings.
FIG. 1 is a schematic diagram of the synthesis process of a graphdiyne/heme composite material;
FIG. 2 is a spherical aberration electron microscope characterization of the graphdine/heme composite material;
FIG. 3 is a Raman spectrum characterization of a graphdyne/heme composite;
FIG. 4 is an electron spin resonance spectrum characterization of a graphdiyne/heme composite;
FIG. 5 is detection of glutathione by the graphdiyne/heme composite; (A, detection principle, B, relationship graph of glutathione with different concentrations and system fluorescence intensity, C, linear curve);
FIG. 6 shows the results of a specificity test for glutathione detection;
FIG. 7 is a UV spectrum and a system color change result of the test results in example 4.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Example 1
(1) Adding the graphdiyne into isopropanol to prepare a graphdiyne solution with the concentration of 1 mg/mL; hemin is added into N-methyl pyrrolidone to prepare hemin solution with the concentration of 1 mg/mL. Mixing the hemin solution and the graphite alkyne solution in a volume ratio of 4:3, continuously stirring for 24 hours at 30 ℃ until the reaction is complete, then centrifuging to remove supernatant, and washing for 3 times by using an isopropanol solution to obtain the graphite alkyne/hemin compound solution. The synthetic process schematic diagram of the graphite alkyne/heme composite material prepared in this example is shown in fig. 1, the spherical aberration electron microscope diagram is shown in fig. 2, the raman spectrum diagram is shown in fig. 3, and the electron spin resonance spectrum diagram is shown in fig. 4. As can be seen from FIG. 4, with DMPO as the trapping agent, the methanol-formulated solution can shield hydroxyl radicals well, and the measured ESR spectrum is a six-fold peak, which is the peak of the oxidation product of DMPO after the oxidation of superoxide anion, indicating that a large amount of superoxide anion is generated in the solution.
(2) mu.L of a graphdine/hemin complex solution was added to 710. mu.L of PBS buffer (10mM), followed by 40. mu.L of vitamin B1 solution and 100. mu.L of glutathione solutions (10nM, 50nM, 100nM, 150nM, 200nM, 250nM, 300nM, 400nM, 500nM) at different concentrations, stirred and reacted at 40 ℃ for 22.5min, and the fluorescence emission spectrum of the resulting solution upon excitation at 445nM was measured and the fluorescence intensity at the maximum emission wavelength was recorded. The standard curve was established as shown in FIG. 5, with a linear range of 10.0 to 500.0 nM.
Example 2
(1) Adding the graphdiyne into isopropanol to prepare a graphdiyne solution with the concentration of 1 mg/mL; hemin is added into N-methyl pyrrolidone to prepare hemin solution with the concentration of 1 mg/mL. Mixing the hemin solution and the graphite alkyne solution in a volume ratio of 4:3, continuously stirring for 24 hours at 30 ℃ until the reaction is complete, then centrifuging to remove supernatant, and washing for 3 times by using an isopropanol solution to obtain the graphite alkyne/hemin compound solution.
(2) mu.L of a graphdine/hemin complex solution was added to 710. mu.L of PBS buffer (10mM), followed by 40. mu.L of vitamin B1 solution and 100. mu.L of a solution to be tested, shaken up and left to react at 40 ℃ for 22.5min, and the fluorescence emission spectrum of the resulting solution upon excitation at 445nm was measured and the fluorescence intensity at the maximum emission wavelength was recorded.
The fluorescence intensity is substituted into the standard curve, the accuracy is up to 100%, and the detection limit is 0.7 nM.
Example 3 specific detection
And replacing the solution to be detected containing the glutathione with a solution containing other small molecules. The rest of the procedure was the same as in example 2, and the results are shown in FIG. 6. Therefore, in a system for detecting glutathione, the specificity to a target substance is good, and the influence of other small molecular substances is small.
Example 4
(1) Adding the graphyne into ethanol to prepare a graphyne solution with the concentration of 1 mg/mL; hemin is added into N-methyl pyrrolidone to prepare hemin solution with the concentration of 1 mg/mL. Mixing the hemin solution and the graphite alkyne solution in a volume ratio of 3:2, continuously stirring for 48 hours at room temperature in a dark condition until the reaction is complete, then centrifuging to remove supernatant, washing for 3 times by using an ethanol solution, and dispersing the obtained precipitate into ethanol to obtain the graphite alkyne/hemin compound solution.
(2) To 30 μ L of HAc-NaAc buffer (PH 3.6), 10 μ L of graphene/hemin complex solution, 30 μ L H was added2O2And 30. mu.L of 3,3',5,5' -tetramethylbenzidine, reacted at room temperature for 30min, followed by addition of 10. mu.L of ascorbic acid solutions of different concentrations (10. mu.M, 20. mu.M, 40. mu.M, 60. mu.M, 100. mu.M), after mixing, reacted at room temperature for 5min, the resulting solution was diluted and its ultraviolet absorption spectrum at 400-800nm was measured, and the absorbance value at the maximum absorption wavelength was recorded. As a result, as shown in FIG. 7, it was found that the absorbance value decreased with the increase in the concentration of reduced molecules, and it was found that the method of the present invention can quantitatively detect reduced molecules. The embodiment of the invention only uses glutathione and ascorbic acid as examples to demonstrate the detection effect, and the thiol solution, the uric acid solution, the catechol solution, the reducing coenzyme I solution, the epicatechin solution, the glucose solution, the dopamine solution and the like can all obtain the same curve as the above, so that the quantitative detection of the reducing small molecules in the solution to be detected can be realized.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. Application of the graphdine/heme composite material in preparing superoxide radical.
2. Use according to claim 1, characterized in that: placing the graphdine/heme composite in an aerobic environment.
3. The use of claim 1, wherein the graphdine/heme composite is prepared by the steps of: and mixing the graphdiyne solution with the heme solution, and carrying out self-assembly to obtain the graphdiyne/heme composite material.
4. Use according to claim 3, characterized in that: the graphite alkyne solution is obtained by dispersing graphite alkyne in isopropanol or ethanol.
5. Use according to claim 3, characterized in that: the heme solution is obtained by dissolving heme and/or heme derivatives in an alkaline solution.
6. A method for detecting reduced small molecules is characterized by comprising the following steps:
under the aerobic condition, placing the graphdiyne/heme composite material in an alkaline environment, adding detection auxiliary substances and reduced small molecules with different concentrations, detecting the fluorescence intensity of the mixed solution, establishing a standard curve of the fluorescence intensity and the reduced small molecule concentration, replacing the reduced small molecules with different concentrations with samples to be detected, determining the fluorescence intensity of the samples to be detected according to the same method, and calculating the content of the reduced small molecules in the samples to be detected according to the fluorescence intensity of the samples to be detected; the detection auxiliary substance can generate fluorescence after being oxidized, and the reduced small molecules can inhibit the oxidation of the detection auxiliary substance;
or placing the graphite alkyne/heme composite material in an acid environment, adding hydrogen peroxide, detection auxiliary substances and reduced small molecules with different concentrations, detecting the absorbance value of the mixed solution at the maximum absorption wavelength, establishing a standard curve of the absorbance value and the reduced small molecule concentration, replacing the reduced small molecules with different concentrations with samples to be detected, determining the absorbance value of the samples to be detected according to the same method, and obtaining the content of the reduced small molecules in the samples to be detected according to the absorbance value of the samples to be detected.
7. The detection method according to claim 6, characterized in that: the reduced micromolecules are one or more of glutathione, ascorbic acid, mercaptan, uric acid, catechol, reduced coenzyme I, epicatechin, glucose and dopamine.
8. The detection method according to claim 6, characterized in that: the detection auxiliary substance is vitamin B1 and/or 3,3',5,5' -tetramethyl benzidine.
9. The detection method according to claim 6, characterized in that: the pH of the alkaline environment is 12-14.
10. The detection method according to claim 6, characterized in that: and (3) placing the graphdiyne/heme composite material, the detection auxiliary and a sample to be detected in an alkaline environment, and reacting for 20-60min at 30-50 ℃.
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