CN107340278B - Method for detecting oxygen by adopting fluorescent molecular probe based on fullerene or fullerene derivative - Google Patents

Abstract

The invention discloses a method for detecting oxygen by adopting a fluorescent molecular probe based on fullerene or a derivative thereof, belonging to the application field of fullerene materials. The method comprises the following steps: mixing fullerene or fullerene derivatives and fluorescent molecules to form fullerene solution containing the fluorescent molecules, vacuumizing, introducing an oxygen sample, generating singlet oxygen under the illumination condition, generating epoxy compounds by the fluorescent molecules, carrying out fluorescence quenching, detecting the intensity of fluorescent signals in a system, and further detecting the oxygen content in the system. The invention solves the problems that the existing oxygen detection has low precision and is difficult to detect trace oxygen. The fullerene or fullerene derivative can generate singlet oxygen under the illumination condition, the oxygen content can be indirectly detected according to the reduced fluorescence intensity, the detection sensitivity is high, the endoperoxide generated after the reaction can generate over 90 percent of reverse reaction, and the high recycling rate is achieved.

Description

A method for detecting oxygen based on fullerenes or their derivatives using fluorescent molecular probes

technical field

The invention relates to the application field of fullerene materials, in particular to a method for detecting oxygen based on fullerene or a derivative thereof using a fluorescent molecular probe.

Background technique

Oxygen plays an important role in biological life activities. Cells in living organisms require oxygen for aerobic metabolism to maintain daily physiological activities. The lack of oxygen will seriously damage the life activities of the organism, and in severe cases, coma or even death may occur. Excessive oxygen can cause "oxygen toxicity", leading to symptoms such as dizziness, dullness, tingling, impaired vision and hearing, and decreased consciousness. Only the proper oxygen concentration can maintain the normal progress of biological life activities. Therefore, it is very important to detect the oxygen content in the living body.

At present, there are some oxygen detection methods such as titration, amperometric, and thermoluminescence. Although these methods can effectively detect the content of oxygen, there are also some disadvantages, such as: long response time, unable to continuously detect, easily interfered by other gases, and the cost is relatively high, it is difficult for trace oxygen Precise observation and measurement through instruments.

Currently, fluorescent probes can be used to detect reactive oxygen species. Singlet oxygen is an excited state of oxygen, a highly reactive molecule, and a typical reactive oxygen molecule. Most singlet oxygen fluorescent probes are based on its reaction with anthracene. Most singlet oxygen fluorescent probes select anthracene or 9,10-diphenylanthracene as the recognition group. Under the action of singlet oxygen, the fluorescent probe undergoes a cycloaddition reaction to generate endoperoxide, and the fluorescence of the fluorophore is quenched, thereby achieving the purpose of detecting singlet oxygen.

Therefore, oxygen can be converted into singlet oxygen under certain conditions, and a fast response time, good selectivity, high sensitivity and simple operation can be designed with the help of the characteristics of the fluorescence change significantly after the interaction between fluorescent molecules and singlet oxygen. Fluorescent molecular probes for detecting oxygen concentration are expected to be widely used in biological sciences, basic medicine and environmental detection.

SUMMARY OF THE INVENTION

In order to solve the above problems in the prior art, the present invention provides a method for detecting oxygen using fluorescent molecular probes, specifically a method for detecting oxygen using fluorescent molecular probes based on fullerenes or fullerene derivatives.

The method for detecting oxygen using a fluorescent molecular probe provided by the present invention includes the following steps:

(1) dissolving fullerenes and/or fullerene derivatives in halogenated benzene, alkylbenzene or carbon disulfide, to prepare a solution containing fullerenes and/or fullerene derivatives, namely solution 1;

(2) Dissolving fluorescent molecules in halogenated benzene, alkylbenzene or carbon disulfide to prepare a solution containing fluorescent molecules, namely solution 2;

(3) mixing solution 1 and solution 2 to obtain a fluorescent molecule solution containing fullerenes and/or fullerene derivatives;

(4) vacuumize the mixed solution obtained in step (3) to reduce the oxygen concentration to 0 ml/cm ³ to obtain a detection system;

(5) Under illumination conditions, establish a linear relationship between the fluorescence signal intensity and the oxygen content in the detection system;

(6) Pass the sample to be tested into the same detection system as step (4), and measure the fluorescence signal intensity in the detection system under the same illumination conditions as step (5), and then calculate the oxygen in the sample to be tested. content.

Fullerenes and/or fullerene derivatives can interact with different concentrations of oxygen to generate singlet oxygen under illumination conditions, and fluorescent molecules react with singlet oxygen to generate epoxy compounds of fluorescent molecules, namely endoperoxy compounds, epoxy compounds. When the fluorescence intensity of the compound is low or does not fluoresce, fluorescence quenching occurs.

The reaction between fluorescent molecules and singlet oxygen is a reversible reaction: because the epoxy compound generated by the reaction between fluorescent molecules and singlet oxygen is thermally unstable, under heating conditions, the temperature range is 100 ~ 120 ° C, and the heating time is 20 ~ Under the condition of 60min, the epoxy compound can undergo a reversible reaction and become a fluorescent molecule with a high fluorescence intensity, which makes this fluorescent probe reusable, efficient and convenient. Using the characteristic ultraviolet absorption of the fluorescent molecular body and the change of the characteristic ultraviolet absorption after the epoxy compound is formed, it can be found that almost more than 90% of the epoxy compounds can undergo reversible reactions (see Figure 1).

The fullerenes include at least one of hollow fullerenes and embedded fullerenes.

The hollow fullerene includes a cage-like structure fullerene composed of carbon atoms with a general formula of C _2m , wherein 30≤m≤60, optional C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C At least one of ₈₂ and C ₈₄ .

The inner fullerenes include N@C ₆₀ , La@C ₇₂ , Sc ₂ @C ₇₄ , Sc ₂ @C ₇₆ , La ₂ @C ₈₀ , Sc ₃ N@C ₈₀ , Tm@C ₈₂ , Gd@ At least one of C ₈₂ and Sc ₂ C ₂ @C ₈₄ ;

The fullerene derivatives include at least one of fullerene oxides and fullerene addition products, the optional fullerene oxides are at least one of C ₆₀ O and C ₇₀ O, and fullerenes The alkene addition product is at least one of a fullerene 1,3-dipolar cycloaddition product and a fullerene Binger addition product.

The fluorescent molecule is a conjugated organic molecule with a biphenyl structure, and optional 9,10-diphenylanthracene and 9-anthracene-β-propionic acid.

The halogenated benzene is chlorobenzene, and the alkylbenzene is toluene.

The concentration of fullerenes and/or fullerene derivatives in the solution 1 is 10 ^-6 mol/L to 10 ^-2 mol/L.

The concentration of fluorescent molecules in the solution 2 is 10 ^-6 mol/L to 10 ^-2 mol/L.

When the solution 1 and the solution 2 are mixed in the step (3), the volume ratio of the solution 1:the solution 2=1:3～3:1.

The incoming sample to be tested may include a gaseous sample or a liquid sample.

The illumination conditions include xenon lamp irradiation, halogen lamp irradiation, mercury lamp irradiation, optional xenon lamp irradiation, and further optional xenon lamp white light source irradiation.

The light intensity is 1mw～30mw, and the light time is 1min～60min.

The specific steps of establishing the linear relationship between the fluorescence signal intensity and the oxygen content in the detection system described in step (5) are: in the detection system, according to a plurality of oxygen concentrations and the fluorescence intensity corresponding to each oxygen concentration, the abscissa is drawn as the oxygen concentration. , and the ordinate is the standard curve of fluorescence signal intensity and determines the linear range.

Compared with the prior art, the present invention has the following beneficial effects:

(1) Fullerenes and/or fullerene derivatives can interact with different concentrations of oxygen under light conditions. The detection of ESR (electron spin resonance) signal changes proves that the interaction can efficiently produce different amounts of oxygen. The singlet oxygen ( ¹ O ₂ ), and the final product obtained by the interaction of the fluorescent molecule and the singlet oxygen can be proved to be an epoxy compound by proton nuclear magnetic resonance spectroscopy. Since the formation of singlet oxygen from oxygen and the reaction between singlet oxygen and fluorescent molecules are very rapid under illumination conditions and in the case of sufficient amounts of fullerenes and/or fullerene derivatives and fluorescent molecules, it can be roughly estimated. It is considered that the oxygen concentration when oxygen is first detected is the lowest oxygen concentration that can be detected by this detection method. Under the experimental conditions of Example 1, the decrease in fluorescence could be detected after oxygen was introduced for 2 s. At this time, the oxygen concentration in the detection system was 0.0707ml/cm ³ , the detection limit was low, and the detection sensitivity was high; in the experiment of Example 3 Under the conditions, the fluorescence intensity of the detection system decreased significantly after 2 minutes of illumination, and the decrease rate was about 89%.

(2) There are many kinds of fullerenes that can be selected, and the conditions for preparation, separation and purification are relatively mature.

(3) The selected fluorescent molecules have stable properties, low cost and obvious fluorescent properties.

(4) After the oxygen detection is completed, 90% of the epoxy compound obtained under heating conditions, namely the endoperoxide, can undergo a reversible reaction and become a fluorescent molecule with a high fluorescence intensity again, so that the fluorescent probe can be reused.

Description of drawings

Figure 1 is the UV-Vis absorption spectrum of the reversible change of 9,10-dibenzoanthracene fluorescent molecules.

FIG. 2 is a process diagram of the interaction between the fluorescent probe 9,10-dibenzoanthracene of Example 1 and singlet oxygen in the presence of hollow fullerenes.

Figure 3 is the 1H NMR spectra before and after the reaction of the fluorescent probe 9,10-diphenylanthracene with ¹ O ₂ .

FIG. 4 is a graph showing the change of ESR (electron spin resonance) electron spin resonance before and after irradiation with the capture agent TEMP (2,2,6,6-tetramethylpiperidinol) added to the detection system in Example 1. FIG.

FIG. 5 is a fluorescence quenching spectrum of the detection system obtained in the verification step of the detection result in Example 1 under illumination at different times.

6 is a diagram showing the interaction process between the fluorescent probe 9-anthracene-β-propionic acid of Example 2 and singlet oxygen in the presence of hollow fullerenes.

Fig. 7 is the 1H NMR spectra before and after the reaction of the fluorescent probe 9-anthracene-β-propionic acid with ¹ O ₂ .

FIG. 8 is a fluorescence quenching spectrum of the detection system obtained in the verification step of the detection result of Example 2 under illumination at different times.

FIG. 9 is a process diagram of the interaction between the fluorescent probe 9,10-dibenzoanthracene of Example 3 and singlet oxygen in the presence of endofullerene.

FIG. 10 is a fluorescence quenching spectrum of the detection system obtained in the verification step of the detection result of Example 3 under illumination at different times.

FIG. 11 is a graph showing the decreasing trend of fluorescence signal intensity corresponding to different oxygen contents under the conditions of Example 1.

Detailed ways

The specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings, but it should be understood that the protection scope of the present invention is not limited by the specific embodiments.

The following examples are without special instructions, and the detection systems are all set up in a 4cm ³ airtight container, wherein the detection systems in the container are all 3ml, that is, the fluorescent molecule solutions containing fullerenes and/or fullerene derivatives are all 3ml.

In the detection systems of Examples 1 to 3, the fluorescence intensity values were all read out under the detection conditions with a maximum absorption value of 445 nm.

Example 1

A method for detecting oxygen based on fullerene C ₆₀ using a fluorescent molecular probe 9,10-diphenylanthracene, the reaction scheme is shown in Figure 2, including the following steps:

(1) fullerene C ₆₀ is dissolved in carbon disulfide, and the solution 1 of fullerene C ₆₀ concentration is 10 ^-3 mol/L is prepared;

(2) dissolving the fluorescent molecule 9,10-diphenylanthracene in carbon disulfide, and preparing a solution 2 with a 9,10 ^- diphenylanthracene concentration of ^10-2 mol/L;

(3) according to the volume ratio of solution 2: solution 1 to be 1: 1, adding solution 2 to solution 1 to obtain a fluorescent molecule solution containing fullerene C ₆₀ ;

(4) The mixed solution obtained in step (3) was evacuated to reduce the oxygen concentration to 0ml/cm ³ to obtain a detection system, and then 0ml, 0.555ml, 1.11ml, 1.665ml, 2.22ml, 2.775ml, 3.33ml The pure oxygen in ml volume was passed into 7 independent detection systems, and the oxygen concentration in each detection system was 0ml/cm ³ , 0.1388ml/cm ³ , 0.2775ml/cm ³ , 0.4163ml/cm ³ , 0.555ml in turn. /cm ³ , 0.6938ml/cm ³ , 0.8325ml/cm ³ ;

(5) Irradiate the above detection system with a 20mw xenon lamp white light source with a wavelength of 200-1000nm (where the sample has a maximum absorption at 445nm) for 2 minutes, the oxygen in the airtight container generates singlet oxygen, and the fluorescent molecules and singlet oxygen generate epoxy compounds , the fluorescence quenching occurs, the fluorescence signal intensity in the system is detected, and the standard curve shown in Figure 11 is drawn with the abscissa as the oxygen concentration and the ordinate as the signal intensity.

Wherein, the specific process of introducing oxygen is as follows: through a small hole with a diameter of 0.3mm, oxygen is introduced into the airtight container containing the above 3ml detection system at a flow rate of 2m/s.

When oxygen is introduced for 2s, the fluorescence can be detected to decrease, indicating that after oxygen is introduced into the detection system for 2s, in the presence of fullerenes, epoxy compounds begin to be generated. At this time, the corresponding volume of oxygen introduced is: (2m/ s×2s×10 ² )×(π×(0.3mm/2) ² ×10 ⁻² )=0.2826ml, and the oxygen concentration of the detection system when it was passed for 2s was obtained as: 0.2826/4=0.0707ml/cm ³ .

It can be concluded from Figure 11 that in the range of oxygen concentration from 0.707ml/cm ³ to 0.555ml/cm ³ , the fluorescence signal intensity changes linearly with the increase of oxygen concentration, and the obtained function is:

y=3398.2-4173.8x

where x is the oxygen concentration and y is the fluorescence intensity

According to this formula, under the same conditions (that is, fullerenes and fluorescent molecules have the same type and content, and the light type and irradiation time of the system to be tested are the same), the intensity value of the fluorescence signal of the detected sample to be tested can be obtained. The concentration of oxygen in the sample is detected, so as to detect the oxygen content in the sample to be tested.

Verification of test results: Prepare a new airtight container with a volume of 4ml. The detection system is the same as that in step (4) above. The detection system is evacuated, and then 0.74ml of pure oxygen is introduced. After 2min of light, the system is detected. The fluorescence intensity of 2700a.u.; In addition, this oxygen concentration 0.74/4=0.185ml/ ^cm3 is substituted into the linear function y=3398.2-4173.8x described in step (5), and the theoretical fluorescence intensity is 2626a. u., is only 74a.u. different from the detected fluorescence intensity 2700a.u., which is within the tolerance range of error, so the detection method adopted in the present invention can be used to detect the specific content of oxygen in the sample to be tested. Therefore, this detection method can accurately detect lower concentrations of oxygen content.

In the H NMR spectrum of Figure 3 (using DMSO as the deuterated reagent), a, b, c, d, and e represent five hydrogens corresponding to 9,10-diphenylanthracene, a', b', and c', respectively. , d', e' represent the five hydrogens of 9,10-dibenzoanthracene endoperoxide. The top image in Fig. 3 represents the H NMR spectrum of 9,10-diphenylanthracene and fullerene mixed uniformly and not illuminated. It can be seen from the hydrogen spectrum that 9,10-diphenylanthracene has not changed, indicating that in the 9,10-Diphenylanthracene and fullerene do not chemically react under unilluminated conditions; the following two figures represent the homogeneous mixture of 9,10-diphenylanthracene and fullerene through oxygen for 20s, 100s and The nuclear magnetic hydrogen spectrum after 2 minutes of illumination under the xenon light source, it can be seen that new substances appear in the hydrogen spectrum, indicating that the mixed solution has undergone a chemical reaction under the illumination condition. When the oxygen flow was 20s, 9,10-dibenzoanthracene remained, and the hydrogen spectrum showed a mixture of 9,10-dibenzoanthracene and 9,10-dibenzoanthracene endoperoxide; when the oxygen was passed for 100s When 9,10-dibenzoanthracene reacted completely, all the products were 9,10-dibenzoanthracene endoperoxide. From the hydrogen spectrum, it can be concluded that the number of hydrogen did not change when comparing the two substances before and after the system was illuminated, but the relative displacement changed, indicating that new substances were formed. Comparing the position of hydrogen can determine the new formation. The substance is 9,10-dibenzoanthracene endoperoxide.

Singlet oxygen is also detected by ESR electron spin resonance. The detection process is: because TEMP has a strong ability to capture ¹ O ₂ , a very small amount of ¹ O ₂ can be captured, so TEMP (2,2,6,6- Tetramethylpiperidinol) was used as a capture agent, and TEMP captured ¹ O ₂ in the detection system after illumination to generate TEMPOL (1-oxy-2,2,6,6-tetramethyl-4-hydroxyl). piperidine), the ESR signal of TEMPOL was significantly enhanced (see Figure 4), which proved that singlet oxygen ¹ O ₂ was generated in the detection system, thus proving that under the action of fullerene C ₆₀ , under the action of light, the Oxygen is converted to singlet oxygen, causing quenching of fluorescence.

At the same time, it can be seen from Figure 5 that the fluorescence intensity of the system before illumination is 3500a.u., and after 2min illumination, the fluorescence intensity of the system becomes _2700a.u . The fluorescence intensity of the system decreased obviously after being irradiated, and the decrease rate of the fluorescence intensity was 23%, and the response time was fast.

Description: The fluorescence signal intensity in Figure 5 is from top to bottom in 9,10-dibenzoanthracene+C ₆₀ (no light), 9,10-dibenzoanthracene+C ₆₀ (light for 2min), 9,10- Dibenzoanthracene+C ₆₀ (illumination 4min), 9,10-dibenzoanthracene+C ₆₀ (illumination 6min), 9,10-dibenzoanthracene+C ₆₀ (illumination 8min), 9,10-dibenzoanthracene+C Fluorescence signal intensity obtained under the conditions of ₆₀ (10min light) and 9,10-diphenylanthracene + C ₆₀ (12min light).

Example 2

A method for detecting oxygen based on fullerene C ₆₀ using fluorescent molecular probe 9-anthracene-β-propionic acid, the reaction scheme is shown in Figure 6, including the following steps:

(1) fullerene C ₆₀ is dissolved in carbon disulfide, and the solution 1 of fullerene C ₆₀ concentration is 10 ^-3 mol/L is prepared;

(2) dissolving the fluorescent molecule 9-anthracene-β-propionic acid in carbon disulfide, and preparing a solution 2 with a concentration of 9 ^- anthracene ^- β-propionic acid of 10-4 mol/L;

(3) according to the volume ratio of solution 2: solution 1 to be 1:1, add solution 1 to solution 2 to obtain a fluorescent molecule solution containing fullerene C ₆₀ ;

(4) construct 7 detection systems according to the step (4) in the above-mentioned embodiment 1, and simultaneously draw the standard curve graph with the oxygen concentration as the abscissa and the signal intensity as the ordinate according to the step (5) in the above-mentioned embodiment 1, and then A linear function of the fluorescence intensity and the oxygen concentration is obtained, so the concentration of oxygen in the sample to be detected can be obtained according to the intensity value of the detected fluorescence signal of the sample to be detected.

Verification of test results: Prepare a new airtight container with a volume of 4ml. The detection system is the same as that in step (4) above. The detection system is evacuated, and then 0.74ml of pure oxygen is introduced. After 2min of light, the system is detected. At the same time, according to the function obtained in step (4) and the oxygen concentration 0.74/4=0.185ml/cm ³ , the theoretical fluorescence intensity is 2320a.u., and the detected fluorescence intensity is 2400a .u. only differs by 80a.u., which is within the tolerance range. Therefore, this detection method can accurately detect lower concentrations of oxygen content.

In the 1H NMR spectrum of Figure 7 (using CDCl ₃ as the deuterated reagent), a, b, c, d, e, and f represent the six hydrogens corresponding to 9-anthracene-β-propionic acid, respectively, a', b ', c', d', e', f' represent the six hydrogens of 9-anthracene-β-propionic acid endoperoxide. The top image in Figure 7 represents the 1H NMR spectrum of 9-anthracene-β-propionic acid and fullerene mixed uniformly without illumination. It can be seen from the hydrogen spectrum that 9-anthracene-β-propionic acid has not changed. It shows that 9-anthracene-β-propionic acid and fullerene do not chemically react under unilluminated conditions; The nuclear magnetic hydrogen spectrum after 2 minutes of illumination under the xenon lamp light source, it can be seen that new substances appear in the hydrogen spectrum, indicating that a chemical reaction has occurred in the mixed solution under the condition of illumination. When oxygen was passed for 20 s, 9-anthracene-β-propionic acid remained, and the hydrogen spectrum showed a mixture of 9-anthracene-β-propionic acid and 9-anthracene-β-propionic acid endoperoxide. From the hydrogen spectrum, it can be concluded that the number of hydrogen does not change when comparing the two substances before and after the system is illuminated, but the relative displacement changes, which proves that new substances are formed. By comparing the position of hydrogen, the new generation can be determined. The substance is 9-anthracene-β-propionic acid endoperoxide.

It can be seen from Figure 8 that the fluorescence intensity of the system before illumination is 5500a.u., and after 2min illumination, the fluorescence intensity of the system is 2400a.u. Therefore, the detection system containing 9-anthracene-β-propionic acid and fullerene C ₆₀ is After illumination, the fluorescence intensity decreased significantly, the decrease rate of fluorescence intensity was 56%, and the response time was fast; meanwhile, the fluorescence signal intensity of the molecule decreased not obviously with the prolongation of illumination time.

Description: The fluorescence signal intensity in Figure 8 is from top to bottom in 9-anthracene-β-propionic acid + C ₆₀ (no light), 9,10-diphenylanthracene + C ₆₀ (light for 2min), 9,10 -Dibenzoanthracene+C ₆₀ (light 4min), 9,10-dibenzoanthracene+C ₆₀ (light 6min), 9,10-dibenzoanthracene+C ₆₀ (light 8min), 9,10-dibenzoanthracene+ Fluorescence signal intensity obtained under the conditions of C ₆₀ (illumination for 10 min) and 9,10-diphenylanthracene+C ₆₀ (illumination for 12 min).

Example 3

A method for detecting oxygen using fluorescent molecular probe 9,10-diphenylanthracene based on embedded fullerene Sc ₃ N@C ₈₀ , comprising the following steps:

(1) dissolving the embedded fullerene Sc ₃ N@C ₈₀ in carbon disulfide to prepare a solution 1 with a concentration of the embedded fullerene Sc ₃ N@C ₈₀ of 10 ^-3 mol/L;

(2) dissolving the fluorescent molecule 9,10-diphenylanthracene in carbon disulfide, and preparing a solution 2 with a 9,10-diphenylanthracene concentration of 10 ^{- 4} mol/L;

(3) according to the volume ratio of solution 1 and solution 2 to be 1:1, adding solution 1 to solution 2 to obtain a fluorescent molecule solution containing embedded fullerene Sc ₃ N@C ₈₀ ;

(4) construct 7 detection systems according to the step (4) in the above-mentioned embodiment 1, and simultaneously draw the standard curve graph with the oxygen concentration as the abscissa and the signal intensity as the ordinate according to the step (5) in the above-mentioned embodiment 1, and then A linear function of the fluorescence intensity and the oxygen concentration is obtained, so the concentration of oxygen in the sample to be detected can be obtained according to the intensity value of the detected fluorescence signal of the sample to be detected.

Verification of test results: Prepare a new airtight container with a volume of 4ml. The detection system is the same as that in step (4) above. The detection system is evacuated, and then 0.74ml of pure oxygen is introduced. After 2min of light, the system is detected. At the same time, according to the function obtained in step (4) and the oxygen concentration 0.74/4=0.185ml/cm ³ , the theoretical fluorescence intensity is 350a.u., and the detected fluorescence intensity is 300a .u. only differs by 50a.u., which is within the tolerance range of error. Therefore, this detection method can accurately detect lower concentrations of oxygen content.

It can be seen from Figure 10 that the fluorescence intensity of the system is 2750a.u. before illumination, and the fluorescence intensity of the system is _300a.u. The fluorescence intensity of the detection system of ₈₀ decreased significantly after being illuminated, the decrease rate of fluorescence intensity was 89%, and the response time was fast.

Description: The fluorescence signal intensities in Figure 10 are from top to bottom in 9,10-diphenylanthracene+Sc ₃ N@C ₆₀ (without light), 9,10-diphenylanthracene+Sc ₃ N@C ₆₀ ( Illumination 2min), 9,10-Diphenylanthracene+Sc ₃ N@C ₆₀ (Illumination 4min), 9,10-Diphenylanthracene+Sc ₃ N@C ₆₀ (Illumination 6min), 9,10-Diphenylanthracene+ Conditions of Sc ₃ N@C ₆₀ (lighting 8min), 9,10-dibenzoanthracene+Sc ₃ N@C ₆₀ (lighting 10min), 9,10-diphenylanthracene+Sc ₃ N@C ₆₀ (lighting 12min) The fluorescence signal intensity obtained below.

The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. These descriptions are not intended to limit the invention to the precise form disclosed, and obviously many changes and modifications are possible in light of the above teachings. The exemplary embodiments were chosen and described for the purpose of explaining certain principles of the invention and their practical applications, to thereby enable one skilled in the art to make and utilize various exemplary embodiments and various different aspects of the invention. Choose and change. The scope of the invention is intended to be defined by the claims and their equivalents.

Claims (12)

1. A method for detecting oxygen using a fluorescent molecular probe, comprising the steps: (1) Dissolving fullerenes and/or fullerene derivatives in halobenzene, alkylbenzene or carbon disulfide to prepare a solution containing fullerenes and/or fullerene derivatives, namely solution 1; (2) Dissolving fluorescent molecules in halogenated benzene, alkylbenzene or carbon disulfide to prepare a solution containing fluorescent molecules, namely solution 2; (3) Mixing solution 1 and solution 2 to obtain a fluorescent molecule solution containing fullerenes and/or fullerene derivatives; (4) evacuating the mixed solution obtained in step (3) to reduce the oxygen concentration to 0ml/cm ³ to obtain a detection system; (5) Under light conditions, establish a linear relationship between the fluorescence signal intensity and the oxygen content in the detection system; (6) Pass the sample to be tested into the same detection system as in step (4), and measure the intensity of the fluorescence signal in the detection system under the same illumination conditions as in step (5), and then calculate the oxygen content in the sample to be tested. content; Wherein, the fullerene is an endofullerene, and the endofullerene includes N@C ₆₀ , La@C ₇₂ , Sc ₂ @C ₇₄ , Sc ₂ @C ₇₆ , La ₂ @C ₈₀ , At least one of Sc ₃ N@C ₈₀ , Tm@C ₈₂ , Gd@C ₈₂ , Sc ₂ C ₂ @C ₈₄ ; The fullerene derivatives include at least one of fullerene oxides and fullerene addition products; The concentration of fullerenes and/or fullerene derivatives in the solution 1 is ^10-6 mol/L～ ^10-2 mol/L, and the concentration of the fluorescent molecules in the solution 2 is ^10-6 mol/L～10 ^-2 mol/L. 2. The method according to claim 1, wherein the fullerene oxide is at least one of C ₆₀ O and C ₇₀ O, and the fullerene addition product is fullerene 1,3- At least one of a dipolar cycloaddition product and a fullerene Bingel addition product. 3 . The method according to claim 1 , wherein the fluorescent molecule is a conjugated organic molecule having a biphenyl structure. 4 . 4 . The method according to claim 3 , wherein the fluorescent molecule is one of 9,10-diphenylanthracene and 9-anthracene-β-propionic acid. 5 . 5. method according to claim 1 is characterized in that: described halogenated benzene is chlorobenzene, and alkylbenzene is toluene. 6 . The method according to claim 1 , wherein when the solution 1 and the solution 2 are mixed in the step (3), the volume ratio of the solution 1 to the solution 2 is 1:3 to 3:1. 7 . 7 . The method according to claim 1 , wherein the sample to be tested in step (6) is a gaseous sample or a liquid sample. 8 . 8 . The method according to claim 1 , wherein the illumination conditions include xenon lamp irradiation, halogen lamp irradiation, and mercury lamp irradiation. 9 . 9. The method of claim 8, wherein the illumination conditions comprise xenon lamp illumination. 10 . The method according to claim 9 , wherein the xenon lamp irradiation is a xenon lamp white light source irradiation. 11 . 11. The method according to claim 1 or 8, wherein the illumination intensity is 1mW～30mW, and the illumination time is 1min～60min. 12 . The method according to claim 1 , wherein the specific step of establishing the linear relationship between the fluorescence signal intensity and the oxygen content in the detection system in step (5) is: in the detection system, according to a plurality of oxygen concentrations As well as the fluorescence intensity corresponding to each oxygen concentration, draw a standard curve with the oxygen concentration as the abscissa and the fluorescence signal intensity as the ordinate, and determine the linear range.

Images