CN107340278A - Method based on fullerene or derivatives thereof using fluorescent molecular probe detection oxygen - Google Patents
Method based on fullerene or derivatives thereof using fluorescent molecular probe detection oxygen Download PDFInfo
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- CN107340278A CN107340278A CN201710419871.0A CN201710419871A CN107340278A CN 107340278 A CN107340278 A CN 107340278A CN 201710419871 A CN201710419871 A CN 201710419871A CN 107340278 A CN107340278 A CN 107340278A
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Abstract
The invention discloses the method based on fullerene or derivatives thereof using fluorescent molecular probe detection oxygen, belong to the application field of fullerene-based material.This method includes：Fullerene or fullerene derivate are mixed to form the fullerene solution containing fluorescence molecule with fluorescence molecule, vacuumize, it is passed through oxygen sample, under illumination condition, singlet oxygen is produced, fluorescence molecule generation epoxide, fluorescent quenching occurs, fluorescence signal intensity in detection architecture, and then detect the oxygen content in system.The present invention solves the problems, such as that existing oxygen detection rate of precision is low, is difficult to detect trace oxygen.Singlet oxygen can be produced under illumination condition using fullerene or fullerene derivate, can be with the content of indirect detection oxygen according to the fluorescence intensity of decline, detection sensitivity is high, and more than 90% back reaction can occur for the endoperoxide generated after reacting, have higher recycling rate of waterused.
Description
Technical field
The present invention relates to the application field of fullerene-based material, more particularly to based on fullerene or derivatives thereof using fluorescence point
The method of sub- probe in detecting oxygen.
Background technology
Oxygen plays very important effect in biological life activity.Cell in organism needs oxygen to carry out
Aerobic metabolism is so as to maintaining daily physiological activity.Anoxic can make the vital movement of biology seriously may be used by serious infringement, situation
It can occur that stupor is even dead.And oxygen excess can then cause " oxygen poisoning ", cause dizziness, insensitive, tingling sensation, vision
And the symptom such as hearing impaired, consciousness decline.Only appropriate oxygen concentration can just maintain being normally carried out for biological life activity.Institute
Just seem most important with the detection to the oxygen content in organism.
Have some oxygen detection methods such as titration, amperometry, thermoluminescence method at present.Although these methods
The content of oxygen can be effectively detected, but there is also some drawbacks, such as：Response time is grown, and can not continue to detect, pole
Easily disturbed by other gases, and the cost needed is also higher etc., is difficult accurately to be entered by instrument for micro oxygen
Row observation and measurement.
It is existing that active oxygen is detected using fluorescence probe.Singlet oxygen is a kind of excitation state of oxygen, and a kind of high living
The molecule of property, and a kind of typical active oxygen species.Most of singlet oxygen fluorescence probes are all based on the reaction of it and anthracene.
Most of singlet oxygen fluorescence probes are selection anthracene or 9,10- dibenzanthracenes as recognition group.Fluorescence probe is in singlet oxygen
In the presence of, cycloaddition reaction generation endoperoxide occurs, the fluorescence of fluorogen is quenched, so as to reach detection singlet
The purpose of oxygen.
Therefore, oxygen can be transformed into singlet oxygen under certain condition, by fluorescence molecule and singlet oxygen phase interaction
With the characteristic of rear fluorescence significant changes, to design, a kind of response time is fast, selectivity is good, high sensitivity, simple to operate is used for examining
The fluorescent molecular probe of oxygen determination gas concentration, it is expected in the fields such as bioscience, preclinical medicine and environment measuring extensively should
With.
The content of the invention
In order to solve above-mentioned the problems of the prior art, the invention provides one kind using fluorescent molecular probe detection oxygen
Method, detect the method for oxygen specially based on fullerene or fullerene derivate and using fluorescent molecular probe.
The method provided by the present invention that oxygen is detected using fluorescent molecular probe, is comprised the following steps：
(1) fullerene and/or fullerene derivate are dissolved in halogeno-benzene, alkylbenzene or carbon disulfide, are configured to contain
There are the solution of fullerene and/or fullerene derivate, as solution 1；
(2) fluorescence molecule is dissolved in halogeno-benzene, alkylbenzene or carbon disulfide, be configured to containing the molten of fluorescence molecule
Liquid, as solution 2；
(3) solution 1 and solution 2 are mixed, obtains the fluorescence molecule solution containing fullerene and/or fullerene derivate；
(4) mixed solution that step (3) obtains is vacuumized, oxygen concentration is reduced to 0ml/cm3, obtain detection architecture；
(5) under illumination condition, the linear relationship of fluorescence signal intensity and oxygen content in detection architecture is established；
(6) by testing sample be passed into step (4) identical detection architecture in, and with step (5) identical illumination
Under the conditions of determine fluorescence signal intensity in detection architecture, and then the oxygen content in testing sample is calculated.
Fullerene and/or fullerene derivate can produce single under illumination condition with the oxygen interaction of various concentrations
Line state oxygen, the epoxide of fluorescence molecule and singlet oxygen reaction generation fluorescence molecule are endoperoxides compound, epoxy compound
Thing fluorescence intensity is low or does not send fluorescence, that is, fluorescent quenching occurs.
The reaction of fluorescence molecule and singlet oxygen is reversible reaction：Due to fluorescence molecule and the ring of singlet oxygen reaction generation
Oxygen compound has thermal instability, in a heated condition, temperature range be 100~120 DEG C, the heat time be 20~
Under conditions of 60min, epoxide can occur reversible reaction and become the very big fluorescence molecule of fluorescence intensity again, and this makes
Obtaining this fluorescence probe can recycle, efficient, convenient.Utilize the feature UV absorption and epoxidation of fluorescence molecule body
Compound generation after feature UV absorption change, it can be found that almost more than 90% epoxide can carry out it is reversible
Reaction (referring to Fig. 1).
The fullerene includes at least one of empty fullerene and embedded fullerene.
The empty fullerene is C including formula2mThe cage structure being made up of carbon atom fullerene, wherein 30≤m
≤ 60, it is optionally C60、C70、C76、C78、C82、C84At least one of.
The embedded fullerene includes N@C60、La@C72、Sc2@C74、Sc2@C76、La2@C80、Sc3N@C80、Tm@C82、Gd@
C82、Sc2C2@C84At least one of；
The fullerene derivate includes at least one of fowler olefinic oxide and fullerene addition compound product, optional rich
Le olefinic oxide is C60O、C70At least one of O, fullerene addition compound product are fullerene 1,3- dipole-diople interactions product, richness
Strangle at least one of alkene objective case that addition compound product.
The fluorescence molecule is the conjugated structure organic molecule with biphenyl structural, is optionally 9,10- dibenzanthracenes, 9-
Anthracene-β-propionic acid.
The halogeno-benzene is chlorobenzene, and alkylbenzene is toluene.
The concentration of fullerene and/or fullerene derivate is 10 in the solution 1-6Mol/L~10-2mol/L。
The concentration of fluorescence molecule is 10 in the solution 2-6Mol/L~10-2mol/L。
When solution 1 and solution 2 are mixed in the step (3), solution 1: volume ratio=1 of solution 2: 3~3: 1.
The testing sample being passed through may include gaseous sample or liquid sample.
The illumination condition includes xenon lamp irradiation, halogen lamp irradiation, Hg lamp irradiation, optionally irradiates for xenon lamp, further may be used
Choosing is irradiated for xenon lamp white light source.
The intensity of illumination is 1mw~30mw, and light application time is 1min~60min.
The specific steps of the linear relationship of fluorescence signal intensity and oxygen content in detection architecture are established described in step (5)
It is：In detection architecture, it is oxygen to draw abscissa according to fluorescence intensity corresponding to multiple oxygen concentrations and each oxygen concentration
Gas concentration, the canonical plotting that ordinate is fluorescence signal intensity simultaneously determine the range of linearity.
Compared with prior art, the present invention has the advantages that：
(1) fullerene and/or fullerene derivate can interact under illumination condition with the oxygen of various concentrations, warp
Detection ESR (electron spin resonance) electron spin resonance signal change proves that the interaction can be produced efficiently
The different amounts of singlet oxygen of life (1O2), and fluorescence molecule and singlet oxygen interaction gained end-product are examined through proton nmr spectra
Survey, be provably epoxide.Due under illumination condition and in fullerene and/or fullerene derivate and fluorescence molecule
In the case of enough, the speed that oxygen forms singlet oxygen and singlet oxygen with fluorescence molecule reacts is very fast, therefore
Oxygen concentration when can think to detect oxygen at first roughly is the detectable minimum oxygen concentration of the detection method.In reality
Under the experiment condition for applying example 1, it is passed through after oxygen 2s i.e. detectable fluorescence and declines, now oxygen concentration is in detection architecture
0.0707ml/cm3, test limit is low, and detection sensitivity is high；Under the experiment condition of embodiment 3, detection architecture is glimmering after illumination 2min
Luminous intensity just occurs significantly to decline, and rate of descent is about 89%, the fast response time of detection method, therefore the detection method is high
Effect, it is workable.
(2) the fullerene species that can be selected is more, the condition comparative maturity of preparative separation purifying.
(3) the fluorescence molecule property selected is stable, and cost is cheap, and fluorescent characteristic is obvious.
(4) after oxygen detection, gained epoxide is that endoperoxide 90% can occur in a heated condition
Reversible reaction, become the very big fluorescence molecule of fluorescence intensity again so that fluorescence probe can be recycled.
Brief description of the drawings
Fig. 1 is the uv-visible absorption spectra of 9,10- dibenzanthracene fluorescence molecule reversible changes.
Fig. 2 be embodiment 1 fluorescence probe 9,10- dibenzanthracenes under the conditions of existing for empty fullerene with singlet oxygen
Mechanism figure.
Fig. 3 be fluorescence probe 9,10- dibenzanthracenes with1O2The front and rear hydrogen nuclear magnetic resonance spectrogram of reaction.
Fig. 4 is that the detection architecture in embodiment 1 adds light under the conditions of capturing agent TEMP (2,2,6,6- tetramethylpiperidinols)
According to front and rear ESR (electron spin resonance) electron spin resonance variation diagram.
Fig. 5 is that fluorescence of the detection architecture through different time illumination obtained in the testing result verification step of embodiment 1 is sudden
Go out spectrogram.
Fig. 6 be embodiment 2 fluorescence probe 9- anthracenes-β-propionic acid under the conditions of existing for empty fullerene with singlet oxygen
Mechanism figure.
Fig. 7 be fluorescence probe 9- anthracenes-β-propionic acid with1O2The front and rear hydrogen nuclear magnetic resonance spectrogram of reaction.
Fig. 8 is that fluorescence of the detection architecture through different time illumination obtained in the testing result verification step of embodiment 2 is sudden
Go out spectrogram.
Fig. 9 be embodiment 3 fluorescence probe 9,10- dibenzanthracenes with the conditions of existing for embedded fullerene with singlet oxygen
Mechanism figure.
Figure 10 is that fluorescence of the detection architecture through different time illumination obtained in the testing result verification step of embodiment 3 is sudden
Go out spectrogram.
Figure 11 is the downward trend figure of the fluorescence signal intensity corresponding to different oxygen contents under the conditions of embodiment 1.
Embodiment
Below in conjunction with the accompanying drawings, the embodiment of the present invention is described in detail, it is to be understood that the guarantor of the present invention
Shield scope is not limited by embodiment.
Unless otherwise specified, detection architecture is built upon 4cm to following examples3Closed container in, the wherein container
In detection architecture be 3ml, i.e., the fluorescence molecule solution containing fullerene and/or fullerene derivate is 3ml.
Fluorescence intensity level is in the detector bar that obtained the maximum absorption is 445nm in the detection architecture of 1~embodiment of embodiment 3
Read out under part.
Embodiment 1
One kind is based on fullerene C60Using fluorescent molecular probe 9,10- dibenzanthracenes detect the method for oxygen, reaction scheme figure
Referring to Fig. 2, comprise the following steps：
(1) by fullerene C60It is dissolved in carbon disulfide, is configured to fullerene C60Concentration is 10-3Mol/L solution 1；
(2) fluorescence molecule 9,10- dibenzanthracenes are dissolved in carbon disulfide, are configured to 9,10- dibenzanthracenes concentration as 10- 2Mol/L solution 2；
(3) solution 2 is pressed: the volume ratio of solution 1 is 1: 1, and solution 2 is added in solution 1, obtained containing fullerene C60's
Fluorescence molecule solution；
(4) mixed solution that step (3) obtains is vacuumized, oxygen concentration is reduced to 0ml/cm3, detection architecture is obtained,
Then the purity oxygen of 0ml, 0.555ml, 1.11ml, 1.665ml, 2.22ml, 2.775ml, 3.33ml volume is passed through 7 respectively
In independent detection architecture, the oxygen concentration in each detection architecture is followed successively by 0ml/cm3、0.1388ml/cm3、0.2775ml/
cm3、0.4163ml/cm3、0.555ml/cm3、0.6938ml/cm3、0.8325ml/cm3；
(5) irradiated with the xenon lamp white light source for the 20mw that wavelength is 200~1000nm (wherein has most in 445nm samples
It is big to absorb) above detection architecture 2min, the oxygen in closed container produces singlet oxygen, fluorescence molecule and singlet oxygen generation ring
Oxygen compound, fluorescent quenching occurs, fluorescence signal intensity in detection architecture, the abscissa drawn shown in Figure 11 is oxygen concentration,
Ordinate is the strong canonical plotting of signal.
Wherein, the detailed process that oxygen is passed through is：By a diameter of 0.3mm aperture, detected to containing above 3ml
Oxygen is passed through with 2m/s flow velocity in the closed container of system.
After oxygen 2s is passed through, detectable fluorescence declines, and illustrates after being passed through oxygen 2s to detection architecture, in fowler
In the presence of alkene, epoxide starts to produce, and now corresponds to the oxygen volume being passed through and is：(2m/s×2s×102)×(π×
(0.3mm/2)2×10-2)=0.2826ml, and then the oxygen concentration of detection architecture is when obtaining being passed through 2s：0.2826/4=
0.0707ml/cm3。
It can be drawn by Figure 11, be 0.707ml/cm in oxygen concentration3To 0.555ml/cm3In the range of, fluorescence signal is strong
Linear change is presented with the increase of oxygen concentration in degree, and obtained function is：
Y=3398.2-4173.8x
In formula, x is oxygen concentration, and y is fluorescence intensity
, can (i.e. fullerene be identical with the species of fluorescence molecule, content is identical, treats under the same conditions according to this formula
Light species, the irradiation time of survey system are identical), it is worth to according to the intensity of the fluorescence signal of the testing sample of detection to be detected
The concentration of oxygen in sample, so as to detect oxygen content in testing sample.
Testing result is verified：Again the closed container that a new volume is 4ml, its detection architecture and above-mentioned steps are prepared
(4) it is identical in, detection architecture is vacuumized, then passes to 0.74ml purity oxygens, after illumination 2min, detects the fluorescence of system
Intensity is 2700a.u.；In addition, by this oxygen concentration 0.74/4=0.185ml/cm3Substitute into linear function y described in step (5)
In=3398.2-4173.8x, the fluorescence intensity for obtaining theory is 2626a.u., with the fluorescence intensity 2700a.u. that detects only
74a.u. is differed, in error permissible range, therefore the detection method that the present invention uses can be used for oxygen in detection testing sample
Concrete content.Therefore, this detection method can accurately detect the oxygen content of low concentration.
(using DMSO as deuterated reagent) in Fig. 3 hydrogen nuclear magnetic resonance spectrograms, a, b, c, d, e represent 9,10- bis- respectively
Five kinds of hydrogen corresponding to benzene anthracene, a ', b ', c ', d ', e ' represent five kinds of hydrogen of 9,10- dibenzanthracene endoperoxides.In Fig. 3 topmost
Figure represent the nucleus magnetic hydrogen spectrum figure that 9,10- dibenzanthracenes and fullerene are well mixed non-illumination, it can be seen that 9,10- bis- from hydrogen spectrum
Benzene anthra does not change, illustrates that 9,10- dibenzanthracenes do not chemically react with fullerene under conditions of non-illumination；Following
Two width figures represent to the well mixed solution of 9,10- dibenzanthracenes and fullerene respectively leads to oxygen 20s, 100s and under xenon source
Nucleus magnetic hydrogen spectrum after illumination 2min, it can be seen that new material occur in hydrogen spectrum, illustrate that mixed solution occurs under illumination condition
Chemical reaction.When oxygen-supply quantity is 20s, 9,10- dibenzanthracenes also have residue, and 9,10- dibenzanthracenes and 9,10- are shown in hydrogen spectrum
The mixture of dibenzanthracene endoperoxide；When being passed through 100s, 9,10- dibenzanthracenes react completely, and product is entirely 9,10- hexichol
Anthracene endoperoxide.It can be drawn from hydrogen spectrum, compare system illumination both front and back material, the number of hydrogen does not change,
But there occurs relative change in displacement, illustrate there is new material generation, compare the position of hydrogen, it may be determined that newly-generated material
For 9,10- dibenzanthracene endoperoxides.
Singlet oxygen is also detected by ESR electron spin resonance, detection process is：Because TEMP is captured1O2Ability very
By force, it is minimal amount of1O2It can capture, therefore be capturing agent from TEMP (2,2,6,6- tetramethylpiperidinol), TEMP is captured
Into the detection architecture after illumination1O2, TEMPOL (1- epoxides -2,2,6,6- tetramethyl -4- hydroxy piperidines) is generated, is examined
The ESR signals for measuring TEMPOL are remarkably reinforced (referring to Fig. 4), it was demonstrated that detection architecture generates singlet oxygen1O2, so as to prove
Fullerene C60In the presence of, through illumination, the oxygen in detection architecture is transformed to singlet oxygen, so as to cause the sudden of fluorescence
Go out.
Meanwhile as shown in Figure 5, system fluorescence intensity is 3500a.u. before illumination, after illumination 2min, system fluorescence intensity becomes
For 2700a.u., therefore, contain 9,10- dibenzanthracenes and fullerene C60Detection architecture after illumination fluorescence intensity be decreased obviously,
The rate of descent of fluorescence intensity is 23%, and the response time is fast；Simultaneously with the extension of light application time, under the fluorescence signal intensity of molecule
Unobvious drop.
Explanation：Fluorescence signal intensity in Fig. 5 is followed successively by 9,10- dibenzanthracenes+C from top to bottom60(non-illumination), 9,10-
Dibenzanthracene+C60(illumination 2min), 9,10- dibenzanthracenes+C60(illumination 4min), 9,10- dibenzanthracenes+C60(illumination 6min), 9,10-
Dibenzanthracene+C60(illumination 8min), 9,10- dibenzanthracenes+C60(illumination 10min), 9,10- dibenzanthracenes+C60The bar of (illumination 12min)
The fluorescence signal intensity obtained under part.
Embodiment 2
One kind is based on fullerene C60Using the method for fluorescent molecular probe 9- anthracenes-β-propionic acid detection oxygen, reaction scheme figure
Referring to Fig. 6, comprise the following steps：
(1) by fullerene C60It is dissolved in carbon disulfide, is configured to fullerene C60Concentration is 10-3Mol/L solution 1；
(2) fluorescence molecule 9- anthracenes-β-propionic acid is dissolved in carbon disulfide, is configured to 9- anthracenes-β-propionate concentration as 10- 4Mol/L solution 2；
(3) solution 2 is pressed：The volume ratio of solution 1 is 1:1, solution 1 is added in solution 2, obtained containing fullerene C60's
Fluorescence molecule solution；
(4) press the step (4) in above-described embodiment 1 and build 7 detection architectures, while by the step in above-described embodiment 1
(5) draw that abscissa is oxygen concentration, ordinate is the strong canonical plotting of signal, and then obtains fluorescence intensity and oxygen concentration
Linear function, therefore oxygen in detected sample can be worth to according to the intensity of the fluorescence signal of the testing sample of detection
Concentration.
Testing result is verified：Again the closed container that a new volume is 4ml, its detection architecture and above-mentioned steps are prepared
(4) it is identical in, detection architecture is vacuumized, then passes to 0.74ml purity oxygens, after illumination 2min, detects the fluorescence of system
Intensity is 2400a.u.；Meanwhile the function and oxygen concentration 0.74/4=0.185ml/cm obtained according to step (4)3, obtain
Theoretical fluorescence intensity is 2320a.u., differs only by 80a.u. with the fluorescence intensity 2400a.u. detected, allows model in error
In enclosing.Therefore, this detection method can accurately detect the oxygen content of low concentration.
(CDCl is used in Fig. 7 hydrogen nuclear magnetic resonance spectrogram3As deuterated reagent), a, b, c, d, e, f represent respectively 9- anthracenes-
Six kinds of hydrogen corresponding to β-propionic acid, a ', b ', c ', d ', e ', f ' represent six kinds of hydrogen of 9- anthracenes-β-propionic acid endoperoxide.In Fig. 7 most
Draw above represents 9- anthracenes-β-propionic acid and fullerene is well mixed the nucleus magnetic hydrogen spectrum figure of non-illumination, it can be seen that 9- from hydrogen spectrum
Anthracene-β-propionic acid does not change, and illustrates that 9- anthracenes-β-propionic acid does not chemically react with fullerene under conditions of non-illumination；
Following figure, which is represented to the well mixed solution of 9- anthracenes-β-propionic acid and fullerene, leads to oxygen 20s and the illumination under xenon source
Nucleus magnetic hydrogen spectrum after 2min, it can be seen that new material occur in hydrogen spectrum, illustrate to send out in mixed solution under conditions of illumination
Chemical reaction is given birth to.As logical oxygen 20s, 9- anthracenes-β-propionic acid also has residue, hydrogen spectrum be shown 9- anthracenes-β-propionic acid and 9- anthracenes-β-
The mixture of propionic acid endoperoxide.It can be drawn from hydrogen spectrum, compare system illumination both front and back material, the number of hydrogen does not have
Change, but there occurs relative change in displacement, it was demonstrated that have new material generation, compare the position of hydrogen, it may be determined that new
The material of generation is 9- anthracenes-β-propionic acid endoperoxide.
As shown in Figure 8, system fluorescence intensity is 5500a.u. before illumination, and after illumination 2min, system fluorescence intensity is
2400a.u., therefore, contain 9- anthracenes-β-propionic acid and fullerene C60Detection architecture after illumination fluorescence intensity be decreased obviously, it is glimmering
The rate of descent of luminous intensity is 56%, and the response time is fast；Simultaneously as the extension of light application time, the fluorescence signal intensity of molecule decline
Unobvious.
Explanation：Fluorescence signal intensity in Fig. 8 is followed successively by 9- anthracenes-β-propionic acid+C from top to bottom60(non-illumination), 9,10-
Dibenzanthracene+C60(illumination 2min), 9,10- dibenzanthracenes+C60(illumination 4min), 9,10- dibenzanthracenes+C60(illumination 6min), 9,10-
Dibenzanthracene+C60(illumination 8min), 9,10- dibenzanthracenes+C60(illumination 10min), 9,10- dibenzanthracenes+C60The bar of (illumination 12min)
The fluorescence signal intensity obtained under part.
Embodiment 3
One kind is based on embedded fullerene Sc3N@C80The method that oxygen is detected using fluorescent molecular probe 9,10- dibenzanthracenes, bag
Include following steps：
(1) by embedded fullerene Sc3N@C80It is dissolved in carbon disulfide, is configured to embedded fullerene Sc3N@C80Concentration is
10-3Mol/L solution 1；
(2) fluorescence molecule 9,10- dibenzanthracenes are dissolved in carbon disulfide, are configured to 9,10- dibenzanthracenes concentration as 10- 4Mol/L solution 2；
(3) it is 1 by the volume ratio of solution 1 and solution 2:1, solution 1 is added in solution 2, obtained containing embedded fowler
Alkene Sc3N@C80Fluorescence molecule solution；
(4) press the step (4) in above-described embodiment 1 and build 7 detection architectures, while by the step in above-described embodiment 1
(5) draw that abscissa is oxygen concentration, ordinate is the strong canonical plotting of signal, and then obtains fluorescence intensity and oxygen concentration
Linear function, therefore oxygen in detected sample can be worth to according to the intensity of the fluorescence signal of the testing sample of detection
Concentration.
Testing result is verified：Again the closed container that a new volume is 4ml, its detection architecture and above-mentioned steps are prepared
(4) it is identical in, detection architecture is vacuumized, then passes to 0.74ml purity oxygens, after illumination 2min, detects the fluorescence of system
Intensity is 300a.u.；Meanwhile the function and oxygen concentration 0.74/4=0.185ml/cm obtained according to step (4)3, obtain
Theoretical fluorescence intensity is 350a.u., 50a.u. is differed only by with the fluorescence intensity 300a.u. detected, in error permissible range
It is interior.Therefore, this detection method can accurately detect the oxygen content of low concentration.
As shown in Figure 10, fluorescence intensity is 2750a.u. before illumination, and after illumination 2min, system fluorescence intensity is 300a.u.,
Therefore, containing 9- anthracenes-β-propionic acid and embedded fullerene Sc3N@C80Detection architecture after illumination fluorescence intensity be decreased obviously, it is glimmering
Luminous intensity rate of descent is 89%, and the response time is fast；Simultaneously as the extension of light application time, the fluorescence signal intensity of molecule decline not
Substantially.
Explanation：Fluorescence signal intensity in Figure 10 is followed successively by 9,10- dibenzanthracenes+Sc from top to bottom3N@C60(non-illumination),
9,10- dibenzanthracenes+Sc3N@C60(illumination 2min), 9,10- dibenzanthracenes+Sc3N@C60(illumination 4min), 9,10- dibenzanthracenes+Sc3N@
C60(illumination 6min), 9,10- dibenzanthracenes+Sc3N@C60(illumination 8min), 9,10- dibenzanthracenes+Sc3N@C60(illumination 10min), 9,
10- dibenzanthracenes+Sc3N@C60The fluorescence signal intensity obtained under conditions of (illumination 12min).
The description of the foregoing specific illustrative embodiment to the present invention is to illustrate and the purpose of illustration.These descriptions
It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to above-mentioned teaching, can be much changed
And change.The purpose of selecting and describing the exemplary embodiment is that explain that the certain principles of the present invention and its reality should
With so that those skilled in the art can realize and utilize the present invention a variety of exemplaries and
Various chooses and changes.The scope of the present invention is intended to be limited by claims and its equivalents.
Claims (10)
1. a kind of method that oxygen is detected using fluorescent molecular probe, is comprised the following steps：
(1) fullerene and/or fullerene derivate are dissolved in halogeno-benzene, alkylbenzene or carbon disulfide, are configured to containing richness
Strangle the solution of alkene and/or fullerene derivate, as solution 1；
(2) fluorescence molecule is dissolved in halogeno-benzene, alkylbenzene or carbon disulfide, is configured to the solution containing fluorescence molecule, i.e.,
For solution 2；
(3) solution 1 and solution 2 are mixed, obtains the fluorescence molecule solution containing fullerene and/or fullerene derivate；
(4) mixed solution that step (3) obtains is vacuumized, oxygen concentration is reduced to 0ml/cm3, obtain detection architecture；
(5) under illumination condition, the linear relationship of fluorescence signal intensity and oxygen content in detection architecture is established；
(6) by testing sample be passed into step (4) identical detection architecture in, and with step (5) identical illumination condition
Fluorescence signal intensity in lower measure detection architecture, and then the oxygen content in testing sample is calculated.
2. according to the method for claim 1, it is characterised in that：The fullerene includes empty fullerene and embedded fullerene
At least one of, the empty fullerene is C including formula2mThe cage structure being made up of carbon atom fullerene, wherein
30≤m≤60, it is optionally C60、C70、C76、C78、C82、C84At least one of, the embedded fullerene includes N@C60、La@
C72、Sc2@C74、Sc2@C76、La2@C80、Sc3N@C80、Tm@C82、Gd@C82、Sc2C2@C84At least one of；The fullerene
Derivative includes at least one of fowler olefinic oxide and fullerene addition compound product, and optional fowler olefinic oxide is C60O、
C70At least one of O, fullerene addition compound product are fullerene 1, your addition compound product of 3- dipole-diople interactions product, fullerene objective case
At least one of.
3. according to the method for claim 1, it is characterised in that：The fluorescence molecule is the conjugated structure with biphenyl structural
Organic molecule, it is optionally 9,10- dibenzanthracenes, 9- anthracenes-β-propionic acid.
4. according to the method for claim 1, it is characterised in that：The halogeno-benzene is chlorobenzene, and alkylbenzene is toluene.
5. according to the method for claim 1, it is characterised in that：Fullerene and/or fullerene derivate in the solution 1
Concentration is 10-6Mol/L~10-2Mol/L, the concentration of fluorescence molecule is 10 in the solution 2-6Mol/L~10-2mol/L。
6. according to the method for claim 5, it is characterised in that：When solution 1 and solution 2 are mixed in step (3), solution
1: volume ratio=1 of solution 2: 3~3: 1.
7. according to the method for claim 1, it is characterised in that：Testing sample described in step (6) is gaseous sample or liquid
Aspect product.
8. according to the method for claim 1, it is characterised in that：The illumination condition includes xenon lamp irradiation, halogen lamp irradiation, mercury
Light irradiation, optionally irradiated for xenon lamp, it is further alternative to be irradiated for xenon lamp white light source.
9. the method according to claim 1 or 8, it is characterised in that：Intensity of illumination is 1mw~30mw, and light application time is
1min~60min.
10. according to the method for claim 1, it is characterised in that：Step establishes fluorescence signal in detection architecture described in (5)
The linear relationship of intensity and oxygen content comprises the concrete steps that：In detection architecture, according to multiple oxygen concentrations and each oxygen
Fluorescence intensity corresponding to concentration draw abscissa be oxygen concentration, the canonical plotting that ordinate is fluorescence signal intensity and determination
The range of linearity.
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