CN109894103A - The method adsorbed carbon dioxide using conjugated polymer and boron nitride composite and monitor its slow release - Google Patents
The method adsorbed carbon dioxide using conjugated polymer and boron nitride composite and monitor its slow release Download PDFInfo
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Abstract
The present invention provides a kind of methods adsorbed carbon dioxide adsorption using conjugated polymer and boron nitride composite and monitored its slow release.Shown in the structural formula of the conjugated polymer such as formula (I).Absorption of this method according to carbon dioxide to fluorescence resonance energy transfer (FRET) technology and boron nitride of the stimuli responsive conjugated polymer to carbon dioxide assigns composite material dual function, to detect composite material to CO2Absorption and slow release process.Meanwhile this process can promote stimulus responsive polymers and boron nitride further to assemble by hydrophobic effect and electrostatic interaction again, form supermolecule polymer system, and then regulate and control the coherent condition or conformation of conjugated polymer and boron nitride by carbon dioxide.
Description
Technical field
The invention belongs to environment/food/medicine/bioassay determination techniques and chemical sensitisation/analysis fields, specifically relate to
And the method adsorbed carbon dioxide adsorption using conjugated polymer and boron nitride composite and monitor its slow release.
Background technique
Carbon dioxide (CO2) as a kind of common gas, it has very important significance for every vital movement.Greatly
CO in gas2It is life on earth body as primary carbon source available in carbon cycle, content in an atmosphere is mainly planted
Object, the adjusting of the nature geological phenomenon such as the organisms such as algae photosynthesis and volcano.CO2It is most important greenhouse in earth atmosphere
Gas, high speed development of the modern age with human society, CO2Discharge gradually increase-burning mainly from fossil fuel and vapour
CO in discharge-atmosphere of tail gas2Concentration increase sharply, cause Global Temperature to increase, cause " greenhouse effects ".Also, because
Its is water-soluble to lead to Ocean acidification, can also cause irrecoverability to destroy the ecosystem.Meanwhile in higher concentration, two
Carbonoxide has acidic smell, and causes tremendous influence to human health, for example, stimulation respiratory tract even death by suffocation.Therefore,
For CO2The detection of release process seems particularly significant, CO2Detection absorption and slow release research increasingly by researcher
Attention.
Currently, the wide CO used2Determination method usually require large-scale experiment instrument, instrument cost and people
Work is relatively expensive, cannot achieve detection real-time to ambient enviroment, inexpensive.The fluorescence signal that conjugated polymer has is put
The ability of big function and strong capture light, assigns detection architecture higher sensitivity, be widely used in pathogenic microorganism, metal ion,
The highly sensitive diagnosis of small molecule compound and disease associated biomarkers and detection field.In recent years, with to novel thorn
The research for swashing response conjugated polymer deepens continuously, and scientific research personnel develops a series of multi-functional conjugated polymers.But altogether
Conjugated polymer there are still some drawbacks in processability, such as in terms of structural modification, the introducing of photosynthesis-carbon dioxide response group
The preparation cost of polymer can be improved.
Summary of the invention
An object of the present invention is to provide a kind of conjugated polymer and boron nitride composite.
Conjugated polymer and boron nitride composite provided by the present invention, conjugated polymer and boron nitride as shown in Formulas I
Composition.
In above-mentioned Formulas I, n represents the degree of polymerization, n=4~25, and concretely 7~22；X+y+z=1, x=0.80~0.97, y
=0.01~0.2, z=0~0.1, m=1~12, concretely 3, q=2~12, concretely 2；X is C element, N element, Si
Element, concretely C element；Y is C element, N element, concretely C element；Z is C element, N element, concretely C element；
R1It can be selected from any one in following radicals:
Specifically:
Specifically, conjugated polymer shown in above-mentioned Formulas I is polymer shown in Formula II:
In above-mentioned Formula II, x+y=1, x:y=19:1 (x=0.95, y=0.05, z=0), n=4~25.
In above-mentioned conjugated polymer and boron nitride composite, the mass ratio of conjugated polymer and boron nitride shown in Formulas I can
For 1:1-1:10, concretely 1:1.
Above-mentioned conjugated polymer and boron nitride composite are in absorption carbon dioxide and monitoring carbon dioxide slow release
Application also belong to protection scope of the present invention.
Dioxy is adsorbed using above-mentioned conjugated polymer and boron nitride composite it is a further object of the present invention to provide a kind of
The method changed carbon and monitor carbon dioxide slow release.
Absorption carbon dioxide provided by the present invention and the method for monitoring carbon dioxide slow release, it is a series of comprising detecting
CO2Concentration and polymer and the change in fluorescence relationship for nitrogenizing boron compound, concrete operations are as follows:
(1) conjugated polymer shown in Formulas I is dissolved in water, obtains the aqueous solution of conjugated polymer；
(2) boron nitride is distributed in water, obtains boron nitride dispersion；
(3) a series of CO of known concentrations is prepared2Aqueous solution；
(4) by a series of CO of known concentrations2Aqueous solution distinguishes the water with the conjugated polymer in step (1) one by one
Boron nitride dispersion in solution and step (2) is mixed with identical volume ratio, obtains a series of CO2Concentration is different
Mixed solution containing conjugated polymer and nitridation boron compound；
(5) in the case where exciting light action, fluorescence measurement is carried out to a series of mixed solutions obtained in step (4), is remembered respectively
The fluorescence emission spectrum of conjugated polymer in a series of mixed solutions is recorded, and calculates its FRET ratio；
Wherein, the FRET ratio refers to containing different CO2The fluorescence resonance energy of conjugated polymer in the solution of concentration turns
The fluorescence intensity ratio of two special receptors and donor peak value that move；
(6) in a series of mixed solutions according to obtained in step (5) the FRET ratio of conjugated polymer and its
CO in corresponding mixed solution2Concentration, make FRET ratio with CO2The curve of concentration variation.
(7) curve of obtained curve and non-nitrogen boron is done into difference, difference and the CO2Non- nitrogen boron under concentration
The ratio of FRET ratio is composite material CO absorption2Percentage.
In above method step (1), the concentration of the conjugated polymer in the aqueous solution of the conjugated polymer can for 0.1~
20mg/mL；Concretely 0.5mg/mL.
In step (2), the concentration of the boron nitride in the boron nitride dispersion can be 0.1~20mg/mL；Concretely
1.0mg/mL。
In step (3), a series of CO of known concentrations2Aqueous solution can be prepared by following methods: first prepare saturation
CO2Aqueous solution, then by the saturation CO2Aqueous solution is mixed with ultrapure water by different proportion, obtains a series of evenly spaced 0
The CO of~saturated concentration2Aqueous solution, i.e., the CO of a series of known concentrations2Aqueous solution, wherein the concentration interval can for 0.10~
20mM。
Specifically, a series of known concentrations be concretely and sequentially 0mM, 0.15mM, 0.30mM, 0.45mM, 0.60mM,
0.75mM、0.90mM、1.50mM、3.00mM。
In step (4), the volume ratio concretely: the volume of the aqueous solution of conjugated polymer: boron nitride dispersion
Volume: CO2The volume of aqueous solution=10.0 μ L:5.0 μ L:485 μ L.
A series of CO2In the different mixed solutions containing conjugated polymer and nitridation boron compound of concentration, conjugation
The mass ratio of polymer and boron nitride can be 1:1-1:10, concretely 1:1.
In step (5), the wavelength of the exciting light can be 375-450nm, concretely 380nm.
In step (5), the FRET ratio is fluorescence of the conjugated polymer at 531nm wavelength in the mixed solution
Intensity I2With fluorescence intensity I of the conjugated polymer in the mixed solution at 418nm wavelength1Ratio, it may be assumed that I2/I1
In step (6), by obtained curve, there are CO with individual polymer (being free of boron nitride i.e. in system)2The case where
The curve comparison measured after lower incubation, FRET ratio decrease, and illustrate the ability that composite material has absorption carbon dioxide.
Absorption carbon dioxide provided by the present invention and the method for monitoring carbon dioxide slow release, are also fixed comprising detection
Concentration C O2It acts on lower polymer and nitrogenizes the change in fluorescence relationship that boron compound changes with incubation time, concrete operations are as follows:
1) conjugated polymer shown in Formulas I is dissolved in water, obtains the aqueous solution of conjugated polymer；
2) boron nitride is distributed in water, obtains boron nitride dispersion；
3) arbon dioxide solution of any known concentration is prepared；
4) by the aqueous solution of the conjugated polymer in the arbon dioxide solution of any known concentration and step 1) with
And the boron nitride dispersion in step 2) is mixed in fixed volume ratio, obtains fixed CO2Concentration contains conjugated polymer
With the mixed solution containing conjugated polymer and nitridation boron compound of the mixed solution of nitridation boron compound；
5) in the case where exciting light action, fluorescence measurement is carried out to mixed solution obtained in step (4), when recording different incubations
Between the mixed solution in conjugated polymer fluorescence emission spectrum, and calculate its FRET ratio；
6) in the mixed solution according to obtained in step 5) the FRET ratio of conjugated polymer and its corresponding incubate
The time is educated, the curve that FRET ratio changes with incubation time is made.
7) the FRET value that the corresponding FRET value of any incubation time of above-mentioned curve and incubation time are 0min is done into difference,
The ratio for the FRET value that difference and incubation time are 0min is that composite material discharges CO2Percentage.
In above method step 1), in the aqueous solution of the conjugated polymer concentration of conjugated polymer can for 0.1~
20mg/mL；Concretely 0.5mg/mL.
In step 2), the concentration of boron nitride can be 0.1~20mg/mL in the boron nitride dispersion；Concretely
1.0mg/mL。
In step 3), the arbon dioxide solution of any known concentration concretely CO2Concentration is the two of 0.75mM
Carbonoxide aqueous solution.
The volume ratio is concretely: the volume of the aqueous solution of conjugated polymer: the volume of boron nitride dispersion: CO2Water
The volume of solution=10.0 μ L:5.0 μ L:485 μ L.
In step 5), the wavelength of the exciting light is 375-450nm, concretely 380nm.
In step 6), as time went on, FRET transfer constantly increases obtained curve, illustrates have carbon dioxide constantly to release
It puts, FRET is caused to increase；Individual polymer and CO2The FRET of system constantly drops at any time after aqueous solution incubation different time
It is low.
The absorption of the composite material of polymer and boron nitride and release CO2It is to be obtained by two processes: first, control the time
It is constant, change CO2Concentration, composite material and polymer carry out the comparison of FRET ratio, and composite material FRET ratio is relatively low, says
Bright CO2It is adsorbed by composite material；Second, control CO2Concentration is constant, changes incubation time, and composite material and polymer carry out FRET
Ratio comparison, composite material FRET ratio extend at any time and increase, and polymer is then to reduce, and illustrate composite material absorption
CO2It is slowly released, and polymer is then without this performance.
The present invention also provides a kind of supermolecule polymer systems.
The supermolecule polymer system, is prepared via a method which to obtain:
Arbon dioxide solution is mixed with the aqueous solution of conjugated polymer shown in Formulas I and boron nitride dispersion, is incubated for,
During this, carbon dioxide is first adsorbed, then slow release, and the carbon dioxide released promotes conjugated polymer shown in Formulas I
It is further assembled with boron nitride by hydrophobic effect and electrostatic interaction, forms supermolecule polymer system.
Inventor has found that the conjugated polymer can specifically respond carbon dioxide according to research, is based on carbon dioxide pair
The effective absorption of the special fluorescent quenching effect of the conjugated polymer and boron nitride (BN) to carbon dioxide, thus by the stimulation
It responds conjugated polymer and boron nitride composite is applied to absorption carbon dioxide and detects the process of carbon dioxide slow release.
Substantive distinguishing features of the invention are as follows: the composite material formed using conjugated polymer and boron nitride passes through composite wood
Expect the property of the carbon dioxide stimuli responsive of the absorption and conjugated polymer to carbon dioxide, realizes composite material to titanium dioxide
The detection of carbon adsorption and slow release process.Meanwhile in this process, the carbon dioxide of release promotes stimuli responsive to be conjugated
Polymer and boron nitride are further assembled by hydrophobic effect and electrostatic interaction, form supermolecule polymer system, into
And regulate and control the coherent condition or conformation of conjugated polymer and boron nitride by carbon dioxide.Pass through energy between polymer chain or in chain
The change for measuring transfer efficiency develops the CO of fluorescence resonance energy transfer (FRET) technology based on aggregation inducing2Intelligent response material
With sensing system, detect to CO2Absorption and slow release process.
With traditional CO2Detection adsorption method is compared, and the present invention, which has, handles quick, easy, highly sensitive and specificity
The characteristics of；Compared with various advanced systems, for the present invention without complicated instrument and equipment, sample treatment is simple, at low cost.Cause
This, the present invention has application value in medicine/food/environment/bioassay determination techniques and chemical sensitisation/analysis field.
Detailed description of the invention
Fig. 1 contains different CO for what is measured in the embodiment of the present invention 12The conjugated polymer and boron nitride composite of concentration
Fluorescence spectrum.
Fig. 2 is difference CO in the embodiment of the present invention 22Concentration exists with polymer P FBT and there is no the FRET of boron nitride ratios
The relationship comparison diagram of value.
Fig. 3 is the conjugated polymer and boron nitride composite slow release carbon dioxide measured in the embodiment of the present invention 3
Fluorescence FRET ratio change over time relational graph.Wherein, the polymer that Fig. 3 a is free from boron nitride changes with incubation time
Fluorescence emission spectrum, Fig. 3 b is the fluorescence emission spectrum that the composite material of polymer and boron nitride changes with incubation time, figure
3c is to calculate fluorescence intensity ratio of Fig. 3 a and Fig. 3 b in 531nm and 418nm (to be abbreviated as (I531nm/I418nm))。
Fig. 4 is the SEM that conjugated polymer and boron nitride composite are passed through carbon dioxide assembling in the embodiment of the present invention 4
Figure.
Specific embodiment
The present invention will be described below by way of specific embodiments, but the present invention is not limited thereto.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments
Reagent, material etc., are commercially available unless otherwise specified.
Following embodiments are based on polymer shown in Formula II and carry out experiment detection.
Formula II compound is prepared by the method comprising the following steps:
By 1,3- dibromopropane (2.3ml, 22.61mmol) and 2,7- dibromo fluorenes (0.5g, 1.55mmol) is mixed and heated to
60 DEG C, TBAB (tetrabutylammonium bromide) (0.14g, 0.43mmol) is sequentially added into mixture and KOH (10ml, 50%) is molten
Liquid, and 75 DEG C are heated to, it stirs 20 minutes, then cools to room temperature and organic layer is used into H respectively2O, 1M HCl and H2O washing, is used
Methylene chloride repeatedly extracts mixture, then dry with anhydrous sodium sulfate, and vacuum distillation removes solvent and excessive 1,3- dibromo
Propane obtains mixture petroleum ether/methylene chloride (9:1) white as eluant, eluent by silica gel chromatographic column method purified product
Color solid (compound 2).
Under nitrogen protection, by compound 2 and sodium azide (NaN3) and dimethyl sulfoxide be placed in flask, at 70 DEG C
Lower mixing 8h.After being cooled to room temperature, suitable quantity of water is added, is extracted with chloroform, organic layer is washed with water, and then uses anhydrous slufuric acid
Magnesium is dry.Remaining DMSO is removed under reduced pressure and passes through silica gel color by mixture petroleum ether/methylene chloride (9:1) as eluant, eluent
Column method purified product is composed, white solid (compound 3) is obtained.
By 3 (0.03g, 0.061mmol), tetrahydrofuran (0.03g, 0.137mmol), water and triphenylphosphine (PPh3)
0.04g, 0.153mmol) it is stirred at room temperature 12 hours, solvent is removed, residue is dried under vacuum.By residue and two carbon
Sour di tert butyl carbonate is dissolved in tetrahydrofuran, and the solution is stirred at room temperature 12 hours.Solvent, petroleum ether/second is removed under reduced pressure
Acetoacetic ester (3:1) obtains faint yellow solid (compound 4) by column chromatography purified product for solvent.
By hydrochloric acid (1.5mL, 37%), compound 4 (0.25g, 0.39mmol) and methylene chloride 16mL are added to round bottom
In flask.Mixture is stirred 16 hours at 50 DEG C.After being cooled to room temperature, solvent is removed under reduced pressure.Residue is dissolved in
In methanol, and the KOH solution of addition 26%.Methanol is removed, residue is extracted with dichloromethane.Organic layer is washed with water, so
It is dry with anhydrous magnesium sulfate afterwards.Solvent is removed, in methyl alcohol by residue dissolution.And methyl acrylate is added into this solution
(0.175ml), boric acid (2.45mg) and water.Mixture is stirred at room temperature 12 hours.Remove solvent and excessive propene acid first
Ester, residue are extracted with dichloromethane.Organic layer is washed with water and dry with anhydrous magnesium sulfate.After removing methylene chloride, use
Residue (1:1) is used as eluant, eluent, isolated grease (monomer 5) by petrol ether/ethyl acetate.
The synthesis of PFBT (compound shown in Formula II): under nitrogen protection, monomer 5 (100mg, 0.128mmol), 2,2- diformazans
Base -1,3-PD-Isosorbide-5-Nitrae-benzene diborate (40.77mg, 0.135mmol), 4,7- bis- bromo- 2,1,3- diazosulfide
(2.06mg, 0.007mmol) is added in 2mL toluene, and the Na of 1.6mL is added after dissolution2CO3The palladium of solution (2.0M) and catalytic amount
Catalyst PdCl2(dppf) (10mg) is warming up to 85 DEG C and reacts two days after mixing.After reaction solution is cooled to room temperature, solvent is removed
Afterwards, methanol is added.Solution is added in acetone, sediment is obtained.The NaOH that sediment is re-dissolved in methanol and 3mL is water-soluble
Liquid (9.1%).Mixture is stirred 12 hours at 50 DEG C.After being cooled to room temperature, methanol is removed, obtained mixture is seeped
Analysis bag dialysis three days (M=3500g/mol) obtains brown solid.
Embodiment 1, detection conjugated polymer and boron nitride composite and various concentration CO2The fluorescence spectrum of effect
(a) CO is prepared in the environment of mixture of ice and water2Saturated aqueous solution: be continuously continually fed into ultrapure water pure
CO2Gas 30min or more obtains the CO of saturation2Aqueous solution, at this time CO2Concentration be 74.94mM；
(b) CO will be saturated2Aqueous solution is mixed with ultrapure water by different proportion, is made a series of containing different CO2The mark of concentration
Quasi- solution (0mM, 0.15mM, 0.30mM, 0.45mM, 0.60mM, 0.75mM, 0.90mM, 1.50mM, 3.00mM)；
(c) 10.0 μ LPFBT (0.5mg/mL) and 5.0 μ LBN (1.0mg/mL) are added in 485 μ L steps (b) respectively
The CO of various concentration2In solution；
(d) with sepectrophotofluorometer or the fluorescence spectrum of the sample of multi-function microplate reader measuring process (c), excitation wavelength
For 380nm；Emission spectrum is 390-700nm；
Fig. 1 is the conjugated polymer measured in the embodiment of the present invention 1 and boron nitride composite and different CO2Concentration effect
Fluorescence spectrum, it can be seen from the figure that with CO2The FRET ratio of the raising of concentration, conjugated polymer gradually rises.
Embodiment 2, difference CO2Concentration exists with polymer P FBT and there is no the fluorescence intensity FRET ratios of boron nitride
(I531nm/I418nm) relationship comparison diagram
According to the fluorescence spectrum that step (d) obtains in embodiment 1, the fluorescence intensity ratio in 531nm and 418nm is calculated
(it is abbreviated as (I531nm/I418nm)), ratio is bigger to illustrate that polymer P FBT fluorescence resonance energy transfer is bigger, is quenched brighter
It is aobvious.
Fig. 2 is CO2Concentration exists with polymer P FBT and there is no the relationship comparison diagrams of the FRET ratio of boron nitride.
As shown in Figure 2, FRET ratio is bigger illustrates CO2Concentration it is higher.The case where comparison exists and boron nitride is not present
Under, FRET ratio decreases, and illustrates a portion CO2It is adsorbed by composite material.
The fluorescence of embodiment 3, stimuli responsive conjugated polymer and boron nitride composite detection slow release carbon dioxide
Spectrum and FRET ratio change over time relational graph
Gas concentration lwevel is 0.75mM, the volume of the aqueous solution of conjugated polymer: the volume of boron nitride dispersion: CO2
The volume of aqueous solution=10.0 μ L:5.0 μ L:485 μ L.
Fig. 3 is that the stimuli responsive conjugated polymer measured in the embodiment of the present invention 3 and boron nitride composite detection are slow
The fluorescence FRET ratio of release carbon dioxide changes over time relational graph.
Fig. 3 a is free from the fluorescence emission spectrum that the polymer of boron nitride changes with incubation time, Fig. 3 b be polymer and
The fluorescence emission spectrum that the composite material of boron nitride changes with incubation time,
Fig. 3 c is to calculate fluorescence intensity ratio of Fig. 3 a and Fig. 3 b in 531nm and 418nm (to be abbreviated as (I531nm/I418nm))。
It can be seen that the extension with incubation time from Fig. 3 c, the FRET ratio of the polymer without boron nitride is at any time
Between be in decreasing trend, the FRET ratio of the composite material of polymer and boron nitride is in raised trend at any time.Illustrate CO2Constantly
It is released from composite material, and it is caused further to have an effect with stimulus responsive polymers, and this process will promote
So that polymer and boron nitride is further passed through electrostatic and hydrophobic effect assembling, and forms super-molecule assembling body.
Embodiment 4, observation stimuli responsive conjugated polymer and boron nitride are passed through CO2Assembling afterwards
Using the observation apparent form of scanning electron microscope, it is necessary first to (refer specifically to be passed through carbon dioxide sample
Polymer and nitridation boron compound) freeze-drying, finally observe the microstructure of assembly.
Fig. 4 is the SEM figure that stimuli responsive conjugated polymer and boron nitride composite are passed through carbon dioxide assembling.
Fig. 4 a is not to be passed through CO2Polymer/boron nitride composite, Fig. 4 b is to be passed through CO2Polymer/boron nitride it is multiple
Condensation material assembly.By pattern comparative illustration, it is passed through CO2Afterwards, hence it is evident that discovery polymer aggregational is to boron surface is nitrogenized, but still
It is clear that boron nitride fiber skeleton, further proves CO2It can promote the assembling of polymer and boron nitride.
Claims (10)
1. a kind of conjugated polymer and boron nitride composite, conjugated polymer and boron nitride shown in Formulas I are formed,
In Formulas I, n represents the degree of polymerization, n=4~25；X+y+z=1, x=0.80~0.97, y=0.01~0.2, z=0~0.1,
M=1~12, q=2~12；X is C element, N element, Si element；Y is C element, N element；Z is C element, N element；R1It is selected from
Any one in following radicals:
2. conjugated polymer according to claim 1 and boron nitride composite, it is characterised in that: conjugation shown in Formulas I is poly-
The mass ratio for closing object and boron nitride is 1:1-1:10.
3. conjugated polymer of any of claims 1 or 2 and boron nitride composite are in absorption carbon dioxide and monitoring titanium dioxide
Application in carbon slow release.
4. a kind of absorption carbon dioxide and the method for monitoring carbon dioxide slow release, comprising detecting a series of CO2Concentration with polymerize
The change in fluorescence relationship of object and nitridation boron compound；
It operates as follows:
(1) conjugated polymer shown in Formulas I is dissolved in water, obtains the aqueous solution of conjugated polymer；
(2) boron nitride is distributed in water, obtains boron nitride dispersion；
(3) a series of CO of known concentrations is prepared2Aqueous solution；
(4) by a series of CO of known concentrations2Aqueous solution distinguishes the aqueous solution with the conjugated polymer in step (1) one by one
And the boron nitride dispersion in step (2) is mixed with identical volume ratio, obtains a series of CO2Concentration is different to be contained
The mixed solution of conjugated polymer and nitridation boron compound；
(5) in the case where exciting light action, fluorescence measurement is carried out to a series of mixed solutions obtained in step (4), records institute respectively
A series of fluorescence emission spectrum of conjugated polymer in mixed solutions is stated, and calculates FRET ratio；
Wherein, the FRET ratio refers to containing different CO2The two of the fluorescence resonance energy transfer of conjugated polymer in the solution of concentration
The fluorescence intensity ratio of a special receptor and donor peak value；
(6) the FRET ratio of conjugated polymer and its correspondence in a series of mixed solutions according to obtained in step (5)
Mixed solution in CO2Concentration, make FRET ratio with CO2The curve of concentration variation.
(7) curve of obtained curve and non-nitrogen boron is done into difference, difference and the CO2Non- nitrogen boron FRET under concentration
The ratio of ratio is composite material CO absorption2Percentage.
5. absorption carbon dioxide as claimed in claim 4 and the method for monitoring carbon dioxide slow release, further includes: detection is fixed
Concentration C O2It acts on lower polymer and nitrogenizes the change in fluorescence relationship that boron compound changes with incubation time, operate as follows:
1) conjugated polymer shown in Formulas I is dissolved in water, obtains the aqueous solution of conjugated polymer；
2) boron nitride is distributed in water, obtains boron nitride dispersion；
3) arbon dioxide solution of any known concentration is prepared；
4) by the aqueous solution and step of the conjugated polymer in the arbon dioxide solution of any known concentration and step 1)
It is rapid 2) in boron nitride dispersion mixed in fixed volume ratio, obtain fixed CO2Concentration contains conjugated polymer and nitrogen
Change the mixed solution containing conjugated polymer and nitridation boron compound of the mixed solution of boron compound；
5) in the case where exciting light action, fluorescence measurement is carried out to mixed solution obtained in step 4), records different incubation times
The fluorescence emission spectrum of conjugated polymer in the mixed solution, and calculate FRET ratio；
6) the FRET ratio of conjugated polymer and when its corresponding incubation in the mixed solution according to obtained in step 5)
Between, make the curve that FRET ratio changes with incubation time.
7) difference for the FRET value for being 0min by the corresponding FRET value of any incubation time of above-mentioned curve and incubation time, difference
Ratio with the FRET value that incubation time is 0min is that composite material discharges CO2Percentage.
6. method according to claim 4 or 5, it is characterised in that: step (1) or 1) in, the conjugated polymer it is water-soluble
The concentration of conjugated polymer is 0.1~20mg/mL in liquid；
Step (2) or 2) in, the concentration of the boron nitride in the boron nitride dispersion is 0.1~20mg/mL.
7. method according to claim 4, it is characterised in that: in step (3), a series of CO of known concentrations2Aqueous solution passes through
Following methods are prepared: first preparing saturation CO2Aqueous solution, then by the saturation CO2Aqueous solution and ultrapure water press different proportion
Mixing, obtains a series of CO of evenly spaced 0~saturated concentrations2Aqueous solution, i.e., the CO of a series of known concentrations2Aqueous solution,
Wherein, the concentration interval is 0.10~20mM.
8. method according to claim 4 or 5, it is characterised in that: step (4) or 4) in, the volume ratio are as follows: conjugated polymers
The volume of the aqueous solution of object: the volume of boron nitride dispersion: CO2The volume of aqueous solution=10.0 μ L:5.0 μ L:485 μ L.
9. method according to claim 4 or 5, it is characterised in that: step (5) or 5) in, the wavelength of the exciting light is
375-450nm；
The FRET ratio is fluorescence intensity I of the conjugated polymer at 531nm wavelength in the mixed solution2It is mixed with described
Close fluorescence intensity I of the conjugated polymer in solution at 418nm wavelength1Ratio, it may be assumed that I2/I1。
10. a kind of supermolecule polymer system, is prepared via a method which to obtain:
Arbon dioxide solution is mixed with the aqueous solution of conjugated polymer shown in Formulas I and boron nitride dispersion in claim 1,
It is incubated for, in the process, carbon dioxide is first adsorbed, then slow release, and the carbon dioxide released promotes conjugation shown in Formulas I
Polymer and boron nitride are further assembled by hydrophobic effect and electrostatic interaction, form supermolecule polymer system.
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