CN109054805A - A kind of preparation method of the fluorescence cholesteric phase Cellulose nanocrystal body thin film with Acid-base Gas response - Google Patents
A kind of preparation method of the fluorescence cholesteric phase Cellulose nanocrystal body thin film with Acid-base Gas response Download PDFInfo
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 32
- 239000001913 cellulose Substances 0.000 title claims abstract description 32
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 230000003098 cholesteric effect Effects 0.000 title claims abstract description 19
- 230000004044 response Effects 0.000 title claims abstract description 18
- 239000010409 thin film Substances 0.000 title claims abstract description 17
- 239000010408 film Substances 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 37
- 239000000725 suspension Substances 0.000 claims abstract description 26
- 238000013019 agitation Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 14
- 239000000835 fiber Substances 0.000 claims abstract description 10
- 230000006698 induction Effects 0.000 claims abstract description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 3
- 239000006194 liquid suspension Substances 0.000 claims abstract 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 150000003384 small molecules Chemical group 0.000 claims description 12
- -1 Oxazine compound Chemical class 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 4
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- UVHXEHGUEKARKZ-UHFFFAOYSA-N 1-ethenylanthracene Chemical class C1=CC=C2C=C3C(C=C)=CC=CC3=CC2=C1 UVHXEHGUEKARKZ-UHFFFAOYSA-N 0.000 claims description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 230000001276 controlling effect Effects 0.000 claims description 3
- 238000002189 fluorescence spectrum Methods 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 6
- 238000005191 phase separation Methods 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 2
- 230000000737 periodic effect Effects 0.000 abstract description 2
- 230000000717 retained effect Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 239000012071 phase Substances 0.000 description 13
- 235000010980 cellulose Nutrition 0.000 description 12
- 239000002585 base Substances 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000000502 dialysis Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 210000000232 gallbladder Anatomy 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004038 photonic crystal Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003431 steroids Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- MUGVFODJPVTKOB-WGDLNXRISA-N 4-[(E)-2-[10-[(E)-2-pyridin-4-ylethenyl]anthracen-9-yl]ethenyl]pyridine Chemical compound N1=CC=C(C=C1)/C=C/C=1C2=CC=CC=C2C(=C2C=CC=CC=12)\C=C\C1=CC=NC=C1 MUGVFODJPVTKOB-WGDLNXRISA-N 0.000 description 1
- UOSROERWQJTVNU-UHFFFAOYSA-N 9,10-bis(chloromethyl)anthracene Chemical compound C1=CC=C2C(CCl)=C(C=CC=C3)C3=C(CCl)C2=C1 UOSROERWQJTVNU-UHFFFAOYSA-N 0.000 description 1
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000009610 hypersensitivity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- GCSHUYKULREZSJ-UHFFFAOYSA-N phenyl(pyridin-2-yl)methanone Chemical compound C=1C=CC=NC=1C(=O)C1=CC=CC=C1 GCSHUYKULREZSJ-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
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- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
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Abstract
The invention discloses a kind of preparation method of fluorescence cholesteric phase Cellulose nanocrystal body thin film with Acid-base Gas response, 1) prepare Cellulose nanocrystal liquid suspension；2) AIE organic micromolecule fluorescent material is synthesized；3) AIE class fluorescence suspension is made；4) Cellulose nanocrystal liquid suspension is mixed with AIE organic micromolecule fluorescent material, after magnetic agitation, ultrasonic treatment；5) it is evaporated induction assembling process altogether, obtains the fluorescent fiber element film with cholester structure.The present invention solves the problem of phase separation of Cellulose nanocrystal body Yu water-insoluble small organic molecule fluorescent material, so that cholester structure is retained, successfully prepares the fluorescent color film with periodic structure.This laminated film for having both fluorescent characteristic and cholester structure shows the variation of fluorescence, visible light and a variety of optical characteristics of circularly polarized light under acid, alkaline atmosphere, can accurately and efficiently be applied to acid, alkaline gas detection, can be with repeated recycling utilize.
Description
Technical field
The invention belongs to optics and technical field of composite materials, are related to a kind of gas response and Ke Xunhuanliyong high efficiency
Sensor, the in particular to system of the cholesteric phase Cellulose nanocrystal body thin film with fluorescent characteristic sensitive to acid, alkaline gas
It is standby.
Background technique
With industrialized fast development, various toxic and harmful gas and pollution dust are discharged into atmosphere, this is to people
Class and environment cause significant damage.Wherein, the harm of acid-base property exhaust gas is especially serious, generates in numerous industries.Severe
Volatile gas such as hydrochloric acid, ammonia etc. is also always the environmental problem of global concern, therefore, for the day of acidic and alkaline gas
Often monitoring is highly important.
Known Conventional electrochemical gas sensor usually selects metal oxide and conducting polymer as sensing material,
This is because the characteristic that this kind of material has hypersensitivity and selectively detects.However, many sensors with auxiliary electrode operations are more complex
And it is costly, which limits it effectively to implement and develop.Therefore, a kind of with easy to operate, highly sensitive there is an urgent need to develop
The gas response sensor of degree, cheap, stable circulation and environmentally friendly feature.
Cellulose can be formed as natural reproducible macromolecule the most abundant on the earth after the processing such as sour water solution
Cellulose nanocrystal body (cellulose nanocrystal, CNC) molten cause cholesteric liquid crystal, after evaporation drying forms a film, cholesteric
Phase structure is still retained, and the characteristic of photonic crystal is shown, and can choose the light of sexual reflex specific wavelength, this characteristic
It makes it possible to and is applied to sensory field.Small organic molecule fluorescent material is many kinds of, and structure is easy to adjust, and photoelectric property is thus
It can change, some of organic fluorescence materials have stronger responsiveness to soda acid, such as sour gas can lead to certain
Fluorescent quenching occurs for kind of organic fluorescence small molecule, this allows for it in terms of gas detection with good application prospect.
Different from the fluorescence detector of single characteristic traditional in patent CN102702558B, we are by CNC film gallbladder here
The photonic crystal properties of steroid phase structure and the fluorescent characteristic of small organic molecule fluorescent material combine, organic glimmering improving
While the machinability and application of light small molecule, the more accurate detection of this material is also gived.Preparing composite wood
When material, the compatibility of presoma and basis material is firstly the need of solving the problems, such as.With carbon quantum dot, terres rares up-conversion luminescence
The fluorescent materials such as material and plasmon Gold nanoparticle difference soluble easily in water, most small organic molecule fluorescent material are dissolved only in
Organic solvent, and CNC suspension is present in aqueous phase system, if only CNC and small organic molecule fluorescent material simply mixed
It is combined, it will phenomenon of phase separation occur.And the method generallyd use be CNC is transferred to using solvent displacement it is organic molten
It in agent, then mixes with small organic molecule fluorescent material, still an alternative is that being connect organic fluorescence small molecule by chemical modification
Branch arrives the surface of CNC.Both methods is more complex, time-consuming and laborious, and cholester structure is difficult to retain after mixing.Therefore, exist
Small organic molecule fluorescent material there are while, guarantee CNC remain to complete self assembly be problem to be solved.
Summary of the invention
Cause sensor operations more complex for fluorescence detecting sensor single characteristic in the prior art and costly
Problem, the purpose of the present invention is to provide a kind of fluorescence cholesteric phase Cellulose nanocrystal body thin films with Acid-base Gas response
Preparation method prepares a variety of optical characteristics detections of achievable Acid-base Gas and Ke Xunhuanliyong fluorescence cholesteric phase CNC film.
The transducer sensitivity is high, and the accurate detection of acid, alkaline gas may be implemented.
The technical scheme adopted by the invention is as follows:
A kind of preparation method of the fluorescence cholesteric phase Cellulose nanocrystal body thin film with Acid-base Gas response, specifically includes
Following steps:
1) CNC suspension is prepared using sulphuric acid hydrolysis or TEMPO oxidative treatment cellulose；
Sulphuric acid hydrolysis prepares the molten cause N*-LCs suspension of nano-cellulose: being with mass fraction by microcrystalline cellulose powder
64% sulfuric acid is mixed according to the ratio of 1g:17.5ml, is heated and is stirred to react 0.5-1.5h at 40-50 DEG C, is added
A large amount of deionized water terminates reaction, then by excessive acid in centrifugation and dialysis removal solution, using high-power ultrasonics pair
It is ultrasonically treated, and the molten cause N*-LCs suspension of nano-cellulose of different screw pitch is obtained after concentration；Its large power supersonic
The power bracket of wave processing is 100-1200W, operating frequency range 21-25KHz, time range 1-180min, amplitude transformer
Diameter is 2-30mm；
2) have by chemical reactive synthesis aggregation-induced emission (aggregation-induced emission, AIE) class
Machine small molecule fluorescent material ((2- phenyl -2- (2- the pyridyl group)) vinyl anthracene of 9,10- bis- (9,10-bis ((E) -2-phenyl-
2- (pyridin-2-yl) vinyl) anthracene, BPP2VA), 9,10- bis- (p- pyridine vinyl) anthracenes ((9,10-bis
((E) -2- (pyridin-4-yl) vinyl) anthracene, BP4VA), tetraphenyl ethylene oxazolidine
(tetraphenylethyleneoxazoline, TPE-OX) etc.), AIE organic micromolecule fluorescent material is dissolved in respective
In good solvent, being configured to concentration is 10-3The solution of mol/L；
3) solution prepared in a certain amount of step 2) is pipetted, is added drop-wise in a certain amount of deionized water dropwise, magnetic agitation
It is to be mixed for a period of time uniformly after, AIE class fluorescent small molecule forms stable Micelle-like Nano-structure of Two in water, be made AIE class fluorescence
Suspension；
4) mixed proportion different from AIE organic micromolecule fluorescent material according to CNC suspension, takes a certain amount of step 1)
The CNC suspension of middle preparation is added drop-wise to dropwise in AIE class fluorescence suspension made from step 3), magnetic agitation for a period of time to
It is uniformly mixed after stablizing, by ultrasonic treatment, the screw pitch of cholester structure is regulated and controled；
5) it takes mixing suspension obtained in step 4) to be placed in polystyrene ware, stands at normal temperature, be evaporated and lure
Total assembling process is led, the fluorescent fiber element film with cholester structure can be obtained after 3-5 days.
Further, in the step (2) there are many AIE organic micromolecule fluorescent materials, such as spiropyran or spiral shell
Oxazine compound is (9,10- bis- (2- phenyl -2- (2- pyridyl group)) vinyl anthracenes, 9,10- bis- (p- pyridine vinyl)
Any one in anthracene, tetraphenyl ethylene oxazolidine.
Further, in the step (3) during magnetic agitation, the small magneton of diameter 5mm long 10mm is selected, it is accurate to control
The velocity interval for making this process magnetic agitation is 500-1500rpm, to prevent fluorescent material precipitation to be hanging on chamber wall；Control
The magnetic agitation time, until observing apparent Tyndall phenomenon.
Further, in the step (4) during magnetic agitation, the small magneton of diameter 5mm long 10mm is selected, it is accurate to control
The velocity interval for making this process magnetic agitation is 500-1500rpm, controls the magnetic agitation time, prevents the generation mutually separated.
Further, the condition being ultrasonically treated in the step (4) is ice water bath environment, 60W power, time 1-15min.
Further, the fluorescent fiber element laminated film being prepared in the step (5) is placed under volatile acid atmosphere,
Its cholester structure screw pitch changes the variation for causing film color, and fluorescence intensity can also weaken；Under alkaline atmosphere, gallbladder
The variation of steroid phase structure screw pitch causes the variation of film color to restore, and corresponding uv-vis spectra and fluorescence spectrum generation are regular
Variation.
Further, the sour gas is in volatile acid nitric acid, formic acid, acetic acid, trifluoroacetic acid or hydrobromic acid
Any one.
Further, the alkaline gas is any one in volatile base ammonium hydroxide, diethylamine or triethylamine.
Further, the cholester structure for the fluorescent fiber element THIN COMPOSITE being prepared in the step (5) has photon
Forbidden band effect, the variation of screw pitch will lead to the variation of circularly polarized light.
Further, in the step (4) additive amount of AIE organic micromolecule fluorescent material solution in 100-1000 μ L
In range, best dripping quantity is between 200-600 μ L, this is amount (3-10g) determination based on deionized water in suspension, such as
Fruit additive amount, which is excessively easy to happen, mutually to be separated.
Further, the range of solid content of added CNC is 0.1-0.3g in the step (4), and optimum addition exists
Between 0.15-0.2g, this is amount (3-10g) determination based on deionized water in suspension, very few to be not easy to form a film, excessive film
Too thick influence fluorescent effect.
The invention has the benefit that
In the present invention, we select AIE organic micromolecule fluorescent material, it is therefore an objective to assemble after preventing drying and forming-film
Induction quenching (aggregation caused quenching, ACQ) phenomenon, and by accurate rationally control CNC with it is organic small
The ratio and mixing condition of molecular fluorescence material, well solve the problem of phase separation of two-phase substance.In the stirred of high speed
The organic fluorescence small molecule solution of Cheng Zhong, dropwise addition can soon scatter in water, and this biggish centrifugal force is effectively prevented from
The reunion of organic fluorescence small molecule, makes it possible to and is stabilized in aqueous phase system.After CNC suspension is added, high speed
Stirring is full of whole system further such that two kinds of substances quickly move in water, the aggregation that both effectively prevents and
Layering.Fluorescent fiber element is prepared compared to fluorophor is grafted on cellulose molecular chain by chemical modification, this method is more
Add environmental protection, simplicity.Prepared laminated film also shows fluorescence while showing periodic spin structure.This two
Kind characteristic makes laminated film under acid, alkaline atmosphere, can show the variation of fluorescence and visible light, and cholesteric phase knot simultaneously
Forbidden photon band effect specific to structure also results in the variation of circularly polarized light.Therefore, a variety of optics possessed by laminated film are special
Property make it possible to accurately and efficiently be applied to acid, alkaline gas detection.
Detailed description of the invention
Point that Fig. 1 is AIE organic micromolecule fluorescent material BPP2VA, BP4VA and TPE-OX of acidic and alkaline gas sensitivity
Minor structure figure.
Fig. 2 is the petrographic microscope photo of the CNC/BPP2VA fluorescent composite thin film in embodiment 1 with cholester structure.
Fig. 3 is fluorescence spectra of the CNC/BPP2VA laminated film in different time under hydrochloric acid atmosphere in embodiment 1.
Fig. 4 is the fluorescence light of the CNC/BPP2VA laminated film that restores under triethylamine atmosphere in embodiment 1 in different time
Spectrogram.
Fig. 5 is ultraviolet-visible spectrogram of the CNC/BPP2VA laminated film in different time under hydrochloric acid atmosphere in embodiment 1.
Fig. 6 is the CNC/BPP2VA after recovery under original CNC/BPP2VA laminated film in embodiment 1 and triethylamine atmosphere
The ultraviolet-visible spectrogram of laminated film.
The digital photograph of the CNC/BPP2VA laminated film prepared in Fig. 7 comparative example 1 by direct mixing method.
Specific embodiment
The technical characteristic that the present invention is further illustrated by the following examples, but protection scope of the present invention is not
It is confined to the following example.
Embodiment 1:
A kind of preparation method of the fluorescence cholesteric phase Cellulose nanocrystal body thin film with Acid-base Gas response:
1) it prepares CNC suspension: the sulfuric acid solution of 10gWhatmanCF11 cellulose powder and 175mL 64w% being taken to distinguish
It is added in round-bottomed flask, magnetic agitation reacts 1h at 45 DEG C, and 1L deionized water is added and terminates reaction.After standing 1 day, outwell
Layer clear liquid, lower layer's turbid solution is centrifuged repeatedly at 10000rpm and collects upper layer turbid solution, being subsequently placed in molecular cut off is
1.4×104Bag filter in carry out dialysis treatment, to remove free acid extra in suspension, dialysis 15 days until CNC suspends
Liquid is in neutrality, for use；
2) BPP2VA is prepared: according to determining ratio by anthracene (38.0mmol), paraformaldehyde (200.0mmol), zinc chloride
(51.4mmol) and Isosorbide-5-Nitrae-dioxane (80.0ml) sequentially add in single necked round bottom flask, are added dropwise a certain amount of concentrated hydrochloric acid, and 50 DEG C
Lower back flow reaction 3h obtains 9,10- bis- (chloromethyl) anthracene, it is reacted to obtain 9,10- bis- (phosphatide base) with triethyl phosphite
Anthracene, then by the product (2.1mmol) and 2- benzoyl pyridine (8.4mmol), potassium tert-butoxide (17.8mmol) and tetrahydrofuran
(80.0ml) mixing, obtains yellow powder BPP2VA after reaction treatment；
3) the fluorescent material BPP2VA of above-mentioned preparation is dissolved in its good solvent tetrahydrofuran, being configured to concentration is 10- 3The solution of mol/L, for use；
4) the BPP2VA solution that 200 μ L preparation is pipetted with liquid-transfering gun, is added drop-wise to dropwise in 4g deionized water.To avoid precipitating
Generation, this process needs the speed (1000rpm) of accurate control magnetic agitation, to be uniformly dispersed out fluorescent material,
The magneton that also select suitable size prevents fluorescent material precipitation to be hanging on chamber wall.Stir 10min it is to be mixed uniformly after,
BPP2VA fluorescent small molecule forms stable Micelle-like Nano-structure of Two in water, and is observed that apparent Tyndall phenomenon；
5) according to CNC and the certain mixed proportion of BPP2VA fluorescent small molecule, the CNC suspension of 1g 15wt% is taken, dropwise
It is added drop-wise in suspension made from step 4).This process also needs accurately to control magnetic stirring speed (1000rpm), this is anti-
The committed step of the generation only mutually separated.Stir 10min it is to be mixed it is uniform and stable after, can be with by being ultrasonically treated different time
The screw pitch of cholester structure is regulated and controled；
6) CNC/BPP2VA mixing suspension obtained in 4.5g step 5) is taken to be placed in the polystyrene ware of 38mm, 25 DEG C
It is stood in lower, it is ensured that evaporation induces the progress of assembling process altogether, and the fluorescent fiber element with cholester structure can be obtained after about 3 days
Film.
7) CNC/BPP2VA laminated film is placed under hydrochloric acid atmosphere, since the variation of cholester structure screw pitch can cause film
The variation of color, and fluorescence intensity can also weaken, and can restore under triethylamine atmosphere, corresponding uv-vis spectra and fluorescence
Regular variation can also occur for spectrum.Further, since cholester structure has forbidden photon band effect, the variation of screw pitch can also be led
Cause the variation of circularly polarized light.
Apparent characteristic fingerprint texture, explanation can be observed by petrographic microscope in the product film prepared in embodiment 1
It is with cholester structure, as shown in Figure 2.
The product film prepared in embodiment 1 is under hydrochloric acid atmosphere, and with time change, fluorescence intensity obviously weakens, and
And certain red shift occurs for fluorescence emission peak, as shown in Figure 3.
Recovery situation of the product film prepared in embodiment 1 after acid gas is handled under triethylamine atmosphere, with
Time change, fluorescence intensity gradually become by force, as shown in Figure 4.
The product film prepared in embodiment 1 is under hydrochloric acid atmosphere, and with time change, red shift occurs for ultraviolet absorption peak,
Illustrate that screw pitch variation causes the variation of film color, as shown in Figure 5.
Recovery situation of the product film prepared in embodiment 1 after acid gas is handled under triethylamine atmosphere, it is ultraviolet
Absorption peak returns to initial position, illustrates that film color has been restored to initial conditions, as shown in Figure 6.
Embodiment 2:
The present embodiment is same as Example 1, the difference is that AIE organic micromolecule fluorescent material used, may be used also
To be spiropyran or spirooxazine class compound to acid, alkaline gas response, including BP4VA, TPE-OX etc..
Embodiment 3:
The present embodiment is same as Example 1, the difference is that sour gas used can also be nitric acid, formic acid, second
The volatile acids such as acid, trifluoroacetic acid and hydrobromic acid.
Embodiment 4:
The present embodiment is same as Example 1, the difference is that alkaline gas used can also be the volatility such as ammonium hydroxide
Alkali.
Embodiment 5:
The present embodiment is same as Example 1, the difference is that preparation CNC suspension is to utilize TEMPO oxidizing process, referring to
Chinese patent: the preparation method in CN106317423A is used the hydrochloric acid hydrolysis process cotton cellulose crystallite of 4mol/L first, is obtained
Cellulose suspension after reducing to size, so with the fiber obtained after TEMPO-NaBr-NaClO system oxidation processes sour water solution
Plain suspension obtains certain density CNC suspension using centrifugation, dialysis and concentration process.
It is reported that the CNC by TEMPO oxidation enhances the adsorption capacity of fluorescent material, luminescent properties are improved.
Embodiment 6:
The present embodiment is same as Example 1, the difference is that the BPP2VA amount of solution being added dropwise in step 4) can be
Within the scope of 100-1000 μ L, best dripping quantity is between 200-600 μ L.The very few fluorescence intensity of dripping quantity can be too weak, excessively then can
Destroy cholester structure.
Embodiment 7:
The present embodiment is same as Example 1, the difference is that the velocity interval of magnetic agitation is 500- in step 4)
1500rpm, speed is excessively slow easily to be occurred mutually to separate, and fluorescent small molecule would not form Micelle-like Nano-structure of Two, excessive velocities meeting in water
Fluorescent small molecule precipitation is caused to be hanging on chamber wall.
Embodiment 8:
The present embodiment is same as Example 1, the difference is that the added CNC range of solid content in step 5) is
0.1-0.3g, optimum addition is between 0.15-0.2g.Additive amount is very few to be not easy to form a film, and excessively may then influence fluorescent effect.
Comparative example 1:
Organic fluorescence materials BPP2VA is dissolved in organic solvent (tetrahydrofuran or dimethylformamide), concentration is configured to
It is 10-3The solution of mol/L, the CNC suspension for taking the 300 prepared solution of μ L to be 3% with 5g mass fraction directly mix, and select
The small magneton of diameter 5mm long 10mm, the speed for controlling magnetic agitation is 1000rpm, stirs 10min, surpasses under ice-water bath 60W power
Sound 10min.There is apparent lamination in observation discovery two-phase substance, and fluorescent material BPP2VA is precipitated, this shows two-phase substance
Generation mutually separates, and can not achieve total assembling.In the film formed by evaporation drying, CNC and BPP2VA distribution are very uneven,
Fluorescent material is precipitated, and adheres on the membrane surface, as shown in Figure 7.
The above is not limitation of the present invention, it should be pointed out that: those skilled in the art are come
It says, under the premise of not departing from essential scope of the present invention, several variations, modifications, additions or substitutions can also be made, these improvement
It also should be regarded as protection scope of the present invention with retouching.
Claims (9)
1. a kind of preparation method of the fluorescence cholesteric phase Cellulose nanocrystal body thin film with Acid-base Gas response, feature exist
In, specifically includes the following steps:
1) Cellulose nanocrystal liquid suspension is prepared using sulphuric acid hydrolysis or TEMPO oxidative treatment cellulose；
2) by chemical reactive synthesis AIE organic micromolecule fluorescent material, AIE organic micromolecule fluorescent material is dissolved in respectively
From good solvent in, be configured to concentration be 10-3The solution of mol/L；
3) solution prepared in a certain amount of step 2) is pipetted, is added drop-wise in a certain amount of deionized water dropwise, one section of magnetic agitation
Time it is to be mixed uniformly after, AIE class fluorescent small molecule forms stable Micelle-like Nano-structure of Two in water, be made AIE class fluorescence suspend
Liquid；
4) according to the range of Cellulose nanocrystal liquid suspension and AIE class fluorescence suspension vol ratio 1:5-1:6, a certain amount of step is taken
Rapid 1) the middle Cellulose nanocrystal liquid suspension prepared, is added drop-wise in AIE class fluorescence suspension made from step 3), magnetic force dropwise
Stirring a period of time it is to be mixed it is uniform and stable after, by ultrasonic treatment, the screw pitch of cholester structure is regulated and controled；
5) it takes mixing suspension obtained in step 4) to be placed in polystyrene ware, stands at normal temperature, be evaporated induction altogether
Assembling process can obtain the fluorescent fiber element film with cholester structure after 3-5 days.
2. a kind of system of the fluorescence cholesteric phase Cellulose nanocrystal body thin film with Acid-base Gas response according to claim 1
Preparation Method, which is characterized in that in the step (2) there are many AIE organic micromolecule fluorescent materials, such as spiropyran or spiral shell
Oxazine compound is (9,10- bis- (2- phenyl -2- (2- pyridyl group)) vinyl anthracenes, 9,10- bis- (p- pyridine vinyl)
Anthracene, any one in tetraphenyl ethylene oxazolidine.
3. a kind of system of the fluorescence cholesteric phase Cellulose nanocrystal body thin film with Acid-base Gas response according to claim 1
Preparation Method, which is characterized in that in the step (3) during magnetic agitation, select the small magneton of diameter 5mm long 10mm, accurately
The velocity interval for controlling this process magnetic agitation is 500~1500rpm, to prevent fluorescent material precipitation to be hanging on chamber wall；
The magnetic agitation time is controlled, until observing apparent Tyndall phenomenon.
4. a kind of system of the fluorescence cholesteric phase Cellulose nanocrystal body thin film with Acid-base Gas response according to claim 1
Preparation Method, which is characterized in that in the step (4) during magnetic agitation, select the small magneton of diameter 5mm long 10mm, accurately
The velocity interval for controlling this process magnetic agitation is 500~1500rpm, controls the magnetic agitation time, prevents the generation mutually separated.
5. a kind of system of the fluorescence cholesteric phase Cellulose nanocrystal body thin film with Acid-base Gas response according to claim 1
Preparation Method, which is characterized in that the condition being ultrasonically treated in the step (4) are as follows: ice water bath environment, 60W power, time 1-
15min。
6. a kind of system of the fluorescence cholesteric phase Cellulose nanocrystal body thin film with Acid-base Gas response according to claim 1
Preparation Method, which is characterized in that the fluorescent fiber element laminated film being prepared in the step (5) is placed in volatile acid atmosphere
Under, cholester structure screw pitch changes the variation for causing film color, and fluorescence intensity can also weaken；Under alkaline atmosphere,
The variation of its cholester structure screw pitch causes the variation of film color to restore, and corresponding uv-vis spectra and fluorescence spectrum have
The variation of rule.
7. a kind of system of the fluorescence cholesteric phase Cellulose nanocrystal body thin film with Acid-base Gas response according to claim 6
Preparation Method, which is characterized in that the sour gas is appointing in volatile acid nitric acid, formic acid, acetic acid, trifluoroacetic acid or hydrobromic acid
It anticipates one kind.
8. a kind of system of the fluorescence cholesteric phase Cellulose nanocrystal body thin film with Acid-base Gas response according to claim 6
Preparation Method, which is characterized in that the alkaline gas is any one in volatile base ammonium hydroxide, diethylamine or triethylamine.
9. a kind of system of the fluorescence cholesteric phase Cellulose nanocrystal body thin film with Acid-base Gas response according to claim 1
Preparation Method, which is characterized in that the cholester structure for the fluorescent fiber element THIN COMPOSITE being prepared in the step (5) has photon
Forbidden band effect, the variation of screw pitch will lead to the variation of circularly polarized light.
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