CN116144069B - Polysaccharide-based fluorescence response sponge and preparation method and application thereof - Google Patents
Polysaccharide-based fluorescence response sponge and preparation method and application thereof Download PDFInfo
- Publication number
- CN116144069B CN116144069B CN202310049348.9A CN202310049348A CN116144069B CN 116144069 B CN116144069 B CN 116144069B CN 202310049348 A CN202310049348 A CN 202310049348A CN 116144069 B CN116144069 B CN 116144069B
- Authority
- CN
- China
- Prior art keywords
- polysaccharide
- sponge
- responsive
- based fluorescence
- ciaa
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 150000004676 glycans Chemical class 0.000 title claims abstract description 144
- 229920001282 polysaccharide Polymers 0.000 title claims abstract description 144
- 239000005017 polysaccharide Substances 0.000 title claims abstract description 144
- 230000004044 response Effects 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000004005 microsphere Substances 0.000 claims abstract description 100
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 96
- 238000003756 stirring Methods 0.000 claims abstract description 74
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 66
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 66
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 66
- 239000007789 gas Substances 0.000 claims abstract description 58
- 239000006185 dispersion Substances 0.000 claims abstract description 51
- 239000007788 liquid Substances 0.000 claims abstract description 42
- UGTZMIPZNRIWHX-UHFFFAOYSA-K sodium trimetaphosphate Chemical compound [Na+].[Na+].[Na+].[O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 UGTZMIPZNRIWHX-UHFFFAOYSA-K 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 32
- 239000007787 solid Substances 0.000 claims abstract description 27
- 239000003960 organic solvent Substances 0.000 claims abstract description 25
- 238000002189 fluorescence spectrum Methods 0.000 claims abstract description 24
- 239000011148 porous material Substances 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 230000008859 change Effects 0.000 claims abstract description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 106
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 68
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 53
- 238000000502 dialysis Methods 0.000 claims description 38
- 239000000084 colloidal system Substances 0.000 claims description 32
- 238000004108 freeze drying Methods 0.000 claims description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 24
- 239000012298 atmosphere Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 239000008346 aqueous phase Substances 0.000 claims description 19
- 239000002105 nanoparticle Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 18
- -1 perylene imide Chemical class 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 15
- 238000001338 self-assembly Methods 0.000 claims description 15
- 230000006835 compression Effects 0.000 claims description 14
- 238000007906 compression Methods 0.000 claims description 14
- 239000012071 phase Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 230000003993 interaction Effects 0.000 claims description 13
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 12
- 239000012498 ultrapure water Substances 0.000 claims description 12
- 238000007710 freezing Methods 0.000 claims description 11
- 230000008014 freezing Effects 0.000 claims description 11
- 125000000524 functional group Chemical group 0.000 claims description 10
- 238000001514 detection method Methods 0.000 claims description 9
- 238000006862 quantum yield reaction Methods 0.000 claims description 8
- 230000002209 hydrophobic effect Effects 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000005462 imide group Chemical class 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000003147 glycosyl group Chemical group 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 66
- 238000012360 testing method Methods 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000002077 nanosphere Substances 0.000 description 12
- 238000004440 column chromatography Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 239000005457 ice water Substances 0.000 description 7
- 238000002356 laser light scattering Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000010998 test method Methods 0.000 description 7
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 239000002026 chloroform extract Substances 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- FVDOBFPYBSDRKH-UHFFFAOYSA-N perylene-3,4,9,10-tetracarboxylic acid Chemical compound C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=O)C2=C1C3=CC=C2C(=O)O FVDOBFPYBSDRKH-UHFFFAOYSA-N 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005259 measurement Methods 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
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 208000016853 pontine tegmental cap dysplasia Diseases 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/048—Elimination of a frozen liquid phase
- C08J2201/0484—Elimination of a frozen liquid phase the liquid phase being aqueous
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/26—Cellulose ethers
- C08J2301/28—Alkyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3437—Six-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/378—Thiols containing heterocyclic rings
-
- 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
- G01N2021/6417—Spectrofluorimetric devices
Abstract
The invention relates to a polysaccharide-based fluorescence response sponge and a preparation method and application thereof, wherein sodium carboxymethyl cellulose powder, sodium hydroxide and sodium trimetaphosphate are sequentially added into a nano microsphere aqueous dispersion liquid under the stirring condition until the sodium carboxymethyl cellulose powder, the sodium hydroxide and the sodium trimetaphosphate are completely dissolved to prepare a transparent precursor solution, and the polysaccharide-based fluorescence response sponge is prepared from the transparent precursor solution; the prepared polysaccharide-based fluorescence response sponge consists of a polysaccharide-based sponge and nanometer microspheres with fluorescence response, wherein the nanometer microspheres are distributed among pores of the polysaccharide-based sponge; the polysaccharide-based fluorescence-responsive sponge shows color change under the conditions of a certain temperature and a certain organic solvent gas concentration, and the emission peak value in the solid fluorescence spectrum changes. The preparation method of the polysaccharide-based fluorescence response sponge is simple, and the prepared polysaccharide-based fluorescence response sponge has higher selectivity, sensitivity and good fluorescence response to various organic solvent gases.
Description
Technical Field
The invention belongs to the technical field of gas detection materials, and relates to a polysaccharide-based fluorescence response sponge, a preparation method and application thereof.
Background
Technological development is continuously increasing the modern industrialization degree, and in recent years, the types and the amounts of gases used in the production process and gases generated in the production process are also increasing. Many of these gases are flammable, explosive, toxic (e.g., ethanol, CO, THF, methylene chloride, etc.). Thus, in order to ensure safe production, the monitoring and management of the gas must be enhanced in terms of storage, transportation, use, etc.
The natural polymers of cellulose, starch, chitosan and other polysaccharides have the advantages of easy chemical modification, biodegradability, good biocompatibility and the like, and can directly achieve the effect of detecting gas through the change of color under the condition of not using any instrument by introducing a specific fluorescent group through chemical modification.
The sponge is a porous material prepared from gel through freeze drying, and has the characteristics of high porosity and ultra-low density. As a porous material, the high porosity of the sponge enables the sponge to have high specific surface area, and the unique property enables the sponge to have good gas adsorption and capturing effects, so that the sponge is often applied to the fields of adsorption materials, heat insulation materials, functional templates and the like.
Sodium carboxymethyl cellulose (CMC-Na) is used as a polysaccharide natural polymer material, has the advantages of wide source, low price, low toxicity and the like, and is a good sponge skeleton source.
Therefore, the fluorescent group is attached to the sponge made of sodium carboxymethyl cellulose, and the fluorescent group is very practical for detecting gas.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a polysaccharide-based fluorescence response sponge, and a preparation method and application thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
sequentially adding sodium carboxymethylcellulose (CMC-Na) powder, sodium hydroxide and Sodium Trimetaphosphate (STMP) into a nano microsphere aqueous dispersion liquid under the stirring condition until the sodium carboxymethylcellulose powder, the sodium hydroxide and the sodium trimetaphosphate are completely dissolved to prepare a transparent precursor solution, pouring the prepared transparent precursor solution into a mould, and refrigerating, freezing and freeze-drying to prepare the polysaccharide-based fluorescence-responsive sponge;
the preparation method of the nano microsphere aqueous dispersion liquid comprises the following steps: dissolving CIAA in tetrahydrofuran (THF, wherein a solvent is required to be mutually soluble with water and can dissolve CIAA molecules) to form a uniform CIAA/tetrahydrofuran solution, then rapidly (within 5-10 s) adding ultrapure water into the CIAA/tetrahydrofuran solution (the experiment is performed strictly to remove the influence of other ions in water, so that ultrapure water is selected, if the influence of other ions is not considered, ultrapure water can be not selected), obtaining colloid, and finally removing tetrahydrofuran in the colloid by a dialysis method (the removal of tetrahydrofuran in the colloid by the dialysis method is specifically that the colloid is transferred into a dialysis bag with the interception molecular weight of 500, the colloid is dialyzed by pure water, the pure water for dialysis is replaced after the dialysis is started for 1.5h, 4h and 8h respectively, the volume ratio of the pure water for dialysis to the dispersion is 2000-4000:11 each time, and the dialysis is finished after 24 h), so as to obtain the water-phase dispersion of the nano microsphere;
The CIAA forms nano microspheres in the water phase through self-assembly; the CIAA is formed by chemically bonding 1 assembler containing hydrophilic functional groups and 1-2 nonpolar limiting assemblers, and the CIAA is nonpolar;
the assembly is a perylene imide group or a perylene imide derivative group; the nonpolar limiting assembly is a group with a nano-sized three-dimensional structure or a group capable of shrinking into a nano-sized three-dimensional structure in an aqueous phase due to a hydrophobic function;
the mass volume ratio of CIAA to tetrahydrofuran is 1mg to 1mL, 1mg to 10mg to 1mL, the volume ratio of CIAA/tetrahydrofuran solution to ultrapure water is 1:5 to 1:10, molecules can be assembled into colloid only under the condition, a system with too small water content is a solution, and the water content is too large and becomes precipitation.
As a preferable technical scheme:
the preparation method of the polysaccharide-based fluorescence response sponge comprises the steps of Wherein is the chemical bonding position.
The nonpolar limiting assembly as described above is a group having a nano-sized three-dimensional structure, or a group capable of shrinking into a nano-sized three-dimensional structure due to a hydrophobic interaction in an aqueous phase;
the group with the nano-size three-dimensional structure is Wherein R is isobutyl or isooctyl, R is a chemical bond site 1 And R is 2 Each independently selected from alkyl chains having less than 20 carbon atoms.
In the method for preparing the polysaccharide-based fluorescence-responsive sponge, the group capable of shrinking into a nano-sized three-dimensional structure due to the hydrophobic action in the water phase is an alkyl chain with more than 6 carbons (because the alkyl chain is hydrophobic, the group is shrunk due to the hydrophobic action in the water, and more than 6 carbons can be shrunk into the three-dimensional structure).
The preparation method of the polysaccharide-based fluorescence response sponge comprises the step of forming a die into a round culture dish with the diameter of 5-150 mm or a rectangular culture dish with the length of 5-150 mm and the width of 5-150 mm.
According to the preparation method of the polysaccharide-based fluorescence response sponge, the particle size of the aqueous dispersion liquid of the nano-microspheres is 50-200 nm, the polydispersity index is 0.1-0.7 (the dispersion index of the nano-microspheres is smaller, the distribution of the illustrated size is more uniform), the particle size and the polydispersity index are measured by a dynamic laser light scattering (DLS) test method, the test temperature is 25-30 ℃, and the test time is 3-5 min; the Zeta potential is-60 to-40 mV (the Zeta potential is less than-40 mV indicates that the microsphere has good stability in the water phase), and the testing temperature of the Zeta potential is 25-30 ℃.
According to the preparation method of the polysaccharide-based fluorescence response sponge, after the aqueous dispersion liquid of the nano microsphere is placed for 7-10 days, the particle size of the microsphere is floated by +/-5 to +/-10 nm on the original size, the polydispersity index is floated by +/-0.01 to +/-0.05 on the original value, the zeta potential is floated by +/-2 to +/-10 mV on the original value, and all the numerical value floating ranges are within measurement errors, so that the stability of the microsphere is good.
The preparation method of the polysaccharide-based fluorescence response sponge comprises the following specific steps of:
(1) Adding sodium carboxymethyl cellulose powder into the nano microsphere aqueous phase dispersion liquid under the stirring condition of 200-400 rpm, and continuously stirring until the sodium carboxymethyl cellulose powder is completely dissolved to prepare sodium carboxymethyl cellulose/nano microsphere solution;
(2) Adding sodium hydroxide into the sodium carboxymethyl cellulose/nano microsphere solution obtained in the step (1) under the same stirring condition as the step (1), and continuously stirring until the sodium hydroxide is completely dissolved;
(3) Adding sodium trimetaphosphate into the solution obtained in the step (2) under the same stirring condition as the step (1), and continuously stirring until the sodium trimetaphosphate is completely dissolved to prepare a transparent precursor solution;
(4) Pouring the transparent precursor solution prepared in the step (3) into a mould, refrigerating for 1-12 h at the temperature of 0-10 ℃, freezing for 6-24 h at the temperature of minus 60-minus 30 ℃ to ensure that the solution is frozen into uniform and smooth ice cubes, freeze-drying for 36-72 h under vacuum, obtaining porous spongy materials after all sublimation of the ice cubes, washing with water for multiple times at the temperature of 15-45 ℃ to ensure that corresponding nano microsphere particles are firmly attached to a porous structure, and finally freeze-drying again to obtain the polysaccharide-based fluorescence response sponge.
According to the preparation method of the polysaccharide-based fluorescence response sponge, the concentration of the aqueous dispersion liquid of the nano microsphere in the step (1) is 0.1-2 mg/mL, and the mass concentration of the sodium carboxymethyl cellulose in the sodium carboxymethyl cellulose/nano microsphere solution is 1-4%;
the mass ratio of the sodium carboxymethyl cellulose powder in the step (1), the sodium hydroxide in the step (2) and the sodium trimetaphosphate in the step (3) is 2-6:0.5-1:0.6-1.8.
According to the preparation method of the polysaccharide-based fluorescence response sponge, in the step (1), the time required for continuous stirring until the sodium carboxymethylcellulose powder is completely dissolved is 3-5 h, the time required for continuous stirring until the sodium hydroxide is completely dissolved is 20-40 min in the step (2), and the time required for continuous stirring until the sodium trimetaphosphate is completely dissolved is 20-40 min in the step (3);
The vacuum degree of all freeze drying in the step (4) is 0.1-10 Pa, and the cold trap temperature is-70 to-50 ℃; the vacuum degree is too high, the pressure in the drying chamber is high, and ice crystals can not reach a cold trap in time after sublimating into water vapor, so that incomplete drying is easily caused; the vacuum degree is too small, the pressure in the drying chamber is low, the heat transfer of the product is unfavorable, and the sublimation rate is reduced. The temperature of the cold trap is too low, the electric energy consumption is aggravated, the water capturing capacity is not obviously improved, and the drying rate is not greatly changed; the temperature of the cold trap is too high, and sublimated water vapor cannot be changed into ice crystals in time, so that incomplete drying is easily caused.
The invention also provides the polysaccharide-based fluorescence-responsive sponge prepared by the method according to any one of the above, which consists of the polysaccharide-based sponge and the fluorescence-responsive nano-microspheres distributed among the pores of the polysaccharide-based sponge, wherein the fluorescence-responsive nano-microspheres are formed by self-assembly of CIAA in a water phase; the polysaccharide-based fluorescence response sponge has the advantages of high porosity, large specific surface area, good elasticity, good biocompatibility, degradability and the like, can be reused, and overcomes the defects of slow response, inconvenient carrying, incapability of being reused and the like of a gas detection material in the prior art.
As a preferable technical scheme:
the polysaccharide-based fluorescence-responsive sponge as described above, which has an average pore diameter of 1 to 100 μm (the sponge having the average pore diameter range is stable in structure and good in elasticity), a porosity of 80 to 99%, and a specific surface area of 12 to 200m 2 Per g (the sponge with the specific surface area range has higher adsorption capacity and adsorption level) and the density is 0.01-0.1 g/cm 3 (the sponge under the density can keep a stable structure and has better mechanical property); the gas response time of the polysaccharide-based fluorescence response sponge is 60-120 s, and the fluorescence quantum yield is 10-80%; the polysaccharide-based fluorescence response sponge can rebound to the original volume after being compressed by 50-90% of the volume, and the compression strength is 0.5-1.0 kPa.
The invention also provides application of the polysaccharide-based fluorescence-responsive sponge, which is used for detecting organic solvent gas;
the polysaccharide-based fluorescence response sponge shows color change under the conditions of a certain temperature and a certain organic solvent gas concentration, and the emission peak value in the solid fluorescence spectrum changes;
the organic solvent is dichloromethane, chloroform, toluene or tetrahydrofuran, and in the organic solvent, the molecular movement capability is strong, and the organic solvent can be converted from an oligomer state to a monomer state or an intermediate state exists.
As a preferable technical scheme:
in the application, the emission peak in the solid fluorescence spectrum of the polysaccharide-based fluorescence response sponge is blue-shifted by 2-8 nm in the gas atmosphere of 100ppm of organic solvent at 15-45 ℃, and the fluorescence color of the polysaccharide-based fluorescence response sponge is changed from dark red to orange red; after the organic solvent gas atmosphere is removed, the emission peak in the solid fluorescence spectrum of the polysaccharide-based fluorescence-responsive sponge is restored to a state before blue shift (the peak is restored to 645-655 nm), and the fluorescence color of the polysaccharide-based fluorescence-responsive sponge is restored to dark red.
The principle of the invention is as follows:
the formation principle of the nano microsphere aqueous dispersion liquid of the invention is as follows: in the nano microsphere, CIAA molecules have great steric hindrance due to limited assemblers, and continuous pi-pi accumulation is not formed among molecules, but aggregation is formed by taking oligomers (the number of aggregated molecules is less than 3) as primitives. Since the confinement assembly has a three-dimensional structure of nano-size, and the confinement assembly is a composition structure which can be regarded as a two-dimensional plate-like plane, the confinement assembly and the confinement assembly have three-dimensional and two-dimensional structures respectively in space size, and thus have shape anisotropy in arrangement, thus, the CIAA molecule has many cavities in the assembly structure, in the nano-microsphere, the CIAA molecule exists in a loose state, many holes are provided in the arrangement structure, water molecules enter the holes, and dynamic hydrogen bonds are formed between the internal water and the bulk water (water except the internal water in the system) in the nano-microsphere (because the hydrogen bonds are non-covalent bonds, are weak interactions among molecules, and the hydrogen bonds in the water are literature indicates dynamic, that is, the hydrogen bonds are likely to break at the last moment or the next moment), in the three-dimensional network structure which is commonly framed by the internal water and the bulk water, the nano-particle can exist stably in the water phase for a long time (the internal water and the bulk water have a certain interaction, so that the result of the water is three-dimensional network like that the internal water in the nano-microsphere is framed in the three-dimensional network structure.
The polysaccharide-based fluorescence response sponge prepared by the invention based on the nano microsphere aqueous dispersion liquid has the detection capability on organic solvent gas, and specifically comprises the following components: 100ppm of organic solvent gas can cause the fluorescence of the polysaccharide-based fluorescence-responsive sponge to change, the fluorescence emission is blue-shifted by 2-8 nm, and the color of the sponge is changed from dark red to orange red; after the organic solvent gas is removed, the color of the polysaccharide-based fluorescence-responsive sponge is recovered to be dark red; the lower limit of detection of fluorescent molecules applied in the invention is 10ppm, and the volume of the sponge material and the volume space occupied by the solution before and after freeze drying are unchanged, so that the concentration of the fluorescent molecules in the space is unchanged to be 10ppm, and 10 THF can cause molecular arrangement change around one molecule, so that the sponge can generate fluorescence change under the atmosphere of 100ppm of organic gas.
The polysaccharide-based fluorescence-responsive sponge has the detection capability on organic solvent gas, and the root cause is that CIAA molecules in the nano-microsphere refer to perylene imide derivatives with large-volume substituents in the molecular structure, and the large-volume substituents prevent the perylene imide derivatives from multimeric aggregation, so that the aggregation state of the perylene imide derivatives stays in an oligomer state; the oligomer state of the perylene imide derivative refers to the oligomer state that two perylene imide derivatives are combined to form a fixed arrangement structure through pi-pi interaction between perylene nucleus structures of the perylene imide derivatives; pi-pi interaction is a weak interaction, is sensitive to environmental changes, the distance between oligomers of the weak interaction changes along with the environmental changes, and conjugated molecules combined through the weak interaction can change the charge arrangement of the molecules, so that the photoelectric properties of the molecules, such as the color and fluorescence emission, are changed, and the more tightly the conjugated molecules are combined through the pi-pi interaction, the more the color of the molecules tends to be in the long wave direction (red shift);
The polysaccharide-based fluorescence response sponge shows color change along with the gas concentration of an organic solvent under a certain temperature condition, and specifically comprises the following components:
under excitation of 440-460 nm wavelength (excitation wavelength of perylene imide molecule is in the range), peak value of emission peak in solid fluorescence spectrum of polysaccharide-based fluorescence response sponge changes and fluorescence color of polysaccharide-based fluorescence response sponge changes:
the peak value of the emission peak in the solid fluorescence spectrum of the polysaccharide-based fluorescence response sponge in the 15-45 ℃ state is 645-655 nm; the fluorescence color of the polysaccharide-based fluorescence-responsive sponge is dark red;
at 15-45 ℃, in the gas atmosphere of 100ppm of organic solvent, the emission peak in the solid fluorescence spectrum of the polysaccharide-based fluorescence response sponge is blue-shifted by 2-8 nm; the fluorescence color of the polysaccharide-based fluorescence-responsive sponge is orange red; the perylene imide derivative oligomer and the corresponding fluorescence emission in a single molecular state are different, and the emission peak in the oligomer state is more biased to long-wavelength emission than that in the single molecular state. So that the fluorescence spectrum changes after the organic solvent affects the molecular aggregation state.
After the gas atmosphere is removed, the peak value of the emission peak in the solid fluorescence spectrum of the polysaccharide-based fluorescence response sponge is recovered to 645-655 nm, and the fluorescence color of the polysaccharide-based fluorescence response sponge is recovered to dark red. In the gas removal process, pi-pi interaction leads to mutual identification of perylene imide derivatives, the perylene imide derivatives are restored to the original oligomer state, pi-pi interaction exists between molecules of the perylene imide derivatives in the oligomer state, and after the organic solvent gas is removed, the molecules are identified to be assembled into the oligomer state due to stronger interaction.
The beneficial effects are that:
(1) The polysaccharide-based sponge has the advantages of simple preparation method, good elasticity, convenient carrying, good biocompatibility, degradability and the like, and can be repeatedly used;
(2) The nanometer microspheres among the pores of the polysaccharide-based sponge are attached to the inner walls of the pores of the sponge in the preparation and molding process, so that the preparation process of the sponge is not influenced, and the preparation is simple;
(3) For the detection of organic solvent gas, the polysaccharide-based sponge not only can change color, but also can change fluorescence emission, and has higher selectivity, sensitivity and good fluorescence responsiveness to various organic solvent gases, and the detection is convenient without secondary sample preparation detection;
(4) The preparation method of the invention comprises the steps of nucleating and growing ice crystals by controlling the freezing temperature, extruding and repelling nano-microspheres and other solutes (CMC-Na, STMP and the like) into a non-frozen liquid micro-area, and when the non-frozen liquid micro-area is sufficiently small, the CMC-Na and the STMP can generate a crosslinking reaction, and the nano-microspheres can be attached to a crosslinked three-dimensional network structure through the entanglement action of molecular chains;
(5) The polysaccharide-based sponge prepared by the method is a porous material, has high porosity, large specific surface area, simple structure and low manufacturing cost, and the three-dimensional reticular pore structure is favorable for permeation and diffusion of organic solvent gas and has rapid fluorescence response.
Drawings
FIG. 1 is a schematic diagram of the internal structure of a nanoparticle in an aqueous dispersion of the nanoparticle.
Detailed Description
The invention is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Fig. 1 is a schematic diagram of an internal structure of a nanoparticle in a nanoparticle aqueous dispersion prepared based on nonpolar molecules, specifically, the nanoparticle is formed by the existence of CIAA molecules in an oligomer state, and the nanoparticle has more internal water due to the existence of cavities in a molecular arrangement structure, and can exist stably in a network of hydrogen bonds due to dynamic hydrogen bonds between the internal water and bulk water.
TABLE 1
TABLE 2
Example 1
A preparation method of CIAA comprises the following specific steps:
(1) Into a 100mL three-necked flask, 2g was sequentially charged(perylene tetracarboxylic anhydride) and 29.40mL of concentrated sulfuric acid, stirring at 55 ℃ for 24 hours, then adding 0.05g of iodine into the mixed solution, continuously stirring for 5 hours, then dropwise adding 0.58mL of liquid bromine, controlling the speed to be 1 hour, heating to 85 ℃ and continuously stirring for 24 hours. Excess bromine N 2 Atmosphere ofTaking away, adding 30.00mL of ice water, cooling, filtering, and using 18mL of H with the mass concentration of 86% 2 SO 4 Washing followed by double ice water gave crude (2.70 g, 96%). The crude product is marked as PTCDA-Br without separation and purification and is directly used for the next step of synthesis;
(2) After adding 0.5g of the crude PTCDA-Br prepared above and 15mL of 1-methyl-2-pyrrolidone (NMP) to a 100mL three-necked flask, the mixture was stirred at 25℃for 1 hour; then 0.587g of 2-ethylhexyl amine followed by 16.80g of glacial acetic acid are added, the temperature is raised to 85℃under N 2 Continuing to react for 7 hours under protection; cooled to room temperature, 120mL of methanol was added, stirred and overnight; finally, carrying out suction filtration, vacuum drying and silica gel (200 meshes) column chromatography separation and purification to obtain a red solid which is recorded as 1,7-Br-PDI-EH;
(3) Into a round bottom flask, 100mg of isolated 1,7-Br-PDI-EH was added, dissolved in 20mL of Tetrahydrofuran (THF), stirred with a magnetic stirrer for 1h to allow 1,7-Br-PDI-EH to dissolve well, followed by 60.8mg of potassium carbonate and 108.48mg of 18-crown-6-ether, followed by 0.2g ofStirring at room temperature for 2h to stop the reaction, adding water and chloroform for extraction after rotary evaporation to obtain chloroform extract, and finally purifying by column chromatography to obtain the target product, namely CIAA.
The prepared CIAA is formed by chemically bonding 1 assembly containing hydrophilic functional groups and 1 nonpolar limiting assembly, and the CIAA is nonpolar; wherein, the assembler is S-5 in Table 1; the nonpolar limiting assembler is Q-1 in table 2; the CIAA can form nano-microspheres by self-assembly in an aqueous phase.
Example 2
A preparation method of CIAA comprises the following specific steps:
(1) To a 100mL three-necked flask, 2.00g of perylene tetracarboxylic acid anhydride and 29.40mL of concentrated sulfuric acid were sequentially added, and stirred at 55℃for 24 hours, then 0.05g of iodine was added to the mixed solution, stirring was continued for 5 hours, then 0.58mL of liquid bromine was added dropwise, and the dropwise addition was completed at a controlled speed of 1 hour, and the temperature was raised to 85℃and stirring was continued for 24 hours. Excess bromine N 2 Taking away the atmosphere, add 30Ice water with the volume of 18mL, cooling, suction filtering, and using H with the mass fraction of 86% 2 SO 4 Washing followed by double ice water gave crude (2.70 g, 96%). The crude product is marked as PTCDA-Br without separation and purification and is directly used for the next step of synthesis;
(2) A100 mL three-necked flask was charged with 0.50g of the crude PTCDA-Br prepared above and 15mL of 1-methyl-2-pyrrolidone, followed by stirring at 25℃for 1 hour; followed by the addition of 0.587g of 2-ethylhexyl amine followed by 16.8g of glacial acetic acid, and heating to 85℃under N 2 Continuing to react for 7 hours under protection; cooling to room temperature, adding 120mL of methanol, stirring overnight, filtering, vacuum drying, separating and purifying by silica gel (200 mesh) column chromatography to obtain red solid 1,7-Br-PDI-EH;
(3) Into a round bottom flask, 100mg of 1,7-Br-PDI-EH separated was added, dissolved in 20mL of tetrahydrofuran, stirred with a magnetic stirrer for 1 hour to sufficiently dissolve 1,7-Br-PDI-EH, followed by 60.8mg of potassium carbonate and 108.48mg of 18-crown-6-ether, followed by 0.45g ofStirring at room temperature for 2h to stop the reaction, adding water and chloroform for extraction after rotary evaporation to obtain chloroform extract, and finally purifying by column chromatography to obtain the target product, namely CIAA.
The prepared CIAA is formed by chemically bonding 1 assembler containing hydrophilic functional groups and 2 nonpolar limiting assemblers, and the CIAA is nonpolar; wherein, the assembler is S-3 in Table 1; the nonpolar limiting assembler is Q-2 in table 2; the CIAA can form nano-microspheres by self-assembly in an aqueous phase.
Example 3
A preparation method of CIAA comprises the following specific steps:
will be 0.11g C 60 -COOH、0.024g(naphthalene tetraanhydride), 1g imidazole and 4ml o-dichlorobenzene (ODCB) are placed in a round bottom flask, heated in an oil bath under the protection of argon atmosphere at 140 ℃ and stirred for 6h, and cooled Then dispersed in 25ml of ethanol and 25ml of HCl solution (concentration 2 mol/L) overnight, and then extracted with chloroform, the mixture was extracted with 5% NaHCO 3 Washing to neutrality, dewatering with anhydrous calcium carbonate, and separating and purifying by column chromatography to obtain the target product, namely CIAA.
The prepared CIAA is formed by chemically bonding 1 assembly containing hydrophilic functional groups and 1 nonpolar limiting assembly, and the CIAA is nonpolar; wherein, the assembler is S-4 in Table 1; the nonpolar limiting assembler is Q-3 in table 2; the CIAA can form nano-microspheres by self-assembly in an aqueous phase.
Example 4
A preparation method of CIAA comprises the following specific processes:
will be 0.12gC 8 H 17 -NH 2 Placing 0.024g of naphthalene tetracarboxylic anhydride, 1g of imidazole and 4ml of o-dichlorobenzene into a round bottom flask, heating an oil bath at 140 ℃ under the protection of an argon atmosphere under the condition of condensation reflux, stirring for 6 hours, and dispersing in 25ml of ethanol and 25ml of HCl solution with the concentration of 2mol/L after cooling overnight; after extraction with chloroform, the mixture was extracted with 5% NaHCO 3 Washing to neutrality, dewatering with anhydrous calcium carbonate, and separating and purifying by column chromatography to obtain the target product, namely CIAA.
The prepared CIAA is formed by chemically bonding 1 assembler containing hydrophilic functional groups and 2 nonpolar limiting assemblers, and the CIAA is nonpolar; wherein, the assembler is S-1 in Table 1; the nonpolar limiting assembler is Q-4 in table 2; the CIAA can form nano-microspheres by self-assembly in an aqueous phase.
Example 5
A preparation method of CIAA comprises the following specific steps:
(1) To a 100mL three-necked flask, 2g of perylene tetracarboxylic acid anhydride and 29.4mL of concentrated sulfuric acid were sequentially added, and stirred at 55℃for 24 hours, then 0.05g of iodine was added to the mixture, and stirring was continued for 5 hours, then 0.58mL of liquid bromine was added dropwise, and the dropwise addition was completed at a controlled rate of 1 hour, and the temperature was raised to 85℃and stirring was continued for 24 hours. Excess bromine N 2 Taking away the atmosphere, adding 30mL of ice water, cooling, filtering, and using 18.00mL of H with the mass concentration of 86% 2 SO 4 Washing followed by double ice water gave the crude product (2.70 g, 96%) which was designated PTCD without isolation and purificationA-Br is directly used for the next synthesis;
(2) After adding 0.50g of the crude PTCDA-Br prepared above and 15mL of 1-methyl-2-pyrrolidone to a 100mL three-necked flask, the mixture was stirred at 25℃for 1 hour; subsequently 0.587g of 2-ethylhexyl amine followed by 16.8g of glacial acetic acid are added, the temperature is raised to 85℃under N 2 Continuing to react for 7 hours under protection; cooled to room temperature, 120mL of methanol was added, and stirred overnight; finally, carrying out suction filtration, vacuum drying and silica gel (300 meshes) column chromatography separation and purification to obtain a red solid which is recorded as 1,7-Br-PDI-EH.
(3) A round bottom flask was charged with 100mg of isolated 1,7-Br-PDI-EH, dissolved in 20mL of tetrahydrofuran, stirred with a magnetic stirrer for 1h to allow 1,7-Br-PDI-EH to dissolve well, followed by 60.8mg of potassium carbonate and 108.48mg of 18-crown-6-ether followed by 0.2g of (n=12), and stirring at room temperature for 2 hours to stop the reaction; adding water and chloroform for extraction after rotary evaporation to obtain chloroform extract, and finally purifying by column chromatography to obtain a target product, namely CIAA.
The prepared CIAA is formed by chemically bonding 1 assembler containing hydrophilic functional groups and 2 nonpolar limiting assemblers, and the CIAA is nonpolar; wherein, the assembler is S-2 in Table 1; the nonpolar limiting assembler is Q-5 in table 2; the CIAA can form nano-microspheres by self-assembly in an aqueous phase.
Example 6
A preparation method of CIAA comprises the following specific processes:
(1) To a 100mL three-necked flask, 2g of perylene tetracarboxylic acid anhydride and 29.40mL of concentrated sulfuric acid were sequentially added, and stirred at 55℃for 24 hours, then 0.05g of iodine was added to the mixed solution, stirring was continued for 5 hours, then 0.29mL of liquid bromine was added dropwise, and the dropwise addition was completed at a controlled speed of 1 hour, and the temperature was raised to 85℃and stirring was continued for 24 hours. Excess bromine N 2 Taking away the atmosphere, adding 30.00mL of ice water, cooling, filtering, and using 18.00mL of H with the mass concentration of 86% 2 SO 4 Washing followed by double ice water gave crude product. The crude product is marked as PTCDA-Br without separation and purification and is directly used for the next step of synthesis;
(2) Into a 100mL three-necked flask, 0.50g of the crude PTCDA-Br prepared above and 15.00mL of 1-methyl-2-pyrrolidone were successively added, and the mixture was stirred at 25℃for 1 hour. Then, 0.84g of ethylenediamine was added followed by 16.80g of glacial acetic acid and the temperature was raised to 90℃under N 2 The reaction was continued for 7h under protection. Cooled to room temperature, 120.00mL of methanol was added, stirred and overnight; finally, carrying out suction filtration, vacuum drying and column chromatography separation and purification on silica gel (200 meshes) (mobile phase: chloroform/normal hexane=2:3) to obtain red solid which is recorded as 1-Br-PDI-C 12 ；
(3) 100mg of isolated 1-Br-PDI-C was placed in a round bottom flask 12 Dissolving in 20mL tetrahydrofuran, adding magnetic stirrer, stirring for 1 hr to obtain 1-Br-PDI-C 12 Fully dissolved in the solution, 60.80mg of potassium carbonate and 108.48mg of 18-crown-6-ether were added followed by a slight excess of 0.1gThe solution is observed to be purple immediately, the reaction is stopped after stirring for 2 hours at room temperature, water and chloroform are added for extraction after rotary evaporation, chloroform extract is obtained, and finally, the target product, namely CIAA, is obtained after column chromatography separation.
The prepared CIAA is formed by chemically bonding 1 assembly containing hydrophilic functional groups and 1 nonpolar limiting assembly, and the CIAA is nonpolar; wherein, the assembler is S-6 in Table 1; the nonpolar limiting assembler is Q-1 in table 2; the CIAA can form nano-microspheres by self-assembly in an aqueous phase.
Example 7
A preparation method of a non-polar molecule-based nano microsphere aqueous dispersion liquid comprises the following specific steps:
(1) Dissolving the CIAA prepared in the example 1 in tetrahydrofuran according to the mass-volume ratio of 1mg to 1mL to form a uniform CIAA/tetrahydrofuran solution, and rapidly (within 5 s) adding ultrapure water (with the resistivity of 18MΩ cm) into the CIAA/tetrahydrofuran solution according to the volume ratio of 1:10 to obtain a colloid with the Tyndall effect;
(2) Transferring the colloid prepared in the step (1) into a dialysis bag with the molecular weight cut-off of >500, dialyzing the colloid with pure water, then replacing pure water for dialysis respectively at 1.5h, 4h and 8h after the beginning of dialysis, wherein the volume ratio of the pure water for dialysis to the dispersion liquid is 2000:11 each time, and after 24h, the dialysis is finished, removing tetrahydrofuran in the colloid, and obtaining the non-polar molecule-based nano microsphere aqueous phase dispersion liquid with the concentration of 0.1 mg/mL.
In the prepared nonpolar molecule-based nano microsphere aqueous dispersion liquid, the average particle size of the nano microsphere is 50nm, the polydispersity index is 0.1, the Zeta potential is-60 mV, the particle size and the polydispersity index of the nano microsphere are measured by a dynamic laser light scattering (DLS) test method, the test temperature is 25 ℃, the test time is 5min, and the test temperature of the Zeta potential is 25 ℃.
Example 8
A preparation method of a non-polar molecule-based nano microsphere aqueous dispersion liquid comprises the following specific steps:
(1) Dissolving the CIAA prepared in the example 2 in tetrahydrofuran according to the mass-volume ratio of 2mg to 1mL to form a uniform CIAA/tetrahydrofuran solution, and rapidly (within 6 s) adding ultrapure water (with the resistivity of 18MΩ cm) into the CIAA/tetrahydrofuran solution according to the volume ratio of 1:8 to obtain a colloid with the Tyndall effect;
(2) Transferring the colloid prepared in the step (1) into a dialysis bag with the molecular weight cut-off of >500, dialyzing the colloid with pure water, then replacing pure water for dialysis respectively at 1.5h, 4h and 8h after the beginning of dialysis, wherein the volume ratio of the pure water for dialysis to the dispersion liquid is 2000:11 each time, and after 24h, the dialysis is finished, removing tetrahydrofuran in the colloid, and obtaining the non-polar molecule-based nano microsphere aqueous phase dispersion liquid with the concentration of 0.25 mg/mL.
In the prepared nonpolar molecule-based nano microsphere aqueous dispersion liquid, the average particle size of the nano microsphere is 70nm, the polydispersity index is 0.15, the Zeta potential is-55 mV, the particle size and the polydispersity index of the nano microsphere are measured by a dynamic laser light scattering (DLS) test method, the test temperature is 26 ℃, the test time is 5min, and the test temperature of the Zeta potential is 26 ℃.
Example 9
A preparation method of a non-polar molecule-based nano microsphere aqueous dispersion liquid comprises the following specific steps:
(1) Dissolving the CIAA prepared in the example 3 in tetrahydrofuran according to the mass-volume ratio of 4mg to 1mL to form a uniform CIAA/tetrahydrofuran solution, and rapidly (within 7 s) adding ultrapure water (with the resistivity of 18MΩ cm) into the CIAA/tetrahydrofuran solution according to the volume ratio of 1 to 7 to obtain a colloid with the Tyndall effect;
(2) Transferring the colloid prepared in the step (1) into a dialysis bag with the molecular weight cut-off of >500, dialyzing the colloid with pure water, then replacing pure water for dialysis respectively 1.5h, 4h and 8h after the beginning of dialysis, wherein the volume ratio of the pure water for dialysis to the dispersion liquid is 3000:11 each time, and after 24h, the dialysis is finished, removing tetrahydrofuran in the colloid, and obtaining the non-polar molecule-based nano microsphere aqueous phase dispersion liquid with the concentration of 0.57 mg/mL.
In the prepared nonpolar molecule-based nano microsphere aqueous dispersion liquid, the average particle size of the nano microsphere is 100nm, the polydispersity index is 0.3, the Zeta potential is-53 mV, the particle size and the polydispersity index of the nano microsphere are measured by a dynamic laser light scattering (DLS) test method, the test temperature is 27 ℃, the test time is 5min, and the test temperature of the Zeta potential is 27 ℃.
Example 10
A preparation method of a non-polar molecule-based nano microsphere aqueous dispersion liquid comprises the following specific steps:
(1) Dissolving the CIAA prepared in the example 4 in tetrahydrofuran according to the mass-volume ratio of 6mg to 1mL to form a uniform CIAA/tetrahydrofuran solution, and rapidly (within 8 s) adding ultrapure water (with the resistivity of 18MΩ cm) into the CIAA/tetrahydrofuran solution according to the volume ratio of 1 to 5 to obtain a colloid with the Tyndall effect;
(2) Transferring the colloid prepared in the step (1) into a dialysis bag with the molecular weight cut-off of >500, dialyzing the colloid with pure water, then replacing pure water for dialysis respectively at 1.5h, 4h and 8h after the beginning of dialysis, wherein the volume ratio of the pure water for dialysis to the dispersion liquid is 3000:11 each time, and after 24h, the dialysis is finished, removing tetrahydrofuran in the colloid, and obtaining the non-polar molecule-based nano microsphere aqueous phase dispersion liquid with the concentration of 1.2 mg/mL.
In the prepared nonpolar molecule-based nano microsphere aqueous dispersion, the average particle size of the nano microsphere is 120nm, the polydispersity index is 0.5, the Zeta potential is-50 mV, the particle size and the polydispersity index of the nano microsphere are measured by a dynamic laser light scattering (DLS) test method, the test temperature is 28 ℃, the test time is 4min, and the test temperature of the Zeta potential is 28 ℃.
Example 11
A preparation method of a non-polar molecule-based nano microsphere aqueous dispersion liquid comprises the following specific steps:
(1) Dissolving the CIAA prepared in the example 5 in tetrahydrofuran according to the mass-volume ratio of 7mg to 1mL to form a uniform CIAA/tetrahydrofuran solution, and rapidly (within 9 s) adding ultrapure water (with the resistivity of 18MΩ cm) into the CIAA/tetrahydrofuran solution according to the volume ratio of 1 to 5 to obtain a colloid with the Tyndall effect;
(2) Transferring the colloid prepared in the step (1) into a dialysis bag with the molecular weight cut-off of >500, dialyzing the colloid with pure water, then replacing pure water for dialysis respectively at 1.5h, 4h and 8h after the beginning of dialysis, wherein the volume ratio of the pure water for dialysis to the dispersion liquid is 3000:11 each time, and after 24h, the dialysis is finished, removing tetrahydrofuran in the colloid, and obtaining the non-polar molecule-based nano microsphere aqueous phase dispersion liquid with the concentration of 1.4 mg/mL.
In the prepared nonpolar molecule-based nano microsphere aqueous dispersion, the average particle size of the nano microsphere is 150nm, the polydispersity index is 0.6, the Zeta potential is-47 mV, the particle size and the polydispersity index of the nano microsphere are measured by a dynamic laser light scattering (DLS) test method, the test temperature is 29 ℃, the test time is 4min, and the test temperature of the Zeta potential is 29 ℃.
Example 12
A preparation method of a non-polar molecule-based nano microsphere aqueous dispersion liquid comprises the following specific steps:
(1) Dissolving the CIAA prepared in the example 6 in tetrahydrofuran according to the mass-volume ratio of 10mg to 1mL to form a uniform CIAA/tetrahydrofuran solution, and rapidly (within 9 s) adding ultrapure water (with the resistivity of 18MΩ cm) into the CIAA/tetrahydrofuran solution according to the volume ratio of 1:5 to obtain a colloid with the Tyndall effect;
(2) Transferring the colloid prepared in the step (1) into a dialysis bag with the molecular weight cut-off of >500, dialyzing the colloid by pure water, then replacing pure water for dialysis respectively 1.5h, 4h and 8h after the beginning of dialysis, wherein the volume ratio of the pure water for dialysis to the dispersion liquid is 4000:11 each time, and after 24h, the dialysis is finished, removing tetrahydrofuran in the colloid, and obtaining the non-polar molecule-based nano microsphere aqueous phase dispersion liquid with the concentration of 2 mg/mL.
In the prepared nonpolar molecule-based nano microsphere aqueous dispersion liquid, the average particle size of the nano microsphere is 180nm, the polydispersity index is 0.65, the Zeta potential is-45 mV, the particle size and the polydispersity index of the nano microsphere are measured by a dynamic laser light scattering (DLS) test method, the test temperature is 30 ℃, the test time is 3min, and the test temperature of the Zeta potential is 30 ℃.
Example 13
A preparation method of polysaccharide-based fluorescence response sponge comprises the following specific steps:
(1) Adding sodium carboxymethyl cellulose powder into the nano microsphere aqueous dispersion liquid prepared in the example 7 under the stirring condition of 200rpm, and continuously stirring for 3 hours until the sodium carboxymethyl cellulose powder is completely dissolved to prepare sodium carboxymethyl cellulose/nano microsphere solution, wherein the mass concentration of sodium carboxymethyl cellulose in the sodium carboxymethyl cellulose/nano microsphere solution is 1%;
(2) Adding sodium hydroxide into the sodium carboxymethyl cellulose/nano microsphere solution obtained in the step (1) under the same stirring condition as the step (1), and continuously stirring for 20min until the sodium hydroxide is completely dissolved;
(3) Adding sodium trimetaphosphate into the solution obtained in the step (2) under the same stirring condition as the step (1), and continuously stirring for 20min until the sodium trimetaphosphate is completely dissolved to prepare a transparent precursor solution;
wherein the mass ratio of the sodium carboxymethyl cellulose powder in the step (1), the sodium hydroxide in the step (2) and the sodium trimetaphosphate in the step (3) is 2:0.5:0.6;
(4) Pouring the transparent precursor solution prepared in the step (3) into a round culture dish with the diameter of 60mm, refrigerating for 2 hours at the temperature of 2 ℃, freezing for 9 hours at the temperature of minus 60 ℃, freeze-drying for 72 hours under vacuum, washing with water for 3 times at 45 ℃, and finally freeze-drying again to obtain the polysaccharide-based fluorescence-responsive sponge, wherein the vacuum degree of the two freeze-drying is 2Pa, and the cold trap temperature is minus 53 ℃.
The finally prepared polysaccharide-based fluorescence response sponge consists of polysaccharide-based sponge and fluorescence response nanospheres distributed among pores of the polysaccharide-based sponge, wherein the fluorescence response nanospheres are formed by self-assembly of CIAA in a water phase; the average pore diameter of the polysaccharide-based fluorescence response sponge is 20 mu m, the porosity is 90%, and the specific surface area is 200m 2 Per g, density is 0.025g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The gas response time of the polysaccharide-based fluorescence response sponge is 70s, and the fluorescence quantum yield is 75%; the polysaccharide-based fluorescence-responsive sponge was able to rebound to the original volume after 57% volume compression, with a compression strength of 0.5kPa.
The prepared polysaccharide-based fluorescence response sponge is used for detecting dichloromethane gas, and the emission peak of the polysaccharide-based fluorescence response sponge is blue-shifted by 8nm in a solid fluorescence spectrum of the polysaccharide-based fluorescence response sponge in a dichloromethane gas atmosphere of 100ppm at 45 ℃; after the methylene chloride gas atmosphere was removed, the emission peak in the solid fluorescence spectrum of the polysaccharide-based fluorescence-responsive sponge was restored to the state before blue shift.
Example 14
A preparation method of polysaccharide-based fluorescence response sponge comprises the following specific steps:
(1) Adding sodium carboxymethyl cellulose powder into the nano microsphere aqueous dispersion liquid prepared in the example 8 under the stirring condition of 200rpm, and continuously stirring for 3 hours until the sodium carboxymethyl cellulose powder is completely dissolved to prepare sodium carboxymethyl cellulose/nano microsphere solution, wherein the mass concentration of sodium carboxymethyl cellulose in the sodium carboxymethyl cellulose/nano microsphere solution is 1.6%;
(2) Adding sodium hydroxide into the sodium carboxymethyl cellulose/nano microsphere solution obtained in the step (1) under the same stirring condition as the step (1), and continuously stirring for 20min until the sodium hydroxide is completely dissolved;
(3) Adding sodium trimetaphosphate into the solution obtained in the step (2) under the same stirring condition as the step (1), and continuously stirring for 20min until the sodium trimetaphosphate is completely dissolved to prepare a transparent precursor solution;
wherein the mass ratio of the sodium carboxymethyl cellulose powder in the step (1), the sodium hydroxide in the step (2) and the sodium trimetaphosphate in the step (3) is 2:0.6:0.6;
(4) Pouring the transparent precursor solution prepared in the step (3) into a round culture dish with the diameter of 75mm, refrigerating for 4 hours at the temperature of 4 ℃, freezing for 12 hours at the temperature of-50 ℃, freeze-drying for 66 hours under vacuum, washing for 3 times at the temperature of 40 ℃, and freeze-drying again to obtain the polysaccharide-based fluorescence-responsive sponge, wherein the vacuum degree of the two freeze-drying is 4Pa, and the cold trap temperature is-56 ℃.
The finally prepared polysaccharide-based fluorescence response sponge consists of polysaccharide-based sponge and fluorescence response nanospheres distributed among pores of the polysaccharide-based sponge, wherein the fluorescence response nanospheres are formed by self-assembly of CIAA in a water phase; the average pore diameter of the polysaccharide-based fluorescence response sponge is 36 mu m, the porosity is 90%, and the specific surface area is 170m 2 Per gram, density of 0.04g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The gas response time of the polysaccharide-based fluorescence response sponge is 80s, and the fluorescence quantum yield is 64%; the polysaccharide-based fluorescence-responsive sponge was able to rebound to the original volume after compression by 64% by volume, with a compression strength of 0.6kPa.
The prepared polysaccharide-based fluorescence response sponge is used for detecting dichloromethane gas, and the emission peak of the polysaccharide-based fluorescence response sponge is blue-shifted by 7nm in a solid fluorescence spectrum of the polysaccharide-based fluorescence response sponge in a dichloromethane gas atmosphere of 100ppm at 40 ℃; after the methylene chloride gas atmosphere was removed, the emission peak in the solid fluorescence spectrum of the polysaccharide-based fluorescence-responsive sponge was restored to the state before blue shift.
Example 15
A preparation method of polysaccharide-based fluorescence response sponge comprises the following specific steps:
(1) Adding sodium carboxymethyl cellulose powder into the nano microsphere aqueous dispersion liquid prepared in the embodiment 9 under the stirring condition of 300rpm, and continuously stirring for 4 hours until the sodium carboxymethyl cellulose powder is completely dissolved to prepare sodium carboxymethyl cellulose/nano microsphere solution, wherein the mass concentration of sodium carboxymethyl cellulose in the sodium carboxymethyl cellulose/nano microsphere solution is 2.2%;
(2) Adding sodium hydroxide into the sodium carboxymethyl cellulose/nano microsphere solution obtained in the step (1) under the same stirring condition as the step (1), and continuously stirring for 30min until the sodium hydroxide is completely dissolved;
(3) Adding sodium trimetaphosphate into the solution obtained in the step (2) under the same stirring condition as the step (1), and continuously stirring for 30min until the sodium trimetaphosphate is completely dissolved to prepare a transparent precursor solution;
wherein the mass ratio of the sodium carboxymethyl cellulose powder in the step (1), the sodium hydroxide in the step (2) and the sodium trimetaphosphate in the step (3) is 3:0.7:0.9;
(4) Pouring the transparent precursor solution prepared in the step (3) into a round culture dish with the diameter of 90mm, refrigerating for 6 hours at the temperature of 5 ℃, freezing for 15 hours at the temperature of minus 45 ℃, freeze-drying for 60 hours under vacuum, washing for 4 times at 35 ℃, and finally freeze-drying again to obtain the polysaccharide-based fluorescence-responsive sponge, wherein the vacuum degree of the two freeze-drying is 5Pa, and the cold trap temperature is minus 60 ℃.
The finally prepared polysaccharide-based fluorescence response sponge consists of polysaccharide-based sponge and fluorescence response nanospheres distributed among pores of the polysaccharide-based sponge, wherein the fluorescence response nanospheres are formed by self-assembly of CIAA in a water phase; the average pore diameter of the polysaccharide-based fluorescence response sponge is 52 mu m, the porosity is 85%, and the specific surface area is 140m 2 Per gram, density of 0.055g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The gas response time of the polysaccharide-based fluorescence response sponge is 90s, and the fluorescence quantum yield is 10%; the polysaccharide-based fluorescence-responsive sponge was able to rebound to the original volume after 71% compression by volume, with a compression strength of 0.7kPa.
The prepared polysaccharide-based fluorescence response sponge is used for detecting chloroform gas, and the emission peak in the solid fluorescence spectrum of the polysaccharide-based fluorescence response sponge is blue-shifted by 2nm in the atmosphere of 100ppm of chloroform gas at 35 ℃; after the chloroform gas atmosphere is removed, the emission peak in the solid fluorescence spectrum of the polysaccharide-based fluorescence-responsive sponge is restored to the state before blue shift.
Example 16
A preparation method of polysaccharide-based fluorescence response sponge comprises the following specific steps:
(1) Adding sodium carboxymethyl cellulose powder into the nano microsphere aqueous dispersion liquid prepared in the example 10 under the stirring condition of 300rpm, and continuously stirring for 4 hours until the sodium carboxymethyl cellulose powder is completely dissolved to prepare sodium carboxymethyl cellulose/nano microsphere solution, wherein the mass concentration of sodium carboxymethyl cellulose in the sodium carboxymethyl cellulose/nano microsphere solution is 2.8%;
(2) Adding sodium hydroxide into the sodium carboxymethyl cellulose/nano microsphere solution obtained in the step (1) under the same stirring condition as the step (1), and continuously stirring for 30min until the sodium hydroxide is completely dissolved;
(3) Adding sodium trimetaphosphate into the solution obtained in the step (2) under the same stirring condition as the step (1), and continuously stirring for 30min until the sodium trimetaphosphate is completely dissolved to prepare a transparent precursor solution;
wherein the mass ratio of the sodium carboxymethyl cellulose powder in the step (1), the sodium hydroxide in the step (2) and the sodium trimetaphosphate in the step (3) is 4:0.8:1.2;
(4) Pouring the transparent precursor solution prepared in the step (3) into a rectangular culture dish with the length of 60mm and the width of 60mm, refrigerating for 8 hours at the temperature of 6 ℃, freezing for 18 hours at the temperature of minus 40 ℃, freeze-drying for 54 hours under vacuum, washing for 4 times at the temperature of 30 ℃, and finally freeze-drying again to obtain the polysaccharide-based fluorescence-responsive sponge, wherein the vacuum degree of the two freeze-drying is 6Pa, and the cold trap temperature is minus 63 ℃.
The finally prepared polysaccharide-based fluorescence response sponge consists of polysaccharide-based sponge and fluorescence response nanospheres distributed among pores of the polysaccharide-based sponge, wherein the fluorescence response nanospheres are formed by self-assembly of CIAA in a water phase; the average pore diameter of the polysaccharide-based fluorescence response sponge is 68 mu m, the porosity is 85%, and the specific surface area is 110m 2 Per g, density is 0.070g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The gas response time of the polysaccharide-based fluorescence response sponge is 100s, and the fluorescence quantum yield is 14%; the polysaccharide-based fluorescence-responsive sponge was able to rebound to the original volume after 78% compression by volume, with a compression strength of 0.8kPa.
The prepared polysaccharide-based fluorescence response sponge is used for detecting toluene gas, and the emission peak of the polysaccharide-based fluorescence response sponge is blue-shifted by 2nm in a solid fluorescence spectrum of the polysaccharide-based fluorescence response sponge in a toluene gas atmosphere of 100ppm at 30 ℃; after the toluene gas atmosphere was removed, the emission peak in the solid fluorescence spectrum of the polysaccharide-based fluorescence-responsive sponge was restored to the state before blue shift.
Example 17
A preparation method of polysaccharide-based fluorescence response sponge comprises the following specific steps:
(1) Adding sodium carboxymethyl cellulose powder into the nano microsphere aqueous dispersion liquid prepared in the example 11 under the stirring condition of 400rpm, and continuously stirring for 5 hours until the sodium carboxymethyl cellulose powder is completely dissolved to prepare sodium carboxymethyl cellulose/nano microsphere solution, wherein the mass concentration of sodium carboxymethyl cellulose in the sodium carboxymethyl cellulose/nano microsphere solution is 3.4%;
(2) Adding sodium hydroxide into the sodium carboxymethyl cellulose/nano microsphere solution obtained in the step (1) under the same stirring condition as the step (1), and continuously stirring for 40min until the sodium hydroxide is completely dissolved;
(3) Adding sodium trimetaphosphate into the solution obtained in the step (2) under the same stirring condition as the step (1), and continuously stirring for 40min until the sodium trimetaphosphate is completely dissolved to prepare a transparent precursor solution;
wherein the mass ratio of the sodium carboxymethyl cellulose powder in the step (1), the sodium hydroxide in the step (2) and the sodium trimetaphosphate in the step (3) is 5:0.9:1.5;
(4) Pouring the transparent precursor solution prepared in the step (3) into a rectangular culture dish with the length of 75mm and the width of 75mm, refrigerating for 10 hours at the temperature of 7 ℃, freezing for 21 hours at the temperature of minus 35 ℃, freeze-drying for 48 hours at the vacuum condition, washing for 5 times at the temperature of 25 ℃, and finally freeze-drying again to obtain the polysaccharide-based fluorescence-responsive sponge, wherein the vacuum degree of the two freeze-drying is 7Pa, and the cold trap temperature is minus 66 ℃.
The finally prepared polysaccharide-based fluorescence response sponge consists of polysaccharide-based sponge and fluorescence response nanospheres distributed among pores of the polysaccharide-based sponge, wherein the fluorescence response nanospheres are formed by self-assembly of CIAA in a water phase; the average pore diameter of the polysaccharide-based fluorescence-responsive sponge was 84 μm, the porosity was 82%, and the specific surface area was 90m 2 Per gram, density of 0.085g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The gas response time of the polysaccharide-based fluorescence response sponge is 110s, and the fluorescence quantum yield is 60%; the polysaccharide-based fluorescence-responsive sponge was able to rebound to the original volume after 85% volume compression, with a compression strength of 0.9kPa.
The prepared polysaccharide-based fluorescence response sponge is used for detecting tetrahydrofuran gas, and the emission peak in the solid fluorescence spectrum of the polysaccharide-based fluorescence response sponge is blue-shifted by 6nm in the 100ppm tetrahydrofuran gas atmosphere at 25 ℃; after the tetrahydrofuran gas atmosphere was removed, the emission peak in the solid fluorescence spectrum of the polysaccharide-based fluorescence-responsive sponge was restored to the state before blue shift.
Example 18
A preparation method of polysaccharide-based fluorescence response sponge comprises the following specific steps:
(1) Adding sodium carboxymethyl cellulose powder into the nano microsphere aqueous dispersion liquid prepared in the example 12 under the stirring condition of 400rpm, and continuously stirring for 5 hours until the sodium carboxymethyl cellulose powder is completely dissolved to prepare sodium carboxymethyl cellulose/nano microsphere solution, wherein the mass concentration of sodium carboxymethyl cellulose in the sodium carboxymethyl cellulose/nano microsphere solution is 4%;
(2) Adding sodium hydroxide into the sodium carboxymethyl cellulose/nano microsphere solution obtained in the step (1) under the same stirring condition as the step (1), and continuously stirring for 40min until the sodium hydroxide is completely dissolved;
(3) Adding sodium trimetaphosphate into the solution obtained in the step (2) under the same stirring condition as the step (1), and continuously stirring for 40min until the sodium trimetaphosphate is completely dissolved to prepare a transparent precursor solution;
wherein the mass ratio of the sodium carboxymethyl cellulose powder in the step (1), the sodium hydroxide in the step (2) and the sodium trimetaphosphate in the step (3) is 6:1:1.8;
(4) Pouring the transparent precursor solution prepared in the step (3) into a rectangular culture dish with the length of 60mm and the width of 60mm, refrigerating for 12 hours at the temperature of 8 ℃, freezing for 24 hours at the temperature of minus 30 ℃, freeze-drying for 42 hours under vacuum, washing for 5 times at the temperature of 20 ℃, and finally freeze-drying again to obtain the polysaccharide-based fluorescence-responsive sponge, wherein the vacuum degree of the two freeze-drying is 8Pa, and the cold trap temperature is minus 70 ℃.
The finally prepared polysaccharide-based fluorescence response sponge consists of polysaccharide-based sponge and fluorescence response nanospheres distributed among pores of the polysaccharide-based sponge, wherein the fluorescence response nanospheres are formed by self-assembly of CIAA in a water phase; the average pore diameter of the polysaccharide-based fluorescence response sponge is 100 mu m, the porosity is 80%, and the specific surface area is 60m 2 Per gram, density of 0.1g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The gas response time of the polysaccharide-based fluorescence response sponge is 120s, and the fluorescence quantum yield is 80%; the polysaccharide-based fluorescence-responsive sponge was able to rebound to original volume after 90% volume compression, with a compression strength of 1.0kPa.
The prepared polysaccharide-based fluorescence response sponge is used for detecting tetrahydrofuran gas, and the emission peak in the solid fluorescence spectrum of the polysaccharide-based fluorescence response sponge is blue-shifted by 5nm in the 100ppm tetrahydrofuran gas atmosphere at 20 ℃; after the tetrahydrofuran gas atmosphere was removed, the emission peak in the solid fluorescence spectrum of the polysaccharide-based fluorescence-responsive sponge was restored to the state before blue shift.
Claims (12)
1. A preparation method of polysaccharide-based fluorescence response sponge is characterized by comprising the following steps: sequentially adding sodium carboxymethyl cellulose powder, sodium hydroxide and sodium trimetaphosphate into a nano microsphere aqueous dispersion liquid under the stirring condition until the sodium carboxymethyl cellulose powder, sodium hydroxide and sodium trimetaphosphate are completely dissolved to prepare transparent precursor solution, pouring the prepared transparent precursor solution into a mould, and refrigerating, freezing and freeze-drying to prepare the polysaccharide-based fluorescence response sponge;
the preparation method of the nano microsphere aqueous dispersion liquid comprises the following steps: dissolving CIAA in tetrahydrofuran to form CIAA/tetrahydrofuran solution, adding ultrapure water into the CIAA/tetrahydrofuran solution to obtain colloid, and removing tetrahydrofuran in the colloid through dialysis to obtain nanometer microsphere water phase dispersion;
The CIAA is formed by chemically bonding 1 assembler containing hydrophilic functional groups and 1-2 nonpolar limiting assemblers, and the CIAA is nonpolar;
the assembly containing hydrophilic functional groups is perylene imide groups or perylene imide derivative groups; the nonpolar limiting assembly is a group with a nano-sized three-dimensional structure or a group capable of shrinking into a nano-sized three-dimensional structure in an aqueous phase due to a hydrophobic function;
the group with the nano-size three-dimensional structure isWherein R is isobutyl or isooctyl, R is a chemical bond site 1 And R is 2 Each independently selected from alkyl chains having less than 20 carbon atoms;
the mass volume ratio of the CIAA to the tetrahydrofuran is 1mg to 10mg to 1mL, and the volume ratio of the CIAA/tetrahydrofuran solution to the ultrapure water is 1 to 5 to 1 to 10.
2. The method for preparing a polysaccharide-based fluorescence-responsive sponge according to claim 1, wherein the hydrophilic functional group-containing assembly is
Wherein is the chemical bonding position.
3. The method for producing a polysaccharide-based fluorescent responsive sponge according to claim 1, wherein the group capable of shrinking into a nano-sized three-dimensional structure due to a hydrophobic interaction in an aqueous phase is an alkyl chain of 6 carbons or more.
4. The method for preparing a polysaccharide-based fluorescent responsive sponge according to claim 1, wherein the mold is a circular culture dish with a diameter of 5-150 mm or a rectangular culture dish with a length of 5-150 mm and a width of 5-150 mm.
5. The method for preparing a polysaccharide-based fluorescence-responsive sponge according to claim 1, wherein the particle size of the particles in the aqueous dispersion of the nanoparticle is 50-200 nm, and the polydispersity index is 0.1-0.7; the Zeta potential of the nano microsphere aqueous dispersion is-60 to-40 mV.
6. The method for preparing the polysaccharide-based fluorescence-responsive sponge according to claim 1, wherein the specific preparation steps of the polysaccharide-based fluorescence-responsive sponge are as follows:
(1) Adding sodium carboxymethyl cellulose powder into the nano microsphere aqueous phase dispersion liquid under the stirring condition of 200-400 rpm, and continuously stirring until the sodium carboxymethyl cellulose powder is completely dissolved to prepare sodium carboxymethyl cellulose/nano microsphere solution;
(2) Adding sodium hydroxide into the sodium carboxymethyl cellulose/nano microsphere solution obtained in the step (1) under the same stirring condition as the step (1), and continuously stirring until the sodium hydroxide is completely dissolved;
(3) Adding sodium trimetaphosphate into the solution obtained in the step (2) under the same stirring condition as the step (1), and continuously stirring until the sodium trimetaphosphate is completely dissolved to prepare a transparent precursor solution;
(4) Pouring the transparent precursor solution prepared in the step (3) into a mould, refrigerating for 1-12 h at the temperature of 0-10 ℃, freezing for 6-24 h at the temperature of minus 60-minus 30 ℃, freeze-drying for 36-72 h under vacuum, washing for multiple times at the temperature of 15-45 ℃, and finally freeze-drying again to obtain the polysaccharide-based fluorescence response sponge.
7. The method for preparing the polysaccharide-based fluorescence-responsive sponge according to claim 6, wherein the concentration of the aqueous dispersion of the nano-microspheres in the step (1) is 0.1-2 mg/mL, and the mass concentration of sodium carboxymethyl cellulose in the sodium carboxymethyl cellulose/nano-microsphere solution is 1-4%;
the mass ratio of the sodium carboxymethyl cellulose powder in the step (1), the sodium hydroxide in the step (2) and the sodium trimetaphosphate in the step (3) is 2-6:0.5-1:0.6-1.8.
8. The method for producing a polysaccharide-based fluorescent responsive sponge according to claim 6, wherein the time required for continuous stirring until sodium carboxymethylcellulose powder is completely dissolved in step (1) is 3 to 5 hours, the time required for continuous stirring until sodium hydroxide is completely dissolved in step (2) is 20 to 40 minutes, and the time required for continuous stirring until sodium trimetaphosphate is completely dissolved in step (3) is 20 to 40 minutes;
The vacuum degree of freeze drying in the step (4) is 0.1-10 Pa, and the cold trap temperature is-70 to-50 ℃.
9. A polysaccharide-based fluorescent responsive sponge made by the method of any one of claims 1-8, wherein: the fluorescent nanoparticle consists of a polysaccharide-based sponge and fluorescent-responsive nanoparticle distributed among pores of the polysaccharide-based sponge, wherein the fluorescent-responsive nanoparticle is formed by self-assembly of CIAA in an aqueous phase.
10. The polysaccharide-based fluorescence-responsive sponge according to claim 9, wherein the average pore diameter of the polysaccharide-based fluorescence-responsive sponge is 1 to 100 μm, the porosity is 80 to 99%, and the specific surface area is 12 to 200m 2 Per gram, the density is 0.01 to 0.1g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The gas response time of the polysaccharide-based fluorescence response sponge is 60-120 s, and the fluorescence quantum yield is 10-80%; the multipleThe glycosyl fluorescent responsive sponge can rebound to the original volume after being compressed by 50-90% of the volume, and the compression strength is 0.5-1.0 kPa.
11. Use of a polysaccharide-based fluorescent responsive sponge according to claim 9 or 10 for the detection of organic solvent gases;
the polysaccharide-based fluorescence response sponge shows color change under the conditions of a certain temperature and a certain organic solvent gas concentration, and the emission peak value in the solid fluorescence spectrum changes;
The organic solvent is dichloromethane, chloroform, toluene or tetrahydrofuran.
12. The use according to claim 11, wherein the emission peak in the solid fluorescence spectrum of the polysaccharide-based fluorescence-responsive sponge is blue-shifted by 2 to 8nm at 15 to 45 ℃ in an atmosphere of 100ppm of an organic solvent gas; and after the organic solvent gas atmosphere is removed, the emission peak in the solid fluorescence spectrum of the polysaccharide-based fluorescence response sponge is restored to the state before blue shift.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310049348.9A CN116144069B (en) | 2023-02-01 | 2023-02-01 | Polysaccharide-based fluorescence response sponge and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310049348.9A CN116144069B (en) | 2023-02-01 | 2023-02-01 | Polysaccharide-based fluorescence response sponge and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116144069A CN116144069A (en) | 2023-05-23 |
| CN116144069B true CN116144069B (en) | 2024-04-09 |
Family
ID=86372991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310049348.9A Active CN116144069B (en) | 2023-02-01 | 2023-02-01 | Polysaccharide-based fluorescence response sponge and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116144069B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117530929B (en) * | 2024-01-10 | 2024-03-29 | 东华大学 | Weight-losing capsule |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105251420A (en) * | 2015-09-08 | 2016-01-20 | 哈尔滨工程大学 | Preparation method for multifunctional composite microspheres |
| CN107632002A (en) * | 2017-09-13 | 2018-01-26 | 北京理工大学 | A kind of composite fluorescence biology sensor and its production and use |
| CN110350193A (en) * | 2019-07-02 | 2019-10-18 | 华南师范大学 | A kind of double ion embedded type crosslinking net triphenylamine anode of polymer lithium ion battery material and preparation method thereof |
| CN111875731A (en) * | 2020-07-09 | 2020-11-03 | 上海慧翌新材料科技有限公司 | Porous high-fluorescence polyacrylate microsphere and preparation method thereof |
-
2023
- 2023-02-01 CN CN202310049348.9A patent/CN116144069B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105251420A (en) * | 2015-09-08 | 2016-01-20 | 哈尔滨工程大学 | Preparation method for multifunctional composite microspheres |
| CN107632002A (en) * | 2017-09-13 | 2018-01-26 | 北京理工大学 | A kind of composite fluorescence biology sensor and its production and use |
| CN110350193A (en) * | 2019-07-02 | 2019-10-18 | 华南师范大学 | A kind of double ion embedded type crosslinking net triphenylamine anode of polymer lithium ion battery material and preparation method thereof |
| CN111875731A (en) * | 2020-07-09 | 2020-11-03 | 上海慧翌新材料科技有限公司 | Porous high-fluorescence polyacrylate microsphere and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 胆甾醇基-普鲁兰多糖疏水改性材料的制备及其自组装性质的研究;杨文智;李学敏;陈红丽;陈名懋;刘玲蓉;张其清;;中国新药杂志;20090115(第01期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116144069A (en) | 2023-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Meshkat et al. | Comparison between ZIF-67 and ZIF-8 in Pebax® MH-1657 mixed matrix membranes for CO2 separation | |
| Yang et al. | Highly water-permeable and stable hybrid membrane with asymmetric covalent organic framework distribution | |
| CN116144069B (en) | Polysaccharide-based fluorescence response sponge and preparation method and application thereof | |
| CN102617646B (en) | Preparation method of nanoscale metal organic framework materials | |
| CA3120865C (en) | Multivariate and other metal-organic frameworks, and uses thereof | |
| Gu et al. | Template-free synthesis of N-doped porous carbons and their gas sorption properties | |
| Zhong et al. | Carbon composite membrane derived from a two-dimensional zeolitic imidazolate framework and its gas separation properties | |
| CN112023702B (en) | Hydroxylated boron nitride composite film and preparation method and application thereof | |
| CN114570296A (en) | Chitosan-based covalent organic framework aerogel material and preparation method and application thereof | |
| CN110054782B (en) | Cyclodextrin-based metal organic framework material and preparation method thereof | |
| KR20170117916A (en) | Synthetic soluble polymer for graphene dispersion stabilizer, graphene solutions with high colloidal stability comprising the polymer, graphene hydrogel comprising the solution, and graphene aerogel produced form the hydrogel | |
| CN112341630A (en) | Method for continuously preparing nano metal-organic framework material by using supergravity technology | |
| CN107754775B (en) | Solvent supported compaction of metal organic framework materials | |
| CN111484602B (en) | 1,3,6,8-tetra (p-formylphenyl) pyrene-based conjugated microporous polymer and preparation method thereof | |
| CN103483392B (en) | A kind of there is hollow structure polymer microballoon and preparation method and use for storing hydrogen | |
| CN115161016B (en) | Sensor for detecting kaempferol and quercetin in tobacco leaves and preparation method thereof | |
| CN115194143B (en) | Method for separating and purifying nano particles in suspension of polyvinylpyrrolidone coated nano particles | |
| CN116715232B (en) | Preparation method of independently-supportable three-dimensional graphite alkyne foam and product thereof | |
| CN112657469B (en) | Preparation method of amino-functionalized silsesquioxane-based heavy metal ion adsorbent | |
| CN115161016A (en) | Sensor for detecting kaempferol and quercetin in tobacco leaves and preparation method thereof | |
| CN116173887A (en) | Cu-Fe-ZIF-8/GCN composite material and preparation method and application thereof | |
| US20210381132A1 (en) | Transition metal dichalcogenide fiber and method of producing the same | |
| CN114097774B (en) | Preparation method of mesoporous silica nano double-layer microsphere controlled release agent | |
| CN117101558B (en) | Preparation method and application of covalent organic framework aerogel | |
| CN111484643B (en) | Self-supporting MnO2Nanowire imprinted membrane and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |