CN116606382A - Cellulose with mercury ion recognition group and preparation method and application thereof - Google Patents
Cellulose with mercury ion recognition group and preparation method and application thereof Download PDFInfo
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- CN116606382A CN116606382A CN202310344722.8A CN202310344722A CN116606382A CN 116606382 A CN116606382 A CN 116606382A CN 202310344722 A CN202310344722 A CN 202310344722A CN 116606382 A CN116606382 A CN 116606382A
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- cellulose
- mercury ion
- mercury
- hydroxyethyl cellulose
- ion recognition
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- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229920002678 cellulose Polymers 0.000 title claims abstract description 42
- 239000001913 cellulose Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- -1 mercury ions Chemical class 0.000 claims abstract description 56
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims abstract description 51
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims abstract description 51
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims abstract description 51
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000001514 detection method Methods 0.000 claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 230000004044 response Effects 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 19
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 17
- 230000008859 change Effects 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 229940126062 Compound A Drugs 0.000 claims description 9
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229920006295 polythiol Polymers 0.000 claims description 8
- 150000003568 thioethers Chemical class 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 6
- 230000002152 alkylating effect Effects 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000002168 alkylating agent Substances 0.000 claims description 3
- 229940100198 alkylating agent Drugs 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- 230000003113 alkalizing effect Effects 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims 2
- 230000000007 visual effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 4
- 239000004005 microsphere Substances 0.000 description 25
- 239000000047 product Substances 0.000 description 25
- 239000013078 crystal Substances 0.000 description 20
- 229920000642 polymer Polymers 0.000 description 19
- 239000004793 Polystyrene Substances 0.000 description 18
- 229920002223 polystyrene Polymers 0.000 description 18
- 239000000499 gel Substances 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 108010025899 gelatin film Proteins 0.000 description 10
- 239000000523 sample Substances 0.000 description 10
- PTHCMJGKKRQCBF-UHFFFAOYSA-N Cellulose, microcrystalline Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC)C(CO)O1 PTHCMJGKKRQCBF-UHFFFAOYSA-N 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 8
- 229910001385 heavy metal Inorganic materials 0.000 description 7
- 239000004038 photonic crystal Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 6
- 230000008961 swelling Effects 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 5
- 238000000502 dialysis Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000000017 hydrogel Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920000896 Ethulose Polymers 0.000 description 4
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- ADXGNEYLLLSOAR-UHFFFAOYSA-N tasosartan Chemical compound C12=NC(C)=NC(C)=C2CCC(=O)N1CC(C=C1)=CC=C1C1=CC=CC=C1C=1N=NNN=1 ADXGNEYLLLSOAR-UHFFFAOYSA-N 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 238000000985 reflectance spectrum Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000009777 vacuum freeze-drying Methods 0.000 description 3
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 2
- 241000252506 Characiformes Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229920013820 alkyl cellulose Polymers 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 238000003491 array Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000000638 stimulation Effects 0.000 description 2
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- NWLUZGJDEZBBRH-UHFFFAOYSA-N 2-(propan-2-yloxymethyl)oxirane Chemical compound CC(C)OCC1CO1 NWLUZGJDEZBBRH-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical group OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/20—Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
-
- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/29—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands using visual detection
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Analytical Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention belongs to the technical field of aquatic product detection, and particularly relates to cellulose with mercury ion recognition groups, and a preparation method and application thereof. And grafting functional molecules with hydroxyethyl cellulose serving as a framework to obtain the cellulose with the mercury ion recognition group, wherein the functional molecules are the mercury ion recognition group and the modified group. The application of the method in detecting mercury ions is disclosed. The material disclosed by the invention is applied to detection of mercury ions in aquatic products, and can be visually and conveniently and rapidly identified by naked eyes, so that a brand new, sensitive, convenient and accurate method is provided for detection of mercury ions in aquatic products.
Description
Technical Field
The invention belongs to the technical field of aquatic product detection, and particularly relates to cellulose with mercury ion recognition groups, and a preparation method and application thereof.
Background
The detection of the kind and the content of heavy metal ions in the aquatic products has extremely important significance for protecting human health. Although the traditional detection methods such as atomic absorption spectrometry, chromatography and mass spectrometry can accurately identify metal ions in water, the methods are complex in operation and require professional operators, and consumers can hardly detect whether the edible aquatic products have the problems of exceeding the standard of the heavy metal ions or not. Therefore, how to conveniently and rapidly detect the heavy metal ion species in the aquatic products and determine whether the concentration exceeds the national standard is more and more concerned by relevant researchers and consumers.
The gel photonic crystal photochemical sensor is characterized in that a photonic crystal is embedded in a stimulus response gel, when external stimulus interacts with the gel, the water content and the volume in the gel change, so that the color of a photonic crystal structure changes, and the core content of the polymer colloidal crystal array for identifying an analyte is the gel volume change caused by molecular identification, and the gel volume change is converted into naked eye visible color change through the colloidal crystal array. The research result provides a brand new method for converting the identification information into the optical signal, and becomes an important research direction of the photochemical sensor. However, such sensors have been reported to have a weak ability to identify metal ions in a body of water, and are susceptible to the influence of the test environment (especially pH, organics, ionic strength), reducing or even losing their ability to identify target metal ions.
At present, the method for preparing the response polymer colloidal crystal array at home and abroad mainly utilizes thermal initiation polymer crosslinking, namely, monomer, crosslinking agent and initiator are mixed and injected into a photonic crystal array template, and the photonic crystal array is fixed in stimulus response hydrogel through thermal initiation polymerization to form the response polymer colloidal crystal array. The response material prepared by the polymerization method has a series of defects and is mainly divided into the following two points: (1) harsh polymerization conditions: the thermal initiation polymerization reaction temperature requirement is high, the reaction system is complex, and the control degree of the reaction process is poor; (2) structural and compositional defects of the polymer hydrogel itself: the main composition of the hydrogel used for preparing the responsive polymer colloidal crystal array is polyacrylamide and derivative polymers thereof; (3) the test accuracy cannot be guaranteed: the aquatic products are rich in inorganic salts such as potassium, sodium, magnesium, calcium salt and the like, the swelling rate of the hydrogel is obviously influenced by the inorganic salts in the water body, the hydrogel is easy to dehydrate and shrink, and the accuracy of detecting target metal ions by the polymer colloidal crystal array photochemical sensor is finally influenced.
Disclosure of Invention
The invention aims to provide a photochemical sensor for visually and rapidly detecting mercury ions in aquatic products and application thereof.
In order to achieve the above purpose, the invention adopts the technical scheme that:
the cellulose with the mercury ion recognition group is obtained by taking hydroxyethyl cellulose as a framework and grafting functional molecules, wherein the functional molecules are the mercury ion recognition group and the modified group.
The mercury ion recognition group is provided by an open chain thioether oligomer or an open chain aza thioether oligomer; the modifying group provides for an alkylating agent with a short chain alkane.
The preparation method of the cellulose with the mercury ion recognition group comprises the steps of firstly taking hydroxyethyl cellulose as a framework, grafting an open-chain thioether oligomer or an open-chain aza thioether oligomer as the mercury ion recognition group, and grafting an alkylating reagent with short-chain alkane as a modifying group to obtain the stimulus-responsive alkyl hydroxyethyl cellulose with the capability of selectively complexing mercury ions, namely the cellulose with the mercury ion recognition group.
Further, the cellulose with the mercury ion recognition group is:
(1) Mercury ion recognition group synthesis: 3-5 g of allyl glycidyl ether and 0.5-2 g of open-chain thioether oligomer or open-chain aza thioether oligomer are fully mixed, and the mixture is continuously irradiated for 2-4 h by ultraviolet to obtain a compound A containing an epoxy ring in a molecular structure;
(2) Mercury ion stimulus response hydroxyethyl cellulose synthesis: adding sodium hydroxide into 10-25wt% of hydroxyethyl cellulose solution, alkalizing for 1-2 h at 50-70 ℃ to obtain alkalized hydroxyethyl cellulose solution, slowly dripping a compound A into the alkalized hydroxyethyl cellulose solution, reacting for 48-72 h in the presence of nitrogen in a dark place, and drying to obtain mercury ion stimulus response hydroxyethyl cellulose;
(3) Cellulose with mercury ion recognition groups: dissolving the mercury ion stimulus response hydroxyethyl cellulose in a mixed solvent, then dropwise adding a mixed solution of an alkylating reagent with short-chain alkane and sodium hydroxide, heating to 60-70 ℃ for reacting for 5-7 h, obtaining a product after the reaction, and performing light-blocking reaction for 48-72 h, and drying.
The power of the ultraviolet lamp in the step (1) is 60-120W; the compound A is polythioether glycidyl ether or polyaza thioether glycidyl ether;
the mol ratio of the hydroxyethyl cellulose to the sodium hydroxide in the hydroxyethyl cellulose aqueous solution in the step (2) is 1:0.5-1:1.3;
the molecular weight of the hydroxyethyl fiber is 20-38 ten thousand (Mw), and the degree of substitution of hydroxyethyl is more than 2.5; hydroxyethyl cellulose and compound A molar ratio n Hydroxyethyl cellulose :n Polythioether glycidyl ethers =1:1.2 to 1.7 or n Hydroxyethyl cellulose :n Polyaza thioether glycidyl ethers =1:1.0 to 1.9; the Degree of Substitution (DS) of compound a on the hydroxyethyl fiber backbone is: 0.05<DS Polythioether glycidyl ethers <0.12；0.03<DS Polythioether glycidyl ethers <0.10；
V in the mixed solvent in the step (3) Water and its preparation method ：V Organic solvents =1: 0.1 to 0.3, wherein the organic solvent is one or more of ethanol, isopropanol and ethyl acetate; the alkylating reagent with short-chain alkane is one or more of alkyl glycidyl ether; the degree of substitution of the alkyl glycidyl ether was 2.3<DS Alkyl glycidyl ethers <2.8；
The alkyl glycidyl ether is one or more of ethyl glycidyl ether, isopropyl glycidyl ether and butyl glycidyl ether.
The molar ratio of the mercury ion stimulus response alkyl hydroxyethyl cellulose to the addition of alkyl glycidyl ether hydrogen to sodium oxide is 1:3.0-5.0:0.5-1.8.
Use of said cellulose with a mercury ion recognition group for detecting mercury ions.
The application of the cellulose with the mercury ion recognition group in a photochemical sensor for detecting and visualizing the mercury ions in the aquatic products is provided.
A photochemical sensor for visually and rapidly detecting mercury ions in aquatic products comprises cellulose with mercury ion identification groups.
Further, the cellulose aqueous solution with the mercury ion recognition group and the polystyrene microsphere are self-assembled to form a colloidal crystal array which is coupled and gelled to prepare the mercury ion photochemical sensor.
Specifically: fully mixing the cross-linking agent with 8-15 wt% of cellulose water solution with mercury ion recognition groups, removing bubbles, injecting into an assembled styrene microsphere template, and carrying out ultraviolet light (700-1500 mW/cm 2 ) Curing and crosslinking for 40-100 s to obtain the photochemical sensor of mercury ions.
The cross-linking agent is diphenyl ketone, 2-hydroxy diphenyl ketone or 2-methyl diphenyl ketone, and the volume ratio of the cross-linking agent to the cellulose aqueous solution with mercury ion recognition group is 0.52-1.88:30.
The preparation method of the styrene microsphere template comprises the following steps: weighing a polystyrene microsphere (particle size 240-360 nm) dispersion liquid with the concentration of 0.5-1.3 g/L by using a liquid-transferring gun, spreading the dispersion liquid on a glass plate (the glass plate is soaked in a piranha etching liquid for 24 hours), and then placing the glass plate into an oven for self-assembly at the temperature of 40-60 ℃ to obtain the polystyrene microsphere template.
The preparation of the polystyrene microsphere adopts an emulsion polymerization method, 10g of styrene is weighed and added into a three-neck flask, 100mL of deionized water is added into the flask, the flask is heated and stirred at the speed of 300r/min, 0.0496-0.0951 g of emulsifier (sodium dodecyl sulfate) is added, the reaction temperature is controlled to be 100 ℃, when a reflux phenomenon occurs in a condensing tube in a reaction device, the timing is started for 2min, 5mL of potassium persulfate with the mass fraction of 2% is added as an initiator for reaction for 2h, after the reaction is stopped, the room temperature is cooled, the mixture is centrifuged for three times at the speed of 9500r/min to remove supernatant, and then the supernatant is dispersed into the deionized water for standby, and the particle size of the morphology of the microsphere is represented by a scanning electron microscope.
A method for detecting mercury ions in aquatic products by using the sensor is characterized in that a sample to be detected is dripped to the sensor, and gel volume change in the sensor caused by an identification signal generated after an identification group in the sensor identifies the mercury ions is converted into color change visible to naked eyes, so that the detection of the mercury ions in the sample is realized.
The method is used for rapidly identifying mercury ions in the aquatic products, and comprises the following specific steps: sucking 0.5-1 mL of aquatic product sample solution, dripping the solution onto the surface of a gel film of the sensor, and observing the color change condition of the gel film after 2 minutes to finish the rapid recognition of mercury ions.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention takes hydroxyethyl cellulose with the advantages of resources, structure and performance as a gel skeleton, and is an ideal raw material for preparing functional biomass-based gel. The mercury ion stimulus responsive alkyl hydroxyethyl cellulose provided by the invention has better water solubility, so that the alkyl cellulose gel can be ensured to have higher swelling rate. Therefore, the application of the alkyl cellulose gel as the filling material to the response polymer colloidal crystal array can not only improve the sensitivity and the signal amplification effect of the photochemical sensor, but also enlarge the application range of the photochemical sensor, and can still ensure the accuracy of the detection result in the complex-composition detection sample.
2. The invention has the advantages of instantaneity, capability of rapidly detecting the types and the concentrations of the heavy metal ions in the sample before the composition of the sample solution is unchanged, lower detection cost, simple and convenient operation method, and capability of automatically detecting whether the mercury ions in the aquatic products exceed the standard or not by consumers.
3. The detection method has strong universality, and a series of naked eye visible cellulose-based gel photochemical sensors for detecting heavy metal ions can be prepared by designing different special recognition groups for the heavy metal ions.
Drawings
FIG. 1 is a flow chart showing a preparation process and a detection process of a polymer colloid crystal array film of a photochemical sensor-stimulus-responsive alkyl hydroxyethyl cellulose gel for detecting mercury ions in aquatic products.
FIG. 2 shows that the inorganic salt and pH of the gel provided by the embodiment of the invention have no obvious influence on the swelling rate of the stimulus-responsive alkyl hydroxyethyl cellulose gel, and the accuracy of the detection result is ensured.
Fig. 3 is an SEM image of polystyrene microspheres according to an embodiment of the present invention.
Fig. 4 is a reflectance spectrum and a digital photo of a real object for identifying mercury ions by the photochemical sensor for mercury ions according to example 1 of the present invention.
FIG. 5 shows the selective recognition of mercury ions by a photochemical sensor for mercury ions according to an embodiment of the invention.
Fig. 6 is a reflectance spectrum and a digital photo of a real object for identifying mercury ions by the photochemical sensor for mercury ions according to example 2 of the present invention.
Detailed Description
The following description of the embodiments of the present invention is further provided in connection with the accompanying examples, and it should be noted that the embodiments described herein are for the purpose of illustration and explanation only, and are not limiting of the invention.
According to the invention, a cellulose gel precursor with stimulus response performance and a cross-linking agent are injected into a colloidal crystal array formed by self-assembly of polystyrene nano-microspheres, so that a novel response polymer colloidal crystal array film material is prepared. The sensor formed by the invention converts the volume change caused by molecular recognition into orderly amplification of the space between photonic crystal arrays, and further rapidly converts a recognition signal into a large-amplitude color change. According to the Bragg equation, the ordered increase of the distance between the photonic crystal arrays causes a large-scale color change, and the color change can be conveniently and rapidly observed by naked eyes. The cellulose gel colloidal crystal array with the characteristics can be used as a photochemical sensor visible to naked eyes, and can be used for rapidly, conveniently and real-timely detecting harmful substances such as mercury ions in aquatic products.
Example 1
The general flow of the preparation and application of the polymer colloidal crystal array film in response to the stimulus of alkyl hydroxyethyl cellulose gel is shown in figure 1, and the specific method is as follows:
(1) Preparation of mercury ion stimulus responsive ethyl hydroxyethyl cellulose:
(1) ion recognition group synthesis: 3.0g of allyl glycidyl ether and 0.5g of tetrasulfide oligomer are fully mixed, and are continuously irradiated for 2 hours by an 80W ultraviolet lamp, and the compound polytetrasulfide glycidyl ether containing epoxy rings in the molecular structure is obtained through reduced pressure distillation and purification;
(2) mercury ion stimulus response hydroxyethyl cellulose synthesis: sodium hydroxide (mol ratio of hydroxyethyl cellulose to sodium hydroxide is 1:1.3) is added into 5g,15wt% of hydroxyethyl cellulose solution, alkalization is carried out for 1h at 70 ℃ to obtain alkalized hydroxyethyl cellulose solution, and the compound polytetrathioether glycidyl ether (n Hydroxyethyl cellulose ：n Polytetrathioether glycidyl ethers =1:1.4), the process should be carried out under the condition of avoiding light and nitrogen is introduced until the reaction is finished, the obtained product after the reaction is put into a dialysis bag for closed photodialysis for 72 hours, then the solution is rotationally evaporated to remove most of the solvent, and the viscous product is subjected to vacuum freeze drying for 48 hours to obtain the dried mercury ion stimulus response hydroxyethyl cellulose, DS Polytetrathioether glycidyl ethers ＝0.12；
(3) Synthesis of cellulose with mercury ion recognition group on alkane base band: dissolving ion-stimulus-responsive hydroxyethylcellulose in a mixed solvent (V Water and its preparation method ：V Ethanol =1: 0.3 Dropwise adding a mixed solution of ethyl glycidyl ether and sodium hydroxide, wherein the molar ratio of the added hydroxyethyl cellulose to the added ethyl glycidyl ether sodium hydroxide is 1.0:5.0:1.2 in response to mercury ion stimulation, heating to 60 ℃ for reaction for 5 hours, and reactingThe obtained product is put into a dialysis bag to be subjected to closed photo dialysis for 48 hours, then the solution is subjected to rotary evaporation to remove most of the solvent, and the viscous product is subjected to vacuum freeze drying for 48 hours to obtain the dried cellulose with mercury ion recognition groups, DS Ethyl glycidyl ether ＝2.8。
The cellulose with the mercury ion recognition group obtained above was gelled in a conventional manner (petrochemical industry, 2002,31 (8), 622-625) and then examined, see fig. 2.
As shown in FIG. 2 (a), when the inorganic salt concentration was increased from 0mol/L to 0.5mol/L (which is far higher than the inorganic salt content in the aquatic products), the swelling ratio of the gel prepared from the mercury ion stimulus responsive ethyl hydroxyethyl cellulose was not significantly changed. In addition, as can be seen from fig. 2 (b), the swelling ratio of the gel does not change significantly when the pH value of the solution system is between 2 and 12, which indicates that the influence of the sample organic salt and other impurities on the swelling ratio of the gel is effectively reduced by using alkylation modification, thereby ensuring the accuracy of the detection result.
(2) Preparation of polystyrene microspheres and templates thereof: 10g of styrene is weighed by adopting an emulsion polymerization method and added into a three-neck flask, 100mL of deionized water is added into the flask, the flask is heated and stirred at a speed of 300r/min, the mass of an emulsifier (sodium dodecyl sulfate) is 0.0805g, the reaction temperature is controlled to be 100 ℃, the timing is started for 2min when a reflux phenomenon occurs in a condensing tube in a reaction device, 5mL of potassium persulfate with mass fraction of 2% is added as an initiator for reaction for 2h, the reaction is cooled to room temperature after stopping, and the solution is centrifuged for three times at a speed of 9500r/min to remove supernatant, and then dispersed into the deionized water for standby. The average particle size of the polystyrene microsphere under the condition is 266nm. The polystyrene microsphere prepared by the method has a polydispersity index (PDI) of 0.031, and the obtained microsphere has uniform size and good dispersion effect, and is beneficial to preparing polystyrene microsphere templates with bright colors.
1mL of polystyrene microsphere dispersion liquid with the concentration of 1.3g/L is weighed by a liquid-transferring gun, is paved on a glass plate (the glass plate is soaked in piranha etching liquid for 24 hours), and is then put into an oven to be self-assembled at the temperature of 60 ℃ to obtain the polystyrene microsphere template.
(3) Preparation of a polymer colloidal crystal array based on a mercury ion stimulus responsive ethyl hydroxyethyl cellulose gel: mixing 310 μl benzophenone with 5mL 8wt% cellulose aqueous solution containing mercury ion recognition group, removing bubbles, injecting into assembled styrene microsphere template (assembled polystyrene microsphere shown in figure 3, average particle diameter of polystyrene microsphere 266 nm), and ultraviolet light (700 mW/cm 2 ) Curing and crosslinking for 100s to obtain a green cellulose-based mercury ion response polymer colloidal crystal array (see figure 4).
(4) Use of a cellulose-based mercury ion responsive polymer colloidal crystal array. The method is used for rapidly identifying mercury ions in the aquatic products, and comprises the following specific steps: sucking 0.5-1 ml of aquatic product sample solution, dripping the solution onto the surface of a polymer colloid crystal array (hereinafter referred to as gel film) of the stimulus-responsive ethyl hydroxyethyl cellulose gel, and observing the color change condition of the gel film after 2 minutes to finish the rapid identification of mercury ions. The adding concentration of the aquatic product variety is 0.1mol/L mercury ions.
As can be seen from fig. 4, when the sample to be measured is not dropped, the sample is green, and when the sample to be measured is dropped onto the surface of the gel film, the gel film changes from green to red, and the reflection spectrum is red shifted, and the maximum absorption peak is red shifted from 582nm to 720nm.
The surface of the gel film prepared in the embodiment 1 of the invention is respectively dripped with different kinds of heavy metal ion solutions comprising Ni according to the step (5) 2+ ，Cd 2+ ，Cu 2+ ，Pb 2+ And Hg 2+ As can be seen from fig. 5, in addition to Hg 2+ In addition, the reflection spectrum of other metal ions does not have red shift, and the color of the gel film has no change, which indicates that the cellulose-based mercury ion photochemical sensor prepared by the invention has no red shift to Hg 2+ Has excellent selective recognition function.
Example 2
(1) Preparation of mercury ion stimulus responsive butyl hydroxyethyl cellulose:
(1) mercury ion recognition group synthesis: 3.0g of allyl glycidyl ether and 1.0g of open-chain aza thioether oligomer are fully mixed, and are irradiated by a 120W ultraviolet lamp for continuous irradiation for 4 hours, and are purified by reduced pressure distillation, so as to obtain the compound diazathioether glycidyl ether containing epoxy rings in the molecular structure;
(2) mercury ion stimulus responsive hydroxyethylcellulose synthesis was essentially the same as in example 1, except in this example: the added compound A is diazathioether glycidyl ether and the added amount is (n Hydroxyethyl cellulose ：n Diazathioether glycidyl ethers ＝1:1.9)，DS Diazathioether glycidyl ethers ＝0.10；
(3) Mercury ion stimulus response butyl hydroxyethyl cellulose synthesis: dissolving ion-stimulus-responsive hydroxyethylcellulose in a mixed solvent (V Water and its preparation method ：V Acetic acid ethyl ester =1: 0.3 Dropwise adding a mixed solution of alkyl glycidyl ether and sodium hydroxide, wherein the molar ratio of the mercury ion stimulus response hydroxyethyl cellulose to the addition of butyl glycidyl ether sodium hydroxide is 1.0:3.0:0.8, heating to 70 ℃ for reaction for 5 hours, placing the obtained product after the reaction into a dialysis bag, closing the dialysis for 48 hours, then rotationally evaporating the solution to remove most of the solvent, and performing vacuum freeze drying on the viscous product for 48 hours to obtain the dried mercury ion stimulus response butyl hydroxyethyl cellulose, wherein DS ethyl glycidyl ether=2.3.
(2) The preparation of polystyrene microspheres and templates thereof was substantially the same as in example 1, except that in this example, an emulsifier (sodium lauryl sulfate) was added in an amount of 0.0595g, and the average particle size of the polystyrene microspheres was 315nm.
The dispersion index (PDI) of the polystyrene microsphere obtained by the preparation is measured to be 0.028, and the obtained microsphere is uniform in size and approximately spherical, has good dispersion effect and is favorable for being used as a template for preparing the polystyrene microsphere with bright colors. (3) Preparation of a polymer colloidal crystal array based on a mercury ion stimulus responsive butyl hydroxyethyl cellulose gel: 86. Mu.L of 2-hydroxybenzophenone was thoroughly mixed with 5mL of 15wt% aqueous solution of a cellulose derivative responsive to mercury ion stimulation, the bubbles removed, and then injected into an assembled styrene microsphere template under ultraviolet light (1500 mW/cm 2 ) Curing and crosslinking for 100s to obtain red cellulose-based mercury ion response polymer colloidA crystal array.
(4) The application of the cellulose-based mercury ion-responsive polymer colloidal crystal array was the same as in example 1. As can be seen from FIG. 6, the sample to be measured was not dropped and was yellow, and when the sample to be measured was dropped onto the surface of the gel film, the gel film was changed from yellow to red, and the reflectance spectrum was red-shifted, and the maximum absorption peak was red-shifted from 618nm to 710nm.
Claims (10)
1. A cellulose having a mercury ion recognition group, characterized in that: and grafting functional molecules with hydroxyethyl cellulose serving as a framework to obtain the cellulose with the mercury ion recognition group, wherein the functional molecules are the mercury ion recognition group and the modified group.
2. The cellulose according to claim 1, wherein: the mercury ion recognition group is provided by an open chain thioether oligomer or an open chain aza thioether oligomer; the modifying group provides for an alkylating agent with a short chain alkane.
3. A method for preparing cellulose with mercury ion recognition groups according to claim 1, characterized in that: firstly, hydroxyethyl cellulose is taken as a framework, an open-chain thioether oligomer or an open-chain aza thioether oligomer is grafted to serve as a mercury ion recognition group, and then an alkylating agent with short-chain alkane is grafted to serve as a modification group, so that the stimulus-response alkyl hydroxyethyl cellulose with the capability of selectively complexing mercury ions, namely the cellulose with the mercury ion recognition group, is obtained.
4. A process for the preparation of cellulose having a mercury ion recognition group according to claim 3, wherein: the cellulose with the mercury ion recognition group is:
(1) Mercury ion recognition group synthesis: 3-5 g of allyl glycidyl ether and 0.5-2 g of open-chain thioether oligomer or open-chain aza thioether oligomer are fully mixed, and the mixture is continuously irradiated for 2-4 h by ultraviolet to obtain a compound A containing an epoxy ring in a molecular structure;
(2) Mercury ion stimulus response hydroxyethyl cellulose synthesis: adding sodium hydroxide into 10-25wt% of hydroxyethyl cellulose solution, alkalizing for 1-2 h at 50-70 ℃ to obtain alkalized hydroxyethyl cellulose solution, slowly dripping a compound A into the alkalized hydroxyethyl cellulose solution, reacting for 48-72 h in the presence of nitrogen in a dark place, and drying to obtain mercury ion stimulus response hydroxyethyl cellulose;
(3) Cellulose with mercury ion recognition groups: dissolving the mercury ion stimulus response hydroxyethyl cellulose in a mixed solvent, then dropwise adding a mixed solution of an alkylating reagent with short-chain alkane and sodium hydroxide, heating to 60-70 ℃ for reacting for 5-7 h, obtaining a product after the reaction, and performing light-blocking reaction for 48-72 h, and drying.
5. A process for preparing cellulose having mercury ion-recognizing groups according to claim 4, wherein: the power of the ultraviolet lamp in the step (1) is 60-120W; the compound A is polythioether glycidyl ether or polyaza thioether glycidyl ether;
6. a process for preparing cellulose having mercury ion-recognizing groups according to claim 4, wherein: the mol ratio of the hydroxyethyl cellulose to the sodium hydroxide in the hydroxyethyl cellulose aqueous solution in the step (2) is 1:0.5-1:1.3;
the molecular weight of the hydroxyethyl fiber is 20-38 ten thousand (Mw), and the degree of substitution of hydroxyethyl is more than 2.5; hydroxyethyl cellulose and compound A molar ratio n Hydroxyethyl cellulose :n Polythioether glycidyl ethers =1:1.2 to 1.7 or n Hydroxyethyl cellulose :n Polyaza thioether glycidyl ethers =1:1.0 to 1.9; the Degree of Substitution (DS) of compound a on the hydroxyethyl fiber backbone is: 0.05<DS Polythioether glycidyl ethers <0.12；0.03<DS Polythioether glycidyl ethers <0.10；
V in the mixed solvent in the step (3) Water and its preparation method ：V Organic solvents =1: 0.1 to 0.3, wherein the organic solvent is one or more of ethanol, isopropanol and ethyl acetate; the alkylating reagent with short-chain alkane is one or more of alkyl glycidyl ether; the degree of substitution of the alkyl glycidyl ether was 2.3<DS Alkyl glycidyl ethers <2.8；。
7. Use of a cellulose with a mercury ion recognition group according to claim 1, characterized in that: the application of the cellulose with the mercury ion recognition group in detecting mercury ions.
8. Use of a cellulose with a mercury ion recognition group according to claim 1, characterized in that: the application of the cellulose with the mercury ion recognition group in the photochemical sensor for detecting the mercury ions in the visual and rapid detection aquatic products is provided.
9. A photochemical sensor for visually and rapidly detecting mercury ions in aquatic products, which is characterized in that the sensor is cellulose with mercury ion recognition groups according to claim 1.
10. A method of detecting mercury ions in an aquatic product using the sensor of claim 9, wherein: the sample to be detected is dripped into the sensor device of claim 9, and gel volume change in the sensor caused by an identification signal generated after the identification group in the sensor identifies mercury ions is converted into color change visible to naked eyes, so that the detection of mercury ions in the sample is realized.
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| CA2353828A1 (en) * | 1998-12-11 | 2000-06-22 | Akzo Nobel N.V. | Anionic cellulose ethers having temperature-dependent associative properties |
| CN101871164A (en) * | 2010-06-17 | 2010-10-27 | 浙江大学 | Preparation method of mercury ion colorimetric sensing cellulose material |
| CN102476044A (en) * | 2010-11-26 | 2012-05-30 | 中国科学院理化技术研究所 | Cellulose base adsorbing material for removing cations of heavy metal in water and preparation method of cellulose base adsorbing material |
| CN108181304A (en) * | 2017-12-29 | 2018-06-19 | 漳州职业技术学院 | The detection method of ion concentration of mercury in a kind of water |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2353828A1 (en) * | 1998-12-11 | 2000-06-22 | Akzo Nobel N.V. | Anionic cellulose ethers having temperature-dependent associative properties |
| CN101871164A (en) * | 2010-06-17 | 2010-10-27 | 浙江大学 | Preparation method of mercury ion colorimetric sensing cellulose material |
| CN102476044A (en) * | 2010-11-26 | 2012-05-30 | 中国科学院理化技术研究所 | Cellulose base adsorbing material for removing cations of heavy metal in water and preparation method of cellulose base adsorbing material |
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