CN109908876A - A kind of preparation method and application of the chitosan-based bionical attractive gel of polysaccharide nano microcrystalline doping - Google Patents
A kind of preparation method and application of the chitosan-based bionical attractive gel of polysaccharide nano microcrystalline doping Download PDFInfo
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- CN109908876A CN109908876A CN201910322382.2A CN201910322382A CN109908876A CN 109908876 A CN109908876 A CN 109908876A CN 201910322382 A CN201910322382 A CN 201910322382A CN 109908876 A CN109908876 A CN 109908876A
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- bionical
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 125
- 229920001282 polysaccharide Polymers 0.000 title claims abstract description 79
- 239000005017 polysaccharide Substances 0.000 title claims abstract description 79
- 150000004676 glycans Chemical class 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 46
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 19
- 238000007711 solidification Methods 0.000 claims abstract description 19
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 22
- 239000000706 filtrate Substances 0.000 claims description 18
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 12
- 229960003638 dopamine Drugs 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
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- 238000006243 chemical reaction Methods 0.000 claims description 9
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- 238000004065 wastewater treatment Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 39
- 238000004043 dyeing Methods 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 101
- 239000000243 solution Substances 0.000 description 40
- 239000000975 dye Substances 0.000 description 25
- 239000003431 cross linking reagent Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
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- 239000000980 acid dye Substances 0.000 description 11
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- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 9
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- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 7
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- 238000005303 weighing Methods 0.000 description 7
- UHXQPQCJDDSMCB-UHFFFAOYSA-L disodium;3-[[9,10-dioxo-4-(2,4,6-trimethyl-3-sulfonatoanilino)anthracen-1-yl]amino]-2,4,6-trimethylbenzenesulfonate Chemical compound [Na+].[Na+].CC1=CC(C)=C(S([O-])(=O)=O)C(C)=C1NC(C=1C(=O)C2=CC=CC=C2C(=O)C=11)=CC=C1NC1=C(C)C=C(C)C(S([O-])(=O)=O)=C1C UHXQPQCJDDSMCB-UHFFFAOYSA-L 0.000 description 6
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 5
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- -1 cationic polysaccharide Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000004964 aerogel Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
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- 239000002585 base Substances 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
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- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
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- 230000009467 reduction Effects 0.000 description 2
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- 229920001817 Agar Polymers 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 description 1
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- 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 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
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- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
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- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000003147 glycosyl group Chemical group 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
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- NALMPLUMOWIVJC-UHFFFAOYSA-N n,n,4-trimethylbenzeneamine oxide Chemical compound CC1=CC=C([N+](C)(C)[O-])C=C1 NALMPLUMOWIVJC-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
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Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Medicinal Preparation (AREA)
Abstract
The invention discloses a kind of preparation method and applications of the chitosan-based bionical attractive gel of polysaccharide nano microcrystalline doping, including, prepare polysaccharide nano microcrystalline；Prepare chitosan-acetic acid solution；Dopamine hydrochloride and polysaccharide nano microcrystalline, mixing are added into the chitosan-acetic acid solution, magnetic agitation processing is stored at room temperature solidification for 24 hours until forming the bionical gel of chitosan of dark red；By the bionical gel of chitosan after solidification, dry 24~48h, obtains the bionical attractive gel of porous spongy chitosan under the conditions of -50 DEG C.The bionical attractive gel elasticity of chitosan produced by the present invention is splendid, has good biocompatibility, has strong adsorption capacity to dye molecule in dyeing waste water.
Description
Technical field
The present invention relates to adsorbent material preparation field more particularly to a kind of polysaccharide nano microcrystalline adulterate it is chitosan-based bionical
The preparation method and application of attractive gel.
Background technique
Macromolecule hydrogel typically refers to the three of crosslinked polymer formation as a kind of more and more concerned " soft material "
Swelling but the insoluble substance for being formed by a kind of object between liquid and solid occur after dimension network structure lyosoption.
It can be crosslinked by hydrophilic high-molecular compound by ionic bond, covalent bond, hydrogen bond etc., there is good film forming, suction
The characteristics such as aqueous, caking property.The natural polymers such as starch, chitosan, alginates, agar, protein are preferably raw due to having
Object compatibility and source abundant and cheap price, thus application is more, is usually used in drug loading, organizational project, environment and protects
Shield.
Chitosan is natural cationic polysaccharide, itself is nontoxic, renewable, rich reserves in nature, biodegradable, raw
Object compatibility is good, and sequestering power is strong, strong to Adsorption of Organic ability.Porous chitosan gel is in pharmaceutical carrier, thermal insulating material
Material, tissue engineering bracket material, the carrier of adsorbent or photochemical catalyst or water-oil separating material etc. have important answer
With value.But pure chitosan gel strength is low, is not sufficiently stable in acid condition.In order to solve this problem, there is researcher sharp
With glutaraldehyde, stability of the alkyl such as glyoxal, the formaldehyde organic aldehyde as crosslinking agent enhancing chitosan aerogel structure, but this
Class method and step is cumbersome, and the organic aldehyde crosslinking agent of small molecule is because there are certain influences to environment for toxicity problem.Therefore, ability
Domain needs the bionical elastic gel preparation method of chitosan and product of a kind of simple and convenient ecological, environmental protective.
Summary of the invention
The purpose of this section is to summarize some aspects of the embodiment of the present invention and briefly introduce some preferable implementations
Example.It may do a little simplified or be omitted to avoid our department is made in this section and the description of the application and the title of the invention
Point, the purpose of abstract of description and denomination of invention it is fuzzy, and this simplification or omit and cannot be used for limiting the scope of the invention.
The problem of in view of above-mentioned and/or existing chitosan-based bionical attractive gel, propose the present invention.
Therefore, the one of purpose of the present invention is to overcome the shortcomings of in chitosan-based bionical attractive gel, and it is more to provide one kind
The preparation method of the bionical gel of chitosan of sugared nano microcrystalline doping.
In order to solve the above technical problems, according to an aspect of the present invention, the present invention provides the following technical scheme that a kind of
The preparation method of the chitosan-based bionical attractive gel of polysaccharide nano microcrystalline doping, including, prepare polysaccharide nano microcrystalline；Prepare shell
Glycan acetum；Dopamine hydrochloride and polysaccharide nano microcrystalline, mixing, magnetic force are added into the chitosan-acetic acid solution
Stir process is stored at room temperature solidification for 24 hours until forming the bionical gel of chitosan of dark red；Chitosan after solidification is bionical
Gel, dry 24~48h, obtains the bionical attractive gel of porous spongy chitosan under the conditions of -50 DEG C.
One kind of the preparation method of chitosan-based bionical attractive gel as polysaccharide nano microcrystalline of the present invention doping
Preferred embodiment, in which: it is described to prepare polysaccharide nano microcrystalline, including, by sodium metaperiodate and polysaccharide material be in molar ratio 1:0.5~
2 mixing are placed under the conditions of 30 DEG C in constant temperature oscillation dye model machine after being protected from light 1~3h, 30~60mL, 0.1mol/L are added
Ethylene glycol the reaction was continued 0.5h takes out suspension, is filtered with circulating water type vacuum pump, takes out filtrate, 150mL is added in filtrate
Acetone is protected from light and precipitates 2h, up to the polysaccharide nano microcrystalline after suction filtration.
One kind of the preparation method of chitosan-based bionical attractive gel as polysaccharide nano microcrystalline of the present invention doping
Preferred embodiment, in which: the polysaccharide material, including chitosan.
One kind of the preparation method of chitosan-based bionical attractive gel as polysaccharide nano microcrystalline of the present invention doping
Preferred embodiment, in which: it is described to prepare chitosan-acetic acid solution, including, 1~10g chitosan is weighed, under room temperature, is dissolved in
In the glacial acetic acid solution that 100mL concentration is 1~10%, the chitosan-acetic acid solution is obtained.
One kind of the preparation method of chitosan-based bionical attractive gel as polysaccharide nano microcrystalline of the present invention doping
Preferred embodiment, in which: it is described that dopamine hydrochloride and polysaccharide nano microcrystalline are added into the chitosan-acetic acid solution,
In, in terms of mL:g, chitosan-acetic acid solution: polysaccharide nano microcrystalline is 1000:1.
One kind of the preparation method of chitosan-based bionical attractive gel as polysaccharide nano microcrystalline of the present invention doping
Preferred embodiment, in which: it is described that dopamine hydrochloride and polysaccharide nano microcrystalline are added into the chitosan-acetic acid solution,
In, the mass ratio of dopamine hydrochloride and polysaccharide nano microcrystalline is 1~2:1~2.
One kind of the preparation method of chitosan-based bionical attractive gel as polysaccharide nano microcrystalline of the present invention doping
Preferred embodiment, in which: magnetic agitation processing, wherein speed of agitator is 500~1000rpm, the stir process time is 3~
8h。
Another object of the present invention is to provide a kind of chitosan-based bionical elastic absorption gel of polysaccharide nano microcrystalline doping
It is applied in dye wastewater treatment field.
Advantageous effects of the invention:
(1) the present invention provides a kind of preparation method of the chitosan-based bionical attractive gel of nano microcrystalline doping, made
Chitosan low in raw material price is easy to get, the mature preparation process of polysaccharide crystallite, and dopamine is as biological binder, ecological ring
It protects, the chemical reagent being related to is all green ecological environment-friendly type degradable substance, will not cause secondary pollution to environment.
(2) present invention is crosslinking agent using the dialdehyde polysaccharide nano microcrystalline of sodium metaperiodate selective oxidation, by poly-dopamine
It is cross-linked to form the bionical gel of three-dimensional honeycomb shape network porous structure chitosan with shitosan macromolecule polymer chain interpenetrating, acquisition
Chitosan gel rubber has stable structure, and excellent adsorption, compatibility is good, degradable, can be used in dye wastewater treatment field, right
Acid red G adsorption rate has reached 85.95%.
(3) present invention is coupling agent, crosslinking agent using the dialdehyde polysaccharide nano microcrystalline of sodium metaperiodate selective oxidation, will be gathered
Dopamine and shitosan macromolecule polymer chain interpenetrating are cross-linked to form the bionical gel of three-dimensional honeycomb shape network porous structure chitosan,
With stable structure, elasticity is good, and preparation process is simple, overcomes that aeroge preparation process is lengthy and tedious, and aeroge is brittle
" defect ".
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Attached drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this
For the those of ordinary skill of field, without any creative labor, it can also be obtained according to these attached drawings other
Attached drawing.Wherein:
Fig. 1 is the bionical gel surface scanning electron microscope (SEM) photograph that the embodiment of the present invention 1 is formed.
Fig. 2 is the bionical gel surface scanning electron microscope (SEM) photograph that the embodiment of the present invention 2 is formed.
Fig. 3 is the bionical gel surface scanning electron microscope (SEM) photograph that the embodiment of the present invention 3 is formed.
Fig. 4 is the bionical gel of poly-dopamine/chitosan of different crystallite dopamine mass ratioes in the embodiment of the present invention to dye
The absorption figure of material.
Fig. 5 is influence diagram of the anti-raw gel difference pH of chitosan to Dye Adsorption amount of the preparation of the embodiment of the present invention 1.
Fig. 6 is to reply situation map after the anti-raw gel of chitosan prepared by the embodiment of the present invention 1 compresses.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, below with reference to specification embodiment
Specific embodiments of the present invention will be described in detail.
In the following description, numerous specific details are set forth in order to facilitate a full understanding of the present invention, but the present invention can be with
Implemented using other than the one described here other way, those skilled in the art can be without prejudice to intension of the present invention
In the case of do similar popularization, therefore the present invention is not limited by the specific embodiments disclosed below.
Secondly, " one embodiment " or " embodiment " referred to herein, which refers to, may be included at least one realization side of the invention
A particular feature, structure, or characteristic in formula." in one embodiment " that different places occur in the present specification not refers both to
The same embodiment, nor the individual or selective embodiment mutually exclusive with other embodiments.
Chitosan of the present invention, commercially available, degree of deacetylation 85%, molecular weight general 85000；Dopamine hydrochloride, it is commercially available, it is pure
Degree 99%.
Embodiment 1
(1) prepare polysaccharide nano microcrystalline: it is that 1:1 is mixed that periodic acid is received with chitosan in molar ratio, under the conditions of 30 DEG C
It is placed in constant temperature oscillation dye model machine after being protected from light 2h, ethylene glycol the reaction was continued the 0.5h of 40mL, 0.1mol/L is added, take out outstanding
Supernatant liquid is filtered with circulating water type vacuum pump, takes out filtrate, and 150mL acetone is added in filtrate, is protected from light precipitating 2h, is after suction filtration
Obtain the polysaccharide nano microcrystalline；
(2) it prepares chitosan-acetic acid solution: weighing 2g chitosan, under room temperature, be dissolved in the ice that 100mL concentration is 10%
In acetum, chitosan-acetic acid solution is obtained；
(3) 0.1g dopamine hydrochloride and 0.1g polysaccharide nano microcrystalline will be added in the chitosan-acetic acid solution in (2),
Mixing, 1000rpm magnetic agitation handle 3h, form the bionical gel of chitosan of dark red, are stored at room temperature solidification for 24 hours；
(4) it by the bionical gel of chitosan after solidification, is freeze-dried under the conditions of -50 DEG C for 24 hours, obtains nano microcrystalline doping
Chitosan-based bionical attractive gel, gel surface form scanning electron microscope (SEM) photograph (× 5000,20 μm), is shown in Fig. 1.
Embodiment 2
(1) prepare polysaccharide nano microcrystalline: it is that 1:1 is mixed that periodic acid is received with chitosan in molar ratio, under the conditions of 30 DEG C
It is placed in constant temperature oscillation dye model machine after being protected from light 2h, ethylene glycol the reaction was continued the 0.5h of 40mL, 0.1mol/L is added, take out outstanding
Supernatant liquid is filtered with circulating water type vacuum pump, takes out filtrate, and 150mL acetone is added in filtrate, is protected from light precipitating 2h, is after suction filtration
Obtain the polysaccharide nano microcrystalline；
(2) it prepares chitosan-acetic acid solution: weighing 2g chitosan, under room temperature, be dissolved in the ice that 100mL concentration is 10%
In acetum, the chitosan-acetic acid solution is obtained；
(3) 0.1g dopamine hydrochloride and 0.2g polysaccharide nanometer will be added in chitosan-acetic acid solution obtained in (2)
Crystallite, mixing, 1000rpm magnetic agitation handle 3h, form the bionical gel of chitosan of dark red, are stored at room temperature solidification for 24 hours；
(4) by the bionical gel of chitosan after solidification, for 24 hours, the shell for obtaining nano microcrystalline doping is poly- for drying under the conditions of -50 DEG C
The bionical attractive gel of glycosyl, gel surface form scanning electron microscope (SEM) photograph (× 5000,20 μm), is shown in Fig. 2.
Embodiment 3
(1) prepare polysaccharide nano microcrystalline: it is that 1:1 is mixed that periodic acid is received with chitosan in molar ratio, under the conditions of 30 DEG C
It is placed in constant temperature oscillation dye model machine after being protected from light 2h, ethylene glycol the reaction was continued the 0.5h of 40mL, 0.1mol/L is added, take out outstanding
Supernatant liquid is filtered with circulating water type vacuum pump, takes out filtrate, and 150mL acetone is added in filtrate, is protected from light precipitating 2h, is after suction filtration
Obtain the polysaccharide nano microcrystalline；
(2) it prepares chitosan-acetic acid solution: weighing 10g chitosan, under room temperature, being dissolved in 100mL concentration is 10%
In glacial acetic acid solution, the chitosan-acetic acid solution is obtained；
(3) 0.2g dopamine hydrochloride and 0.1g polysaccharide nanometer will be added in chitosan-acetic acid solution obtained in (2)
Crystallite, mixing, 500~1000rpm magnetic agitation handle 3~8h, form the bionical gel of chitosan of dark red, are stored at room temperature solid
Change for 24 hours；
(4) by the bionical gel of chitosan after solidification, dry 24~48h under the conditions of -50 DEG C obtains nano microcrystalline doping
Chitosan-based bionical attractive gel, gel surface form scanning electron microscope (SEM) photograph (× 5000,20 μm), is shown in Fig. 3.
It carries out the bionical gel of different chitosans prepared by Examples 1 to 3 to adsorb acid dye assay, specific method
Are as follows: 30mL acid dyes (0.032g/L acid red G, 0.032g/L Methanil Yellow G, the gorgeous indigo plant of 0.032g/L faintly acid are taken respectively
RAW) solution is separately added into the gel of different quality (0.01g, 0.02g, 0.03g, 0.04g, 0.05g, 0.06g), 30 DEG C of constant temperature
1h is shaken, draws supernatant liquor with pipette, measures solution absorbance with 722S visible spectrophotometer.
Fig. 4 is adsorption rate figure of the gel made from Examples 1 to 3 to three kinds of acid dyes, is come as can be seen from Figure 4, right
When the absorption of every kind of acid dyes, polysaccharide nano microcrystalline and dopamine hydrochloride mass ratio are 1:1, the gel adsorption effect of formation
Fruit is best, and when this may be 1:1 due to polysaccharide nano microcrystalline and dopamine hydrochloride mass ratio, gel internal crosslinking is more abundant,
It is set to possess stronger adsorption capacity to dyestuff.And gel is also and different to the absorption of three kinds of acid dyes, gel is to acidity
The adsorption effect of bright red G is best, followed by Weakly Acid Brilliant Blue RAW, worst to the adsorption effect of Methanil Yellow G dyestuff.This may
It is to have carbonyl on Weakly Acid Brilliant Blue RAW, more than carbonyl to Dye Adsorption hydroxyl effect because having hydroxyl on acid red G
It is good.
Embodiment 4
It carries out the anti-raw gel of chitosan prepared by embodiment 1 to adsorb acid dye assay, with three sour (phosphoric acid, acetic acid, boron
Acid) mixed solution and sodium hydroxide solution be respectively configured pH value be 1.80,2.56,3.29,4.56,5.72,6.80,7.80 it is slow
Rush solution, then with these buffer solution configuration concentrations be 0.0176g/L acid dyes (acid red G, Methanil Yellow G are weak
Acidic brilliant blue RAW) solution 30mL, it is separately added into the gel of phase homogenous quantities 0.02g, after adsorbing 1 hour under the conditions of 30 DEG C, with shifting
Liquid pipe draws supernatant liquor, then measures solution absorbance with 722S visible spectrophotometer.
Fig. 5 indicates influence of the dye liquor pH value to every gram of gel stain adsorbance, as can be seen from Figure 5 in pH between 2~3
When the bionical gel of poly-dopamine/chitosan it is best to the adsorption effect of acid dyes, respectively to acid red G, Methanil Yellow G,
The adsorption rate of Weakly Acid Brilliant Blue RAW has reached 85.95%, 50.79% and 72.52%, later, with the rising of pH value, dyestuff
Adsorption rate gradually decrease, this may be because solution in it is acid when, more carboxylic is contained in the inside of the bionical gel of chitosan
Base is stronger to the adsorption capacity of acid dyes.And when pH reaches 7~8, gel is decreased obviously the adsorption rate of three kinds of dyestuffs,
Only 4.40%, 12.49% and 6.57%, and every gram of gel adsorption amount of dye is also very low, this may be because of solution when pH is 8
For alkalinity, the carboxylic group in gel is easy to react in hydroxyl, and the active group quantity in gel substantially reduces, to cut
Weak adsorption capacity of the bionical gel of poly-dopamine/chitosan to acid dyes.
Embodiment 5
(1) prepared by polysaccharide nano microcrystalline: being in molar ratio 1:1 by sodium metaperiodate and glucose (analyzing pure, content 99%)
Mixing, be placed under the conditions of 30 DEG C constant temperature oscillation dye model machine in be protected from light 2h after, be added 40mL, 0.1mol/L ethylene glycol after
Continuous reaction 0.5h, takes out suspension, is filtered with circulating water type vacuum pump, take out filtrate, 150mL acetone is added in filtrate, keeps away
Light precipitates 2h, up to the glucose nano microcrystalline after suction filtration；
(2) it prepares chitosan-acetic acid solution: weighing 2g chitosan, under room temperature, be dissolved in the ice that 100mL concentration is 10%
In acetum, chitosan-acetic acid solution is obtained；
(3) 0.1g dopamine hydrochloride and 0.1g polysaccharide nano microcrystalline will be added in the chitosan-acetic acid solution in (2),
Mixing, 1000rpm stir process 3h form the bionical gel of chitosan of dark red, are stored at room temperature solidification for 24 hours；
(4) it by the bionical gel of chitosan after solidification, is freeze-dried under the conditions of -50 DEG C for 24 hours, obtains nano microcrystalline doping
Chitosan-based bionical attractive gel.
Embodiment 6
(1) prepared by polysaccharide nano microcrystalline: sodium metaperiodate and carboxymethyl cellulose (technical grade, commercially available, content 99%) are pressed
Molar ratio is selectively oxidized for 1:1, is placed in constant temperature oscillation dye model machine after being protected from light 2h, is added under the conditions of 30 DEG C
The ethylene glycol of 40mL, 0.1mol/L the reaction was continued 0.5h take out suspension, are filtered with circulating water type vacuum pump, take out filtrate,
150mL acetone is added in filtrate, is protected from light and precipitates 2h, up to the polysaccharide nano microcrystalline after suction filtration；
(2) it prepares chitosan-acetic acid solution: weighing 2g chitosan, under room temperature, be dissolved in the ice that 100mL concentration is 10%
In acetum, chitosan-acetic acid solution is obtained；
(3) 0.1g dopamine hydrochloride and 0.1g polysaccharide nano microcrystalline will be added in the chitosan-acetic acid solution in (2),
Mixing, 1000rpm stir process 3h form the bionical gel of chitosan of dark red, are stored at room temperature solidification for 24 hours；
(4) it by the bionical gel of chitosan after solidification, is freeze-dried under the conditions of -50 DEG C for 24 hours, obtains nano microcrystalline doping
Chitosan-based bionical attractive gel.
Table 1
| Acid red G adsorption rate | |
| Embodiment 1 | 85.95% |
| Embodiment 5 | 43.14% |
| Embodiment 6 | 41.25% |
By utilizing glucose, carboxymethyl cellulose is equally selectively oxidized the present invention, and discovery is high by chitosan
The product obtained after sodium iodate oxidation is best to acid red G absorption property, and acid red G adsorption rate is up to 85.95%, can
Can be related containing more stiff macromolecular chain structure with chitosan, the aldehyde radical of dialdehyde chitin can with amino on chitosan with
And dopamine can be crosslinked, and form Schiff base, dialdehyde chitosan can be used as crosslinking agent use, can accelerate to dopamine
Autohemagglutination is aoxidized, poly-dopamine is quickly formed.Poly-dopamine and shitosan macromolecule polymer chain interpenetrating are cross-linked to form three-dimensional honeycomb
The bionical gel of shape network porous structure chitosan, so that its absorption property is best.
Embodiment 7
(1) it prepares chitosan-acetic acid solution: weighing 2g chitosan, under room temperature, be dissolved in the ice that 100mL concentration is 10%
In acetum, chitosan-acetic acid solution is obtained；
(2) 0.1g dopamine hydrochloride and 0.1g glutaraldehyde will be added in the chitosan-acetic acid solution in (1), mix,
1000rpm magnetic agitation handles 3h, is stored at room temperature solidification for 24 hours；
(3) it by the chitosan gel rubber after solidification, is freeze-dried under the conditions of -50 DEG C for 24 hours, obtains chitosan-based attractive gel.
It is measured to acid red G adsorption rate, is shown in Table 2.
Table 2
| Compression modulus (MPa) | Acid red G adsorption rate | |
| Embodiment 1 | 0.16 | 85.95% |
| Embodiment 7 | 0.33 | 74.14% |
As can be seen that be used as crosslinking agent when chitosan crystallite is added, compared to glutaraldehyde as crosslinking agent, chitosan, gather it is more
There are good compatibility bar between amine and chitosan crystallite, Quick cross-linking inside gel possesses acid red G adsorption rate stronger
Adsorption capacity, and dialdehyde chitin polysaccharide toxicity of the present invention is low, compared with glutaraldehyde environmental protection.Meanwhile inventors have found that polysaccharide crystallite
As crosslinking agent, glutaraldehyde is compared, gel can be quickly formed, within the identical processing time, the anti-raw gel yield of chitosan
Improve about 28.14%.And it may be since there are good compatibility, chitosans between chitosan, poly-dopamine and chitosan crystallite
Base attractive gel has elasticity well.
Embodiment 8
(1) prepare polysaccharide nano microcrystalline: it is that 1:1 is mixed that periodic acid is received with chitosan in molar ratio, under the conditions of 30 DEG C
It is placed in constant temperature oscillation dye model machine after being protected from light 2h, ethylene glycol the reaction was continued the 0.5h of 40mL, 0.1mol/L is added, take out outstanding
Supernatant liquid is filtered with circulating water type vacuum pump, takes out filtrate, and 150mL acetone is added in filtrate, is protected from light precipitating 2h, is after suction filtration
Obtain the polysaccharide nano microcrystalline；
(2) it prepares chitosan-acetic acid solution: weighing 2g chitosan, under room temperature, be dissolved in the ice that 100mL concentration is 10%
In acetum, chitosan-acetic acid solution is obtained；
(3) 0.1g dopamine hydrochloride and 0.1g polysaccharide nano microcrystalline will be added in the chitosan-acetic acid solution in (2),
Mixing, 1000rpm magnetic agitation handle 3h, form the bionical gel of chitosan of dark red, are stored at room temperature solidification for 24 hours；
(4) it by the bionical gel of chitosan after solidification, is freeze-dried for 24 hours under the conditions of -30 DEG C, -50 DEG C, -80 DEG C respectively,
Obtain the chitosan-based bionical attractive gel of nano microcrystalline doping.
Table 3
| Compression modulus (MPa) | Acid red G adsorption rate | |
| - 30 DEG C of temperature of freeze-drying | 0.13 | 78.25% |
| - 50 DEG C of temperature of freeze-drying | 0.16 | 85.95% |
| - 80 DEG C of temperature of freeze-drying | 0.21 | 82.14% |
As can be seen that the cooling temperature of system is affected to gel, when temperature is at -50 DEG C, gel has preferable
Elasticity and higher acid red G adsorption rate, may be due to different cooling temperatures, cooling rate is different, corresponding solvent
Chilling rate has differences before the ice of ice crystal, thus will affect ice crystal thickness, the elasticity and adsorption effect finally influenced.
The anti-raw gel of chitosan prepared by embodiment 1 is compressed, as shown in Figure 6, it can be seen that lightweight chitosan gas
Gel has elasticity well, and the anti-raw gel of 0.6683g chitosan is taken away counterweight, remained to slow with after 200g counterweight compacting 0.5h
Slowly original state is returned to, resilience is splendid.For polymer, crosslink density can improve intensity, but will lead to toughness reduction, become
It is crisp, it is the technology " problem " of this field, the present invention provides a kind of preparation of the bionical gel of chitosan of polysaccharide nano microcrystalline doping
Method, for chitosan crystallite as crosslinking agent, gel internal crosslinking is abundant, while possessing stronger adsorption capacity to dyestuff, returns
Elasticity is splendid, may be since there is good compatibilities between chitosan and chitosan crystallite.
Embodiment 9
Prepare polysaccharide nano microcrystalline: it is that 1:0.5~3 mix that periodic acid is received with chitosan in molar ratio, in 30 DEG C of conditions
Under be placed in constant temperature oscillation dye model machine and be protected from light 2h after, ethylene glycol the reaction was continued the 0.5h of 40mL, 0.1mol/L is added, takes out
Suspension is filtered with circulating water type vacuum pump, takes out filtrate, and 150mL acetone is added in filtrate, is protected from light and is precipitated 2h, after suction filtration
Up to the chitosan crystallite.
Table 4
| Periodic acid is received with polysaccharide material in molar ratio | Acid red G adsorption rate |
| 1:0.5 | 68.14% |
| 1:1 | 85.95% |
| 1:1.5 | 81.27% |
| 1:2 | 72.45% |
| 1:3 | 61.58% |
It is between 1:1~1.5 that periodic acid is received with polysaccharide material in molar ratio, and acid red G adsorption rate is higher, may be due to
The diameter of whiskers obtained within this range is preferable, and gel internal crosslinking is more abundant, it is made to possess stronger adsorption capacity to dyestuff；
Sodium metaperiodate dosage is very little, and diameter of whiskers is bigger, micro-scaled range, and gel internal crosslinking effect is poor；Sodium metaperiodate dosage
More, diameter is too small, and Precipitation is relatively difficult, the bad control of dialdehyde yield of acquisition.
Aeroge be a kind of network structure for replacing liquid in gel with gas and not changing gel itself substantially or
The special gel of volume is the product after hydrogel or organogel drying, has the characteristics that porous structure and high porosity, be
One of currently known the smallest solid material of density.Currently, aeroge is there are preparation process is loaded down with trivial details and tediously long, and brittle etc. lack
Point, the present invention is crosslinking agent using the dialdehyde polysaccharide nano microcrystalline of sodium metaperiodate selective oxidation, by poly-dopamine and chitosan
High molecular polymer chain interpenetrating is cross-linked to form the bionical gel of three-dimensional honeycomb shape network porous structure chitosan, the chitosan gas of acquisition
Gel has stable structure, and elastic good, excellent adsorption has incorporated the excellent of itself while having traditional aerogel property
Performance, such as good biocompatibility and degradability, can be widely applied for water process adsorbing domain.
The present invention prepares the chitosan-based bionical suction of nano microcrystalline doping using specific polysaccharide nano microcrystalline as crosslinking agent
Attached gel, compared to utilizing cellulose family carbohydrate to be raw material in art technology, it is solidifying that strong acid hydrolysis prepares the obtained absorption of nano microcrystalline
Glue, energy Quick cross-linking of the present invention form gel, and production efficiency is higher.And the chitosan low in raw material price that the present invention uses is easy
, the mature preparation process of polysaccharide crystallite, dopamine is as biological binder, and ecological, environmental protective, the chemical reagent being related to is all green
Color ecological environment-friendly type degradable substance will not cause secondary pollution to environment.
The chitosan-based bionical attractive gel of nano microcrystalline doping prepared by the present invention has elasticity well, 0.6683g
After the anti-raw gel of chitosan suppresses 0.5h with 200g counterweight, counterweight to be taken away, remains to slowly return to original state, resilience is splendid, for
For polymer, crosslink density can improve intensity, but will lead to toughness reduction, become fragile, be the technology " problem " of this field, this hair
A kind of preparation method of the bright bionical gel of chitosan for providing polysaccharide nano microcrystalline doping, chitosan crystallite are coagulated as crosslinking agent
Glue internal crosslinking is abundant, and while possessing strong adsorption capacity to dyestuff, resilience is splendid, may be due to dopamine, chitosan
There is good compatibilities between chitosan crystallite.Simultaneously inventors have found that the chitosan of polysaccharide nano microcrystalline doping is bionical
Gel is different to the adsorption effect of acid red G, Methanil Yellow G, Weakly Acid Brilliant Blue RAW dyestuff, when polysaccharide crystallite and dopamine
Mass ratio is that the gel adsorption effect of 1:1 is best, this may be because chitosan crystallite and dopamine hydrochloride quality are 1:1
When, gel internal crosslinking is more abundant, it is made to possess stronger adsorption capacity to dyestuff.Meanwhile the nano microcrystalline doping of preparation
Chitosan-based bionical attractive gel is also and different to the absorption of three kinds of acid dyes, adsorption effect of the gel to acid red G
Preferably, followed by Weakly Acid Brilliant Blue RAW, it is worst to the adsorption effect of Methanil Yellow G dyestuff.This may be because of acid red G
It is upper to have hydroxyl, carbonyl is had on Weakly Acid Brilliant Blue RAW, it is more preferable than carbonyl to Dye Adsorption hydroxyl effect.
To sum up, chitosan-acetic acid solution, polysaccharide nano microcrystalline, dopamine are mixed system for the first time by the present invention in acid condition
The standby anti-angry gel of chitosan, polysaccharide nano microcrystalline are mutual by poly-dopamine and shitosan macromolecule polymer chain as crosslinking agent
It wears and is cross-linked to form the bionical gel of three-dimensional honeycomb shape network porous structure chitosan, the biological binder of dopamine conduct, ecological, environmental protective,
The chemical reagent being related to is all green ecological environment-friendly type degradable substance, will not cause secondary pollution to environment, is had good
Biocompatibility and degradability can be widely applied for water process adsorbing domain, and gel has stable structure, and elasticity is good, system
Standby process is simple, overcomes that aeroge preparation process is lengthy and tedious, aeroge brittle " defect ".
It should be noted that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to preferable
Embodiment describes the invention in detail, those skilled in the art should understand that, it can be to technology of the invention
Scheme is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be covered in this hair
In bright scope of the claims.
Claims (8)
1. a kind of preparation method of the chitosan-based bionical attractive gel of polysaccharide nano microcrystalline doping, it is characterised in that: including,
Prepare polysaccharide nano microcrystalline；
Prepare chitosan-acetic acid solution；
Dopamine hydrochloride and polysaccharide nano microcrystalline, mixing are added into the chitosan-acetic acid solution, magnetic agitation is handled,
Until forming the bionical gel of chitosan of dark red, it is stored at room temperature solidification for 24 hours；
By the bionical gel of chitosan after solidification, dry 24~48h, it is imitative to obtain porous spongy chitosan under the conditions of -50 DEG C
Raw attractive gel.
2. the preparation method of the chitosan-based bionical attractive gel of polysaccharide nano microcrystalline doping as described in claim 1, special
Sign is: it is described to prepare polysaccharide nano microcrystalline, including, it with polysaccharide material is in molar ratio that 1:0.5~2 mix by sodium metaperiodate,
It is placed under the conditions of 30 DEG C in constant temperature oscillation dye model machine after being protected from light 1~3h, the ethylene glycol of 30~60mL, 0.1mol/L is added
The reaction was continued 0.5h takes out suspension, is filtered with circulating water type vacuum pump, takes out filtrate, and 150mL acetone is added in filtrate,
It is protected from light and precipitates 2h, up to the polysaccharide nano microcrystalline after suction filtration.
3. the preparation method of the chitosan-based bionical attractive gel of polysaccharide nano microcrystalline doping as claimed in claim 2, special
Sign is: the polysaccharide material, including chitosan.
4. the preparation method of the chitosan-based bionical attractive gel of polysaccharide nano microcrystalline doping as described in claim 1, special
Sign is: it is described to prepare chitosan-acetic acid solution, including, 1~10g chitosan is weighed, under room temperature, is dissolved in 100mL concentration
To obtain the chitosan-acetic acid solution in 1~10% glacial acetic acid solution.
5. the preparation method of the chitosan-based bionical attractive gel of polysaccharide nano microcrystalline doping as described in claim 1, special
Sign is: described that dopamine hydrochloride and polysaccharide nano microcrystalline are added into the chitosan-acetic acid solution, wherein with mL:g
Meter, chitosan-acetic acid solution: polysaccharide nano microcrystalline is 1000:1.
6. the preparation method of the chitosan-based bionical attractive gel of polysaccharide nano microcrystalline doping as described in claim 1, special
Sign is: described that dopamine hydrochloride and polysaccharide nano microcrystalline are added into the chitosan-acetic acid solution, wherein dopamine
The mass ratio of hydrochloride and polysaccharide nano microcrystalline is 1~2:1~2.
7. the preparation method of the chitosan-based bionical attractive gel of polysaccharide nano microcrystalline doping as described in claim 1, special
Sign is: the magnetic agitation processing, wherein speed of agitator is 500~1000rpm, and the stir process time is 3~8h.
8. a kind of chitosan-based bionical attractive gel system of the polysaccharide nano microcrystalline doping as described in any in claim 1~7
The chitosan-based bionical attractive gel of Preparation Method preparation is applied in dye wastewater treatment field.
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Application publication date: 20190621 Assignee: DONGTAI GAOKE TECHNOLOGY INNOVATION PARK Co.,Ltd. Assignor: YANCHENG INSTITUTE OF TECHNOLOGY Contract record no.: X2024980001259 Denomination of invention: Preparation and application of chitosan based biomimetic adsorption gel doped with polysaccharide nanocrystals Granted publication date: 20220408 License type: Common License Record date: 20240123 |