CN111607007B - Cellulose-based Schiff base fluorescent material and preparation method and application thereof - Google Patents
Cellulose-based Schiff base fluorescent material and preparation method and application thereof Download PDFInfo
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- 239000001913 cellulose Substances 0.000 title claims abstract description 82
- 239000000463 material Substances 0.000 title claims abstract description 40
- 239000002262 Schiff base Substances 0.000 title claims abstract description 29
- 150000004753 Schiff bases Chemical class 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000001514 detection method Methods 0.000 claims abstract description 4
- 239000002585 base Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 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 abstract description 23
- VJHLGVSMMJVSGU-UHFFFAOYSA-N 6-[4-(dimethylamino)phenyl]-1,11,11-trimethyl-3,5-diazatricyclo[6.2.1.02,7]undeca-2,4,6-trien-4-amine Chemical compound CN(C1=CC=C(C=C1)C1=NC(=NC=2C3(CCC(C1=2)C3(C)C)C)N)C VJHLGVSMMJVSGU-UHFFFAOYSA-N 0.000 abstract description 15
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 abstract description 12
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- 238000002189 fluorescence spectrum Methods 0.000 description 6
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- 150000003384 small molecules Chemical class 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
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- 238000005406 washing Methods 0.000 description 3
- -1 4-dimethylaminophenyl Chemical group 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- 238000012984 biological imaging Methods 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 229940036248 turpentine Drugs 0.000 description 1
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
- C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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Abstract
The invention discloses a cellulose-based Schiff base fluorescent material and a preparation method and application thereof. The preparation method comprises the steps of taking natural cellulose as a raw material, oxidizing by using sodium periodate to prepare dialdehyde cellulose, and carrying out condensation reaction on the dialdehyde cellulose and 4- (4-dimethylamino phenyl) -8, 9, 9-trimethyl-5, 6, 7, 8-tetrahydro-5, 8-methanoquinazoline-2-amine to prepare the cellulose-based Schiff base fluorescent material. The raw materials are rich in source and low in price, the prepared cellulose-based Schiff base fluorescent material is high in fluorescence intensity, blue fluorescence is generated under ultraviolet irradiation, the fluorescence color of the material is gradually changed from blue to green within the range of pH 1-7, and the cellulose-based Schiff base fluorescent material can be used for pH detection under an acidic condition and has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of fluorescence detection, and relates to a cellulose-based Schiff base fluorescent material, and a preparation method and application thereof.
Background
Cellulose is a natural polymer with the most abundant natural content. The cellulose has abundant hydroxyl groups in the molecular structure, so that the cellulose has excellent chemical modifiability, and different functional groups are introduced to a cellulose chain, so that the cellulose can be endowed with new properties. Camphor is an important terpenoid, and has wide source, and can be extracted from natural trees of Lauraceae, or prepared from turpentine. Camphor has a rigid bicyclic framework structure, can perform various reactions and generate various camphor derivatives with different functional groups. The 4- (4-dimethylamino phenyl) -8, 9, 9-trimethyl-5, 6, 7, 8-tetrahydro-5, 8-methano quinazoline-2-amine synthesized by camphor has good fluorescence performance, and is coupled to cellulose macromolecules to obtain the cellulose-based fluorescent material, so that the cellulose-based fluorescent material not only has the excellent performance of the cellulose macromolecules, but also can overcome the limitations of small-molecule fluorescent compounds: such as fluorescence quenching due to easy aggregation; difficult to reuse; fluorescent small molecules are difficult to process and form and cannot be used for manufacturing devices; when the fluorescent micromolecules are dissolved in the solution to be detected to form a homogeneous system, the pollution of the system to be detected and the like can be caused. Meanwhile, the fluorescent group is connected with the polymer skeleton by a stable chemical bond, so that the problem that the fluorescent micromolecules are easy to lose in the material prepared by physically mixing the fluorescent micromolecules with the polymer can be effectively avoided. Therefore, the development of various types of cellulose-based functional materials has been of great significance. Has wide application prospect in the fields of biological imaging, detection sensing, information anti-counterfeiting and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a cellulose-based Schiff base fluorescent material which emits bright blue fluorescence under the irradiation of 365nm ultraviolet, and the fluorescence color is gradually changed from blue to green within the pH range of 1-7, so that the cellulose-based Schiff base fluorescent material can be used for detecting the pH under an acidic condition. The invention also provides a preparation method of the cellulose-based Schiff base fluorescent material. The invention also aims to solve the technical problem of providing the application of the cellulose-based Schiff base fluorescent material.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the cellulose-based Schiff base fluorescent material has a structural formula as follows:
the preparation method of the cellulose-based Schiff base fluorescent material comprises the following steps:
(1) taking cellulose as a starting material, and taking sodium periodate as an oxidant, and selectively oxidizing the cellulose to prepare dialdehyde cellulose;
(2) dispersing dialdehyde cellulose in an organic solvent, adding 4- (4-dimethylaminophenyl) -8, 9, 9-trimethyl-5, 6, 7, 8-tetrahydro-5, 8-methanoquinazoline-2-amine to generate 4- (4-dimethylaminophenyl) -8, 9, 9-trimethyl-5, 6, 7, 8-tetrahydro-5, 8-methanoquinazoline-2-amine dialdehyde cellulose.
In the step 1), the synthesis of dialdehyde cellulose comprises the following steps:
1) performing alkali treatment on 3.0g of cellulose, washing the cellulose with distilled water to be neutral, transferring the cellulose into a brown three-neck flask, adding 100-200 mL of water and 4.1-8.13 g of sodium periodate, adjusting the pH value of a reaction system to 2-4 with hydrochloric acid, and reacting for 4-6 hours at 45 ℃. After the reaction, ethylene glycol was added to decompose the excess sodium periodate.
2) After the reaction liquid is filtered, the filter cake is fully washed by distilled water to remove IO3 -And then, vacuum drying is carried out for 24 hours, so as to obtain dialdehyde cellulose.
In the step 2), the synthesis steps of the 4- (4-dimethylaminophenyl) -8, 9, 9-trimethyl-5, 6, 7, 8-tetrahydro-5, 8-methanoquinazoline-2-amine dialdehyde cellulose are as follows:
1) adding 0.5g of dialdehyde cellulose into a reaction bottle, then adding 15-20 mL of absolute ethyl alcohol, and reacting for 4-6 h at 40-60 ℃; 0.01-0.02 g of 4- (4-dimethylaminophenyl) -8, 9, 9-trimethyl-5, 6, 7, 8-tetrahydro-5, 8-methano-quinazolin-2-amine is dissolved in 5-10 mL of absolute ethyl alcohol, slowly added into a reaction bottle, and then 3-5 drops of CH are dropwise added3And performing reflux reaction on the COOH for 36-48 h.
2) And (3) carrying out suction filtration and ethanol washing on the reaction solution, and then carrying out vacuum drying for 24h to obtain the 4- (4-dimethylaminophenyl) -8, 9, 9-trimethyl-5, 6, 7, 8-tetrahydro-5, 8-methanoquinazoline-2-amine dialdehyde cellulose.
The synthesized cellulose-based Schiff base fluorescent material generates blue fluorescence under ultraviolet irradiation, has good luminous performance, and the fluorescence color of the material gradually changes from blue to green within the range of pH 1-7, so that the cellulose-based Schiff base fluorescent material can be used for detecting the pH under an acidic condition.
The dialdehyde cellulose is prepared by taking natural renewable resource cellulose as a raw material and sodium periodate as an oxidant; and condensing the dialdehyde cellulose with 4- (4-dimethylaminophenyl) -8, 9, 9-trimethyl-5, 6, 7, 8-tetrahydro-5, 8-methanoquinazoline-2-amine to obtain the 4- (4-dimethylaminophenyl) -8, 9, 9-trimethyl-5, 6, 7, 8-tetrahydro-5, 8-methanoquinazoline-2-amine dialdehyde cellulose. The synthetic cellulose-based Schiff base fluorescent material is found to generate blue fluorescence under ultraviolet irradiation, the luminous performance is good, and the fluorescence color of the material is gradually changed from blue to green within the range of pH 1-7, so that the material can be used for pH detection under acidic conditions.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) cellulose is the most abundant natural polymer in nature, and has low price.
(2) The preparation process of the dialdehyde cellulose is mature and meets the requirement of sustainable development.
(3) 4- (4-dimethylamino phenyl) -8, 9, 9-trimethyl-5, 6, 7, 8-tetrahydro-5, 8-methano quinazoline-2-amine synthesized by camphor has good fluorescence performance, and is grafted to cellulose macromolecules to obtain the cellulose-based fluorescent material, so that the cellulose-based fluorescent material not only has excellent performance of the cellulose macromolecules, but also overcomes many limitations of small molecular fluorescent compounds.
(4) The cellulose-based Schiff base fluorescent material generates blue fluorescence under ultraviolet irradiation, has good luminous performance, and the fluorescence color of the material gradually changes from blue to green within the range of pH 1-7, so that the cellulose-based Schiff base fluorescent material can be used for detecting the pH under an acidic condition.
Drawings
FIG. 1 is a fluorescence spectrum of a cellulose-based Schiff base fluorescent material;
FIG. 2 is a fluorescence spectrum of cellulose-based Schiff base fluorescent material in different solvents;
FIG. 3 is a fluorescence spectrum of cellulose-based Schiff base fluorescent material under different pH values;
FIG. 4 is (a) an infrared spectrum of microcrystalline cellulose, (b) an infrared spectrum of alkali-treated cellulose, (c) an infrared spectrum of dialdehyde cellulose, (d) an infrared spectrum of 4- (4-dimethylaminophenyl) -8, 9, 9-trimethyl-5, 6, 7, 8-tetrahydro-5, 8-methanoquinazolin-2-aminedialdehyde cellulose, and (e) an infrared spectrum of 4- (4-dimethylaminophenyl) -8, 9, 9-trimethyl-5, 6, 7, 8-tetrahydro-5, 8-methanoquinazolin-2-amine;
FIG. 5 is a photograph of cellulose-based Schiff base fluorescent material under sunlight and under 365nm ultraviolet lamp, respectively.
Detailed description of the preferred embodiments
The invention is further described below with reference to specific embodiments.
Example 1
The preparation method of the cellulose base Schiff base fluorescent material has the following reaction formula:
the method comprises the following specific steps:
(1) preparing dialdehyde cellulose: performing alkali treatment on microcrystalline cellulose by using 14% sodium hydroxide, taking 3.0g of the alkali-treated microcrystalline cellulose, 150mL of deionized water and 4.5g of sodium periodate, adjusting the pH value to be 2.6, performing light-resistant reaction for 5 hours at 45 ℃, adding 15mL of glycol to terminate the reaction after the reaction is finished, filtering, washing IO by using distilled water, and removing IO3 -And vacuum drying at 45 deg.c for 24 hr to obtain dialdehyde cellulose.
(2) 0.5g of dialdehyde cellulose is dispersed in absolute ethyl alcohol, and 0.01g of 4- (4-dimethylaminophenyl) -8, 9, 9-trimethyl-5, 6, 7, 8-tetrahydro-5, 8-methanoquinazolin-2-amine is dissolved in absolute ethyl alcohol and then slowly added. Then 4 drops of acetic acid are dripped, and reflux reaction is carried out for 36-48 h;
(3) after the reaction liquid is filtered, a filter cake is washed by hot ethanol, unreacted 4- (4-dimethylaminophenyl) -8, 9, 9-trimethyl-5, 6, 7, 8-tetrahydro-5, 8-methanoquinazoline-2-amine is removed, and then vacuum drying is carried out for 24 hours, so that 4- (4-dimethylaminophenyl) -8, 9, 9-trimethyl-5, 6, 7, 8-tetrahydro-5, 8-methanoquinazoline-2-amine dialdehyde cellulose is obtained, and the product is light yellow powder.
Example 2
The cellulose-based schiff base fluorescent material prepared in example 1 was pressed into a sheet, and the solid fluorescence emission spectrum of the fluorescent cellulose was measured, as shown in fig. 1. The results show that the maximum emission wavelength of solid fluorescence is at 425 nm.
Example 3
The cellulose-based Schiff base fluorescent material prepared in example 1 is prepared into 0.002g/10mL suspension in DMF, absolute ethyl alcohol and deionized water respectively. Fluorescence emission spectra in DMF, absolute ethanol and deionized water were measured as shown in fig. 2. The result shows that the maximum fluorescence emission wavelength of the compound is 412nm under the DMF system; in an absolute ethyl alcohol system, the maximum fluorescence emission wavelength of the compound is 409 nm; the maximum fluorescence emission wavelength of the compound is 426nm in a deionized water system.
Example 4
The cellulose-based schiff base fluorescent material prepared in example 1 was prepared into 0.002g/mL DMF suspension, and the fluorescence emission spectra of the solution were measured at pH 1, 2, 3, 4, 5, 6, and 7, and the results are shown in fig. 3. When the pH value is from 7 to 4, the fluorescence intensity at 412nm gradually decreases along with the increase of acidity, particularly, the pH value is from 3 to 1, the maximum emission wavelength of fluorescence is red-shifted from 412nm to 487nm, and the fluorescence intensity at 487nm gradually increases. And when the pH value is from 7 to 1, the fluorescence color of the solution is gradually changed from blue to green.
The structure of the obtained fluorescent cellulose was analyzed by a fourier infrared spectrometer. FIG. 4 shows microcrystalline cellulose, alkali-treated cellulose, dialdehyde cellulose, 4- (4-dimethylaminophenyl) -8, 9, 9-trimethyl-5, 6, 7, 8-tetrahydro-5, 8-methanoquinazolin-2-aminedialdehyde cellulose, 4- (4-bis-dimethylaminophenyl) -8, 9, 9-trimethyl-5, 6, 7, 8-tetrahydro-5, 8-methanoquinazolin-2-aminedialdehyde celluloseMethylamino phenyl) -8, 9, 9-trimethyl-5, 6, 7, 8-tetrahydro-5, 8-methanoquinazolin-2-amine. The dialdehyde cellulose is 1730cm higher than microcrystalline cellulose and alkali-treated cellulose-1The C ═ O stretching vibration peak appears, and the characteristic peak disappears after dialdehyde cellulose reacts with fluorescent small molecule 4- (4-dimethylaminophenyl) -8, 9, 9-trimethyl-5, 6, 7, 8-tetrahydro-5, 8-methano quinazoline-2-amine to generate fluorescent cellulose. This indicates that the fluorescent small molecule has been successfully grafted onto dialdehyde cellulose.
As can be seen from fig. 5. Under the irradiation of a 365nm ultraviolet lamp, the product of the embodiment of the invention can indeed emit bright blue fluorescence, namely, the embodiment of the invention obtains the fluorescent cellulose.
Claims (1)
1. The application of the cellulose-based Schiff base fluorescent material in the detection of acid pH; the cellulose-based Schiff base fluorescent material generates blue fluorescence under ultraviolet irradiation, and the fluorescence color of the material gradually changes from blue to green within the pH range of 1-7; the cellulose base Schiff base fluorescent material has a structural formula as follows:
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| CN113402622B (en) * | 2021-06-17 | 2022-10-04 | 南京林业大学 | Quinoline amino carboxymethyl cellulose fluorescent microsphere, preparation method and application thereof |
| CN113621081B (en) * | 2021-08-31 | 2022-06-10 | 南京林业大学 | Dialdehyde cellulose-based Schiff base fluorescent probe for detecting Al3+, and preparation method and application thereof |
| CN114525368B (en) * | 2022-01-21 | 2023-09-26 | 中国皮革制鞋研究院有限公司 | In-situ dyeing type bio-based tanning agent and preparation method and application thereof |
| CN115926008B (en) * | 2022-12-12 | 2024-03-05 | 陕西科技大学 | Anthracene ketone ethylenediamine cellulose fluorescent probe material and preparation method and application thereof |
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