CN111607007A - 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
- Publication number
- CN111607007A CN111607007A CN202010570884.XA CN202010570884A CN111607007A CN 111607007 A CN111607007 A CN 111607007A CN 202010570884 A CN202010570884 A CN 202010570884A CN 111607007 A CN111607007 A CN 111607007A
- Authority
- CN
- China
- Prior art keywords
- cellulose
- fluorescent material
- schiff base
- base fluorescent
- dialdehyde
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002678 cellulose Polymers 0.000 title claims abstract description 99
- 239000001913 cellulose Substances 0.000 title claims abstract description 99
- 239000000463 material Substances 0.000 title claims abstract description 44
- 239000002262 Schiff base Substances 0.000 title claims abstract description 32
- 150000004753 Schiff bases Chemical class 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 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 claims abstract description 32
- 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 claims abstract description 20
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims abstract description 18
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- -1 4-dimethylaminophenyl Chemical group 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 2
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000006482 condensation reaction Methods 0.000 abstract 1
- 235000010980 cellulose Nutrition 0.000 description 71
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 5
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 5
- 239000008108 microcrystalline cellulose Substances 0.000 description 5
- 229940016286 microcrystalline cellulose Drugs 0.000 description 5
- 241000723346 Cinnamomum camphora Species 0.000 description 4
- 229960000846 camphor Drugs 0.000 description 4
- 229930008380 camphor Natural products 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000218195 Lauraceae Species 0.000 description 1
- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N2021/6417—Spectrofluorimetric devices
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Immunology (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Polymers & Plastics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Medicinal Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Molecular Biology (AREA)
- Optics & Photonics (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Paper (AREA)
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 -After that, the air conditioner is started to work,vacuum drying for 24h 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 is an infrared spectrum of microcrystalline cellulose, alkali-treated cellulose, dialdehyde cellulose, 4- (4-dimethylaminophenyl) -8, 9, 9-trimethyl-5, 6, 7, 8-tetrahydro-5, 8-methanoquinazolin-2-aminal dialdehyde cellulose, 4- (4-dimethylaminophenyl) -8, 9, 9-trimethyl-5, 6, 7, 8-tetrahydro-5, 8-methanoquinazolin-2-amine, respectively. 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 (7)
1. A cellulose-based Schiff base fluorescent material is characterized in that the structural formula of the fluorescent material is as follows:
2. the method for preparing the cellulose-based schiff base fluorescent material according to claim 1, comprising the steps of:
(1) taking cellulose as a starting material, taking sodium periodate as an oxidant, and selectively oxidizing the cellulose to prepare dialdehyde cellulose;
(2) dispersing dialdehyde cellulose in an organic solvent, adding fluorescent micromolecule 4- (4-dimethylaminophenyl) -8, 9, 9-trimethyl-5, 6, 7, 8-tetrahydro-5, 8-methanoquinazoline-2-amine and dialdehyde cellulose for condensation to prepare 4- (4-dimethylaminophenyl) -8, 9, 9-trimethyl-5, 6, 7, 8-tetrahydro-5, 8-methanoquinazoline-2-amine dialdehyde cellulose.
3. The method for preparing a cellulose-based schiff base fluorescent material according to claim 2, wherein the step of synthesizing dialdehyde cellulose in the step (1) 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 4.10-8.13 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 is finished, adding ethylene glycol to decompose redundant 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.
4. The method for preparing cellulose-based schiff base fluorescent material according to claim 2, wherein the step (2) of synthesizing 4- (4-dimethylaminophenyl) -8, 9, 9-trimethyl-5, 6, 7, 8-tetrahydro-5, 8-methanoquinazolin-2-aminedialdehydic cellulose comprises the following steps:
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 ℃; dissolving 0.01-0.02 g of 4- (4-dimethylaminophenyl) -8, 9, 9-trimethyl-5, 6, 7, 8-tetrahydro-5, 8-methano-quinazolin-2-amine in 5-10 mL of absolute ethyl alcohol, slowly adding the solution into a reaction bottle, and then dropwise adding 3-5 drops of CH3COOH, and carrying out reflux reaction 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.
5. Use of the cellulose-based schiff base fluorescent material according to claim 1 for detecting pH.
6. Use according to claim 5, characterized in that: 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 range of pH of 1-7.
7. Use according to claim 5, characterized in that: the method is used for detecting the pH value under acidic conditions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010570884.XA CN111607007B (en) | 2020-06-19 | 2020-06-19 | Cellulose-based Schiff base fluorescent material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010570884.XA CN111607007B (en) | 2020-06-19 | 2020-06-19 | Cellulose-based Schiff base fluorescent material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111607007A true CN111607007A (en) | 2020-09-01 |
| CN111607007B CN111607007B (en) | 2022-03-25 |
Family
ID=72198629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010570884.XA Expired - Fee Related CN111607007B (en) | 2020-06-19 | 2020-06-19 | Cellulose-based Schiff base fluorescent material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111607007B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113402622A (en) * | 2021-06-17 | 2021-09-17 | 南京林业大学 | Quinoline amino carboxymethyl cellulose fluorescent microsphere, preparation method and application thereof |
| CN113621081A (en) * | 2021-08-31 | 2021-11-09 | 南京林业大学 | For detecting Al3+Dialdehyde cellulose base Schiff base fluorescent probe and preparation method and application thereof |
| CN114525368A (en) * | 2022-01-21 | 2022-05-24 | 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 |
| CN115926008A (en) * | 2022-12-12 | 2023-04-07 | 陕西科技大学 | Anthracene ketone ethylenediamine cellulose fluorescent probe material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891828A (en) * | 2010-07-26 | 2010-11-24 | 南京林业大学 | Synthesis method for microcrystalline cellulose-based fluorescent material |
| CN107892654A (en) * | 2017-11-30 | 2018-04-10 | 南京林业大学 | A kind of isolonglifolane base fluorescent type acid-base indicator and its synthetic method and application |
| CN108018037A (en) * | 2018-01-08 | 2018-05-11 | 南京林业大学 | 6,8- endo-methylene group tetrahydro quinazoline -2- amine Schiff bases iron ion fluorescence probes and its preparation method and application |
| CN109232444A (en) * | 2018-11-20 | 2019-01-18 | 南京林业大学 | A kind of camphor base fluorescent probe and preparation method thereof for detecting hydrazine |
| CN110551070A (en) * | 2018-05-30 | 2019-12-10 | 南京林业大学 | Synthesis of camphoryl pyrimidine compounds and antitumor activity thereof |
| CN110759871A (en) * | 2018-07-26 | 2020-02-07 | 南京林业大学 | Camphor synthesized quinazoline compound used as fluorescent probe for hypochlorous acid detection |
-
2020
- 2020-06-19 CN CN202010570884.XA patent/CN111607007B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891828A (en) * | 2010-07-26 | 2010-11-24 | 南京林业大学 | Synthesis method for microcrystalline cellulose-based fluorescent material |
| CN107892654A (en) * | 2017-11-30 | 2018-04-10 | 南京林业大学 | A kind of isolonglifolane base fluorescent type acid-base indicator and its synthetic method and application |
| CN108018037A (en) * | 2018-01-08 | 2018-05-11 | 南京林业大学 | 6,8- endo-methylene group tetrahydro quinazoline -2- amine Schiff bases iron ion fluorescence probes and its preparation method and application |
| CN110551070A (en) * | 2018-05-30 | 2019-12-10 | 南京林业大学 | Synthesis of camphoryl pyrimidine compounds and antitumor activity thereof |
| CN110759871A (en) * | 2018-07-26 | 2020-02-07 | 南京林业大学 | Camphor synthesized quinazoline compound used as fluorescent probe for hypochlorous acid detection |
| CN109232444A (en) * | 2018-11-20 | 2019-01-18 | 南京林业大学 | A kind of camphor base fluorescent probe and preparation method thereof for detecting hydrazine |
Non-Patent Citations (2)
| Title |
|---|
| 孙延一等主编: "《仪器分析》", 31 January 2019, 第二版 * |
| 李玥: ""pH荧光探针的原理发展及应用综述"", 《当代化工研究》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113402622A (en) * | 2021-06-17 | 2021-09-17 | 南京林业大学 | Quinoline amino carboxymethyl cellulose fluorescent microsphere, preparation method and application thereof |
| CN113621081A (en) * | 2021-08-31 | 2021-11-09 | 南京林业大学 | For detecting Al3+Dialdehyde cellulose base Schiff base fluorescent probe and 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 |
| CN114525368A (en) * | 2022-01-21 | 2022-05-24 | 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 |
| 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 |
| CN115926008A (en) * | 2022-12-12 | 2023-04-07 | 陕西科技大学 | Anthracene ketone ethylenediamine cellulose fluorescent probe material 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111607007B (en) | 2022-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111607007B (en) | Cellulose-based Schiff base fluorescent material and preparation method and application thereof | |
| CN111607051B (en) | Three-dimensional fluorescent covalent organic framework material and preparation method and application thereof | |
| CN109970044B (en) | Preparation method and application of blue fluorescent carbon quantum dots | |
| CN110511383B (en) | Zinc-containing polyhedral oligomeric silsesquioxane coordination polymer and preparation method and application thereof | |
| CN109135738B (en) | Waste tobacco stem-based nitrogen-doped carbon dots and synthesis method and application thereof | |
| CN110157412B (en) | Long-life room temperature phosphorescent material and preparation method thereof | |
| CN108727576B (en) | Hyperbranched polyaminoester capable of emitting multicolor fluorescence and preparation method thereof | |
| CN105419794A (en) | Orange light emitting carbon nano dot, preparation method and applications thereof | |
| CN111875811B (en) | Supermolecule polymer and preparation method and application thereof | |
| CN107312536B (en) | Red luminescent rare earth composite material, preparation method and application | |
| CN113462383B (en) | Room-temperature phosphorescent material based on cellulose and preparation method and application thereof | |
| CN114933660A (en) | Cellulose-based coumarin fluorescent probe for detecting hydrazine and preparation method and application thereof | |
| CN110283586B (en) | Near-infrared fluorescent dye and preparation method thereof | |
| CN110467916B (en) | Nitrogen-doped carbon quantum dot green fluorescent material and preparation method thereof | |
| CN113528133B (en) | Preparation method of brown coal-based white fluorescent carbon dots | |
| CN111548431B (en) | Marine organism polysaccharide grafted pyridine organic micromolecule multicolor adjustable aggregation-induced emission material and preparation method thereof | |
| CN114805613B (en) | For detecting Fe 3+ Ethyl cellulose base flavonol fluorescent probe and preparation method and application thereof | |
| CN115322262A (en) | For detecting Fe 3+ Dialdehyde cellulose base coumarin fluorescent probe and preparation method and application thereof | |
| CN115160588A (en) | Full-spectrum luminescent nanoscale zirconium-based metal organic framework material and preparation method thereof | |
| CN111057066B (en) | Red solid fluorescent luminescent material and preparation method thereof | |
| CN111978433A (en) | N-chitosan-4-hydroxy-1, 8-naphthalimide fluorescent material and preparation method and application thereof | |
| CN114644562B (en) | Organic small molecule fluorescent compound with red shift fluorescent emission, preparation method and application | |
| CN107597196B (en) | Preparation method of organic graphene nanotube with surface modified with titanium dioxide | |
| CN116041553B (en) | Preparation method for regulating and controlling chiral property of nanocellulose by rare earth complex | |
| CN1197845C (en) | Method for photoisomerizing tachysterol and derivatives thereof into previtamin D and derivatives thereof by using crosslinked macromolecular photosensitizer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20220325 |