阅读说明：本技术 一种用于检测Al3+的双醛纤维素基席夫碱类荧光探针及其制备方法和应用 (For detecting Al3+Dialdehyde cellulose base Schiff base fluorescent probe and preparation method and application thereof ) 是由 杨益琴 孟志远 赵菲 王忠龙 王晓媛 武杨梅 寇佳丽 于 2021-08-31 设计创作，主要内容包括：本发明公开了一种用于检测Al～(3+)的双醛纤维素基席夫碱类荧光探针及其制备方法和应用。本发明以双醛纤维素为原料,与癸二酰肼进行缩合制得双醛纤维素-癸二酰肼单席夫碱；双醛纤维素-癸二酰肼单席夫碱再进一步与2-羟基-1-萘醛缩合,制得双醛纤维素-癸二酰肼-2-羟基-1-萘醛双席夫碱。在365nm紫外光照射下,双醛纤维素-癸二酰肼-2-羟基-1-萘醛双席夫碱的DMF悬浮液加入Al～(3+)后,溶液的荧光颜色由无色变为蓝色,对Al～(3+)的检测极限达到6.06×10～(-7)M,作为检测Al～(3+)离子用荧光探针具有良好的应用前景。(The invention discloses a method for detecting Al 3+ The dialdehyde cellulose base Schiff base fluorescent probe and the preparation method and the application thereof. The method takes dialdehyde cellulose as a raw material, and the dialdehyde cellulose is condensed with sebacoyl hydrazine to prepare dialdehyde cellulose-sebacoyl hydrazine mono Schiff base; and further condensing the dialdehyde cellulose-sebacoyl hydrazine mono-Schiff base with 2-hydroxy-1-naphthaldehyde to prepare the dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base. Adding Al into DMF suspension of dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base under 365nm ultraviolet irradiation 3+ Then, the fluorescence color of the solution changes from colorless to blue, for Al 3+ The detection limit of (2) reaches 6.06 multiplied by 10 ‑7 M as detected Al 3+ Fluorescent probe for ionsThe needle has good application prospect.)

1. For detecting Al³⁺The dialdehyde cellulose base Schiff base fluorescent probe is characterized in that the structural formula is as follows:

2. the method for preparing the dialdehyde cellulose-based Schiff base fluorescent probe as set forth in claim 1, which is characterized by comprising the following steps:

(1) dispersing dialdehyde cellulose in ethylene glycol monomethyl ether by using the dialdehyde cellulose as a raw material, adding sebacoyl hydrazine to perform condensation reaction with the dialdehyde cellulose to prepare dialdehyde cellulose-sebacoyl hydrazine mono-Schiff base;

(2) dispersing dialdehyde cellulose-sebacoyl hydrazine mono-Schiff base in ethanol, adding 2-hydroxy-1-naphthaldehyde, and further condensing with dialdehyde cellulose-sebacoyl hydrazine mono-Schiff base to obtain dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base.

3. The method for preparing the dialdehyde cellulose-based Schiff base fluorescent probe as claimed in claim 2, wherein the preparation steps of the dialdehyde cellulose-sebacoyl dihydrazide mono-Schiff base in the step (1) are as follows:

1) adding 1.0g of dialdehyde cellulose, 40-60 mL of ethylene glycol monomethyl ether and 1.8-2.5 g of sebacoyl hydrazine into a 100mL three-neck flask equipped with a stirrer, a thermometer and a reflux condenser, then dripping 3-5 drops of acetic acid into the flask, and stirring and refluxing for 24 hours at 125 ℃;

2) and (3) carrying out suction filtration on the reaction liquid, washing with hot ethylene glycol monomethyl ether and distilled water, and carrying out vacuum drying at 45 ℃ for 24-36 h to obtain the dialdehyde cellulose-sebacoyl hydrazine mono-Schiff base.

4. The method for preparing the dialdehyde cellulose-based Schiff base fluorescent probe as claimed in claim 2, wherein the preparation steps of the dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde Schiff base in the step (2) are as follows:

1) adding 0.5g of dialdehyde cellulose-sebacoyl hydrazine mono-Schiff base, 40-60 mL of ethanol and 0.8-1.2 g of 2-hydroxy-1-naphthaldehyde into a 100mL three-neck flask equipped with a stirrer, a thermometer and a reflux condenser, then dripping 3-5 drops of acetic acid into the flask, and stirring and carrying out reflux reaction at 80 ℃ for 24 hours;

2) and (3) carrying out suction filtration on the reaction liquid, fully washing with ethanol, and carrying out vacuum drying for 24-36 h at 45 ℃ to obtain the dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base.

5. The dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base of claim 1 for detecting Al³⁺The use of (1).

6. The use according to claim 5, wherein the DMF suspension of dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base does not fluoresce under 365nm ultraviolet irradiation, and Al is added³⁺After that, the fluorescence color of the solution changed from colorless to blue.

7. The dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base as the fluorescent probe in the detection of Al³⁺The use of (1).

Technical Field

The invention belongs to the technical field of fluorescence detection, and relates to a method for detecting Al³⁺The dialdehyde cellulose base Schiff base fluorescent probe and the preparation method and the application thereof.

Background

Cellulose is a natural polymer which is widely distributed and contains most cellulose in nature. Each glucose ring of the cellulose contains 3 hydroxyl groups, and the 3 hydroxyl groups can be subjected to oxidation, etherification, crosslinking, esterification and other reactions, so that the functional modification and application of the cellulose are realized, and the cellulose is endowed with new performance. Periodate is capable of oxidizing hydroxyl groups at positions ortho to the C2 and C3 on cellulose to aldehyde groups, thereby yielding dialdehyde cellulose. 2-hydroxy-1-naphthaldehyde is one of the most widely used fluorophores, is often used for synthesizing excellent precursors of different fluorescence chemical sensors, is grafted to dialdehyde cellulose macromolecules to obtain the dialdehyde cellulose-based fluorescent material, not only has the excellent performance of the dialdehyde cellulose macromolecules, but also can overcome the limitations of small molecular fluorescent compounds: such as fluorescence quenching due to easy aggregation; difficult to reuse; fluorescent small molecules are difficult to process and mold, and cannot be used for manufacturing devices and the like. 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 dialdehyde cellulose-based functional materials has very important significance and has wide application prospects in the fields of biological imaging, detection sensing, information anti-counterfeiting and the like.

Aluminum is the third most abundant element in the earth's crust next to oxygen and silicon, the most abundant metallic element. Because of its advantages of small density, good ductility and strong corrosion resistance, it is widely used in many fields such as food and medicine packaging, kitchen ware, aerospace, etc. Although the use of aluminium brings great importance to our livesGreat convenience, but excessive use of aluminum not only causes harm to the ecological environment, but also aluminum ions are inevitably finally enriched in human bodies through water and food. When the human body contacts or takes excessive Al for a long time³⁺In time, functional disorder of human organs can be caused, and particularly, aluminum ions have strong affinity with human brain tissues and are easy to accumulate in the brain tissues, so that the central nervous system of a human is seriously injured, and then nervous system diseases are caused. The high concentration of aluminum in the body can cause bone decalcification, easily cause bone atrophy, lethargy, anemia, anorexia, ovary atrophy and the like, can inhibit phosphorus absorption of intestinal tracts, interfere normal calcium and phosphorus metabolism in the body, can cause cerebral nerve degeneration, memory deterioration, and influence on intelligence and character, even presents senile dementia. At present, Al³⁺The detection methods mainly comprise an electrochemical method, a chemical titration method, a spectrophotometry and the like, and the technologies have the defects of complicated operation, low practicability, low sensitivity and the like due to more limitation factors. Fluorescence detection technique for detecting Al³⁺Has the advantages of convenient operation, high sensitivity and the like.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a method for detecting Al³⁺The DMF suspension of the dialdehyde cellulose base Schiff base fluorescent probe does not emit fluorescence under the irradiation of 365nm ultraviolet light, but Al is added³⁺The back solution can emit blue fluorescence, and can be used for Al³⁺Detection of (3). The invention also provides a preparation method of the dialdehyde cellulose base Schiff base fluorescent probe. The invention also aims to solve another technical problem of providing an application of the dialdehyde cellulose-based Schiff base fluorescent probe.

In order to solve the technical problems, the invention adopts the technical scheme that:

for detecting Al³⁺The dialdehyde cellulose base Schiff base fluorescent probe is dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde Schiff base, and the structural formula is as follows:

the preparation method of the dialdehyde cellulose base Schiff base fluorescent probe comprises the following steps:

(1) dispersing dialdehyde cellulose in ethylene glycol monomethyl ether by using the dialdehyde cellulose as a raw material, adding sebacoyl hydrazine to perform condensation reaction with the dialdehyde cellulose to prepare dialdehyde cellulose-sebacoyl hydrazine mono-Schiff base;

(2) dispersing dialdehyde cellulose-sebacoyl hydrazine mono-Schiff base in ethanol, adding 2-hydroxy-1-naphthaldehyde, and further condensing with dialdehyde cellulose-sebacoyl hydrazine mono-Schiff base to obtain dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base.

The preparation steps of the dialdehyde cellulose-sebacoyl hydrazine mono-Schiff base in the step (1) are as follows:

1) adding 1.0g of dialdehyde cellulose, 40-60 mL of ethylene glycol monomethyl ether and 1.8-2.5 g of sebacoyl hydrazine into a 100mL three-neck flask equipped with a stirrer, a thermometer and a reflux condenser, then dripping 3-5 drops of acetic acid into the flask, and stirring and refluxing for 24 hours at 125 ℃;

2) and (3) carrying out suction filtration on the reaction liquid, washing with hot ethylene glycol monomethyl ether and distilled water, and carrying out vacuum drying at 45 ℃ for 24-36 h to obtain the dialdehyde cellulose-sebacoyl hydrazine mono-Schiff base.

The preparation steps of the dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base in the step (2) are as follows:

1) adding 0.5g of dialdehyde cellulose-sebacoyl hydrazine mono-Schiff base, 40-60 mL of ethanol and 0.8-1.2 g of 2-hydroxy-1-naphthaldehyde into a 100mL three-neck flask equipped with a stirrer, a thermometer and a reflux condenser, then dripping 3-5 drops of acetic acid into the flask, and stirring and carrying out reflux reaction at 80 ℃ for 24 hours;

2) and (3) carrying out suction filtration on the reaction liquid, fully washing with ethanol, and carrying out vacuum drying for 24-36 h at 45 ℃ to obtain the dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base.

The dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base is prepared by reactingDetection of Al³⁺The use of (1).

The application is that under 365nm ultraviolet irradiation, DMF suspension of dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base does not emit fluorescence, and Al is added³⁺After that, the fluorescence color of the solution changed from colorless to blue.

The dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base is used as a fluorescent probe for detecting Al³⁺The use of (1).

The invention takes dialdehyde cellulose as raw material, firstly, the dialdehyde cellulose and sebacoyl hydrazine are subjected to condensation reaction to prepare dialdehyde cellulose-sebacoyl hydrazine mono-Schiff base, and then the dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base is further condensed with 2-hydroxy-1-naphthaldehyde. The DMF suspension of dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base does not emit fluorescence under the irradiation of 365nm ultraviolet light, and Al is added³⁺Then, the fluorescence color of the solution is gradually changed into blue, which can be used for detecting Al³⁺Using a fluorescent probe.

Has the advantages that: compared with the prior art, the invention has the following advantages: cellulose is used as a natural polymer which is most widely distributed and contained in nature, and has wide sources and low price. The cellulose-based fluorescent probe obtained by grafting the 2-hydroxy-1-naphthaldehyde onto the cellulose macromolecules not only has excellent performance of the cellulose macromolecules, but also overcomes a plurality of limitations of small molecular fluorescent compounds. The prepared dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base fluorescent probe has the characteristics of good luminous performance, stable structure and the like, and Al is added into DMF suspension of the probe under the irradiation of 365nm ultraviolet light³⁺Then, the fluorescence color of the solution is gradually changed from colorless to blue, for Al³⁺The detection limit of (2) reaches 6.06 multiplied by 10^-7M as detected Al³⁺The fluorescent probe for ions has good application prospect.

Drawings

FIG. 1 is a chart showing (a) the IR spectrum of dialdehyde cellulose, (b) the IR spectrum of dialdehyde cellulose-sebacoyl hydrazine mono-Schiff base, and (c) the IR spectrum of dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base;

FIG. 2 is a fluorescence spectrum of dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base;

FIG. 3 shows dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base added with Al in DMF³⁺Front and back fluorescence spectra;

FIG. 4 is a fluorescence spectrum of dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base added with different metal ions in DMF;

FIG. 5 shows that dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base is added with Al with different concentrations in DMF³⁺Fluorescence spectrum of (2).

Detailed Description

In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.

Example 1

The synthesis reaction formula of the dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base is as follows:

1.0g of dialdehyde cellulose, 50mL of ethylene glycol monomethyl ether and 1.84g of sebacoyl hydrazine are added into a 100mL three-neck flask provided with a stirrer, a thermometer and a reflux condenser, then 3-5 drops of acetic acid are dropped into the flask, and the mixture is stirred and refluxed for 24 hours at 125 ℃. And (3) carrying out suction filtration on the reaction liquid, washing the reaction liquid with hot ethylene glycol monomethyl ether and distilled water, and then carrying out vacuum drying for 24 hours at the temperature of 45 ℃ to obtain the dialdehyde cellulose-sebacoyl hydrazine mono-Schiff base. Adding 0.5g of dialdehyde cellulose-sebacoyl hydrazine mono-Schiff base and 0.82g of 2-hydroxy-1-naphthaldehyde into 50mL of ethanol, dripping 3-5 drops of acetic acid, stirring and refluxing at 80 ℃ for reaction for 24 hours, carrying out suction filtration on reaction liquid, fully washing with ethanol, and carrying out vacuum drying at 45 ℃ for 24 hours to obtain the dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base.

The structure of dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base is analyzed by FT-IR. FIG. 4 shows each of the dialdehyde fibersInfrared spectrogram of cellulose, dialdehyde cellulose-sebacoyl hydrazine mono-Schiff base and dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base. As can be seen from the figure, the infrared spectra of the dialdehyde cellulose, the dialdehyde cellulose-sebacoyl hydrazine mono-Schiff base and the dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base appear at 3400cm^-1The left and right strong peaks are stretching vibration of O-H, 2931cm^-1And C-H stretching vibration is achieved through position saturation. The infrared spectrum of the dialdehyde cellulose is at 1725cm^-1The carbonyl group C ═ O stretching vibration, 881cm, appears in the aldehyde group^-1Is the vibration absorption peak of the hemiacetal. Dialdehyde cellulose-sebacoyl hydrazine at 1725cm^-1The characteristic peak disappears and is at 1675cm^-1A new absorption peak appears, which is attributed to C ═ N stretching vibration, 1325cm^-1C-N stretching vibration is adopted, and the reaction between the aldehyde group of the dialdehyde cellulose and the amino group of the sebacoyl hydrazine is shown. The infrared spectrogram of the dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base is 1675cm in comparison with the dialdehyde cellulose-sebacoyl hydrazine mono-Schiff base^-1Stretching vibration of C ═ N also occurred, but the intensity of the peak was reduced due to further consumption of the amino group on the sebacoyl dihydrazide. The results show that the dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base is successfully prepared.

Example 2

The prepared dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-schiff base is pressed into tablets, and the fluorescence emission spectrum of the solid is measured, as shown in figure 2. The results show that the maximum emission wavelength of solid fluorescence is at 425 nm.

Dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base was added to DMF to prepare a DMF suspension with a concentration of 8.0mg/mL, and fluorescence emission spectra in DMF was measured, as shown in FIG. 3. The results show that in the DMF system, Al is not added³⁺When Al is added, the fluorescence intensity is weak³⁺Then, the fluorescence intensity was sharply increased, and the maximum emission wavelength was 450nm (excitation wavelength was 355nm, excitation slit broad band was 15nm, and emission slit broad band was 5.0 nm).

Mixing dialdehyde cellulose-decanediolAdding hydrazide-2-hydroxy-1-naphthaldehyde bis-Schiff base into DMF to prepare DMF suspension with the concentration of 8.0mg/mL, wherein 1 part is used as a blank sample, and Al is added into other parts respectively³⁺、Cu²⁺、La³⁺、Cd²⁺、Cr³⁺、Co²⁺、Mn²⁺、Ni²⁺、Fe²⁺、Na⁺、K⁺、Fe³⁺、Ca²⁺、Zn²⁺、Pb²⁺、Ag⁺、Sn²⁺、Bi³⁺、Mg²⁺、Hg²⁺The fluorescence emission spectrum of the solution was measured, and the results are shown in FIG. 3. As can be seen from FIG. 4, Al is added³⁺Then, the maximum emission wavelength of the solution was 450nm, and the fluorescence intensity of the solution was significantly enhanced. While the fluorescence intensity of the solution changes little when other analytes are added. This shows that dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base pairs with Al³⁺Has good selectivity.

Adding dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base into DMF to prepare DMF suspension with the concentration of 8.0mg/mL, and measuring that Al with different concentrations is added³⁺Fluorescence emission spectra after ionization. As shown in fig. 5. The results show that with Al³⁺The concentration is gradually increased, and the fluorescence signal intensity of the dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base at 450nm is gradually increased, which indicates that the dialdehyde cellulose-sebacoyl hydrazine-2-hydroxy-1-naphthaldehyde bis-Schiff base can be used for detecting Al in the solution³⁺Concentration of, to Al³⁺The detection limit of (2) reaches 6.06 multiplied by 10^-7M。