阅读说明：本技术 点击交联荧光聚合物及其制备与应用 (Click cross-linking fluorescent polymer and preparation and application thereof ) 是由 胡剑青 田锦衡 周曦 周子潇 于 2020-07-09 设计创作，主要内容包括：本发明属于荧光聚合物的技术领域,公开了点击交联荧光聚合物及其制备与应用。方法：1)将柠檬酸与蓖麻油进行反应,获得反应产物；将氨基酸与反应产物继续进行反应,获得生物基荧光聚酯；2)将生物基荧光聚酯与2-叠氮基乙醇反应,获得含有叠氮基的荧光聚酯；将生物基荧光聚酯与1-戊炔-3-醇反应,获得含有炔基的荧光聚酯；3)在催化剂的作用下,将含有叠氮基的荧光聚酯与含有炔基的荧光聚酯进行点击反应,获得点击交联荧光聚合物。本发明的方法简单,所述制备的聚合物,具有良好的机械力学性能和独特的荧光特性,可用于荧光成像、组织工程、药物传递及细胞成像等领域。(The invention belongs to the technical field of fluorescent polymers, and discloses a click crosslinking fluorescent polymer and preparation and application thereof. The method comprises the following steps: 1) reacting citric acid with castor oil to obtain a reaction product; continuously reacting the amino acid with the reaction product to obtain the bio-based fluorescent polyester; 2) reacting the bio-based fluorescent polyester with 2-azido ethanol to obtain fluorescent polyester containing azido; reacting bio-based fluorescent polyester with 1-pentyne-3-ol to obtain alkynyl-containing fluorescent polyester; 3) under the action of a catalyst, carrying out click reaction on the fluorescent polyester containing the azido group and the fluorescent polyester containing the alkynyl group to obtain a click cross-linked fluorescent polymer. The method is simple, and the prepared polymer has good mechanical properties and unique fluorescence characteristics, and can be used in the fields of fluorescence imaging, tissue engineering, drug delivery, cell imaging and the like.)

1. A preparation method of a click crosslinking fluorescent polymer is characterized in that: the method comprises the following steps:

1) reacting citric acid with castor oil to obtain a reaction product; continuously reacting the amino acid with the reaction product to obtain the bio-based fluorescent polyester;

2) reacting the bio-based fluorescent polyester with 2-azido ethanol to obtain fluorescent polyester containing azido; reacting bio-based fluorescent polyester with 1-pentyne-3-ol to obtain alkynyl-containing fluorescent polyester;

3) under the action of a catalyst, carrying out click reaction on the fluorescent polyester containing the azido group and the fluorescent polyester containing the alkynyl group to obtain a click cross-linked fluorescent polymer.

2. The method for preparing a click cross-linking fluorescent polymer according to claim 1, wherein: the citric acid: castor oil: the molar ratio of amino acids is 1: (0.5-0.8): (0.02-0.15).

3. The method for preparing a click cross-linking fluorescent polymer according to claim 1, wherein:

the reaction temperature in the step 1) is 130-150 ℃; the temperature of the continuous reaction is 100-120 ℃.

4. The method for preparing a click cross-linking fluorescent polymer according to claim 1, wherein: in the fluorescent polyester containing azido in the step 2), the molar ratio of citric acid to 2-azido ethanol in the bio-based fluorescent polyester is 1: (0.03-0.15);

in the alkynyl-containing fluorescent polyester, the molar ratio of citric acid to 1-pentyne-3-ol in the bio-based fluorescent polyester is 1: (0.03-0.15).

5. The method for preparing a click cross-linking fluorescent polymer according to claim 1, wherein:

the reaction time in the step 1) is 2-4 h, and the continuous reaction time is 3-6 h;

the reaction in the step 1) is carried out under a vacuum condition, and the continuous reaction is carried out under the vacuum condition;

the molar ratio of the azide groups in the fluorescent polyester containing the azide groups to the alkyne groups in the fluorescent polyester containing the alkyne groups in the step 3) is 1: (0.9-1.1).

6. The method for preparing a click cross-linking fluorescent polymer according to claim 1, wherein: in the step 2), the reaction temperature in the reaction of the bio-based fluorescent polyester and 2-azido ethanol is 50-65 ℃, and the reaction time is 2-4 h;

the reaction temperature of the bio-based fluorescent polyester and 1-pentyne-3-ol in the reaction is 50-65 ℃, and the reaction time is 2-4 h;

the click reaction time in the step 3) is 0.5-1 h.

7. The method for preparing a click cross-linking fluorescent polymer according to claim 1, wherein: the catalyst is a monovalent copper catalyst.

8. A click crosslinking fluorescent polymer obtained by the preparation method of any one of claims 1 to 7.

9. The use of the click cross-linked fluorescent polymer of claim 8, wherein: the click cross-linked fluorescent polymer is used in the fields of fluorescence imaging, tissue engineering, drug delivery and cell imaging.

Technical Field

The invention belongs to the technical field of fluorescent polymer modification, and particularly relates to a click crosslinking fluorescent polymer and preparation and application thereof.

Background

After Kolb, Finn and Sharpless first proposed the concept of Click Chemistry (Click Chemistry) in 2001, Click Chemistry has developed rapidly since. The click reaction has the characteristics of easily obtained preparation raw materials, mild reaction conditions, high product yield, good selectivity, easy separation and purification and the like, and is widely used for polymer modification and crosslinking to enhance the mechanical property of the material and expand the application and application range and field of the polymer material.

Fluorescent polymer materials have been widely used in the fields of dyes, chemical brighteners, photo-oxidizers, coatings, chemical and biochemical analysis, anti-counterfeit marking, drug tracing, lasers, and the like, due to their unique fluorescent properties. The mechanical property of the fluorescent polymer material influences the application range of the fluorescent polymer material, and in the field of fluorescence detection, the fluorescent polymer with poor mechanical property is difficult to prepare into a film to be combined with an optical instrument for use, so that the automatic detection is limited. Therefore, the fluorescent polymer material with excellent mechanical property and good stability is prepared and has great significance.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide a click crosslinking fluorescent polymer and a preparation method thereof. The click-crosslinking fluorescent polymer material is prepared by using 2-azido ethanol, 1-pentyne-3-ol, natural bio-based raw materials such as citric acid, castor oil and amino acid as raw materials. The synthesized click crosslinking fluorescent polymer has better mechanical property and unique fluorescent characteristic.

Still another object of the present invention is to provide the use of the above click-crosslinked fluorescent polymer. The click cross-linked fluorescent polymer can be used in the fields of fluorescence imaging (fluorescent imaging agent), tissue engineering, drug delivery, cell imaging and the like, and aims at non-disease diagnosis and non-treatment.

In order to achieve the purpose, the invention provides the following technical scheme:

a preparation method of a click cross-linking fluorescent polymer comprises the following steps:

1) reacting citric acid with castor oil to obtain a reaction product; continuously reacting the amino acid with the reaction product to obtain the bio-based fluorescent polyester;

2) reacting the bio-based fluorescent polyester with 2-azido ethanol to obtain fluorescent polyester containing azido; reacting bio-based fluorescent polyester with 1-pentyne-3-ol to obtain alkynyl-containing fluorescent polyester;

3) under the action of a catalyst, carrying out click reaction on the fluorescent polyester containing the azido group and the fluorescent polyester containing the alkynyl group to obtain a click cross-linked fluorescent polymer.

The citric acid: castor oil: the molar ratio of amino acids is 1: (0.5-0.8): (0.02-0.15);

the reaction temperature is 130-150 ℃, and the reaction time is 2-4 h; the temperature of the continuous reaction is 100-120 ℃, and the time of the continuous reaction is 3-6 h.

The reaction is carried out under vacuum conditions and the further reaction is carried out under vacuum conditions.

In the fluorescent polyester containing azido in the step 2), the molar ratio of citric acid to 2-azido ethanol in the bio-based fluorescent polyester is 1: (0.03-0.15);

in the alkynyl-containing fluorescent polyester, the molar ratio of citric acid to 1-pentyne-3-ol in the bio-based fluorescent polyester is 1: (0.03-0.15);

the molar ratio of the azide groups to the alkyne groups in the fluorescent polyester containing the azide groups is 1: (0.9-1.1).

The reaction temperature of the bio-based fluorescent polyester and 2-azido ethanol in the reaction is 50-65 ℃, and the reaction time is 2-4 h;

the reaction temperature of the bio-based fluorescent polyester and 1-pentyne-3-ol in the reaction is 50-65 ℃, and the reaction time is 2-4 h.

The click reaction time in the step 3) is 0.5-1 h.

The catalyst is a monovalent copper catalyst, and the monovalent copper catalyst (Cu (I) catalyst) is a system of copper sulfate and sodium ascorbate.

The mass ratio of copper sulfate to the bio-based fluorescent polyester with azido in the catalyst is (0.003-0.01): 1.

the invention uses different amino acids such as cysteine and serine to obtain polymers with different fluorescence luminescent regions, and the mechanical property of the polymers is enhanced after click groups are introduced, and the polymers still have unique fluorescence characteristics.

The structure of the click crosslinking fluorescent polymer is shown as formula I:

in formula I, -SH can be replaced by-OH.

Compared with the prior art, the invention has the following advantages and beneficial effects:

(1) the method is simple, and the reaction can be quickly and efficiently carried out at normal temperature and normal pressure by introducing the groups capable of generating click reaction; after click crosslinking modification, the fluorescent polymer still has unique fluorescent characteristics (when the amino acid is cysteine, the maximum fluorescent intensity is at 449 nm; when the amino acid is serine, the maximum fluorescent intensity is at 462 nm);

(2) the raw materials used in the invention are easy to obtain, the reaction process is simple, and no harmful pollutants are generated in the reaction;

(3) the polymer prepared by the invention has good mechanical properties and unique fluorescence characteristics, and has wide application fields and application ranges.

Drawings

FIG. 1 is an infrared spectrum of a click cross-linked fluorescent polymer prepared in example 1;

FIG. 2 is a mechanical property test chart of the clicked cross-linked fluorescent polymer prepared in example 3 and example 6 and the un-clicked cross-linked polymer of comparative example 1;

FIG. 3 is a fluorescence spectrum of the click cross-linked fluorescent polymer prepared in example 3 and example 4;

FIG. 4 is a fluorescence spectrum of the fluorescent polymer prepared in comparative example 1 without click crosslinking.

Detailed Description

The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.