CN112250978A - Preparation method of phenylboronic acid-based glucose-responsive sugar-sensitive microgel - Google Patents
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Abstract
The invention discloses a preparation method of phenylboronic acid group glucose responsive sugar sensitive microgel. N-isopropyl acrylamide, 3-acrylamidophenylboronic acid and N-dimethylaminopropyl acrylamide are used as monomers, azodiisobutyronitrile is used as an initiator, a polymer is synthesized by adopting a free radical copolymerization method, and the obtained polymer and polyvinyl alcohol are prepared into the glucose-responsive sugar-sensitive microgel by adopting a reverse microemulsion method. The raw materials and equipment used by the invention are the raw materials and equipment which can be obtained at present, the preparation process of the sugar-sensitive microgel is simple, but the obtained sugar-sensitive microgel can quickly respond to the change of the concentration of the glucose in a physiological environment.
Description
Technical Field
The invention belongs to a preparation method of nanogel in the field of high polymer materials, and particularly relates to a preparation method of phenylboronic acid group glucose responsive sugar sensitive microgel.
Background
Diabetes is one of diseases which seriously affect the life health of human beings in the world at present, and the number of diabetes patients reaches 4.25 hundred million in 2017. The traditional treatment mode for diabetes is to inject insulin, but the inaccurate injection dosage can cause hypoglycemia and the like, and seriously endanger the life safety of patients. Therefore, microgels responding to changes in glucose concentration have attracted considerable attention.
In vitro test results show that the volume of the microgel changes regularly along with the change of the concentration of the glucose. By wrapping insulin in the sugar-sensitive microgel, the microgel which can release different amounts of insulin and adjust the blood sugar concentration along with the change of the glucose concentration can be prepared. The sugar-sensitive microgel can also be applied to a sugar-sensitive sensor to detect the concentration of blood sugar in real time, thereby achieving the purposes of preventing diabetes and treating diabetes.
Disclosure of Invention
The invention aims to provide a method for preparing phenylboronic acid based glucose responsive sugar sensitive microgel, which uses the raw materials which can be obtained at present, has simple preparation process, and can respond to the change of the glucose concentration in a physiological environment.
The technical scheme of the invention is as follows:
n-isopropylacrylamide (NIPAM), 3-acrylamidophenylboronic acid (AAPBA) and N-Dimethylaminopropylacrylamide (DMAPAA) are used as monomers, Azobisisobutyronitrile (AIBN) is used as an initiator, a free radical copolymerization method is adopted to synthesize a polymer, and the obtained polymer and polyvinyl alcohol are prepared into the glucose-responsive sugar-sensitive microgel by adopting a reverse microemulsion method. The 3-acrylamidophenylboronic acid (AAPBA) has good glucose responsiveness, the amino group of N-dimethylaminopropyl acrylamide (DMAPAA) is a strong electron-withdrawing group, the pKa of the 3-acrylamidophenylboronic acid (AAPBA) can be reduced, the polyvinyl alcohol (PVA) has low toxicity and good biocompatibility, and can be combined with the 3-acrylamidophenylboronic acid (AAPBA) to form a reversible boric acid ester bond.
The preparation method of the phenylboronic acid group glucose responsive sugar sensitive microgel comprises the following specific steps:
(1) adding N-isopropylacrylamide, 3-acrylamidophenylboronic acid, N-dimethylaminopropylacrylamide, azobisisobutyronitrile and anhydrous methanol into a container provided with a condenser tube, a magneton and a gas guide tube, introducing argon for 30-60min, removing oxygen in the solution, heating the solution, reacting for 12-24h, concentrating the solution after the reaction is finished, precipitating the concentrated solution in 500mL of 300-plus-one ethyl ether, collecting lower-layer white floccule, precipitating for three times, filtering by suction, collecting white solid, and drying the white solid in a vacuum oven to constant weight to obtain the polymer.
(2) Dissolving 5000-4000 mg of Span 80(Span 80) in 120mL of liquid paraffin 100 to obtain a solution, stirring the solution to uniformly mix the solution, and dividing the solution into two parts.
(3) Dissolving 100-200mg of the polymer obtained in the step (1) in 5-10mL of water to obtain a polymer aqueous solution, dropwise adding the obtained polymer aqueous solution into one part of the solution obtained in the step (2), and stirring and mixing uniformly.
(4) Dissolving 100-200mg of polyvinyl alcohol in 5-10mL of water to obtain a polyvinyl alcohol aqueous solution, dropwise adding the obtained polyvinyl alcohol aqueous solution into another part of the solution obtained in the step (2), and uniformly stirring and mixing.
(5) And (4) dropwise adding the aqueous solution of the polymer obtained in the step (3) into the aqueous solution of the polyvinyl alcohol obtained in the step (4), and stirring and uniformly mixing the solution at a stirring speed of 1300 rpm/min.
(6) And (5) centrifuging the solution obtained in the step (5) in a centrifuge, and pouring out the supernatant to obtain a lower-layer product.
(7) Adding 25-30mL of isopropanol into the lower-layer product obtained in the step (6), and placing the mixture into a centrifuge for centrifugation.
(8) And (7) repeating the step (7) for three times, pouring out the supernatant to obtain a lower-layer product, adding 10-20mL of ultrapure water into the lower-layer product, and freeze-drying to obtain the glucose responsive microgel.
The container in the step (1) is a flask.
The flask is a three-neck flask.
The amounts of N-isopropylacrylamide, 3-acrylamidophenylboronic acid, N-dimethylaminopropylacrylamide, azobisisobutyronitrile and anhydrous methanol added in the step (1) were 700-1100mg, 200-310mg, 205-410. mu.L, 15-20mg and 10-20mL, respectively.
The temperature of the heating solution in the step (1) is 60-65 ℃, and the reaction time is 12-24h
The speed of the centrifuge in the step (6) is 3000-4000rpm/min, and the time of the centrifuge is 10-20 min.
The speed of the centrifuge in the step (7) is 4000-5000rpm/min, and the time of the centrifuge is 30-60 min.
The reaction equation of the step (1) is as follows:
the prepared glucose responsive sugar sensitive microgel can be used for detecting the change of the glucose concentration in a physiological environment.
The invention has the beneficial effects that:
the raw materials and equipment used by the invention are the raw materials and equipment which can be obtained at present, the preparation process of the sugar-sensitive microgel is simple, but the obtained sugar-sensitive microgel can quickly respond to the change of the concentration of the glucose in a physiological environment.
Drawings
FIG. 1 is a scanning electron micrograph of a synthetic microgel.
FIG. 2 is a graph showing the effect of glucose concentration on particle size variation.
Detailed Description
The present invention is described in more detail below with reference to the drawings and examples, but the present invention is not limited thereto, and it will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the principle of the present invention, and these modifications and improvements are also considered to be within the scope of the present invention. Those not described in detail in this specification are within the skill of the art.
Example 1:
200.8mg of AAPBA, 951.5mg of NIPAM, 205 mu L of DMAPAA, 17.3mg of AIBN and 10.5mL of anhydrous methanol are added into a three-neck flask provided with a condenser tube, a magnet and an air guide tube, argon is introduced for bubbling for 30min to remove oxygen in the solution, the solution is heated to 60 ℃ for reaction for 24h, the solution is concentrated after the reaction is finished, the concentrated solution is precipitated in 400mL of diethyl ether, a lower layer of white floccule is collected and precipitated for three times, a white solid is collected after suction filtration, and the white solid is put into a vacuum oven to be dried to constant weight to obtain a polymer (NIPAM-co-AAPBA-co-DMAPAA) P (NIPAM-co-AAPBA-co-DMAPAA).
4106.6mg of span 80 is weighed and dissolved in 100mL of liquid paraffin, evenly mixed by stirring and divided into two parts, 5mL of 2 wt% aqueous solution of polymer (isopropylacrylamide-co-acrylamidophenylboronic acid-co-dimethylaminopropylacrylamide) P (NIPAM-co-AAPBA-co-DMAPAA) is dripped into one part, 5mL of 2 wt% aqueous solution of PVA is dripped into the other part, evenly mixed by stirring respectively, the solution of polymer (isopropylacrylamide-co-acrylamidophenylboronic acid-co-dimethylaminopropylacrylamide) P (NIPAM-co-AAPBA-co-DMAPAA) is dripped into the solution of PVA by stirring, the solution is evenly stirred and mixed by the stirring speed of 1300rpm/min, the evenly mixed solution is centrifuged for 10min by a centrifuge at the speed of 3000rpm/min, and after centrifugation, pouring out the supernatant to obtain a lower-layer product, adding 25mL of isopropanol into the lower-layer product, centrifuging the lower-layer product in a centrifuge at the speed of 4000rpm/min for 30min, repeating the step for three times, pouring out the supernatant to obtain a lower-layer product, adding 10mL of ultrapure water into the lower-layer product, and freeze-drying to obtain the glucose-responsive sugar-sensitive microgel.
Example 2:
adding 201.3mg of AAPBA, 831.1mg of NIPAM, 410 mu L of DMAPAA, 17.4mg of AIBN and 10.5mL of anhydrous methanol into a three-neck flask provided with a condenser tube, a magnet and an air guide tube, bubbling for 30min by introducing argon, removing oxygen in the solution, heating the solution to 60 ℃, reacting for 24h, concentrating the solution after the reaction is finished, precipitating the concentrated solution in 400mL of diethyl ether, collecting a lower layer of white floccule, precipitating for three times, collecting a white solid after suction filtration, putting the white solid into a vacuum oven, and drying to constant weight to obtain the polymer (NIPAM-co-AAPBA-co-DMAPAA) P (NIPAM-co-AAPBA-co-DMAPAA).
4103.5mg of Span 80 is weighed and dissolved in 100mL of liquid paraffin, evenly mixed by stirring and divided into two parts, one part is dripped with 5mL of 2 wt% aqueous solution of polymer (isopropylacrylamide-co-acrylamidophenylboronic acid-co-dimethylaminopropylacrylamide) P (NIPAM-co-AAPBA-co-DMAPAA) and the other part is dripped with 5mL of 2 wt% aqueous solution of PVA, evenly mixed by stirring respectively, the solution of polymer (isopropylacrylamide-co-acrylamidophenylboronic acid-co-dimethylaminopropylacrylamide) P (NIPAM-co-AAPBA-co-DMAPAA) is dripped into the solution of PVA, evenly mixed by stirring at 1300rpm/min, the evenly mixed solution is centrifuged in a centrifuge at 3000rpm/min for 10min, and after centrifugation, pouring out the supernatant to obtain a lower-layer product, adding 25mL of isopropanol into the lower-layer product, centrifuging the lower-layer product in a centrifuge at the speed of 4000rpm/min for 30min, repeating the step for three times, pouring out the supernatant to obtain a lower-layer product, adding 10mL of ultrapure water into the lower-layer product, and freeze-drying to obtain the glucose-responsive sugar-sensitive microgel.
In the specific implementation of the invention, the prepared glucose-responsive sugar-sensitive microgel is dissolved in a buffer solution with the pH of 7.4 to prepare an A solution with the concentration of the glucose-responsive sugar-sensitive microgel of 0.25g/L, and a solution with the concentration of glucose of 0, 1, 4 and 10g/L, 2mL of the A solution is added into the solutions with different concentrations of glucose, and the obtained solution is put into a 37 ℃ oven for 24 hours. The particle size of the microgel was then measured at different glucose concentrations using a nanosized zeta potential analyzer (Malvern).
FIG. 1 demonstrates the successful synthesis of glucose responsive sugar sensitive microgels in spherical form, mostly between 150nm and 400nm in diameter
FIG. 2 illustrates that the sugar-sensitive microgel prepared in the invention has a significant increase in particle size with an increase in glucose concentration, which demonstrates that the sugar-sensitive microgel has glucose responsiveness.
Claims (10)
1. A preparation method of phenylboronic acid group glucose responsive sugar sensitive microgel is characterized by comprising the following steps:
n-isopropyl acrylamide, 3-acrylamidophenylboronic acid and N-dimethylaminopropyl acrylamide are used as monomers, azodiisobutyronitrile is used as an initiator, a polymer is synthesized by adopting a free radical copolymerization method, and the obtained polymer and polyvinyl alcohol are prepared into the glucose-responsive sugar-sensitive microgel by adopting a reverse microemulsion method.
2. The method for preparing a phenylboronic glucose-responsive sugar-sensitive microgel according to claim 1, wherein the method comprises the following steps: the method comprises the following specific steps:
(1) adding N-isopropylacrylamide, 3-acrylamidophenylboronic acid, N-dimethylaminopropylacrylamide, azobisisobutyronitrile and anhydrous methanol into a container, introducing argon for 30-60min, removing oxygen in the solution, heating the solution for reaction, concentrating the solution after the reaction is finished, precipitating the concentrated solution in 500mL of 300-plus-one ethyl ether, collecting lower-layer white floccule, precipitating for three times, filtering by suction, collecting white solid, and drying the white solid in a vacuum oven to constant weight to obtain a polymer;
(2) dissolving 5000mg of span 804000-;
(3) dissolving 100-200mg of the polymer obtained in the step (1) in 5-10mL of water to obtain a polymer aqueous solution, dropwise adding the obtained polymer aqueous solution into one part of the solution obtained in the step (2), and uniformly stirring and mixing;
(4) dissolving 100-200mg of polyvinyl alcohol in 5-10mL of water to obtain a polyvinyl alcohol aqueous solution, dropwise adding the obtained polyvinyl alcohol aqueous solution into another part of the solution obtained in the step (2), and uniformly stirring and mixing;
(5) dropwise adding the aqueous solution of the polymer obtained in the step (3) into the aqueous solution of the polyvinyl alcohol obtained in the step (4), and stirring and uniformly mixing the solution at a stirring speed of 1300 rpm/min;
(6) centrifuging the solution obtained in the step (5) in a centrifuge, and pouring out the supernatant to obtain a lower-layer product;
(7) adding 25-30mL of isopropanol into the lower-layer product obtained in the step (6), and placing the mixture into a centrifuge for centrifugation;
(8) and (7) repeating the step (7) for three times, pouring out the supernatant to obtain a lower-layer product, adding 10-20mL of ultrapure water into the lower-layer product, and freeze-drying to obtain the glucose responsive microgel.
3. The method of preparing a microgel responsive to a change in glucose concentration as set forth in claim 2, wherein: the container in the step (1) is a flask.
4. The method of preparing a microgel responsive to a change in glucose concentration as set forth in claim 2, wherein: the flask is a three-neck flask.
5. The method of preparing a microgel responsive to a change in glucose concentration as set forth in claim 2, wherein: the amounts of N-isopropylacrylamide, 3-acrylamidophenylboronic acid, N-dimethylaminopropylacrylamide, azobisisobutyronitrile and anhydrous methanol added in the step (1) were 700-1100mg, 200-310mg, 205-410. mu.L, 15-20mg and 10-20mL, respectively.
6. The method of preparing a microgel responsive to a change in glucose concentration as set forth in claim 2, wherein: the temperature of the heating solution in the step (1) is 60-65 ℃, and the reaction time is 12-24 h.
7. The method of preparing a microgel responsive to a change in glucose concentration as set forth in claim 2, wherein: the speed of the centrifuge in the step (6) is 3000-4000rpm/min, and the time of the centrifuge is 10-20 min.
8. The method of preparing a microgel responsive to a change in glucose concentration as set forth in claim 2, wherein: the speed of the centrifuge in the step (7) is 4000-5000rpm/min, and the time of the centrifuge is 30-60 min.
9. The method of preparing a microgel responsive to a change in glucose concentration as set forth in claim 2, wherein: the reaction equation of the step (1) is as follows:
10. a sugar-sensitive microgel responsive to changes in glucose concentration, comprising: prepared by the method of claim 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113603826A (en) * | 2021-06-30 | 2021-11-05 | 浙江大学 | Preparation method of acryloyl glycinamide-phenylboronic acid group sugar-sensitive microneedle |
| CN115746196A (en) * | 2022-11-15 | 2023-03-07 | 电子科技大学长三角研究院(湖州) | Preparation method and application of isopropyl methacrylamide-fluorophenylboronic acid copolymerized glucose response microgel |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07304971A (en) * | 1994-05-09 | 1995-11-21 | Nippon Oil & Fats Co Ltd | Sugar responsive polymeric material |
| CN111234096A (en) * | 2020-01-10 | 2020-06-05 | 南开大学 | Glucose responsive polymer and preparation method thereof |
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- 2020-10-16 CN CN202011110336.5A patent/CN112250978A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07304971A (en) * | 1994-05-09 | 1995-11-21 | Nippon Oil & Fats Co Ltd | Sugar responsive polymeric material |
| CN111234096A (en) * | 2020-01-10 | 2020-06-05 | 南开大学 | Glucose responsive polymer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| TAKASHI AOKI ET,AL.: "Glucose-Sensitive Lower Critical Solution Temperature Changes of Copolymers Composed of N-Isopropylacrylamide and Phenylboronic Acid Moieties", 《POLYMER JOURNAL》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113603826A (en) * | 2021-06-30 | 2021-11-05 | 浙江大学 | Preparation method of acryloyl glycinamide-phenylboronic acid group sugar-sensitive microneedle |
| CN113603826B (en) * | 2021-06-30 | 2022-06-28 | 浙江大学 | Preparation method of acryloyl glycinamide-phenylboronic acid based sugar-sensitive microneedle |
| CN115746196A (en) * | 2022-11-15 | 2023-03-07 | 电子科技大学长三角研究院(湖州) | Preparation method and application of isopropyl methacrylamide-fluorophenylboronic acid copolymerized glucose response microgel |
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