CN106008808A - Method for preparing thermal-sensitive amino acid chiral gel - Google Patents
Method for preparing thermal-sensitive amino acid chiral gel Download PDFInfo
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- CN106008808A CN106008808A CN201610351926.4A CN201610351926A CN106008808A CN 106008808 A CN106008808 A CN 106008808A CN 201610351926 A CN201610351926 A CN 201610351926A CN 106008808 A CN106008808 A CN 106008808A
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- amino acid
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- chiral
- sensitive
- sensitive amino
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
- C08F220/603—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen and containing oxygen in addition to the carbonamido oxygen and nitrogen
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Medicinal Preparation (AREA)
Abstract
The invention relates to a method for preparing thermal-sensitive amino acid chiral gel. The method comprises the following steps: by taking a thermal-sensitive amino acid chiral monomer M1 and N,N-'-methylene bisacrylamide as raw materials, initializing copolymerization by using an initiator, thereby preparing the thermal-sensitive amino acid chiral gel, wherein the N,N-'-methylene bisacrylamide accounts for 5-10% of the mass of the monomer. The thermal-sensitive amino acid chiral gel has thermal sensitivity and chirality in the chiral center self, and has potential application values in medicine coating-release and chiral separation.
Description
Technical field
The present invention be more particularly directed to the preparation method of a kind of Thermo-sensitive amino acid chiral gel, can be used for the identification of drug loading and chipal compounds and divide
From, particularly belong to high molecular synthetic material technical field.
Background technology
High-molecular gel be by macromolecular chain between chemical bond or physical force formed three-dimensional crosslinking structure, in its structure introduce pH value,
Temperature, illumination, soda acid sensitive polymer, will make whole hydrogel stimulate generation response to external world, thus prepare progress in Intelligent Hydrogel,
Have a wide range of applications in fields such as biomedicine, organizational project, control devices.And in high-molecular gel, introduce chiral radicals, then bear at medicine
Load and the identification of chiral compound and separation aspect have potential using value.
Responsive to temperature type chiral gel is combined with the pluralgel of temperature sensitive performance and chirality function, utilizes chiral radicals coating medicine or chiral compound
Thing, utilizes temperature sensitive performance to discharge the medicine being coated with, owing to different pharmaceutical is different from the active force of chiral radicals, thus produces different rates of release,
Reach the effect of slow release and separation.A kind of chiral gel slow release for tumour medicine it is prepared in patent CN 102525882 A；In patent
CN102659981A, CN104031261A, CN201210157407.6, CN201210157406.1, CN201110287856.8 make respectively
Standby a kind of containing amino acid whose thermo-responsive hydro gel, its temperature sensitive performance derives from the additional alkyl acrylamide with Thermo-sensitive rather than aminoacid
Monomer itself has a temperature sensitive performance, so during cladding-release medicine or chiral Recognition, chiral centre all in a kind of inactivity state,
Passive being driven by the alkyl acrylamide with Thermo-sensitive is coated with and identifies, lacks the motility of chiral centre, impact cladding and the effect identified
Really.
The present invention uses the chiral monomer with self temperature sensitive performance to prepare Thermo-sensitive chiral gel with cross-linking agent copolymerization, containing bisamide bond in monomer
Structure, has strong hydrogen bond action with carrying medicament or chipal compounds, it is simple to load and the identification to medicine；The chiral polymer of preparation itself has temperature
Quick performance, less than critical solution temperature (LCST) himself activeness strengthen, compare additional Thermo-sensitive compound, be more beneficial for targeted drug
Release；During higher than critical solution temperature (LCST), chiral polymer autogenous shrinkage, compare the gel that additional Thermo-sensitive compound is formed, energy
Sensitiveer cladding and chiral Recognition performance.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of Thermo-sensitive amino acid chiral gel, to achieve these goals, preparation of the present invention
Method:
Taking 100g Thermo-sensitive amino acid amide chiral monomer M1 and 5g～10g N, N`-methylene-bisacrylamide is dissolved in the DMF of 400～1000ml
In, add the radical initiator of 0.3～0.5g, after inflated with nitrogen bubbling 30min, under conditions of being placed in 70 DEG C～80 DEG C, react 8～15h；Reaction is produced
Thing first soaks 15h with DMF, and period changes 3 DMF respectively, uses soak with ethanol 12h the most again, and period changes 3 ethanol respectively；Immersion treatment
After product be vacuum dried after filtration treatment, prepare Thermo-sensitive amino acid chiral gel.
Described Thermo-sensitive amino acid amide chiral monomer M1 is modified valine or modified alanine monomer.
Described radical initiator is benzoyl peroxide, the benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide, azodiisobutyronitrile or azo two
Different heptonitrile.
The structural formula of described modified valine is the one in following 8 kinds of structural formulas:
The structural formula of described modified alanine is the one in following 4 kinds of structural formulas:
Beneficial effects of the present invention:
The present invention uses the amino acid monomer self with Thermo-sensitive and chirality, containing bisamide bond structure in this monomer, with carrying medicament or chirality
Compound has strong hydrogen bond action, it is simple to load and the identification to medicine；The chiral polymer of preparation itself has temperature sensitive performance, less than Critical Solution temperature
Degree (LCST) himself activeness strengthen, compare existing additional Thermo-sensitive compound, be more beneficial for the release of targeted drug；Molten higher than critical
When solving temperature (LCST), chiral polymer autogenous shrinkage, compare the gel that additional Thermo-sensitive compound is formed, coating medicine that can be sensitiveer.
Detailed description of the invention
Illustrate the present invention is further details of below in conjunction with embodiment, but present disclosure is not limited solely to the following examples.
Embodiment 1
Take 100g Thermo-sensitive amino acid amide monomer D-Val-M1 and 5g N, N`-methylene-bisacrylamide, be dissolved in 400mL N, N-dimethyl
In Methanamide (DMF), add the benzoyl peroxide of 0.3g, after filling high pure nitrogen bubbling 30min, be placed in the environment of 80 DEG C heating, instead
After answering 8h, first soak 5h with DMF, after changing 3 times, use soak with ethanol 2h, after changing 3 times, vacuum drying.Temperature is shown at 18～21 DEG C
Quick performance.
Embodiment 2
Take 100g Thermo-sensitive amino acid amide monomer L-Val-M4 and 10g N, N`-methylene-bisacrylamide, be dissolved in 900mL N, N-diformazan
In base Methanamide (DMF), add the benzoyl peroxide tert-butyl ester of 0.4g, after filling high pure nitrogen bubbling 30min, be placed in the environment of 80 DEG C
Heating, after reaction 12h, first soaks 5h with DMF, after changing 3 times, uses soak with ethanol 2h, after changing 3 times, and vacuum drying.At 18～22 DEG C
Show temperature sensitive performance.
Embodiment 3
Take 100g Thermo-sensitive amino acid amide monomer L-Ala-M1 and 10g N, N`-methylene-bisacrylamide, be dissolved in 1000mL N, N-diformazan
In base Methanamide (DMF), add the azodiisobutyronitrile of 0.5g, after filling high pure nitrogen bubbling 30min, be placed in the environment of 70 DEG C heating,
After reaction 15h, first soak 5h with DMF, after changing 3 times, use soak with ethanol 2h, after changing 3 times, vacuum drying.Show at 8～13 DEG C
Temperature sensitive performance.
Embodiment 4
Take 100g Thermo-sensitive amino acid amide monomer D-Ala-M2 and 8g N, N`-methylene-bisacrylamide, be dissolved in 600mL N, N-dimethyl
In Methanamide (DMF), add the azodiisobutyronitrile of 0.4g, after filling high pure nitrogen bubbling 30min, be placed in the environment of 70 DEG C heating, instead
After answering 15h, first soak 5h with DMF, after changing 3 times, use soak with ethanol 2h, after changing 3 times, vacuum drying.Show at 8～12 DEG C
Temperature sensitive performance.
Claims (5)
1. the preparation method of a Thermo-sensitive amino acid chiral gel, it is characterised in that: described preparation method: take 100g Thermo-sensitive aminoacid acyl
Amine chiral monomer M1 and 5g～10g N, N`-methylene-bisacrylamide is dissolved in the DMF of 400～1000ml, adds the free radical of 0.3～0.5g
Initiator, after inflated with nitrogen bubbling 30min, reacts 8～15h under conditions of being placed in 70 DEG C～80 DEG C；Product first soaks 15h with DMF, and period divides
Not Geng Huan 3 DMF, use soak with ethanol 12h the most again, period changes 3 ethanol respectively；Product after immersion treatment is carried out after filtration treatment
Vacuum drying, prepares Thermo-sensitive amino acid chiral gel.
The preparation method of a kind of Thermo-sensitive amino acid chiral gel the most according to claim 1, it is characterised in that: described Thermo-sensitive amino
Acid amide chiral monomer M1 is modified valine or modified alanine.
The preparation method of a kind of Thermo-sensitive amino acid chiral gel the most according to claim 1, it is characterised in that: described free radical causes
Agent is benzoyl peroxide, the benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide, azodiisobutyronitrile or 2,2'-Azobis(2,4-dimethylvaleronitrile).
Modified valine the most according to claim 2, it is characterised in that: the structural formula of described modified valine is following 8 kinds of structural formulas
In one:
Modified alanine the most according to claim 2, it is characterised in that: the structural formula of described modified alanine is following 4 kinds of structural formulas
In one:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610351926.4A CN106008808A (en) | 2016-05-25 | 2016-05-25 | Method for preparing thermal-sensitive amino acid chiral gel |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610351926.4A CN106008808A (en) | 2016-05-25 | 2016-05-25 | Method for preparing thermal-sensitive amino acid chiral gel |
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| CN201610351926.4A Pending CN106008808A (en) | 2016-05-25 | 2016-05-25 | Method for preparing thermal-sensitive amino acid chiral gel |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501451A (en) * | 2017-09-01 | 2017-12-22 | 北方民族大学 | Chiral CO2Respond ethyleneamino acid polymer and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432746A (en) * | 2011-09-26 | 2012-05-02 | 天津工业大学 | Temperature-responsive L-amino-acid-modified chiral high-molecular hydrogel |
| CN102659981A (en) * | 2012-05-21 | 2012-09-12 | 天津工业大学 | Temperature sensitive type microgel modified by L-amino acid |
-
2016
- 2016-05-25 CN CN201610351926.4A patent/CN106008808A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432746A (en) * | 2011-09-26 | 2012-05-02 | 天津工业大学 | Temperature-responsive L-amino-acid-modified chiral high-molecular hydrogel |
| CN102659981A (en) * | 2012-05-21 | 2012-09-12 | 天津工业大学 | Temperature sensitive type microgel modified by L-amino acid |
Non-Patent Citations (3)
| Title |
|---|
| CHEN JIAOJIAO等: "Preparation and Recognization Property of Chiral Thermo-sensitive P(NIPAM-co-NALL) Hydrogels", 《CHEMICAL JOURNAL OF CHINESE UNIVERSITIES-CHINESE》 * |
| DENG, KUILIN等: "Preparation of a Thermo-sensitive Poly(N-acryloyl Alanine Methyl Ester) for Controlled Drug Release", 《ADVANCED MATERIALS RESEARCH》 * |
| DOBASHI, AKIRA等: "Control of the solubility transition in novel temperature-responsive linear polymers comprising α-amino acid diamide derivatives", 《ANALYTICAL SCIENCES》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501451A (en) * | 2017-09-01 | 2017-12-22 | 北方民族大学 | Chiral CO2Respond ethyleneamino acid polymer and preparation method thereof |
| CN107501451B (en) * | 2017-09-01 | 2019-07-02 | 北方民族大学 | Chiral CO2Respond ethyleneamino acid polymer and preparation method thereof |
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