CN103289078B - A kind of method and application preparing polyamino acid and derivative thereof fast - Google Patents
A kind of method and application preparing polyamino acid and derivative thereof fast Download PDFInfo
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Abstract
The invention belongs to chemosynthesis technical field, specifically disclose a kind of method and the application of preparing polyamino acid and derivative thereof fast.The present invention is under microwave exposure heating condition, adopt ionic liquid as reaction solvent, prepare polyamino acid and derivative thereof by the ring-opening polymerization of L-type a-amino acid-N-carboxylic acid anhydride and derivative thereof, can greatly Reaction time shorten, improve polymerization efficiency, optimized product quality.The ionic liquid Microwave Emulsifier-Free Polymerization technology that the present invention adopts has that energy consumption is low, efficiency is high, pollution-free, low cost and easily realize the distinguishing feature of serialization large-scale production, is expected to expand further the Application Areas of high molecular polyamino acid and derivative thereof and improves its using value.
Description
Technical field
The invention belongs to chemosynthesis technical field, be specifically related to a kind of method and the application of preparing polyamino acid and derivative thereof fast.
Background technology
As everyone knows, the polyamino acid material prepared by natural amino acid has good physiologically acceptable, biodegradable and good mechanical property, can be widely used in target loading, gene transfection, the biomedical sectors such as tissue engineering bracket hydrogel.
At present, the preparation method of polyamino acid is based on fermentable and chemosynthesis.Wherein, microbe fermentation method amount is pollution-free greatly, but be only limitted to a few non-poly-a-amino acid (as gamma-polyglutamic acid-and epsilon-polylysine), and molecular weight of product is excessive (usually 500,000 more than g/mol), distribute wide, not easily purifying, be difficult to obtain accurate polyamino acid product.And in chemical synthesis, solid phase synthesis can only synthesized micromolecule amount polyamino acid (being less than 100 Amino Acid Units), therefore generally all first a-amino acid cyclisation is generated pentacyclic amino acid-N-carboxylic acid anhydride (NCA) and carry out living radical ring-opening polymerization again and gather a-amino acid and derivative thereof to prepare macromolecule, the better control to polymerisate quality can be realized.
Since the forties in last century, synthesize polyamino acid by NCA ring-opening polymerization and obtained general application.Specifically amino acid-N-the carboxylic acid anhydride prepared is dissolved in organic solvent, under the condition of anhydrous and oxygen-free, add initiator (such as primary amine, alkoxide) to cause NCA and carry out living radical ring-opening polymerization, generate the aminoacid polymers of high molecular.Large result shows, the aminoacid polymers obtained by NCA ring-opening polymerization does not exist racemize phenomenon, can form the secondary tertiary structure that α spiral, β-pleated sheet structure etc. are similar to protein in molecular chain and between molecular chain.
Such as; using dioxane as solvent; being polymerized by causing benzyl glutamate-N-carboxylic acid anhydride monomer under a certain proportion of triethylamine room temperature under the protection of nitrogen, reacting after 3 days reprecipitation in dehydrated alcohol and obtaining poly benzyl glutamate, sloughing benzyl subsequently and namely obtain polyglutamic acid.The method can be used for preparing molecular weight 70,000 ~ 350, the polyglutamic acid within the scope of 000 g/mol, and dispersity major part is between 1.55 ~ 2.01, and minority exists the too high phenomenon of dispersity.But, because the reactive behavior of NCA monomer is high, to high temperature and damp and hot more responsive, easily decompose inactivation before polymerization.And in the course of the polymerization process, water micro-in system and impurity also can cause the generation of the side reaction such as cancellation and chain tra nsfer.Therefore there is many deficiencies in this preparation method: institute's polymerizing condition is harsher, needs anhydrous and oxygen-free; Solvent expends comparatively large, needs through the repeatedly purifying to raw material and product; Reaction times is longer, usually at least needs two to three days just can obtain high monomer conversion.In addition, solvent for use (as dioxane) toxicity is comparatively large, also also exist impair one's health, the potentially dangerous such as contaminate environment.
Summary of the invention
The technical problem to be solved in the present invention is the deficiency overcoming conventional polyamino acid synthetic technology, provides a kind of method preparing polyamino acid and derivative thereof fast.
Another object of the present invention is to provide the application of the above-mentioned polyamino acid for preparing fast and derivative thereof.
Object of the present invention is achieved by the following technical programs:
A kind of preparation method of polyamino acid; after a-amino acid-N-carboxylic acid anhydride or alpha-amino acid derivatives-N-carboxylic acid anhydride monomer being dissolved in ionic liquid under rough vacuum; protection of inert gas also injects initiator, adds thermal synthesis polyamino acid or derivatives thereof by microwave exposure.
The preparation of described a-amino acid-N-carboxylic acid anhydride and derivatives monomer thereof can with reference to conventional synthesis process in prior art.
The preparation method of a kind of PLGA or poly-(L-Aspartic acid); by L-type α-benzyl glutamate-N-carboxylic acid anhydride or after L-type α-aspartic acid benzyl ester-N-carboxylic acid anhydride monomer is dissolved in ionic liquid under rough vacuum; protection of inert gas also injects initiator; add thermal synthesis poly-(Pidolidone benzyl ester) or poly-(L-Aspartic acid benzyl ester) by microwave exposure, then after sour deprotection, obtain PLGA or poly-(L-Aspartic acid).
Preferably; the concrete steps of described polyglutamic acid or poly aspartic acid preparation method are: after L-type α-benzyl glutamate-N-carboxylic acid anhydride or L-type α-aspartic acid benzyl ester-N-carboxylic acid anhydride monomer being dissolved in 1-butyl-3-Methylimidazole hexafluorophosphate under rough vacuum; the primary amine such as triethylamine or n-Butyl Amine 99 initiator is injected under the protection of the rare gas element such as argon gas or nitrogen; add thermal synthesis poly-(Pidolidone benzyl ester) or poly-(L-Aspartic acid benzyl ester) by microwave exposure, then after sour deprotection, obtain PLGA or poly-(L-Aspartic acid).
The synthetic method of polyamino acid or derivatives thereof of the present invention, for ion solvent usage quantity and have no special requirements, can rare can be dense, the usage quantity of ion solvent depends on actual performance completely.For the usage quantity of monomer and initiator also without specificity, the usage quantity (i.e. the mol ratio of initiator and monomer) of monomer and initiator depends on the molecular weight of the product (polyamino acid or derivatives thereof) of setting completely.Set different molecular weight, namely correspond to different mol ratios.
More preferably, the concrete steps of described polyglutamic acid or poly aspartic acid preparation method are: after 0.1 ~ 20 mmol L-type α-benzyl glutamate-N-carboxylic acid anhydride or L-type α-aspartic acid benzyl ester-N-carboxylic acid anhydride monomer being dissolved in 1 ~ 20 mL 1-butyl-3-Methylimidazole hexafluorophosphate or 1-butyl-3-methyl imidazolium tetrafluoroborate under rough vacuum, the primary amine such as 0.01 ~ 2 mmol initiator triethylamine or n-Butyl Amine 99 is injected under the protection of inert gas such as argon gas or nitrogen, heating synthetic molecular weight by microwave exposure is 500 to 500, the poly-L-glutamic acid acid benzyl ester of 000 g/mol or poly-L-Aspartic acid benzyl ester, poly-L-glutamic acid acid benzyl ester or poly-L-Aspartic acid benzyl ester obtain L-glutamic acid or poly-L-Aspartic acid after sour debenzylation.
Ionic liquid is a liquid class organic salt compound at normal temperatures, such organic salt compound has hypotoxicity, conductive capability is strong, solution polarity is large, density is large, specific heat capacity is high and heat-resisting and high chemical stability by force, have simultaneously nonflammable and not volatile and be easy to reclaim feature, these characteristics meet the requirement of Green Chemistry completely.Preferably, ionic liquid of the present invention is imidazole type ion liquid; More preferably, described imidazole type ion liquid is 1-butyl-3-Methylimidazole hexafluorophosphate or 1-butyl-3-methyl imidazolium tetrafluoroborate.
The present invention adopts imidazole type ion liquid as solvent; such as 1-butyl-3-Methylimidazole hexafluorophosphate ([BMIM] PF6) or 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM] BF4); under rough vacuum, amino acid N CA monomer dissolves rear protection of inert gas and injects initiator; thermal synthesis polyamino acid and derivative thereof is added, to realize the object preparing high-quality polymkeric substance quickly and efficiently by microwave exposure.From the angle of thermodynamics and kinetics, the introducing of ionic liquid and microwave exposure all will promote the conversion of NCA monomer greatly, promotes the synthesis of high molecular, low polydispersity polyamino acid.This preparation method is simple and easy to control, be applicable to the polymerization synthesis of most of natural amino acid, greatly can shorten polymerization reaction time, significantly improve reaction efficiency and optimized product quality, and solvent for use ionic liquid easily reclaims, do not cause environmental pollution, one novel green preparation method fast and efficiently will be provided for suitability for industrialized production polyamino acid and derivative thereof.
The synthetic method of polyamino acid or derivatives thereof of the present invention is applicable to the polymerization synthesis of most of natural amino acid.Except proline(Pro), all the other 19 kinds of common amino acids all can adopt the method for the invention to synthesize.Just; wherein; corresponding polymkeric substance can be obtained by direct polymerization as phenylalanine; L-glutamic acid, aspartic acid, Methionin, halfcystine, Histidine then need modified after could utilize NCA polymerization; namely obtain corresponding polyamino acid derivative, then slough blocking group or modification group just can obtain final polyamino acid.
Preferably, described microwave exposure heating power is 5 ~ 300W.
Preferably, described initiator is the primary amine such as triethylamine or n-Butyl Amine 99.
The polyamino acid prepared by aforesaid method and derivative thereof can be widely used in target loading, gene transfection, the biomedical engineering fields such as organizational project.
The invention has the beneficial effects as follows:
(1) the present invention adopts ionic liquid as the solvent of polymerization reaction system, and not only low toxicity easily reclaims, and can improve polyreaction efficiency, ensure that the pollution-free of the method and low cost.Ionic liquid is a liquid class organic salt compound at normal temperatures, such organic salt compound has hypotoxicity, conductive capability is strong, solution polarity is large, density is large, specific heat capacity is high and heat-resisting and high chemical stability by force, have simultaneously nonflammable and not volatile and be easy to reclaim feature, these characteristics meet the requirement of Green Chemistry completely.A small amount of bibliographical information has been had to utilize imidazole type ion liquid to synthesize the novel method of polyglutamic acid homopolymer in recent years.Such as, be dissolved in by benzyl glutamate NCA in a kind of imidazole type ion liquid, use n-Butyl Amine 99 as initiator, react 20 hours at 30 DEG C, then in methyl alcohol, precipitation can obtain corresponding polymkeric substance.Compared with traditional method, although the method productive rate is on the low side and molecular weight is relatively little, substantially reduce polymerization reaction time, obtained polymericular weight dispersity is lower (between 1.08 ~ 1.34).And the existence of ionic liquid, has certain influence to the polymerization methods of NCA, response bias is carried out in the mode of similar ionic polymerization, thus improve polymerization rate.
(2) the present invention utilize the not volatile characteristic of ionic liquid have employed rough vacuum operation, for amino acid N CA open loop cyclopolymerization be extremely conducive to preparing the low poly-a-amino acid of molecular weight high degree of dispersion and derivative thereof.Particularly; protection of inert gas is filled with use ion liquid dissolving NCA monomer under low vacuum after; not only can the drying of guarantee system and anaerobic, can effectively reduce the gas concentration lwevel discharged in reaction simultaneously, greatly reduce monomer and decompose the possibility occurred with side reaction.
(3) the microwave exposure type of heating that adopts of the present invention, have fast compared with the hot type of heating of tradition, evenly, feature that capacity usage ratio is high, and penetration power is by force, has better heat efficiency for polar material and ion.Microwave action, can the motion of acceleration molecular in reactant, carries high molecular translation energy, thus accelerates intermolecular collision frequency to improve speed of reaction.Existing document is pointed out, microwave exposure can effectively reduce reaction barrier and the activation energy of a certain class material.With the ionic liquid of high polarity with the use of, also can further improve the heat effect of microwave.
(4) ionic liquid adopted in the present invention and microwave exposure heating technique easily realize and regulate and control, applied range, go for multiple amino acids and derivative polymerization system thereof;
(5) ionic liquid adopted in the present invention and microwave exposure heating technique are all comparatively ripe, and existing certain applications in the example of suitability for industrialized production, and easily realize continuous prodution, have high industrial value and application potential.
Accompanying drawing explanation
Fig. 1. proton nmr spectra (1H-NMR) spectrogram of the benzyl glutamate-N-carboxylic acid anhydride (BLG-NCA) of preparation in example 1, the displacement spectra peak that in structure, different H atom is corresponding indicates in the accompanying drawings.
Fig. 2. proton nmr spectra (1H-NMR) spectrogram of the poly benzyl glutamate (PBLG) prepared using triethylamine as initiator in example 1, the displacement spectra peak that in structure, different H atom is corresponding indicates in the accompanying drawings.
Embodiment
The present invention is further illustrated below in conjunction with the drawings and specific embodiments.The test method used in embodiment if no special instructions, is ordinary method; The material used, reagent etc. if no special instructions, are the reagent that can obtain from commercial channels and material.The chemical structure of products therefrom and molecular weight adopt proton nmr spectra (1H-NMR) to carry out measure and calculation.
embodiment 1
The preparation of S1. L-type α-benzyl glutamate: 30 g Pidolidones and 28.9g phenylcarbinol are placed in 250ml round-bottomed flask and mix, 70 DEG C are heated to subsequently in oil bath, then the vitriol oil that 55 g massfractions are 66 % is slowly instilled, keep 70 DEG C of heated and stirred become to solution from muddiness completely clarification after, round-bottomed flask is placed in and keeps under Rotary Evaporators vacuum under 60 DEG C of water-baths to revolve sending out 4 hours, subsequently the liquid of the thickness obtained slowly being poured into 250 ml contains in the frozen water of 33g sodium bicarbonate, is not having unnecessary CO
2after releasing, the mixture of ice and water containing precipitation is placed in 4 DEG C of refrigerators lower 24 hours, then filters, the filter cake absolute ethanol washing obtained 4 hours.By white precipitate deionized water reprecipitation 4 times.This side is equally applicable to the preparation of aspartic acid benzyl ester.
The preparation of S2. L-type α-benzyl glutamate-N-carboxylic acid anhydride
Getting L-type α-benzyl glutamate that 2.09 g step S1 prepare dissolves in 40 mL anhydrous tetrahydro furans, in 50 DEG C of heating under the protection of argon gas.2.87 g triphosgene dissolve in 10 mL anhydrous tetrahydro furans, slowly add 40 mL subsequently and contain in the tetrahydrofuran solution of benzyl glutamate, after solution clarification.Use is revolved steaming instrument and solution is revolved the volume steamed to appropriate, pours into subsequently in dry hexane solution.Obtain the crystal powder L-type benzyl glutamate-N-carboxylic acid anhydride (BLG-NCA) of white, re-use the crystal powder recrystallization three time of ethyl acetate to white, to obtain pure monomer.As shown in Figure 1, the displacement spectra peak that in structure, different H atom is corresponding indicates proton nmr spectra (1H-NMR) spectrogram of the Pidolidone benzyl ester-N-carboxylic acid anhydride (BLG-NCA) prepared in the accompanying drawings.
This method is equally applicable to the preparation of aspartic acid benzyl ester-N-carboxylic acid anhydride (BLA-NCA).
S3. the synthesis of poly-(Pidolidone benzyl ester)
Get the BLG-NCA (3.798 mmol) that 1.00 g step S2 prepare and be placed in reaction eggplant bottle, add 10 mL dried ionic liquid 1-butyl-3-methyl imidazolium hexafluorophosphate [BMIM] PF immediately
6under low vacuum, be stirred to monomer dissolve completely, dry rare gas element argon gas is passed into again in eggplant-shape bottle, use sampler to inject n-Butyl Amine 99 7.5 uL (0.0759 mmol) or triethylamine 10.5 uL (0.0759 mmol) by bottleneck plug, the mol ratio of initiator and monomer is 1:50.Use microwave-oven-heating subsequently, maintain 50 DEG C of reactions 2 hours, subsequently the solution of gained is injected methyl alcohol, to obtain polymkeric substance precipitation---the poly benzyl glutamate PBLG of white.To precipitate vacuum-drying, and obtain solid 0.50 g of white, nuclear-magnetism calculates, and the molecular weight of product obtained is about 8000 g/mol.By changing the ratio of initiator and monomer, the polymkeric substance of different molecular weight can be obtained.As shown in Figure 2, the displacement spectra peak that in structure, different H atom is corresponding indicates proton nmr spectra (1H-NMR) spectrogram of poly-(Pidolidone benzyl ester) (PBLG) that prepare in the accompanying drawings.Specific experiment result is as shown in the table:
S4. the deprotection of poly-(Pidolidone benzyl ester) prepares PLGA.
The PBLG that 1g step S3 prepares is dissolved in appropriate trifluoroacetic acid; adding 6 mL mass ratioes is 33% HBr/ glacial acetic acid solution; 0 degree of stirring 2 hours is kept under protection of inert gas; the solution for vacuum obtained is spin-dried for; use subsequently anhydrous diethyl ether repeatedly washing precipitation 2 hours to wash away the benzyl taken off, vacuum-drying product.Then the product obtained is dissolved in the NaHCO of 0.5%
3in solution, subsequently 0.5% NaHCO
3enough hemodialysis in solution, to go out remaining trifluoroacetic acid.By solution freeze-drying, obtain colourless thread solid, be PLGA.
embodiment 2
The preparation of S1. L-type α-aspartic acid benzyl ester: with embodiment 1.
The preparation of S2. L-type α-aspartic acid benzyl ester-N-carboxylic acid anhydride: with embodiment 1.
S3. the synthesis of poly-(L-Aspartic acid benzyl ester): just ion liquid solvent is 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM] BF4), and other step is with embodiment 1.Specific experiment result is as shown in the table:
S4. the deprotection preparation poly-(L-Aspartic acid) of poly-(L-Aspartic acid benzyl ester): with embodiment 1.
comparative example 1(only heating with microwave exposure without ion solvent)
Get the BLG-NCA (3.798 mmol) that in 1.00 g embodiments 1, step S2 prepares and be placed in reaction eggplant bottle, add the dried N of 10 mL immediately, dinethylformamide (DMF), under low vacuum, be stirred to monomer dissolve completely, dry rare gas element argon gas is passed into again in eggplant-shape bottle, use sampler to inject n-Butyl Amine 99 7.5 uL (0.0759 mmol) or triethylamine 10.5 uL (0.0759 mmol) by bottleneck plug, the mol ratio of initiator and monomer is 1:50.Subsequently reactant is drained the oil in bath, use microwave-oven-heating subsequently, react 20 hours at keeping 30 DEG C, subsequently the solution of gained is injected methyl alcohol, to obtain the polymkeric substance precipitation poly benzyl glutamate PBLG of white.To vacuum-drying be precipitated, obtain the solid of white.Specific experiment result is as shown in the table.
comparative example 2(only with ion solvent, but not adopting microwave exposure to heat)
Get the BLG-NCA (3.798 mmol) that in 1.00 g embodiments 1, step S2 prepares and be placed in reaction eggplant bottle, add 10 mL dried ionic liquid 1-butyl-3-methyl imidazolium hexafluorophosphate [BMIM] PF6 immediately, under low vacuum, be stirred to monomer dissolve completely, dry rare gas element argon gas is passed into again in eggplant-shape bottle, use sampler to inject n-Butyl Amine 99 7.5 uL (0.0759 mmol) or triethylamine 10.5 uL (0.0759 mmol) by bottleneck plug, the mol ratio of initiator and monomer is 1:50.Subsequently reactant is drained the oil in bath, react 20 hours at keeping 30 DEG C, subsequently the solution of gained is injected methyl alcohol, to obtain the polymkeric substance precipitation poly benzyl glutamate PBLG of white.To vacuum-drying be precipitated, obtain the solid of white.Shown in experimental result sees the following form.
Claims (7)
1. the preparation method of a polyamino acid or derivatives thereof, it is characterized in that, after a-amino acid-N-carboxylic acid anhydride or alpha-amino acid derivatives-N-carboxylic acid anhydride monomer being dissolved in ionic liquid under rough vacuum, protection of inert gas also injects initiator, adds thermal synthesis polyamino acid or derivatives thereof by microwave exposure; Described ionic liquid is imidazole type ion liquid, and described imidazole type ion liquid is 1-butyl-3-Methylimidazole hexafluorophosphate or 1-butyl-3-methyl imidazolium tetrafluoroborate; Described microwave exposure heating power is 5 ~ 300W.
2. the preparation method of a L-glutamic acid or poly-L-Aspartic acid; it is characterized in that; by L-type α-benzyl glutamate-N-carboxylic acid anhydride or after L-type α-aspartic acid benzyl ester-N-carboxylic acid anhydride monomer is dissolved in ionic liquid under rough vacuum; protection of inert gas also injects initiator; add thermal synthesis L-glutamic acid benzyl ester or poly-L-Aspartic acid benzyl ester by microwave exposure, poly-L-glutamic acid acid benzyl ester or poly-L-Aspartic acid benzyl ester obtain corresponding L-glutamic acid or poly-L-Aspartic acid after sour deprotection.
3. preparation method according to claim 2, it is characterized in that, after 0.1 ~ 20 mmol L-type α-benzyl glutamate-N-carboxylic acid anhydride or L-type α-aspartic acid benzyl ester-N-carboxylic acid anhydride monomer being dissolved in 1 ~ 20 mL 1-butyl-3-Methylimidazole hexafluorophosphate or 1-butyl-3-methyl imidazolium tetrafluoroborate under rough vacuum, the primary amine such as 0.01 ~ 2 mmol initiator triethylamine or n-Butyl Amine 99 is injected under the protection of inert gas such as argon gas or nitrogen, heating synthetic molecular weight by microwave exposure is 500 to 500, the poly-L-glutamic acid acid benzyl ester of 000 g/mol or poly-L-Aspartic acid benzyl ester, poly-L-glutamic acid acid benzyl ester or poly-L-Aspartic acid benzyl ester obtain L-glutamic acid or poly-L-Aspartic acid after sour debenzylation.
4. preparation method according to claim 1 or 2, is characterized in that, described initiator is the primary amine such as triethylamine or n-Butyl Amine 99.
5. preparation method according to claim 1 or 2, is characterized in that, the usage quantity of described monomer and initiator determines according to the molecular weight of the polyamino acid or derivatives thereof that will synthesize.
6. the polyamino acid that described in any one of claim 1 ~ 5, preparation method prepares and derivative thereof.
7. polyamino acid described in claim 6 and derivative thereof are in target loading, gene transfection, the application in tissue engineering bracket hydrogel.
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| CN105199098A (en) * | 2015-11-10 | 2015-12-30 | 南京工业大学 | Synthesis method of related polypeptide |
| CN111635542B (en) * | 2020-07-14 | 2022-11-04 | 华熙生物科技股份有限公司 | Cross-linked polyglutamic acid hydrogel and preparation method thereof |
| CN113201134B (en) * | 2021-03-29 | 2022-01-14 | 中山大学 | Microwave-assisted polypeptide preparation method |
| CN114774158B (en) * | 2022-02-17 | 2023-08-11 | 贵州民族大学 | Preparation method of aromatic polyamino acid low-temperature demulsifier |
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