CN109337084A - The preparation method of active oxygen and pH dual responsiveness and the Intelligent gene carrier of charge reversal characteristic - Google Patents
The preparation method of active oxygen and pH dual responsiveness and the Intelligent gene carrier of charge reversal characteristic Download PDFInfo
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- CN109337084A CN109337084A CN201811047757.0A CN201811047757A CN109337084A CN 109337084 A CN109337084 A CN 109337084A CN 201811047757 A CN201811047757 A CN 201811047757A CN 109337084 A CN109337084 A CN 109337084A
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- active oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N15/00—Mutation or genetic engineering; DNA or RNA concerning genetic engineering, vectors, e.g. plasmids, or their isolation, preparation or purification; Use of hosts therefor
- C12N15/09—Recombinant DNA-technology
- C12N15/87—Introduction of foreign genetic material using processes not otherwise provided for, e.g. co-transformation
Abstract
The invention discloses the preparation methods of a kind of active oxygen and pH dual responsiveness and the Intelligent gene carrier of charge reversal characteristic, belong to biological medical polymer gene and delays controlled-release technology field, it is a kind of utilization atom transfer radical polymerization method (ATRP), segment with different function component is aggregated into one whole section of cation high molecular, functionalization small molecule is reused to be modified, realize have the characteristic of dual responsiveness and charge reversal, and pass through host-guest interaction, introduce the tetraphenylethylene derivative with the phenyl boric acid of photosensitive and aggregation inducing property, nanoparticle is finally self-assembled by positive and negative charge interaction with DNA (DNA).The present invention is simple and easy to do, low in cost, can be widely applied to the fields such as materialogy, biology, medicine, both can control the release of DNA, and controllable light adjusts the generation of active oxygen, and can track carrier by fluorescence.
Description
Technical field
The invention belongs to biological medical polymer genes to delay controlled-release technology field, be a kind of poly- using atom transferred free radical
Segment with different function component is aggregated into one whole section of cation high molecular, and then and deoxyribose by conjunction method (ATRP)
Nucleic acid (DNA) is self-assembled into nanoparticle by positive and negative charge interaction.
Background technique
Atom transfer radical polymerisation technique (ATRP) is matched by initiator, transition metal of simple organohalogen compounds
Conjunction object establishes reversible dynamic equilibrium by redox reaction for halogen atom carrier between reactive species and suspend mode kind, thus
Realize the control to polymerization reaction.The initiator of ATRP polymerization system is mainly alkyl halide RX (X=Br, Cl), Benzyl halides
In addition object, alpha-brominated ester, α-halogenatedketone, alpha-halogenate nitrile etc. also have using aryl sulfonyl chloride, azodiisobutyronitrile etc..
Atom transfer radical polymerisation technique is a kind of activity poly for rapidly developing and having significant application value in recent years
Conjunction technology can effectively be designed the molecular structure of polymer, prepare various different performances, the novel of different function gathers
Close object material, i.e., it is so-called " cutting the garment according to the figure ".It can be made by MOLECULE DESIGN it is a variety of have different topology structure (line style,
Pectination, netted, star, dendritic macromole etc.), the polymer of the structure determination of different composition and different function and organic/
Inorganic hybrid material.Compared with the traditional activated polymerization technique such as ionic polymerization, it has monomer broad covered area, polymerizing condition temperature
With, it is easy to accomplish the remarkable advantages such as industrialization will become a new direction of synthesizing new high molecular material.Its product is in high property
Energy adhesive, dispersing agent, surfactant, high polymer alloy solubilizer and processing aid, thermoplastic elastomer (TPE), Green Chemistry
The high-tech sectors such as product, electronic information material and novel fluorine material are all with a wide range of applications.The unique distinction of ATRP
It is to have used alkyl halide to make initiator, and with the mode of transition-metal catalyst or degenerative transfer, restrained effectively biradical
Terminate reaction.
Compared with traditional living polymerization such as yin or cationic polymerization and group transfer polymerization (GTP), ATRP can be simultaneously
Packet can be prepared such as styrene (St), alkadiene and (methyl) acrylic ester monomer suitable for non-polar and polar monomer
Include the homopolymer and random, block, star and gradient copolymer and over-expense compound (hyper-brench), dendroid of no functional group
Many high-molecular compounds clear in structure including object (dentrimer), relative molecular mass can control 103~
105, MW/Mn is between 1.05~1.5.
Self-assembling technique involved in the present invention is the nanostructure to be formed to be linked by non-bonding, including electrostatic draws
Power, hydrogen bond action, Subjective and Objective tetra-inclusion complex.
Summary of the invention
The purpose of the present invention is analyzing in view of the above technology, a kind of active oxygen and pH dual responsiveness and charge are provided
The preparation method of the Intelligent gene carrier of reverse speed characterisstic, it is the preparation method simple process, low in cost and easy to implement.
Technical solution of the present invention:
A kind of preparation method of active oxygen and pH dual responsiveness and the Intelligent gene carrier of charge reversal characteristic, institute
Stating Intelligent gene carrier is by 2- (lignocaine) ethyl acrylate (DEAEA), 2- (5,5- dimethyl -1,3- dioxanes -2-
Base) three kinds of monomers of ethyl propylene acid esters (DMDEA) and glycidyl methacrylate (GMA) are with atom transfer radical polymerization
Technology (ATRP) carries out copolymerization and forms macromolecule (PD-PDM-PG), then with 4- bromomethyl benzene boric acid pinacol ester and ethylenediamine
Beta-cyclodextrin (CDen) respectively modifies the end PD and GMA, high molecular polymer (BP-PDM-PG) is obtained, finally by master
Object effect, introduces tetraphenylethylene, obtains final nano-carrier (BP-PDM-PG (TPE)), preparation step is as follows:
1) by DEAEA, DMDEA and GMA, 1:2:1 feeds intake in molar ratio, and sequentially adds 1 equivalent according to the degree of polymerization
The cuprous bromide (CuBr) of initiator 2- bromine isobutyl acylbromide, the bipyridyl of 1.5 equivalents and 1 equivalent, is dissolved in appropriate anhydrous dimethyl
In base formamide (DMF), lower 80 DEG C of nitrogen protection are reacted 24 hours, and reacting coarse product is through supercooling, column elution and deposition and purification
After processing, copolymerized macromolecule product (PD-PDM-PG) is obtained；
2) above-mentioned PD-PDM-PG is dissolved in anhydrous DMF, is separately added into 4- bromomethyl benzene boric acid pinacol ester, room temperature mistake
Night stirring, then it is separately added into ethylenediamine beta-cyclodextrin (CDen) and ethylenediamine, 70 DEG C are respectively reacted 24 hours, deionized water dialysis
3 days, BP-PDM-PG is obtained after freeze-drying, takes appropriate BP-PDM-PG and phenyl boric acid tetraphenylethylene (TPEDB), room temperature shaker mistake
Night stirs to arrive nana intelligent genophore (BP-PDM-PG (TPE)).
The beta-cyclodextrin (β-CD) is the macrocycle molecule of 7 glucose unit molecular compositions；The ethylenediamine and PD-
The molar ratio of PDM-PG is 100:1.
Further, the degree of polymerization refers to the molar ratio between monomer and initiator in step 1), and column elution is neutral oxygen
Change aluminium column, to remove the mantoquita generated in reaction.
Further, the dosage of DMF is 30mL in step 2), 4- bromomethyl benzene boric acid frequency is first added where in the above solution
The mass ratio of alcohol ester, ratio and PD-PDM-PG are 2:1.
The invention has the advantages that
The introducing of amphipathic copolymerized macromolecule (BP-PDM-PG) cyclodextrin that the micella preparation method is formed can be effective
Inhibit the toxic effect of cation high molecular, increases biocompatibility.Meanwhile then by host-guest interaction, there is light in modification
The tetraphenylethylene derivative of quick property and aggregation luminescent effect.This method is simple and easy to do, low in cost simultaneously, can be widely applied to
The fields such as materialogy, biology, medicine both can control the release of DNA, and controllable light adjusts the generation of active oxygen, and can lead to
Fluorescence is crossed to track carrier.
Detailed description of the invention
1) Fig. 1 is the design and the mechanism of action of nana intelligent genophore；
2) Fig. 2 is the nucleus magnetic hydrogen spectrum of BP-PDM-PG；
3) Fig. 3 is the particle diameter distribution and scanning electron microscope (SEM) photograph of BP-PDM-PG (TPE)；
4) Fig. 4 is the fluorogram of BP-PDM-PG (TPE)；
5) Fig. 5 is a) the zeta potential and b under BP-PDM-PG (TPE) illumination) change of size figure under acid condition
Specific embodiment
The present invention will be further described with reference to the accompanying drawing.
Attached drawing 1 gives the design of nana intelligent genophore and the mechanism of action of the present invention, by attached drawing 1 it is found that the present invention transports
With ATRP polymerization method, active oxygen responsiveness monomer DEAEA, pH acidity responsiveness monomer DMDEA and GMA monomer is copolymerized into polymerization
Object, then copolymer is modified by 4- bromomethyl benzene boric acid pinacol ester and CDen, and then with host-guest interaction by benzene boron
It is acidified tetraphenylethylene (TPEDB) to introduce, obtains amphipathic intelligent nano genophore (BP-PDM-PG (TPE)).
Self-assembling technique involved in the present invention is the nanostructure to be formed to be linked by non-bonding, including electrostatic draws
Power, hydrogen bond action, Subjective and Objective tetra-inclusion complex.
Specific example of the present invention is given below to illustrate:
3.6mmol GMA, 7.2mmol DEAEA and tri- kinds of monomers of 3.6mmol DMDEA and 0.12mmol 2- bromine is different
Butyryl bromide, 0.18mmol bipyridyl and 0.12mmol cuprous bromide are dissolved in 10mL anhydrous DMF, the lower 80 DEG C of reactions of nitrogen protection
24 hours, crude product was cooled to room temperature, and is used 50mL tetrahydrofuran (THF) to dilute and is passed through neutral alumina using it as mobile phase
Column elution removes mantoquita, then removes excess of solvent using Rotary Evaporators, crude product is concentrated, then precipitate in cold n-hexane
Three times, PD-PDM-PG is obtained.
Above-mentioned PD-PDM-PG is dissolved in 30mL DMF, the CDen of 3 times of quality is added, 70 DEG C are reacted 24 hours, mesh
Be to modify the PG segment in PD-PDM-PG upper beta cyclodextrin (β-CD), the beta-cyclodextrin (β-CD) is 7 glucose lists
The macrocycle molecule of first molecular composition.The ethylenediamine of 10mL is then added, wherein the molar ratio of ethylenediamine and PD-PDM-PG are
100:1, the reaction was continued 24 hours, the purpose is to which the epoxy group on the PG segment of unmodified upper β-CD is carried out ring-opening reaction,
Improve hydrophilicity；After reacting and being cooled to room temperature, the 4- bromomethyl benzene boric acid pinacol ester of 2 times of quality is added, reacts at room temperature
One day, the purpose is to the phenyl boric acid pinacol ester of upper active oxygen response, the component are modified on the PD segment of PD-PDM-PG
Since there is high sensitivity to active oxygen, the characteristic with charge reversal；Then it dialyses 3 days, removes in deionized water
Then unreacted impurity small molecule and oligomerization product are lyophilized up to BP-PDM-PG；40 μ LTPEDB solution (10mM) are dripped again
It is added to 2mg mL-1In BP-PDM-PG solution (pH 7.4, PBS), room temperature shaker reacts 12 hours, obtains BP-PDM-PG (TPE),
This is because β-CD has distinctive hydrophobic cavity, using host-guest interaction, will have aggregation inducing effect and photocatalysis to produce
The TPEDB small molecule of liveliness proof oxygen characteristic is conjugated in the cavity of β-CD.
Fig. 2 is the nucleus magnetic hydrogen spectrum of BP-PDM-PG of the present invention.
Figure explanation: the present invention with ATRP polymerization method and small molecule functionalized modification successfully synthesized active oxygen and
The BP-PDM-PG copolymer of the response of pH acidity and charge reversal characteristic.
Fig. 3 gives the particle diameter distribution and scanning electron microscope (SEM) photograph of BP-PDM-PG of the present invention (TPE) and the compound rear complex of DNA.
Figure explanation: the Intelligent gene carrier that the present invention is finally prepared is regular shape, is distributed single nanoscale grain
Son, therefore there is excellent delivery vehicles in gene and transfer function, and have the potentiality of clinical application.
Fig. 4 is the fluorogram of BP-PDM-PG (TPE).
Figure explanation: confirming that TPE is interacted by host-guest interaction and cyclodextrin and generates aggregation-induced emission effect,
Show there is fluorescence imaging.
Fig. 5 is the zeta potential and b under a) BP-PDM-PG (TPE) illumination) change of size figure under acid condition.
Figure explanation: it proves that BP-PDM-PG (TPE) macromolecule is active oxygen and pH acidity responsiveness, and has
Photosensitive and charge reversal characteristic, shows that it can guarantee that gene effectively discharges in cancer cell.
Claims (7)
1. the preparation method of a kind of active oxygen and pH dual responsiveness and the Intelligent gene carrier of charge reversal characteristic, special
Sign be the following steps are included:
1) by 2- (lignocaine) ethyl acrylate (DEAEA), 2- (5,5- dimethyl -1,3- dioxanes -2- base) ethyl propylene
Three kinds of monomers of acid esters (DMDEA) and glycidyl methacrylate (GMA) are with atom transfer radical polymerisation technique (ATRP)
It carries out copolymerization and forms macromolecule (PD-PDM-PG)；
2) by macromolecule product (PD-PDM-PG) obtained by step 1) with 4- bromomethyl benzene boric acid pinacol ester and ethylenediamine β-ring
Dextrin respectively modifies the end PD and GMA, obtains high molecular polymer (BP-PDM-PG) and draws finally by host-guest interaction
Enter tetraphenylethylene, obtains final nano-carrier (BP-PDM-PG (TPE)).
2. the Intelligent gene carrier of active oxygen according to claim 1 and pH dual responsiveness and charge reversal characteristic
Preparation method, it is characterized in that: in step 1) be that 1:2:1 feeds intake in molar ratio by DEAEA, DMDEA and GMA, and according to
The degree of polymerization sequentially adds initiator 2- bromine isobutyl acylbromide, the bipyridyl of 1.5 equivalents and the cuprous bromide of 1 equivalent of 1 equivalent
(CuBr), it is dissolved in appropriate anhydrous dimethyl formamide (DMF), lower 80 DEG C of nitrogen protection are reacted 24 hours, reacting coarse product
Through supercooling, after column elution and deposition and purification processing, copolymerized macromolecule product (PD-PDM-PG) is obtained.
3. the Intelligent gene carrier of active oxygen according to claim 1 and pH dual responsiveness and charge reversal characteristic
Preparation method be separately added into 4- bromomethyl benzene boric acid it is characterized in that: be dissolved in PD-PDM-PG in anhydrous DMF in step 2)
Pinacol ester, stirred overnight at room temperature, then it is separately added into ethylenediamine beta-cyclodextrin (CDen) and ethylenediamine, 70 DEG C of each reactions 24 are small
When, deionized water dialysis 3 days, BP-PDM-PG is obtained after freeze-drying, takes appropriate BP-PDM-PG and phenyl boric acid tetraphenylethylene
(TPEDB), room temperature shaker is stirred overnight to get nana intelligent genophore (BP-PDM-PG (TPE)) is arrived.
4. the Intelligent gene of active oxygen and pH dual responsiveness and charge reversal characteristic according to claim 1 or 3
The preparation method of carrier, it is characterized in that: the beta-cyclodextrin (β-CD) is the macrocycle molecule of 7 glucose unit molecular compositions.
5. the Intelligent gene of active oxygen and pH dual responsiveness and charge reversal characteristic according to claim 1 or 3
The preparation method of carrier, it is characterized in that: the molar ratio of ethylenediamine and PD-PDM-PG are 100:1.
6. the Intelligent gene carrier of active oxygen according to claim 2 and pH dual responsiveness and charge reversal characteristic
Preparation method, it is characterized in that: the degree of polymerization refers to the molar ratio between monomer and initiator, column elution is neutral alumina
Column, to remove the mantoquita generated in reaction.
7. the Intelligent gene carrier of active oxygen according to claim 3 and pH dual responsiveness and charge reversal characteristic
Preparation method, it is characterized in that: the dosage of DMF be 30mL, in the above solution first be added 4- bromomethyl benzene boric acid pinacol ester,
The mass ratio of its ratio and PD-PDM-PG are 2:1.
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