CN103951801A - Tetraaminophenyl porphyrin-poly(N-isopropyl acrylamide)-poly(N,N-dimethylamino ethyl methacrylate) - Google Patents
Tetraaminophenyl porphyrin-poly(N-isopropyl acrylamide)-poly(N,N-dimethylamino ethyl methacrylate) Download PDFInfo
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- CN103951801A CN103951801A CN201410140326.4A CN201410140326A CN103951801A CN 103951801 A CN103951801 A CN 103951801A CN 201410140326 A CN201410140326 A CN 201410140326A CN 103951801 A CN103951801 A CN 103951801A
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Abstract
Tetraaminophenyl porphyrin-poly(N-isopropyl acrylamide)-poly(N,N-dimethylamino ethyl methacrylate) belongs to the technical field of functional polymer chemistry. Existing porphyrin photosensitizers have phototoxicity, is poor in tumor cell targeting, and is poor in water solubility. The compound of the invention is characterized in that the simple formula is TAPP-PNIPAM-PDMAEMA, wherein TAPP is tetraaminophenyl porphyrin, PNIPAM is poly(N-isopropyl acrylamide), PDMAEMA is poly(N,N-dimethylamino ethyl methacrylate). The bonding force between hydrophobic groups in the PNIPAM chain is enhanced, and the hydrogen bond effect between the hydrophobic groups and water molecules is reduced; the PNIPAM chain contracts into nanometer microgel and hydrophobic porphyrin molecules are wrapped inside the PNIPAM molecules, which obstructs the cytotoxicity of porphyrin; with good water solubility of PNIPAM, porphyrin can well dissolve in human body fluid such as blood and the like, and can be used as a photosensitizer to be distributed in the body with blood circulation; PDMAEMA is weak alkaline, is soluble in acidic solutions, and has pH responsiveness which provides the photosensitizer with tumor targeting.
Description
Technical field
The present invention relates to a kind of tetrakisaminophenyl porphyrin-poly N-isopropyl acrylamide-polymethyl acrylic acid N, N-dimethylaminoethyl, it is a kind of high molecular polymer, with large ring conjugated structure, there is Thermo-sensitive, stronger tumor-targeting and water-soluble preferably, belong to functional polymer technical field of chemistry.
Background technology
PDT(photodynamic therapy, photodynamic therapy) basis be the photosensitizers that first gives the selective absorption effect of tumor tissues, then use the rayed tumor area of a certain wavelength, it is excited state that photosensitizers is subject to exciting by ground state transition, the photosensitizers of excited state is passed to oxygen molecule around energy, produces singlet oxygen (1O
2) active substance.Oxidation-sensitive group effect in they and adjacent biomacromolecule, produces cytotoxicity and causes its oxidation inactivation, finally causes death of neoplastic cells and shows therapeutic action.PDT has local controllable light toxic action.
The photosensitizers that human clinical trial and approved use is all porphyrins.Photodynamic therapy taking Porphyrin-Based Sensitizer as core becomes the 4th kind of ripe cancer treatment method outside continue operation, radiation and chemotherapy, tool has the following advantages: the one, tumour is had to relative selection specificity, can directionally eliminate former and recurrence tumour, seldom injuring normal cell, toxic side effect is little; The 2nd, do not affect other treatment, can carry out with chemotherapy, radiotherapy simultaneously, and there is certain synergy, can repetitive therapy; The 3rd, all effective in cure to various cancers, anticancer scope is wider.
The existing urgent problem of Porphyrin-Based Sensitizer mainly comprises: reduce the color of porphyrin, reduce the phototoxicity of photosensitizers; Strengthen the tumour cell targeting of photosensitizers, make the photosensitizers can enrichment in tumor tissues effectively; Improve water-solublely, to ensure after drug administration by injection, medicament can distribute in vivo with blood circulation.
PNIPAM(poly N-isopropyl acrylamide) be the polymkeric substance with Thermo-sensitive, its LCST(lowest critical solution temperature) be approximately 32 DEG C, can regulate LCST by the quantity that regulates polymerization single polymerization monomer, or introduce various functional groups at the end of this polymkeric substance and form block polymer, thereby change its LCST as a kind of temperature sensing polymer, or make NIPAM(N-N-isopropylacrylamide) form multipolymer with certain monomer generation copolymerization, thus change the LCST of this polymkeric substance.
PDMAEMA(polymethyl acrylic acid N, N-dimethylaminoethyl) belong to cationic polymers, in its molecular structure unit, there is hydrophilic radical simultaneously, as tertiary amine groups, carbonyl, and hydrophobic grouping, as alkyl, two class groups match each other on space structure.The pKa value of PDMAEMA in the aqueous solution, in 7.0～7.3 scopes, is a kind of broad-spectrum pH sensitive polymer.PDMAEMA hydrogel is as a kind of novel intelligent aqueous gel capable, belong to cationic polymers, there is temperature-and pH-sensitivity, and there is certain intensity and good viscoelasticity, contrary with the pH susceptibility of common poly-(methyl) acrylic acid series gel, PDMAEMA hydrogel in pH=3～5 like this compared with under low ph condition in swollen state, accordingly, can be as slow-release material under some special conditionss.
Summary of the invention
The object of the invention is to, obtain a kind of PDT Porphyrin-Based Sensitizer being polymerized by PNIPAM, PDMAEMA and Amino Porphyrins, therefore porphyrin cell phototoxicity wherein can reduce, therefore described PDT can improve with the water-soluble of Porphyrin-Based Sensitizer, therefore described PDT can strengthen by Porphyrin-Based Sensitizer tumour cell targeting, for this reason, we have invented a kind of name and have been called tetrakisaminophenyl porphyrin-poly N-isopropyl acrylamide-polymethyl acrylic acid N, the polymkeric substance of N-dimethylaminoethyl.
Tetrakisaminophenyl porphyrin-poly N-isopropyl acrylamide-polymethyl acrylic acid N of the present invention, N-dimethylaminoethyl is characterized in that, its skeleton symbol is:
TAPP-PNIPAM-PDMAEMA，
In formula: TAPP is tetrakisaminophenyl porphyrin, PNIPAM is poly N-isopropyl acrylamide, and PDMAEMA is polymethyl acrylic acid N, N-dimethylaminoethyl;
Its structural formula is:
Its technique effect of the present invention is as described below.
Adopt ATRP(Transfer Radical Polymerization) taking TAPP-X as initiator initiated polymerization, temperature sensitive polymer PNIPAM good biocompatibility is grafted on Porphyrin Molecule, obtain polymkeric substance TAPP-PNIPAM, polymerization activity is controlled, LCST and the body temperature of polymkeric substance adapt, polymer product is during in vitro lower than LCST, PNIPAM chain and water generation hydrogen bond action and water-soluble, during in vivo higher than LCST, bonding force between hydrophobic group in PNIPAM chain strengthens, hydrogen bond action simultaneously and between water molecules weakens, be shrunk to nano microgel and hydrophobic Porphyrin Molecule is wrapped in PNIPAM molecule, the cytotoxicity of porphyrin is blocked, improve the water-soluble of porphyrin simultaneously, based on good water-soluble of PNIPAM, porphyrin can be dissolved in the human body fluids such as blood thereupon well, can distribute in vivo with blood circulation as photosensitizers.
PDMAEMA in the present invention is weakly alkaline, has resolvability in acidic solution, has pH responding ability.It is acid that near body fluid body tumor tissue is, and in sour environment in vivo, the tertiary amino group in PDMAEMA is by protonated, thereby make to be gathered in acid tumour cell with the porphyrin of PDMAEMA grafting, be specific binding, give photosensitizers with tumor-targeting, avoid forming general and distribute.
Embodiment
The present invention's TAPP-PNIPAM-PDMAEMA system preparation by the following method.
First, adopt the synthetic TNPP(tetranitro phenyl porphyrin of solvent-catalyst method), obtain TAPP(tetrakisaminophenyl porphyrin through reduction); Secondly, TAPP is prepared into ATRP initiator TAPP-X with alpha-halogen carboxylic acid halides, X is halogen; The 3rd, in Cu (I) X/ organic ligand catalyst system, cause NIPAM polymerization by initiator TAPP-X, obtain polymkeric substance TAPP-PNIPAM; Finally, cause DMAEMA polymerization using TAPP-PNIPAM as ATRP initiator, obtain product TAPP-PNIPAM-PDMAEMA.
Described product TAPP-PNIPAM-PDMAEMA is a kind of porphyrin polymer, and molecular weight is within 2500～20000 scopes; The skeleton of described porphyrin polymer is porphin ring, and described porphines is that porphin ring structural formula is by four pyrrole rings and four large pi-conjugated systems that methylene-bridged forms:
Wherein the carbon 5,10,15,20 between pyrrole ring is referred to as meso carbon.
The photodynamics part of the present invention's TAPP-PNIPAM-PDMAEMA is exactly the tetrakisaminophenyl porphyrin of introducing on porphin ring after phenyl and amino group, PNIPAM has good Thermo-sensitive and water-soluble, there is good pH responsiveness and water-soluble, that thereby the polymkeric substance that makes the present invention has is temperature sensitive, target, water miscible feature, can effectively kill cancer cells.
The present invention's method specifically comprises the following steps:
The first step, adopts the synthetic TNPP of solvent-catalyst method.Taking oil of mirbane as solvent, lactic acid in the backflow system of catalyzer, generate TNPP by Benzaldehyde derivatives and pyrroles, described Benzaldehyde derivatives is paranitrobenzaldehyde.Details are as follows for this step: meticulous adjustable constant-pressure dropping funnel, reflux condensing tube and thermometer are housed respectively on three mouthfuls of round-bottomed flasks, add 26ml oil of mirbane and 7ml lactic acid, the former makees solvent, and the latter makees catalyzer, the too much or very few productive rate that all can affect reaction of the consumption of catalyzer lactic acid; Be heated to 130 DEG C, occur refluxing; According to the mol ratio of paranitrobenzaldehyde and pyrroles 1:1,4g paranitrobenzaldehyde is dissolved in 12ml oil of mirbane, 1.83ml is newly steamed to pyrroles to be dissolved in 3ml oil of mirbane, described new steaming pyrroles refers to, if the pyrroles who uses go bad because generate oligopolymer because of the long-time meeting of placement, therefore, use and need re-distillation before; Two kinds of solution are slowly joined in three mouthfuls of round-bottomed flasks by constant pressure funnel, stirring reaction, keeps refluxing, and reflux temperature is controlled at 130 DEG C, reaction times is 2h, this reaction times does not comprise paranitrobenzaldehyde solution and pyrroles's solution time for adding, if the reaction times is long, the by product of generation is too much, be difficult for separating-purifying, if the reaction times is too short, react insufficient, significantly reduce the productive rate of resultant; Reaction is cooled to 60 DEG C after carrying out, and adds 16ml methyl alcohol, after stirring 30min, be cooled to room temperature, leave standstill 8h, decompress filter, by methanol wash, be washed till elutant colourless, isolated dissolution of solid is in 40ml pyridine, return stirring 1h at 120 DEG C of temperature, naturally cools to after room temperature, uses successively cooling bath, ice-water bath cooling, then in cryogenic refrigerator, place and spend the night, suction filtration obtains red-purple crystal, uses washing with alcohol three times, vacuum-drying obtains purple product 0.7300gTNPP, and productive rate is 13.90%.
Second step, with nine hydrated sodium sulfide Na
2s9H
2tNPP is reduced into TAPP by O.Excessive Na
2s9H
2o and TNPP reaction, obtain the different aminophenyl porphyrin mixture of reducing degree, works as Na
2s9H
2when the mol ratio of O and TNPP is 20:1, the productive rate of the TAPP of generation is the highest.Details are as follows for this step: add 60ml solvent DMF (DMF) to being equipped with in the there-necked flask of thermometer and whipping appts, according to Na
2s9H
2the mol ratio of O and TNPP20:1, by the Na of 6.0503g
2s9H
2the TNPP of O and 0.500g joins in there-necked flask, and TNPP is dissolved by DMF; Be 60 DEG C by temperature control, stirring reaction, follows the tracks of with TLC in reaction process, and in 2 hours reaction times, raw material point disappears, and generates aminophenyl porphyrin mixture; Reaction is poured reaction solution in 200ml deionized water into after finishing while hot, puts into the refrigerator hold over night of 0～4 DEG C, decompress filter, and wash filter cake with water to neutral, and 60 DEG C of vacuum-dryings, obtain the aminophenyl porphyrin mixture of brilliant violet look; Do leacheate with the mixture of methylene dichloride and methyl alcohol, both volume ratios are 40:1, and column chromatography for separation is collected mass-tone band material, revolve to steam except desolventizing final vacuum dryly, obtain 3.390g brilliant violet look TAPP, and productive rate is 80%.
The reaction formula of the described the first step and second step is:
The 3rd step, utilizes alpha-halogen carboxylic acid halides that TAPP is prepared into ATRP initiator TAPP-X, and X is halogen, and described alpha-halogen carboxylic acid halides is selected 2-bromo isobutyl acylbromide, needs to add appropriate triethylamine (C in reaction process
2h
5)
3n does acid binding agent, and object is except the HCl generating in dereaction.Details are as follows for this step: the TAPP of 28.4mg is dissolved in 10ml anhydrous methylene chloride solvent, then adds (the C of 70.40 μ l
2h
5)
3n, stirs under normal temperature 30 minutes, then under ice water bath environment, slowly adds the methylene dichloride 1ml of the 2-bromo isobutyl acylbromide that is dissolved with 62.42 μ l, (C
2h
5)
3the mol ratio of N and 2-bromo isobutyl acylbromide and TAPP is 20:1; In reaction process, follow the tracks of with TLC, react after 30 minutes in ice-water bath, at room temperature continue reaction 8 hours, reaction stops; Use successively sodium hydrogen carbonate solution, saturated aqueous common salt, the deionized water wash of 1M.With anhydrous magnesium sulfate drying organic phase whole night, be spin-dried for after solvent, purify with ice methanol extraction, collect and obtain bright purple crystals TAPP-Br.
The reaction formula of the 3rd step is:
The 4th step, in Cu (I) Br/ organic ligand catalyst system, cause NIPAM polymerization with ATRP initiator TAPP-Br, obtain having concurrently Thermo-sensitive, water miscible high molecular polymer TAPP-PNIPAM, described Cu (I) Br is CuBr, and organic ligand is Me
6tREN (three (2-dimethyl aminoethyl) amine).Details are as follows for this step: TAPP-Br, CuBr, Me
6the mol ratio of TREN, NIPAM is 1:10:10:200, adds the initiator TAPP-Br of NIPAM, 0.0083g of 0.5567g and the DMF of 2ml in a side pipe of W pipe, adds DMF and a small amount of deionized water of CuBr, the 1ml of 0.0176g in intervalve; Repetitive operation liquid nitrogen freezing-vacuumize-thaw after three times, to the Me that injects 31.45 μ l in intervalve
6tREN, stirs 20 minutes, makes to generate Cu complex compound; Carry out liquid nitrogen freezing, after the operation that vacuumizes, thaws, the liquid mixture in side pipe poured in intervalve; W pipe is moved into stirring reaction in 60 DEG C of oil baths; After reaction 10h, with cooled with liquid nitrogen W pipe, mixture is exposed in air to termination reaction; Reaction mixture filters through neutral alumina column, and the polymkeric substance obtaining precipitates three times in normal hexane, filters, and vacuum-drying obtains polymkeric substance TAPP-PNIPAM.
The reaction formula of the 4th step is:
The 5th step, uses ATRP initiator TAPP-PNIPAM at CuBr/Me
6in TREN catalyst system, cause DMAEMA polymerization, obtain having cancer targeting, Thermo-sensitive, water miscible high molecular polymer TAPP-PNIPAM-PDMAEMA.Details are as follows for this step: TAPP-PNIPAM, CuBr, Me
6the mol ratio of TREN, DMAEMA is 1:10:10:100, adds DMAEMA, TAPP-PNIPAM and appropriate solvent DMF in a side pipe of W pipe, adds CuBr, appropriate solvent DMF and a small amount of deionized water in intervalve; Repetitive operation liquid nitrogen freezing-vacuumize-thaw after three times injects Me in intervalve
6tREN, stirs 20 minutes, makes to generate Cu complex compound; Carrying out liquid nitrogen freezing, the operation that vacuumizes, thaws pours the liquid mixture in side pipe in intervalve into afterwards; W pipe is moved into stirring reaction in 60 DEG C of oil baths; After reaction appropriate time, with cooled with liquid nitrogen W pipe, mixture is exposed in air to termination reaction; Reaction mixture is filtered through neutral alumina column, and leacheate is THF, collects color band, and rotary evaporation is gone out organic solvent, and the polymkeric substance obtaining is precipitated three times in normal hexane, filters, and vacuum-drying obtains product polymkeric substance TAPP-PNIPAM-PDMAEMA.
The reaction formula of the 5th step is:
Claims (3)
1. tetrakisaminophenyl porphyrin-poly N-isopropyl acrylamide-polymethyl acrylic acid N, N-dimethylaminoethyl, is characterized in that, its skeleton symbol is:
TAPP-PNIPAM-PDMAEMA，
In formula: TAPP is tetrakisaminophenyl porphyrin, PNIPAM is poly N-isopropyl acrylamide, and PDMAEMA is polymethyl acrylic acid N, N-dimethylaminoethyl;
Its structural formula is:
2. tetrakisaminophenyl porphyrin-poly N-isopropyl acrylamide-polymethyl acrylic acid N according to claim 1, N-dimethylaminoethyl, it is characterized in that, described TAPP-PNIPAM-PDMAEMA is a kind of porphyrin polymer, and molecular weight is within 2500～20000 scopes; The skeleton of described porphyrin polymer is porphin ring, and described porphines is that porphin ring structural formula is by four pyrrole rings and four large pi-conjugated systems that methylene-bridged forms:
3. tetrakisaminophenyl porphyrin-poly N-isopropyl acrylamide-polymethyl acrylic acid N according to claim 1, N-dimethylaminoethyl, is characterized in that, the preparation by the following method of described TAPP-PNIPAM-PDMAEMA system:
First, adopt the synthetic TNPP of solvent-catalyst method, described TNPP is tetranitro phenyl porphyrin, and described TNPP obtains TAPP through reduction; Secondly, TAPP is prepared into ATRP initiator TAPP-X with alpha-halogen carboxylic acid halides, X is halogen; The 3rd, in Cu (I) X/ organic ligand catalyst system, cause NIPAM polymerization by initiator TAPP-X, obtain polymkeric substance TAPP-PNIPAM; Finally, cause DMAEMA polymerization using TAPP-PNIPAM as ATRP initiator, obtain product TAPP-PNIPAM-PDMAEMA.
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| US11428440B2 (en) * | 2019-05-09 | 2022-08-30 | Uchicago Argonne, Llc | Method for making porphyrin covalent organic framework-based interface |
| CN112939992A (en) * | 2021-02-19 | 2021-06-11 | 中国人民解放军军事科学院防化研究院 | Synthesis method of tetra (4-aminophenyl) porphyrin metal complex |
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