CN103992451A - Diblock copolymer with sugar, temperature and pH triple sensitivities, and preparing method thereof - Google Patents
Diblock copolymer with sugar, temperature and pH triple sensitivities, and preparing method thereof Download PDFInfo
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- CN103992451A CN103992451A CN201410198944.4A CN201410198944A CN103992451A CN 103992451 A CN103992451 A CN 103992451A CN 201410198944 A CN201410198944 A CN 201410198944A CN 103992451 A CN103992451 A CN 103992451A
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Abstract
The invention belongs to the fields of polymer materials and biomedical engineering, and particularly relates to a diblock copolymer with sugar, temperature and pH sensitivities, and a preparing method thereof. The method includes a main step of synthesizing the diblock copolymer by utilization of an ATRP initiator, poly(phenylboronate ester) initiated by an ABIB initiator and DMAEMA, namely preparing an Ad-PpBDEMA-DMAEMA diblock copolymer. The product structure is linear. Synthetic steps are simple. The molecular size is controllable. The diblock copolymer has sugar, temperature and pH triple responsive properties, and can be used in the fields drug delivery, genetic vectors, memory element switches, and a plurality of other smart materials.
Description
Technical field
The present invention relates to a kind of Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock that possesses sugar, temperature, the triple susceptibility of pH and preparation method thereof.
Background technology
Than the more single stimuli responsive system of research, exploitation has dual and multiple stimulation responsiveness system and scientific research and practical application is had to the meaning of even more important effect.First, the polymeric system with multiple response can Study system release dynamics, and these systems can independently must regulate each respondent behavior for different stimulations, as can be strengthened or weaken drug release simultaneously.Secondly, organism has complicated stimuli responsive behavior, and this class research is to diabetes, and the research of the diseases such as cancer is of great advantage.The polymer drug with multiple response is carried material under different stimulated, can form the micella of different shape or is caused the decomposition of micella, utilizes the self-assembly of micella to realize the controllable release of medicine.
Diabetes are a kind of metabolic diseases that hyperglycemia is feature of take.Hyperglycemia makes due to defect of insulin secretion and biological action is impaired causes, can cause various tissues, particularly eye, kidney, heart, blood vessel, neural chronic lesion, dysfunction, reducing blood sugar is the main method for the treatment of at present diabetes, traditional injection and drug administration need doctor and patient strictly to control the consumption of medicine, and long-time use also can make patient produce resistance and cause Diabetic liver injury of the kidney.So, find a kind of sugared response medicine carrier particularly important for the treatment of diabetes.This sugared Response System can realize the controllable release of medicine, and phenylo boric acid and derivative thereof have sugar response.In the aqueous solution, there is two states in phenylo boric acid derivative, electronegative tetrahedral structure can form stable borate ester structure with glucose complexing, it is water-soluble, and the phenylo boric acid of neutral trihedron structure and glucose form unsettled ring texture.By changing pH, and the concentration of glucose in solutions realizes the object of phenylo boric acid system sustained-release administration.This method can convenient and safely discharge medicine in the high site of disease selectivity of blood sugar concentration intelligently, reaches the object of efficient treatment.
Summary of the invention
The object that the present invention is right is to provide a kind of Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock that possesses sugar, temperature, the triple susceptibility of pH and preparation method thereof.
A kind of Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock that possesses sugar, temperature, the triple susceptibility of pH provided by the invention, its structure is shown below:
Wherein m is 48-80, and n is 54-90.
The preparation method with the Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock of sugar, temperature, the triple susceptibility of pH provided by the present invention, comprises the following steps:
(1) under nitrogen protection, ABIB initiator, cuprous bromide, ATRP part PMDETA and PpBDEMA monomer are dissolved in methyl-phenoxide with mol ratio 1:1.2:1.2:60-100, at 85-95 ℃, stir 18-60 hour, obtain Ad-PpBDEMA polymkeric substance I:
(2) under nitrogen protection; macromole evocating agent Ad-PpBDEMA, cuprous bromide and DMAEMA monomer are dissolved in dry DMF with mol ratio 1:1.2:60-100; at 38-42 ℃, react 50-70 minute; concentrated in normal hexane, precipitate again after removing mantoquita; dialyse and within 42-50 hour, remove DMF freeze-drying except anhydrating, obtain simple linear polymer
ad-PpBDEMA-DMAEMA:
Wherein m is 48-80, and n is 54-90.
The present invention has following beneficial effect:
1) sugared response polymer drug delivering material provided by the present invention has sugar response functional group, and its special hydrophobic segment structure can provide self-assembly power in water, forms nano particle.
2) the small molecules phenylo boric acid sugar ester after sugared response polymer drug delivering material itself provided by the present invention and sugar response and the polymkeric substance that becomes double-hydrophilic all have good biocompatibility.After polymkeric substance provided by the invention and sugar response, phenylo boric acid comes off and sugar forms small molecules complex compound from polymkeric substance, and the metabolism of phenylo boric acid in just can satellite excretes thus, has good biocompatibility.
3) the present invention has sugar, temperature, the triple responsivenesss of pH, can be better must be for the field such as drug release, chemical sensor and polymkeric substance be separated.
Embodiment
Below by embodiment, elaborate: the present embodiment is implemented take technical solution of the present invention under prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to subordinate's embodiment.
Embodiment 1:
1) 0.03g (0.1mmol) ABIB initiator, 0.0208g (0.12mmol) ATRP part PMDETA and 2.73g (10mmol) PpBDEMA monomer are dissolved in 2.5ml methyl-phenoxide, the freezing circulation three times of bleeding, last when freezing to the logical nitrogen of system, add 1.12mg (0.1mmol) cuprous bromide, the logical nitrogen of deoxygenation is at 90 ℃, stir 40 hours, concentrated in the mixed solution of normal hexane and ether, precipitate after removing mantoquita, obtain Ad-PpBDEMA polymkeric substance I:
2) under nitrogen protection; macromole evocating agent 2.738g (0.1mmol) Ad-100PpBDEMA, 1.194g (12mmol) cuprous bromide and 1.5721g (10mmol) DMAEMA monomer are dissolved in dry DMF; at 40 ℃, react four hours; concentrated in normal hexane, precipitate again after removing mantoquita; dialyse and within 48 hours, remove DMF freeze-drying except anhydrating, obtain simple linear polymer II (Ad-PpBDEMA-DMAEMA).
Embodiment 2:
1) 0.03g (0.1mmol) ABIB initiator, 0.0208g (0.12mmol) ATRP part PMDETA and 2.184g (8mmol) PpBDEMA monomer are dissolved in 2.5ml methyl-phenoxide, the freezing circulation three times of bleeding, last when freezing to the logical nitrogen of system, add 1.12mg (0.1mmol) cuprous bromide, the logical nitrogen of deoxygenation is at 90 ℃, stir 40 hours, concentrated in the mixed solution of normal hexane and ether, precipitate after removing mantoquita, obtain Ad-PpBDEMA polymkeric substance I;
2) with embodiment 1 step 2).
Embodiment 3
1) 0.03g (0.1mmol) ABIB initiator, 0.0208g (0.12mmol) ATRP part PMDETA and 1.638g (6mmol) PpBDEMA monomer are dissolved in 2.5ml methyl-phenoxide, the freezing circulation three times of bleeding, last when freezing to the logical nitrogen of system, add 1.12mg (0.1mmol) cuprous bromide, the logical nitrogen of deoxygenation is at 90 ℃, stir 40 hours, concentrated in the mixed solution of normal hexane and ether, precipitate after removing mantoquita, obtain Ad-PpBDEMA polymkeric substance I;
2) with embodiment 1 step 2).
Claims (2)
1. a Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock that possesses sugar, temperature, the triple responsivenesss of pH, is characterized in that structural formula is as follows:
Wherein m is 48-80, and n is 54-90.
2. a preparation method who possesses the Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock of sugar, temperature, the triple responsivenesss of pH as claimed in claim 1, is characterized in that concrete steps are as follows:
(1) under nitrogen protection, by ABIB initiator, cuprous bromide, ATRP part PMDETA and PpBDEMA monomer with mol ratio 1:1.2:1.2:(60-100) be dissolved in methyl-phenoxide, at 85-95 ℃, stir 18-60 hour, obtain Ad-PpBDEMA polymkeric substance I:
Polymkeric substance I
(2) under nitrogen protection; macromole evocating agent Ad-PpBDEMA, cuprous bromide and DMAEMA monomer are dissolved in dry DMF with mol ratio 1:1.2:60-100; at 38-42 ℃, react 50-70 minute; concentrated in normal hexane, precipitate again after removing mantoquita; dialyse and within 42-50 hour, remove DMF freeze-drying except anhydrating, obtain simple linear polymer
ad-PpBDEMA-DMAEMA:
Polymkeric substance II
Wherein m is 48-80, and n is 54-90.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104356576A (en) * | 2014-10-24 | 2015-02-18 | 同济大学 | Preparation method of glucose responsive graphene/polymer nanometer hybrid material |
Citations (4)
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CN1334830A (en) * | 1998-12-29 | 2002-02-06 | B·F·谷德里奇公司 | Hydrophilic ampholytic polymer |
CN101348570A (en) * | 2008-09-03 | 2009-01-21 | 东华理工大学 | Preparation of star copolymer self-assembled nano micelle |
CN101503497A (en) * | 2009-03-02 | 2009-08-12 | 江南大学 | Preparation of star type block acid sensitive nano micelle |
CN102212178A (en) * | 2011-04-11 | 2011-10-12 | 同济大学 | Pentablock copolymer with temperature and pH dual sensitivity, and preparation method and application thereof |
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2014
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1334830A (en) * | 1998-12-29 | 2002-02-06 | B·F·谷德里奇公司 | Hydrophilic ampholytic polymer |
CN101348570A (en) * | 2008-09-03 | 2009-01-21 | 东华理工大学 | Preparation of star copolymer self-assembled nano micelle |
CN101503497A (en) * | 2009-03-02 | 2009-08-12 | 江南大学 | Preparation of star type block acid sensitive nano micelle |
CN102212178A (en) * | 2011-04-11 | 2011-10-12 | 同济大学 | Pentablock copolymer with temperature and pH dual sensitivity, and preparation method and application thereof |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104356576A (en) * | 2014-10-24 | 2015-02-18 | 同济大学 | Preparation method of glucose responsive graphene/polymer nanometer hybrid material |
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