CN103289103A - Self-assembling method of glucose-containing thermosensitive copolymer - Google Patents
Self-assembling method of glucose-containing thermosensitive copolymer Download PDFInfo
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- CN103289103A CN103289103A CN2013102482447A CN201310248244A CN103289103A CN 103289103 A CN103289103 A CN 103289103A CN 2013102482447 A CN2013102482447 A CN 2013102482447A CN 201310248244 A CN201310248244 A CN 201310248244A CN 103289103 A CN103289103 A CN 103289103A
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Abstract
The invention relates to a self-assembling method of a glucose-containing thermosensitive copolymer. The method comprises a step of processing a glucose-containing thermosensitive copolymer synthesized in the presence of a chain transferring agent through an RAFT process to prepare an aqueous solution having different concentrations, a step of self-assembling the aqueous solution at different temperatures to form micelles. The method allows polymer micelles having different forms to be formed through changing the temperature and the concentration, and has the characteristics of simple operation and substantial effect.
Description
Technical field
The invention belongs to the self-assembly field of nano-micelle, particularly a kind of self-assembling method that contains the temperature sensitive multipolymer of glucose.
Background technology
Sugar is being played the part of very important role in biosystem, it relates to the identification of various biomolecules.Sugar is incorporated in the polymkeric substance, can manually obtains the sugar-containing polymer of various different structures and function.These contain sugar copolymer and have good hydrophilicity and biologic specificity, but widespread use and biomedical sector.
To be Rizzardo made the concept that proposes first in the report of " Tailored polymers by free radical processes " the 37th international polymer conference to reversible addition-fragmentation chain transfer free radical polymerization (RAFT) method.The RAFT method was applied in synthesizing of sugar-containing polymer, can obtains compound with regular structure, molecular weight disperses the little superpolymer of width, can improve the application performance that contains sugar copolymer.
The self-assembly of nano-micelle, mainly be by high molecular polymer in solution, respective response is made in the change of environmental factors, thereby thereby changing self form assembles and forms.By the response to temperature, can make polymkeric substance phase co-conversion between the spherical micelle of lax linear aggregation attitude and gathering.Have temperature sensitive specific superpolymer, can be by to the adjusting of its LCST, can obtain to want this type of material to be used the LCST that approaches and biomedical materials field with human body temperature.
Summary of the invention
Technical problem to be solved by this invention provides a kind of self-assembling method that contains the temperature sensitive multipolymer of glucose, and the simple to operate and economic environmental protection of this method can be used this material and biomedicine field by self-assembling technique.
A kind of self-assembling method that contains the temperature sensitive multipolymer of glucose of the present invention comprises:
(1) vinyl hexanodioic acid glucose lipid OVAG and N-N-isopropylacrylamide NIPAm are dissolved in the solvent, under 60～80 ℃ of conditions, add initiator and chain-transfer agent, under nitrogen protection, stirring reaction 10-15h obtains temperature sensitive property copolymer p (NIPAm-co-OVAG); Wherein the mol ratio of OVAG and NIPAm is 1:5～1:15, the mol ratio of chain-transfer agent and initiator is 25:1～15:1, chain-transfer agent and OVAG and NIPAm and mol ratio be 1:120～1:80, the mass volume ratio of monomer vinyl hexanodioic acid glucose ester OVAG and N-N-isopropylacrylamide NIPAm and solvent is 1:1～1:3;
(2) the compound concentration scope is the P(NIPAm-co-OVAG of 0.2～2mg/mL) aqueous solution;
(3) with P(NIPAm-co-OVAG) aqueous solution detects in UV and obtains maximum absorption band;
(4) with P(NIPAm-co-OVAG) aqueous solution places 25-50 ℃, and self-assembly forms and contains the temperature sensitive copolymer micelle of glucose.
Solvent is N in the described step (1), dinethylformamide DMF.
Initiator is Diisopropyl azodicarboxylate AIBN in the described step (1).
Chain-transfer agent is S-dodecyl-S '-(α, α '-dimethyl-α " acetic acid)-trithiocarbonate in the described step (1).
P(NIPAm-co-OVAG in the described step (2)) concentration gradient of the aqueous solution is 0.2～0.4mg/mL.
Maximum absorption wavelength is at 220～310nm place in the described step (3).
Beneficial effect
(1) the present invention adopts that the RAFT method is synthetic to contain sugared superpolymer, and it is narrower that the polymkeric substance of acquisition has the molecular weight distribution width, reacts more controlled advantage;
(2) the present invention use temperature sensing material NIPAm synthetic contain sugar copolymer, have low bio-toxicity, and an excellent biological compatibility, and to the high susceptibility of temperature;
(3) the present invention uses when self-assembly be water as solvent, have safety non-toxic, the advantage of environment-protecting clean;
(4) the present invention can obtain to have containing of Different L CST of sugared superpolymer by the ingredient proportion of regulating monomer, thereby obtains to have the LCST that human body temperature is close, and the self-assembled micelle that obtains goes for medicine carrying material.
Description of drawings
The GPC test pattern of Fig. 1: P (NIPAm-co-OVAG);
The UV spectrogram of Fig. 2: P (NIPAm-co-OVAG);
The 305nm place temperature (T) of Fig. 3: P (NIPAm-co-OVAG)-absorbancy (A) figure.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
(1) 1.8g NIPAm and 0.6g OVAG are dissolved in the N of 2mL; in the dinethylformamide (DMF); under 70 ℃ of temperature; add initiator Diisopropyl azodicarboxylate AIBN1.5mg and chain-transfer agent S-dodecyl-S '-(α; α '-dimethyl-α " acetic acid)-trithiocarbonate 65mg; stirring reaction 12h under nitrogen protection, obtain P (NIPAm-co-OVAG), productive rate is 85%.
(2) above-mentioned acquisition is contained sugared temperature sensitive multipolymer and be configured to solution in different concentration, concentration range is 0.2～2mg/mL, and concentration gradient is 0.2mg/mL.
(3) solution of above-mentioned acquisition is tested its maximum absorption wavelength in ultraviolet-visible spectrophotometer.
(4) above-mentioned solution is placed the alternating temperature ultraviolet-visible spectrophotometer, survey its LCST value, about 37 ℃.
(5) polymers soln of above-mentioned 1mg/mL is placed 37 ℃ water-bath, make its self-assembly, can obtain temperature sensitive property and contain the sugar copolymer micella.
(1) 0.8g NIPAm and 0.6g OVAG are dissolved in the N of 2mL; in the dinethylformamide (DMF); under 70 ℃ of temperature; add initiator Diisopropyl azodicarboxylate AIBN0.75mg and chain-transfer agent S-dodecyl-S '-(α; α '-dimethyl-α " acetic acid)-trithiocarbonate 30mg; stirring reaction 12h under nitrogen protection, obtain P (NIPAm-co-OVAG), its productive rate is 83%.
(2) above-mentioned acquisition is contained sugared temperature sensitive multipolymer and be configured to solution in different concentration, concentration range is 0.2～2mg/mL, and concentration gradient is 0.2mg/mL.
(3) solution of above-mentioned acquisition is tested its maximum absorption wavelength in ultraviolet-visible spectrophotometer.
(4) above-mentioned solution is placed the alternating temperature ultraviolet-visible spectrophotometer, survey its LCST value, about 40 ℃.
(5) polymers soln of above-mentioned 1mg/mL is placed 40 ℃ water-bath, make its self-assembly, can obtain temperature sensitive property and contain the sugar copolymer micella.
(1) 2.8g NIPAm and 0.6g OVAG are dissolved in the N of 2mL; in the dinethylformamide (DMF); under 70 ℃ of temperature; add initiator Diisopropyl azodicarboxylate AIBN2.25mg and chain-transfer agent S-dodecyl-S '-(α; α '-dimethyl-α " acetic acid)-trithiocarbonate 95mg; stirring reaction 12h under nitrogen protection, obtain P (NIPAm-co-OVAG), its productive rate is 80%.
(2) above-mentioned acquisition is contained sugared temperature sensitive multipolymer and be configured to solution in different concentration, concentration range is 0.2～2mg/mL, and concentration gradient is 0.2mg/mL.
(3) solution of above-mentioned acquisition is tested its maximum absorption wavelength in ultraviolet-visible spectrophotometer.
(4) above-mentioned solution is placed the alternating temperature ultraviolet-visible spectrophotometer, survey its LCST value, about 35 ℃.
(5) polymers soln of above-mentioned 1mg/mL is placed 35 ℃ water-bath, make its self-assembly, can obtain temperature sensitive property and contain the sugar copolymer micella.
Claims (5)
1. self-assembling method that contains the temperature sensitive multipolymer of glucose comprises:
(1) vinyl hexanodioic acid glucose lipid OVAG and N-N-isopropylacrylamide NIPAm are dissolved in the solvent, under 60～80 ℃ of conditions, add initiator and chain-transfer agent, under nitrogen protection, stirring reaction 10-15h, obtain temperature sensitive property copolymer p (NIPAm-co-OVAG), wherein the mol ratio of OVAG and NIPAm is 1:5～1:15, the mol ratio of chain-transfer agent and initiator is 25:1～15:1, chain-transfer agent and OVAG and NIPAm and mol ratio be 1:120～1:80, the mass volume ratio of monomer vinyl hexanodioic acid glucose ester OVAG and N-N-isopropylacrylamide NIPAm and solvent is 1:1～1:3;
(2) the compound concentration scope is the P(NIPAm-co-OVAG of 0.2～2mg/mL) aqueous solution;
(3) with P(NIPAm-co-OVAG) aqueous solution places 25-50 ℃, and self-assembly forms and contains the temperature sensitive copolymer micelle of glucose.
2. a kind of self-assembling method that contains the temperature sensitive multipolymer of glucose according to claim 1 is characterized in that: solvent is N in the described step (1), dinethylformamide DMF.
3. a kind of self-assembling method that contains the temperature sensitive multipolymer of glucose according to claim 1 is characterized in that: initiator is Diisopropyl azodicarboxylate AIBN in the described step (1).
4. a kind of self-assembling method that contains the temperature sensitive multipolymer of glucose according to claim 1 is characterized in that: chain-transfer agent is S-dodecyl-S '-(α, α '-dimethyl-α " acetic acid)-trithiocarbonate in the described step (1).
5. a kind of self-assembling method that contains the temperature sensitive multipolymer of glucose according to claim 1, it is characterized in that: the P(NIPAm-co-OVAG in the described step (2)) concentration gradient of the aqueous solution is 0.2～0.4mg/mL.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104045762A (en) * | 2014-06-17 | 2014-09-17 | 东华大学 | Method for synthesizing glucose-containing temperature-sensitive copolymer by adopting RAFT (Reversible Addition-Fragmentation chain Transfer) process |
| CN104761693A (en) * | 2015-04-15 | 2015-07-08 | 东华大学 | Self-assembly method of galactose-containing thermo-sensitive copolymer |
| CN105061702A (en) * | 2015-08-12 | 2015-11-18 | 东华大学 | Self-assembly method of galactose-containing temperature-sensitive block copolymer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101630554A (en) * | 2009-06-19 | 2010-01-20 | 中山大学 | Method for anchoring on surface of Fe3O4 nanoparticles and polymer-Fe3O4 hybrid magnetic nanoparticles preparation method |
| US7732527B2 (en) * | 2003-02-21 | 2010-06-08 | Hymo Corporation | Water-soluble polymers reduced in molecular weight, process for production thereof and usage thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7732527B2 (en) * | 2003-02-21 | 2010-06-08 | Hymo Corporation | Water-soluble polymers reduced in molecular weight, process for production thereof and usage thereof |
| CN101630554A (en) * | 2009-06-19 | 2010-01-20 | 中山大学 | Method for anchoring on surface of Fe3O4 nanoparticles and polymer-Fe3O4 hybrid magnetic nanoparticles preparation method |
Non-Patent Citations (2)
| Title |
|---|
| SHAO-FENG LOU ET AL.: "Fabrication and aggregation of thermoresponsive glucose-functionalized double hydrophilic copolymers", 《COLLOIDS AND SURFACES B: BIOINTERFACES》, vol. 105, 29 December 2012 (2012-12-29), pages 180 - 186, XP029000487, DOI: 10.1016/j.colsurfb.2012.12.012 * |
| 娄少峰等: "葡萄糖基N-异丙基丙烯酰胺共聚物的合成及其温敏性", 《应用化学》, vol. 30, no. 4, 10 April 2013 (2013-04-10), pages 408 - 412 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104045762A (en) * | 2014-06-17 | 2014-09-17 | 东华大学 | Method for synthesizing glucose-containing temperature-sensitive copolymer by adopting RAFT (Reversible Addition-Fragmentation chain Transfer) process |
| CN104761693A (en) * | 2015-04-15 | 2015-07-08 | 东华大学 | Self-assembly method of galactose-containing thermo-sensitive copolymer |
| CN104761693B (en) * | 2015-04-15 | 2018-08-03 | 东华大学 | A kind of self-assembling method of the temperature sensitive copolymer containing galactolipin |
| CN105061702A (en) * | 2015-08-12 | 2015-11-18 | 东华大学 | Self-assembly method of galactose-containing temperature-sensitive block copolymer |
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