CN103450485A - Photosensitive cyclodextrin polymer and nanoparticles thereof - Google Patents
Photosensitive cyclodextrin polymer and nanoparticles thereof Download PDFInfo
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- CN103450485A CN103450485A CN2013104098678A CN201310409867A CN103450485A CN 103450485 A CN103450485 A CN 103450485A CN 2013104098678 A CN2013104098678 A CN 2013104098678A CN 201310409867 A CN201310409867 A CN 201310409867A CN 103450485 A CN103450485 A CN 103450485A
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- KJHPQVXZJOSNAJ-TWKHWXDSSA-N CCC(C)(C)Oc1ccc(C(CC(C(C)(C)C(C)(C)Oc2cc(/C=C/C3=[O]C3(C)O)ccc2OC(C)(C)C(C)(C)C(CC(c(cc2)ccc2OC(C)(C)C(C)=O)S[O]2CC2)=O)=O)SC2=[O]=CC#C2)cc1 Chemical compound CCC(C)(C)Oc1ccc(C(CC(C(C)(C)C(C)(C)Oc2cc(/C=C/C3=[O]C3(C)O)ccc2OC(C)(C)C(C)(C)C(CC(c(cc2)ccc2OC(C)(C)C(C)=O)S[O]2CC2)=O)=O)SC2=[O]=CC#C2)cc1 KJHPQVXZJOSNAJ-TWKHWXDSSA-N 0.000 description 1
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Abstract
The invention discloses a photosensitive cyclodextrin polymer and nanoparticles thereof, which belong to the field of functional polymer materials. According to the photosensitive cyclodextrin polymer and the nanoparticles thereof, a natural plant monomer 3,4-dihydroxy cinnamic acid (caffeic acid, DHCA) is used as a raw material, a homopolymer PDHCA (poly(3,4-dihydroxy cinnamic acid)) of the DHCA is prepared by a gradual condensation polymerization method; a Michael addition reaction is carried out on the homopolymer and thiolated beta-cyclodextrin (6-SH-beta-CD) to prepare a photosensitive graft polymer (PDHCA-g-CD) with CD as a pendant group; the cyclodextrin polymers are self-assembled into nanoparticles under certain conditions and are crosslinked and immobilized by ultraviolet light; the grafting rate, the particle size and the ultraviolet light crosslinking degree of CD are controlled by adjusting the feeding ratio. The polymer and the nanoparticles thereof disclosed by the invention have excellent adsorption inclusion property, biocompatibility and biodegradability and can be applied in such fields as drug slow release systems, tissue engineering, environmental protection, etc.
Description
Technical field
A kind of photosensitivity cyclodextrin and nanoparticle thereof, belong to functional high polymer material field.
Background technology
Cyclodextrin (Cyclodextrin, be called for short CD) be the general name of a series of cyclic oligosaccharides of generating under the cyclomaltodextrin glucanotransferase effect produced by genus bacillus of amylose starch, usually contain 6-8 D (+)-glucopyranose units, each glucose unit is all with 1, the 4-glycosidic link is combined into ring, respectively referred to as α-, β-and γ-CD.The CD molecule has slightly tapered hollow cylinder three-dimensional ring structure, and in its structure, the outside consists of the secondary hydroxyl of C2 and C3 and the primary hydroxyl of C6, has wetting ability; And cavity is interior because the shielding effect that is subject to c h bond has formed hydrophobic region.Hydrophobic and the outside hydrophilic characteristic of its inner chamber makes it form inclusion compound and molecular assembly system according to Van der Waals force, hydrophobic interaction power, the intermolecular matching effect of Subjective and Objective etc. and many organic and inorganic molecules.Therefore, in catalysis, separation, food, makeup and medicine and other fields, cyclodextrin has been subject to great attention and widespread use.At first Cramer has illustrated CD can stablize pigment, then finds again to form the Subjective and Objective inclusion complex, thereby its application in association area is constantly enlarged.At present, lot of domestic and international investigator has prepared a series of CD polymkeric substance, and the super-molecule assembling body such as micella, vesica, gel of unique texture and stimulating responsive is particularly arranged, and these super-molecule assembling bodies can be used for embedding medicinal and aromatic hydroxy compound.But the research to photosensitivity CD polymkeric substance and assembly thereof have not been reported.
Caffeic acid (DHCA is commonly called as coffic acid) can be purified and obtain from the natural phant such as coffee berry, pawpaw, as " vegetalitas monomer ".But the DHCA homopolymerization or with other monomer copolymerization, form the different amorphous polymers that form, the molecule chain rigidity is large, and be branched structure, (Tg) is higher for its second-order transition temperature, and good thermostability and mechanical property are arranged, and has physiological compatibility and degradation property; Contain a large amount of cinnamoyl in the molecular structure of this base polymer, there is photoreactivity, as [2+2] cycloaddition reaction; The PDHCA based polyalcohol can be made into microballoon, fiber and sheet material, at photosensitive nano material, biomedicine field, has wide practical use.
It is raw material that natural plant monomer Caffeic acid (DHCA) is take in the present invention, preparation DHCA homopolymer; It is reacted to the graftomer PDHCA-g-CD that preparation CD is side group with the beta-cyclodextrin (6-SH-β-CD) of sulfhydrylation; Make PDHCA-g-CD carry out self-assembly under certain condition and form nanoparticle, and fix through ultraviolet light cross-linking; The control of the percentage of grafting of CD, particle diameter, ultraviolet light cross-linking degree all can feed intake and recently realize by adjusting.The polymkeric substance that the present invention makes and nanoparticle thereof have excellent absorption inclusion, biocompatibility and biological degradability, can be applicable to the fields such as drug controlled release system, organizational project and environmental protection.
Summary of the invention
The purpose of this invention is to provide a kind of photosensitivity cyclodextrin and nanoparticle thereof.
Technical scheme of the present invention: a kind of photosensitivity cyclodextrin and nanoparticle thereof, (1) this polymkeric substance is with natural plant monomer 3,4-dihydroxycinnamic acid (DHCA) is raw material, β-the CD of sulfhydrylation (6-SH-β-CD) is side group, by the Michael addition reaction, prepare the graftomer of side group with CD, PDHCA:CD is 1:0～1:1; The structure of gained graftomer is:
M=40～350, n=0～310, be expressed as PDACA-g-CD.
(2) further make cyclodextrin carry out self-assembly under certain condition and form nanoparticle, and fix through ultraviolet light cross-linking.By regulating feed ratio, the percentage of grafting of controlling CD control be 0～88.6%, particle diameter is that 50～250nm, ultraviolet light cross-linking degree are 0～90%.
Beneficial effect of the present invention: the present invention, by preparing biomass polymers, gathers Caffeic acid (PDHCA), then reacts with the β-CD (6-SH-β-CD) of sulfhydrylation, the photosensitivity CD graftomer that preparation CD is side group; And further prepare its nanoparticle.The control of the percentage of grafting of CD, particle diameter, ultraviolet light cross-linking degree all can feed intake and recently realize by adjusting: the percentage of grafting of CD on PDHCA is 0～88.6%; Particle diameter is 50～250nm; The ultraviolet light cross-linking degree is 0～90%.The polymer nano-particle made has good photosensitivity, biological degradability and inclusion; This photosensitivity degradable polymer nano particle can be used as the carrier of environment and biomedicine field.
The accompanying drawing explanation
The nuclear magnetic spectrogram of Fig. 1 photosensitive polymers PDHCA-g-CD.
The TEM figure of Fig. 2 PDHCA-g-CD nanoparticle.
Embodiment
The beta-cyclodextrin of embodiment 1, sulfonylation (6-OTs-β-CD)
50g (44mmol) β-CD joins in the 1L water that is dissolved with 16g (400mmol) NaOH, under 0 ℃ of ice bath, high degree of agitation, slowly add system by 36g (187mmol) p-methyl benzene sulfonic chloride (TsCl), produce white precipitate, at 0 ℃ of reaction 2h.Suction filtration removes insolubles, with the HCl of volume fraction 10%, filtrate pH is adjusted to 7.0.With deionized water, precipitation is carried out to recrystallization, vacuum-drying, obtain the β-CD (6-OTs-β-CD) of single sulfonylation.
The beta-cyclodextrin of embodiment 2, sulfhydrylation (6-SH-β-CD)
12g (9.3mmol) 6-OTs-β-CD and 12g (158mmol) thiocarbamide are joined in the 480mL dry DMF to 75 ℃ of reaction 48h.Reaction is cooled to room temperature after finishing.Add again the 1.4L anhydrous diethyl ether to stir, sedimentation and filtration, and with twice of washing with acetone. by the product of gained and 480mg Na
2s
2o
5be dissolved in the NaOH of 400ml1mol/L, under room temperature, stir 30min.Be acidified to pH=3 with the HCl of 1mol/L, then add the 20mL trieline, ultrasonic 10min.Sedimentation and filtration, water recrystallization twice, drying, can obtain 6-SH-β-CD, and products therefrom is white powder.
Embodiment 3, poly-Caffeic acid (PDHCA)
43g (239mmol) DHCA and 4g (48.8mmol) sodium acetate are joined in the 100mL diacetyl oxide, and logical N2, react 1h under 140 ℃ of conditions, under 200 ℃ of conditions, reacts 6h.Washing with alcohol twice for products therefrom, dry under twice, 50 ℃ of deionized water wash, products therefrom is brown powder.
Taking 6-SH-β-CD3.5609g (3.094mmol) joins in 30mLDMF, after to be dissolved, add again 0.5g (0.0156mmol) PDHCA (Mn=32000, PDI=2.37), ultrasonic to dissolving fully, making mole proportioning of two keys in 6-SH-β-CD and PDHCA is 1:1, adds the 0.5mL triethylamine as catalyzer, under 30 ℃ of conditions, reacts 4h.Underpressure distillation is except desolventizing, and products therefrom is dry under 60 ℃, and product is the sorrel powder.
Under the same terms, mole proportioning that changes two keys in 6-SH-β-CD and PDHCA is 1:5,1:25, and 1:50,1:100, prepare the polymkeric substance of different CD percentage of grafting.
The preparation of embodiment 5, PDHCA-g-CD nanoparticle
PDHCA-g-CD (20mg) is dissolved in the solution that is made into 2mg/ml in DMF (DMF), gets polymers soln 5ml, with 25 μ Lmin
-1speed; under agitation in polymers soln, slowly drip the 5ml ultrapure water; stir 12h under room temperature; add 10 times to the ultrapure water of solution to disposable in system; stir 12h, then dialyse 4 days, the gained particle dispersion is placed under ultraviolet lamp and irradiates 6 hours; make photosensitivity cinnamoyl generation photo-crosslinking on polyester chain, realize that microballoon fixes.
Claims (4)
1. a photosensitivity cyclodextrin and nanoparticle thereof, belong to functional high polymer material field.With natural plant monomer Caffeic acid, (coffic acid, DHCA) be raw material, preparation PDHCA homopolymer in the present invention; It is reacted with the beta-cyclodextrin (6-SH-β-CD) of sulfhydrylation, the photosensitivity graftomer that preparation CD is side group, wherein PDHCA:CD is 1:0～1:1; And then make cyclodextrin carry out self-assembly formation microballoon under certain condition, and fix through ultraviolet light cross-linking.
2. photosensitivity cyclodextrin according to claim 1, is characterized in that take that fragrant adoption Caffeic acid (PDHCA) is main chain, and the cyclodextrin (CD) of take is side group, and the structure of gained graftomer is:
M=40～350, n=0～310, be expressed as PDACA-g-CD.
3. cyclodextrin according to claim 1 and nanoparticle thereof is characterized in that percentage of grafting, the particle diameter of CD, the control of ultraviolet light cross-linking degree all can feed intake and recently realize by adjusting:
The percentage of grafting of CD on PDHCA is 0～88.6%; Particle diameter is 50～250nm; The ultraviolet light cross-linking degree is 0～90%.
4. cyclodextrin nanoparticle according to claim 1, is characterized in that PDHCA has certain sensitivity of light and biological degradability; Can pass through UV-irradiation, crosslinked to the crosslinked reconciliation of cyclodextrin nanoparticle; Cyclodextrin on polymer chain makes polymer nano-particle have inclusion, the effective inclusion of small molecules and the release that can mate with size, and this photosensitivity degradable polymer nano particle can be used as the carrier of environment and biomedicine field.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001354A (en) * | 2015-08-13 | 2015-10-28 | 安徽世华化工有限公司 | Synthetic method for mono-6-mercapto-beta-cyclodextrin |
| CN108586636A (en) * | 2018-04-04 | 2018-09-28 | 上海大学 | Multiple stimulation response type cyclodextrine derivatives and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000069282A1 (en) * | 1999-05-13 | 2000-11-23 | The Nutrasweet Company | Modification of the taste and physicochemical properties of neotame using hydrophobic acid additives |
| CN103159962A (en) * | 2011-12-08 | 2013-06-19 | 江南大学 | Preparation method of photosensitive cyclodextrin gel |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000069282A1 (en) * | 1999-05-13 | 2000-11-23 | The Nutrasweet Company | Modification of the taste and physicochemical properties of neotame using hydrophobic acid additives |
| CN103159962A (en) * | 2011-12-08 | 2013-06-19 | 江南大学 | Preparation method of photosensitive cyclodextrin gel |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001354A (en) * | 2015-08-13 | 2015-10-28 | 安徽世华化工有限公司 | Synthetic method for mono-6-mercapto-beta-cyclodextrin |
| CN108586636A (en) * | 2018-04-04 | 2018-09-28 | 上海大学 | Multiple stimulation response type cyclodextrine derivatives and preparation method thereof |
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