CN103524751B - A kind of preparation method of double-sensitivity cyclodextrin supermolecule aggregate - Google Patents
A kind of preparation method of double-sensitivity cyclodextrin supermolecule aggregate Download PDFInfo
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Abstract
A preparation method for double-sensitivity cyclodextrin supermolecule aggregate, belongs to technical field of function materials.First the present invention uses 4-hydroxycinnamic acid (4HCA) to modify beta-cyclodextrin (β-CD) to prepare host molecule---sensitivity of light 4-hydroxycinnamic acid-cyclodextrin (4HCA-CD); Again using three thioesters of end strips diamantane (AD) as chain-transfer agent, by reversible addion-fragmentation chain transfer radical polymerization (RAFT) legal system for temperature sensitivity guest polymer---both arms diamantane-NIPA-diamantane (AD-PNIPAM-AD); Utilize the complex performance between the hydrophobic cavity of β-CD and AD, construct dual-sensitivity super molecule inclusion compound 4HCA-CD/AD-PNIPAM-AD; 4HCA-CD/AD-PNIPAM-AD is carried out self-assembly and form supramolecular aggregation, its form, size can realize reversible transition by change light, temperature.The supramolecular aggregation that the present invention obtains has good light/temperature dual-sensitivity, can stimulate that to carry out intelligence corresponding to external world, makes it have broad application prospects in the field such as drug loading, Co ntrolled release.
Description
Technical field
A preparation method for double-sensitivity cyclodextrin supermolecule aggregate, belongs to technical field of function materials.
Background technology
Cyclodextrin (Cyclodextrins, CDs) is the cyclic oligosaccharide be formed by connecting by α-Isosorbide-5-Nitrae-glycosidic link by D-glucopyranose units, and as typical host molecule, the research of its physical and chemical performance receives much concern recent years.CD molecule has slightly tapered hollow cylinder three-dimensional ring structure, and in its structure, outside is made up of the secondary hydroxyl of C2 and C3 and the primary hydroxyl of C6, has wetting ability; And because the shielding effect being subject to c h bond defines hydrophobic region in cavity.Hydrophobic and the characteristic of external hydrophilic of CD inner chamber makes CD and derivative thereof can according to the hydrophobic molecule inclusion with size match such as Van der Waals force, hydrophobic interaction power, the intermolecular interaction of Subjective and Objective, to prepare cyclodextrin compound, cyclodextrin nano particle and hydrogel etc., can be applicable to the fields such as pharmacy, catalyzer, makeup, food.If can realize stimulating to external world, to carry out intelligence corresponding, then they will have more wide application in the field such as drug loading, Co ntrolled release.
Cinnamic acid derivative is a class bio-based monomer, be distributed widely in the plants such as rice class, beans, bamboo class, there is the performances such as excellent anti-oxidant, antitumor, hypotensive, radioprotective, be widely used in the fields such as biology, medicine, dyestuff, food, daily necessities.Cinnamic acid compound has excellent physiologically active, and has excellent optical characteristics, as tran/cis isomerization and [2+2] cyclisation; Thus, by the selection to illumination frequency, light position, intensity of illumination and light application time length, " intelligence " regulation and control can be realized.
Although more to the research report of the CD super-molecule assembling body with stimulating responsive at present, the cinnamate group also without sensitivity of light is combined the research preparing stimulating responsive supermolecule polymer with CD.Given this, the present invention respectively with photaesthesia cyclodextrin derivative and temperature-sensitive polymers for Subjective and Objective, had the supramolecular aggregation of light/temperature dual-sensitivity by the inclusion complexation effect preparation between cyclodextrin and diamantane, form, the size of supramolecular aggregation can realize reversible transition by change light, temperature.The supramolecular aggregation that the present invention obtains has good sensitivity of light and temperature sensitivity, can stimulate that to carry out intelligence corresponding to external world, makes it have broad application prospects in the field such as drug loading, Co ntrolled release.
Summary of the invention
The object of the invention is to utilize the inclusion complexation effect between a kind of sensitivity of light cyclodextrin derivative and temperature sensitive polymer Subjective and Objective to prepare the cyclodextrin supramolecular aggregation simultaneously with light/temperature dual-sensitivity.
Technical scheme of the present invention: with 4-hydroxycinnamic acid (4HCA) for function base modification cyclodextrin (CD) prepares host molecule---sensitivity of light 4-hydroxycinnamic acid-cyclodextrin (4HCA-CD); Again using three thioesters of end strips diamantane (AD) as chain-transfer agent, with the temperature sensitivity guest polymer of reversible addion-fragmentation chain transfer radical polymerization (RAFT) legal system for end strips AD group---both arms diamantane-NIPA-diamantane (AD-PNIPAM-AD); Utilize the complex performance between the hydrophobic cavity of β-CD and AD, construct micro-response super molecule inclusion compound 4HCA-CD/AD-PNIPAM-AD; Make cyclodextrin carry out self-assembly further under certain condition and form supramolecular aggregation, its preparation method is as follows:
(1) synthesis of 4HCA-CD
For avoiding 4HCA that interior chloride occurs, first with diacetyl oxide, the hydroxyl of 4HCA being carried out acetylize, then using the carboxyl reaction in sulfur oxychloride and 4HCA, obtaining 4-ethanoyl cinnamyl chloride; Itself and β-CD are reacted 5h under room temperature in anhydrous pyridine; Little water termination reaction is added, underpressure distillation removing pyridine after reaction terminates.Excess methanol extraction, and then in methanol-water recrystallization twice, obtain 4HCA-CD, obtaining product is Red-brown powder; It mol ratio 4HCA: CD is 1: 1 ~ 5: 1, and structural formula is as follows:
(2) preparation of AD-PNIPAM-AD
In the mixed solution of dithiocarbonic anhydride, Tetrabutyl amonium bromide, toluene, first drip the sodium hydroxide solution of 50%, drip off the rear mixed solution (a second) continuing instillation acetone and chloroform (1: 1), more than stirring reaction 12h in 15 ~ 20 DEG C, S is obtained after reaction terminates, S-bis-(α, α ' methyl-α " acetic acid) trithiocarbonic acid carbon ester (TTC); Then by itself and sulfur oxychloride heating reflux reaction 7h in dichloromethane solvent, underpressure distillation desolventizes and unreacted sulfur oxychloride, product acid chloride S, S-bis-(α, α ' methyl-α " acetic acid) trithiocarbonic acid carbon ester (TTC-Cl); Instill TTC-Cl by under the THF solution ice bath of 1-adamantanol (AD), after room temperature reaction 4h, be warming up to 60 DEG C and spend the night, obtain the chain-transfer agent AD-TTC-AD that two ends are AD; Finally by NIPAM under AIBN causes, be that chain-transfer agent carries out RAFT polymerization at 70 DEG C with AD-TTC-AD, obtain Thermo-sensitive AD-PNIPAM-AD, the structure of resulting polymers is:
Wherein n=20 ~ 80, are expressed as AD-PNIPAM-AD.
(3) preparation of AD-PNIPAM-AD and 4HCA-CD super molecule inclusion compound
Take AD-PNIPAM-AD respectively, 4HCA-CD is dissolved in DMF, and the concentration of configuration solution is 1mg/mL, and both mix rear ultrasonic 1h; After its inclusion compound ultraviolet lighting 1h, the increase before the molecular weight ratio illumination of super molecule inclusion compound about a times.
(4) preparation of AD-PNIPAM-AD and 4HCA-CD supramolecular aggregation
AD-PNIPAM-AD and 4HCA-CD inclusion compound is dissolved in DMF, be made into the solution of 2mg/mL, in polymers soln, slowly drip the ultrapure water of same volume under agitation with the speed of 25 μ L/min, stirred at ambient temperature 12h, then dialyse 3-5 days, then lyophilize 4-5 days.
Characterized the stuctures and properties of each intermediate product and final product by infrared spectrometer, nuclear magnetic resonance analyser, ultraviolet spectrophotometer, differential scanning calorimeter, gel permeation chromatograph etc., adopt microscopic pattern and the size of transmission electron microscope, dynamic laser light scattering characterize polymers microballoon.Result shows that products therefrom structure is clear and definite; Gained super molecule inclusion compound has sensitivity of light, [2+2] cyclisation can occur, through ultraviolet lighting, and the increase before the molecular weight ratio illumination of super molecule inclusion compound about a times; Form, the size of gained supramolecular aggregation can realize reversible transition by change light, temperature; Gained aggregate dispersion liquid is elevated to 60 DEG C from room temperature 25 DEG C and is reduced to 25 DEG C again, and the particle diameter of aggregate is reduced to 390nm from 3500nm and returns to 3500nm again, occurs reversible change.
Beneficial effect of the present invention: the present invention respectively with photaesthesia cyclodextrin and temperature-sensitive polymers for Subjective and Objective, be there is by the inclusion complexation effect preparation between cyclodextrin and diamantane the supramolecular aggregation of light/temperature dual-sensitivity.The supramolecular aggregation that the present invention obtains has good sensitivity of light and temperature sensitivity, can stimulate that to carry out intelligence corresponding to external world, makes it have broad application prospects in the field such as drug loading, Co ntrolled release.
Accompanying drawing explanation
Figure 1A D-PNIPAM-AD's
1h-NMR nmr spectrum.
The two-dimentional nuclear magnetic spectrum of Fig. 2 AD-PNIPAM-AD/4HCA-CD supramolecular aggregation.
The Changing Pattern that the particle diameter of Figure 34 HCA-CD/AD-PNIPAM-AD supramolecular aggregation raises with temperature and reduces.
The SEM figure of (a) and heat up rear (b) before Figure 44 HCA-CD/AD-PNIPAM-AD supramolecular aggregation heats up.
Embodiment
The synthesis of embodiment 1,4-ethanoyl styracin
To add in 100mL there-necked flask in 4.60g (28mmol) 4HCA and 10mL anhydrous pyridine, constant-temperature heating system, stirring system are installed, 30min is stirred under 0 DEG C of constant temperature ice bath, then 7.5mL diacetyl oxide is added at this temperature, continue to stir 1.5h, stir and terminate gained solution heating reflux reaction 5h under 130 DEG C of constant temperature oil bath magnetic agitation, gained solution is poured in 500mL beaker, wash twice with 0.1mol/L hydrochloric acid soln, suction filtration obtains a large amount of deionized water wash of white powder.Get filter cake vacuum-drying 24h at 50 DEG C, obtain the cinnamic acid derivative 4ACA that hydroxyl is acetylation, products therefrom is white powder.
The synthesis of embodiment 2,4-ethanoyl cinnamyl chloride
4.12g (20mmol) 4-ethanoyl styracin and 20mL sulfur oxychloride are added in 100mL single port flask; then the DMF of 0.018g is added as catalyzer; 10mL methylene dichloride is as solvent; constant-temperature heating system, stirring system are installed; heating reflux reaction 7h under 60 DEG C of constant temperature oil bath magnetic agitation, underpressure distillation desolventizes and unreacted sulfur oxychloride.Products therefrom is buff powder.
The preparation of embodiment 3,4HCA-CD
5g (4.4mmol) β-CD and 150mL anhydrous pyridine are joined in 250mL there-necked flask; under 0 DEG C of constant temperature ice bath, be stirred to β-CD dissolve completely; 0.7633g (3.4mmol) 4-ethanoyl styracin is dissolved in 14mL anhydrous pyridine and is mixed with solution; being dripped by this solution in 20min enters in there-necked flask, continues stirring reaction 5h under being added dropwise to complete rear room temperature.Little water termination reaction is added, underpressure distillation removing pyridine after reaction terminates.Excess methanol extraction, and then in methanol-water recrystallization twice, obtain 4HCA-CD.Obtaining product is Red-brown powder.
The synthesis of embodiment 4, S, S-bis-(α, α ' methyl-α " acetic acid) trithiocarbonic acid carbon ester (TTC)
Dithiocarbonic anhydride 11.45g (0.15mol) is added in the three-necked bottle of 500mL that dropping funnel is housed, Tetrabutyl amonium bromide 1g (3.1mmol), toluene 50mL, under nitrogen atmosphere, the sodium hydroxide solution 84g of slowly instillation 50% in ice bath, drip off in 30min (one second one), drip off the rear mixed solution (a second) continuing instillation acetone 21.8g (0.375mol) and chloroform 44.8g (0.375mol), dripping off rear temperature controls in 15 ~ 20 DEG C, more than stirring reaction 12h.After completion of the reaction, add 250mL water and solid is dissolved completely, instill 60mL concentrated hydrochloric acid (a second, regulate PH < 4) afterwards.Add rear stirring reaction 30min, filter, obtain yellow solid and wash with a large amount of deionization, with ethyl alcohol recrystallization twice, last oven drying is to constant weight.
The synthesis of embodiment 5, chloride S, S-bis-(α, α ' methyl-α " acetic acid) trithiocarbonic acid carbon ester (TTC-Cl)
By 1.128g (4mmol) S, S-bis-(α, α ' methyl-α " acetic acid) trithiocarbonic acid carbon ester and 5mL sulfur oxychloride add in 100mL single port flask; then add 1 ~ 2 DMF as catalyzer; 15mL methylene dichloride is as solvent, and install constant-temperature heating system, stirring system, heating reflux reaction 7h under 60 DEG C of constant temperature oil bath magnetic agitation; underpressure distillation desolventizes and unreacted sulfur oxychloride, obtaining product is chocolate oily matter.
The synthesis of embodiment 6, AD-TTC-AD
1-adamantanol 0.61g (5mmol) and 10mL tetrahydrofuran (THF) are added in 100mL single port flask, 1-adamantanol 0.61g (5mmol) is dissolved in 20mL tetrahydrofuran (THF), instill in single port flask under condition of ice bath, ice bath 1h, after room temperature reaction 4h, be warming up to 60 DEG C and spend the night.Reaction terminates rear underpressure distillation removing tetrahydrofuran (THF), washes twice, then use 5%Na with methanol-water
2cO
3wash twice, last oven drying is to constant weight.
The synthesis of embodiment 7, AD-PNIPAM-AD
By 3.4g (30mmol) NIPA, 0.11g (0.3mmol) AD-TTC-AD and 4.93mg (0.03mmol) azo-bis-isobutyl cyanide is dissolved in 8.7mLDMF, by freezing-bleed-dissolving program removing system in oxygen.Question response system is stirred to normal temperature, then carries out reaction 24h at 70 DEG C.Whole process keeps stirring, and carries out under nitrogen protection, and the product obtained precipitates in anhydrous diethyl ether.After three resolution of precipitates, obtain white powder, last oven drying is to constant weight.
The preparation of embodiment 8, AD-PNIPAM-AD and 4HCA-CD inclusion compound
Take AD-PNIPAM-AD respectively, 4HCA-CD is dissolved in DMF, and the concentration of configuration solution is 1mg/mL, and both mix rear ultrasonic 1h.
The preparation of embodiment 9, AD-PNIPAM-AD and 4HCA-CD supramolecular aggregation
AD-PNIPAM-AD and 4HCA-CD inclusion compound is dissolved in DMF, be made into the solution of 2mg/mL, in polymers soln, slowly drip the ultrapure water of same volume under agitation with the speed of 25 μ L/min, stirred at ambient temperature 12h, then dialyse 3-5 days, then lyophilize 4-5 days; Irradiate 1h under a part for gained aggregate dispersion liquid is placed in ultraviolet lamp, make photosensitivity cinnamoyl generation photo-crosslinking; Gained aggregate dispersion liquid is elevated to 60 DEG C from room temperature 25 DEG C, then is reduced to 25 DEG C from 60 DEG C, test particle diameter and metamorphosis.
Claims (6)
1. a preparation method for double-sensitivity cyclodextrin supermolecule aggregate, to is characterized in that with 4-hydroxycinnamic acid (4HCA) for function base modification cyclodextrin (CD) prepares host molecule---sensitivity of light 4-hydroxycinnamic acid-cyclodextrin (4HCA-CD); Again using three thioesters of end strips diamantane (AD) as chain-transfer agent, with the temperature sensitivity guest polymer of reversible addion-fragmentation chain transfer radical polymerization (RAFT) legal system for end strips AD group---both arms diamantane-NIPA-diamantane (AD-PNIPAM-AD); Utilize the complex performance between the hydrophobic cavity of β-CD and AD, construct micro-response super molecule inclusion compound 4HCA-CD/AD-PNIPAM-AD; Make cyclodextrin carry out self-assembly further under certain condition and form supramolecular aggregation, its preparation method is as follows:
(1) synthesis of 4HCA-CD
For avoiding 4HCA that interior chloride occurs, first with diacetyl oxide, the hydroxyl of 4HCA being carried out acetylize, then using the carboxyl reaction in sulfur oxychloride and 4HCA, obtaining 4-ethanoyl cinnamyl chloride; Itself and β-CD are reacted 5h under room temperature in anhydrous pyridine; Reaction terminate after add little water termination reaction, underpressure distillation removing pyridine, excess methanol extraction, and then in methanol-water recrystallization twice, obtain 4HCA-CD, obtaining product is Red-brown powder;
(2) preparation of AD-PNIPAM-AD
In the mixed solution of dithiocarbonic anhydride, Tetrabutyl amonium bromide, toluene, first drip the sodium hydroxide solution of 50%, drip off rear continuation instillation containing the acetone of same volume ratio and the mixed solution of chloroform, more than stirring reaction 12h in 15 ~ 20 DEG C, S is obtained after reaction terminates, S-bis-(α, α ' methyl-α " acetic acid) trithiocarbonic acid carbon ester (TTC); Then by itself and sulfur oxychloride heating reflux reaction 7h in dichloromethane solvent, underpressure distillation desolventizes and unreacted sulfur oxychloride, product acid chloride S, S-bis-(α, α ' methyl-α " acetic acid) trithiocarbonic acid carbon ester (TTC-Cl); Instill TTC-CI by under the THF solution ice bath of 1-adamantanol (AD), after room temperature reaction 4h, be warming up to 60 DEG C and spend the night, obtain the chain-transfer agent AD-TTC-AD that two ends are AD; Finally by NIPAM under AIBN causes, be that chain-transfer agent carries out RAFT polymerization at 70 DEG C with AD-TTC-AD, obtain Thermo-sensitive AD-PNIPAM-AD;
(3) preparation of AD-PNIPAM-AD and 4HCA-CD super molecule inclusion compound
Take AD-PNIPAM-AD respectively, 4HCA-CD is dissolved in DMF, and the concentration of configuration solution is 1mg/mL, and both mix rear ultrasonic 1h;
(4) preparation of AD-PNIPAM-AD and 4HCA-CD supramolecular aggregation
AD-PNIPAM-AD and 4HCA-CD inclusion compound is dissolved in DMF, be made into the solution of 2mg/mL, in polymers soln, slowly drip the ultrapure water of same volume under agitation with the speed of 25 μ L/min, stirred at ambient temperature 12h, then dialyse 3-5 days, then lyophilize 4-5 days.
2. the photosensitivity host molecule obtained by preparation method according to claim 1, it is characterized in that taking 4HCA as the CD that function base is modified, it mol ratio 4HCA: CD is 1: 1 ~ 5: 1, and the structure of gained photosensitivity CD derivative is:
Be expressed as 4HCA-CD.
3. the temperature sensitivity guest polymer obtained by preparation method according to claim 1, it is characterized in that using three thioesters of end strips AD as chain-transfer agent, with the temperature sensitivity guest polymer of RAFT legal system for end strips AD, the structure of resulting polymers is:
Wherein n=20 ~ 80, are expressed as AD-PNIPAM-AD.
4. the super molecule inclusion compound obtained by preparation method according to claim 1, it is characterized in that it has sensitivity of light, [2+2] cyclisation can occur, through ultraviolet lighting, the increasing before the molecular weight ratio illumination of super molecule inclusion compound is twice.
5. the supramolecular aggregation obtained by preparation method according to claim 1, is characterized in that the form of supramolecular aggregation, size can realize reversible transition by change light, temperature; Gained aggregate dispersion liquid is elevated to 60 DEG C from room temperature 25 DEG C and is reduced to 25 DEG C again, and the particle diameter of aggregate is reduced to 390nm from 3500nm and returns to 3500nm again, occurs reversible change.
6. the sensitive type cyclodextrin supramolecular aggregation obtained by preparation method according to claim 1, it is characterized in that there is good sensitivity of light and temperature sensitivity, can stimulate that to carry out intelligence corresponding to external world, make it have broad application prospects in drug loading, Co ntrolled release field.
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| WO2016026924A1 (en) * | 2014-08-21 | 2016-02-25 | Illumina Cambridge Limited | Reversible surface functionalization |
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| CN105527285B (en) * | 2015-12-21 | 2018-03-06 | 陕西师范大学 | One kind proves that adamantane and beta cyclodextrin assemble successful method |
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| CN109438723B (en) * | 2018-12-29 | 2021-05-11 | 广东工业大学 | Supramolecular material, temperature-sensitive hydrogel and preparation method thereof |
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| CN112940290A (en) * | 2021-02-05 | 2021-06-11 | 广东工业大学 | Double-network self-repairing hydrogel and preparation method thereof |
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