CN103524751A - Preparation method of double-sensitivity cyclodextrin supermolecule aggregate - Google Patents
Preparation method of double-sensitivity cyclodextrin supermolecule aggregate Download PDFInfo
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Abstract
The invention discloses a preparation method of a double-sensitivity cyclodextrin supermolecule aggregate, belonging to the technical field of functional materials. The preparation method comprises the following steps of preparing a host molecule-photosensitive 4-hydroxycinnamic acid-cyclodextrin (4HCA-CD) by using 4-hydroxycinnamic acid (4HCA) to modify beta-cyclodextrin (beta-CD); using trithioester with adamantine (AD) at tail end as a chain transfer agent, and preparing temperature-sensitive object polymer-double-arm adamantine-poly(N-isopropyl acrylamide)-adamantine (AD-PNIPAM-AD) by using a reversible addition-fragmentation chain transfer free radical polymerization (RAFT) method; constructing a double-sensitivity supermolecule inclusion complex 4HCA-CD/AD-PNIPAM-AD by utilizing comprehensive performance of a beta-CD dewatering cavity and AD; and self-assembling the 4HCA-CD/AD-PNIPAM-AD to form the supermolecule aggregate which is capable of realizing reversible conversion in shape and size by changing light and temperature. The supermolecule aggregate prepared by the preparation method disclosed by the invention has good light/temperature double sensitivities and is capable of carrying out smart response onto external stimulus, so that the supermolecule aggregate has a wide application prospect in the fields of drug loading, controlled release, and the like.
Description
Technical field
A preparation method for dual-sensitivity cyclodextrin supramolecular aggregation, belongs to technical field of function materials.
Background technology
Cyclodextrin (Cyclodextrins, CDs) is the cyclic oligosaccharide being 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 consists of the secondary hydroxyl of C2 and C3 and the primary hydroxyl of C6, has wetting ability; And owing to being subject to the shielding effect of c h bond, formed hydrophobic region in cavity.Hydrophobic and the outside hydrophilic characteristic of CD inner chamber make CD and derivative thereof can be according to Van der Waals force, hydrophobic interaction power, the intermolecular interaction of Subjective and Objective etc. the hydrophobic molecule inclusion with size match, 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 to external world, stimulate that to carry out intelligence corresponding, they will have more wide application in fields such as drug loading, control releases.
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 good physiologically active, and has excellent optical characteristics, as tran/cis isomerization and [2+2] cyclisation; Thereby, can pass through the selection to illumination frequency, illumination position, intensity of illumination and light application time length, realize " intelligence " regulation and control.
Although at present more to having the research report of CD super-molecule assembling body of stimulating responsive, the cinnamate group also without sensitivity of light is combined to prepare the research of stimulating responsive supermolecule polymer with CD.Given this, it is Subjective and Objective that photaesthesia cyclodextrin derivative and temperature-sensitive polymers are take respectively in the present invention, the supramolecular aggregation by the inclusion complexation effect preparation between cyclodextrin and diamantane with light/temperature dual-sensitivity, the form of supramolecular aggregation, size can realize reversible transition by change light, temperature.The supramolecular aggregation that the present invention makes has good sensitivity of light and temperature sensitivity, can stimulate to external world that to carry out intelligence corresponding, make its at drug loading, control the fields such as release and have broad application prospects.
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: the 4-hydroxycinnamic acid (4HCA) of take is prepared host molecule as function base modification cyclodextrin (CD)---sensitivity of light 4-hydroxycinnamic acid-cyclodextrin (4HCA-CD); Using three thioesters of end band diamantane (AD) as chain-transfer agent, the temperature sensitivity object polymkeric substance by reversible addition-fragmentation chain transfer free radical polymerization (RAFT) legal system for end band AD group---both arms diamantane-NIPA-diamantane (AD-PNIPAM-AD) again; Utilize the hydrophobic cavity of β-CD and the complex performance between AD, constructed micro-response super molecule inclusion compound 4HCA-CD/AD-PNIPAM-AD; Further make cyclodextrin carry out self-assembly under certain condition and form supramolecular aggregation, its preparation method is as follows:
(1) 4HCA-CD's is synthetic
For avoiding 4HCA that interior chloride occurs, first with diacetyl oxide, the hydroxyl of 4HCA is carried out to acetylize, then use the carboxyl reaction in sulfur oxychloride and 4HCA, obtain 4-ethanoyl cinnamyl chloride; It is reacted to 5h under room temperature with β-CD in anhydrous pyridine; After reaction finishes, add little water termination reaction, pyridine is removed in underpressure distillation.Excess methanol extraction, and then in methanol-water recrystallization twice, obtain 4HCA-CD, obtaining product is sorrel powder; Its mol ratio 4HCA: CD is 1: 1～5: 1, and structural formula is as follows:
(2) preparation of AD-PNIPAM-AD
First in the mixed solution of dithiocarbonic anhydride, Tetrabutyl amonium bromide, toluene, drip 50% sodium hydroxide solution, drip off the rear mixed solution that continues to splash into acetone and chloroform (1: 1) (a second), in 15～20 ℃ more than stirring reaction 12h, after finishing, reaction obtains S, 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 is removed and is desolventized and unreacted sulfur oxychloride, obtain product chloride S, S-bis-(α, α ' methyl-α " acetic acid) trithiocarbonic acid carbon ester (TTC-Cl); To under the THF solution ice bath of 1-adamantanol (AD), splash into TTC-Cl, after room temperature reaction 4h, be warming up to 60 ℃ and spend the night, obtaining two ends is the chain-transfer agent AD-TTC-AD of AD; Finally by NIPAM under AIBN causes, take AD-TTC-AD as chain-transfer agent carries out RAFT polymerization at 70 ℃, 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 respectively AD-PNIPAM-AD, 4HCA-CD is dissolved in DMF, and the concentration of configuration solution is 1mg/mL, and both mix rear ultrasonic 1h; By after its inclusion compound ultraviolet lighting 1h, approximately one times of the increase before the molecular weight ratio illumination of super molecule inclusion compound.
(4) preparation of AD-PNIPAM-AD and 4HCA-CD supramolecular aggregation
AD-PNIPAM-AD and 4HCA-CD inclusion compound are dissolved in DMF, be made into the solution of 2mg/mL, the speed with 25 μ L/min under agitation condition slowly drips the ultrapure water of same volume in polymers soln, under room temperature, stirs 12h, then 3-5 days then lyophilize 4-5 days dialyse.
By infrared spectrometer, nuclear magnetic resonance analyser, ultraviolet spectrophotometer, differential scanning calorimeter, gel permeation chromatograph etc., characterize structure and the performance of each intermediate product and final product, adopt microscopic pattern and the size of transmission electron microscope, dynamic laser scattering of light 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 approximately one times of the increase before the molecular weight ratio illumination of super molecule inclusion compound; The form of gained supramolecular aggregation, size can realize reversible transition by change light, temperature; Gained aggregate dispersion liquid is elevated to 60 ℃ from 25 ℃ of room temperatures and is reduced to 25 ℃ 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: it is Subjective and Objective that photaesthesia cyclodextrin and temperature-sensitive polymers are take respectively in the present invention, has the supramolecular aggregation of light/temperature dual-sensitivity by the inclusion complexation effect preparation between cyclodextrin and diamantane.The supramolecular aggregation that the present invention makes has good sensitivity of light and temperature sensitivity, can stimulate to external world that to carry out intelligence corresponding, make its at drug loading, control the fields such as release and have broad application prospects.
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 and reduces with temperature.
The SEM figure of (a) and heat up rear (b) before Figure 44 HCA-CD/AD-PNIPAM-AD supramolecular aggregation heats up.
Embodiment
Synthesizing of embodiment 1,4-ethanoyl styracin
To in 4.60g (28mmol) 4HCA and 10mL anhydrous pyridine, add in 100mL there-necked flask, constant-temperature heating system, stirring system are installed, under 0 ℃ of constant temperature ice bath, stir 30min, then at this temperature, add 7.5mL diacetyl oxide, continue to stir 1.5h, stir and finish gained solution heating reflux reaction 5h under 130 ℃ of constant temperature oil bath magnetic agitation, gained solution is poured in 500mL beaker, by 0.1mol/L hydrochloric acid soln washed twice, suction filtration obtains a large amount of deionized water wash of white powder.Get filter cake vacuum-drying 24h at 50 ℃, obtain the cinnamic acid derivative 4ACA that hydroxyl is acetylation, products therefrom is white powder.
Synthesizing 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 add the DMF of 0.018g as catalyzer; 10mL methylene dichloride is as solvent; constant-temperature heating system, stirring system are installed; heating reflux reaction 7h under 60 ℃ of constant temperature oil bath magnetic agitation, underpressure distillation is removed and is desolventized 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 ℃ of constant temperature ice bath, being stirred to β-CD dissolves completely; 0.7633g (3.4mmol) 4-ethanoyl styracin is dissolved in 14mL anhydrous pyridine and is mixed with solution; this solution is dripped and entered in there-necked flask in 20min, be added dropwise to complete and under rear room temperature, continue stirring reaction 5h.After reaction finishes, add little water termination reaction, pyridine is removed in underpressure distillation.Excess methanol extraction, and then in methanol-water recrystallization twice, obtain 4HCA-CD.Obtaining product is sorrel powder.
In the three-necked bottle of 500mL that dropping funnel is housed, add dithiocarbonic anhydride 11.45g (0.15mol), Tetrabutyl amonium bromide 1g (3.1mmol), toluene 50mL, under nitrogen atmosphere, in ice bath, slowly splash into 50% sodium hydroxide solution 84g, in 30min, drip off (one second one), drip off the rear mixed solution that continues to splash into acetone 21.8g (0.375mol) and chloroform 44.8g (0.375mol) (a second), drip off rear temperature and be controlled in 15～20 ℃, be more than stirring reaction 12h.After completion of the reaction, add 250mL water that solid is dissolved completely, splash into afterwards 60mL concentrated hydrochloric acid (one second one, regulate PH < 4).Add rear stirring reaction 30min, filter, obtain yellow solid and with a large amount of deionization washings, use ethyl alcohol recrystallization twice, last oven drying is to constant weight.
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; and then add 1～2 DMF as catalyzer; 15mL methylene dichloride, as solvent, is installed constant-temperature heating system, stirring system, heating reflux reaction 7h under 60 ℃ of constant temperature oil bath magnetic agitation; underpressure distillation is removed and desolventized and unreacted sulfur oxychloride, obtaining product is chocolate oily matter.
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), splashes in single port flask ice bath 1h under condition of ice bath, after room temperature reaction 4h, be warming up to 60 ℃ and spend the night.Reaction finishes rear underpressure distillation and removes tetrahydrofuran (THF), washes twice, then use 5%Na with methanol-water
2cO
3wash twice, last oven drying is to constant weight.
By 3.4g (30mmol) NIPA, 0.11g (0.3mmol) AD-TTC-AD and 4.93mg (0.03mmol) azo-bis-isobutyl cyanide are dissolved in 8.7mL DMF, by freezing-bleed-dissolving program, remove the oxygen in system.Question response system is stirred to normal temperature, then at 70 ℃, reacts 24h.Whole process keeps stirring, and carries out under nitrogen protection, and the product obtaining 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 respectively AD-PNIPAM-AD, 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 are dissolved in DMF, be made into the solution of 2mg/mL, the speed with 25 μ L/min under agitation condition slowly drips the ultrapure water of same volume in polymers soln, under room temperature, stirs 12h, then 3-5 days then lyophilize 4-5 days dialyse; A part for gained aggregate dispersion liquid is placed under ultraviolet lamp and irradiates 1h, make photosensitivity cinnamoyl generation photo-crosslinking; Gained aggregate dispersion liquid is elevated to 60 ℃ from 25 ℃ of room temperatures, then is reduced to 25 ℃, test particle diameter and metamorphosis from 60 ℃.
Claims (6)
1. a preparation method for dual-sensitivity cyclodextrin supramolecular aggregation, is characterized in that take that 4-hydroxycinnamic acid (4HCA) prepares host molecule as function base modification cyclodextrin (CD)---sensitivity of light 4-hydroxycinnamic acid-cyclodextrin (4HCA-CD); Using three thioesters of end band diamantane (AD) as chain-transfer agent, the temperature sensitivity object polymkeric substance by reversible addition-fragmentation chain transfer free radical polymerization (RAFT) legal system for end band AD group---both arms diamantane-NIPA-diamantane (AD-PNIPAM-AD) again; Utilize the hydrophobic cavity of β-CD and the complex performance between AD, constructed micro-response super molecule inclusion compound 4HCA-CD/AD-PNIPAM-AD; Further make cyclodextrin carry out self-assembly under certain condition and form supramolecular aggregation, its preparation method is as follows:
(1) 4HCA-CD's is synthetic
For avoiding 4HCA that interior chloride occurs, first with diacetyl oxide, the hydroxyl of 4HCA is carried out to acetylize, then use the carboxyl reaction in sulfur oxychloride and 4HCA, obtain 4-ethanoyl cinnamyl chloride; It is reacted to 5h under room temperature with β-CD in anhydrous pyridine; After reaction finishes, add little water termination reaction, pyridine is removed in underpressure distillation.Excess methanol extraction, and then in methanol-water recrystallization twice, obtain 4HCA-CD, obtaining product is sorrel powder;
(2) preparation of AD-PNIPAM-AD
First in the mixed solution of dithiocarbonic anhydride, Tetrabutyl amonium bromide, toluene, drip 50% sodium hydroxide solution, drip off the rear mixed solution that continues to splash into acetone and chloroform (1: 1) (a second), in 15～20 ℃ more than stirring reaction 12h, after finishing, reaction obtains S, 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 is removed and is desolventized and unreacted sulfur oxychloride, obtain product chloride S, S-bis-(α, α ' methyl-α " acetic acid) trithiocarbonic acid carbon ester (TTC-Cl); To under the THF solution ice bath of 1-adamantanol (AD), splash into TTC-Cl, after room temperature reaction 4h, be warming up to 60 ℃ and spend the night, obtaining two ends is the chain-transfer agent AD-TTC-AD of AD; Finally by NIPAM under AIBN causes, take AD-TTC-AD as chain-transfer agent carries out RAFT polymerization at 70 ℃, obtain Thermo-sensitive AD-PNIPAM-AD;
(3) preparation of AD-PNIPAM-AD and 4HCA-CD super molecule inclusion compound
Take respectively AD-PNIPAM-AD, 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 are dissolved in DMF, be made into the solution of 2mg/mL, the speed with 25 μ L/min under agitation condition slowly drips the ultrapure water of same volume in polymers soln, under room temperature, stirs 12h, then 3-5 days then lyophilize 4-5 days dialyse.
2. photosensitivity host molecule according to claim 1, is characterized in that take that 4HCA is the CD that function base is modified, and its mol ratio 4HCA: CD is 1: 1～5: 1, and the structure of gained photosensitivity CD derivative is:
Be expressed as 4HCA-CD.
3. temperature sensitivity object polymkeric substance according to claim 1, it is characterized in that usining that three thioesters of end band diamantane (AD) are as chain-transfer agent, the temperature sensitivity object polymkeric substance for preparing standby end band AD by RAFT legal system, the structure of resulting polymers is:
Wherein n=20～80, are expressed as AD-PNIPAM-AD.
4. super molecule inclusion compound according to claim 1, is characterized in that having sensitivity of light, [2+2] cyclisation can occur, through ultraviolet lighting, and approximately one times of the increase before the molecular weight ratio illumination of super molecule inclusion compound.
5. supramolecular aggregation 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 ℃ from 25 ℃ of room temperatures and is reduced to 25 ℃ again, and the particle diameter of aggregate is reduced to 390nm from 3500nm and returns to 3500nm again, occurs reversible change.
6. sensitive type cyclodextrin supramolecular aggregation according to claim 1, it is characterized in that thering is good sensitivity of light and temperature sensitivity, can stimulate to external world that to carry out intelligence corresponding, make its at drug loading, control the fields such as release and have broad application prospects.
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