CN101367949A - Preparation method for calix[4]arene-based supermolecule self-assembly vesicle - Google Patents
Preparation method for calix[4]arene-based supermolecule self-assembly vesicle Download PDFInfo
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Abstract
The invention relates to a method for preparing calyx[4]arene supermolecule self-assembly vesicles, particularly including the following steps: a. under nitrogen protection, kalium carbonate is taken as base, calyx[4]arene and terminal methyl polyethylene glycol p-methyl benzene sulfonic ester react in anhydrous acetonitrile, and the solution of sodium hydroxide is added into and stirred, the acetonitrile is removed by revolving evaporation, extracted by ethyl acetate water phase, and the product is separated and purified by silica-gel column chromatography; b. hexadecanoyl chloride, phenols and potassium carbonate are heated to react in anhydrous acetonitrile, the coarse product is re-crystallized by the mixed solvent of dichloroethane and petroleum ether to achieve white crystal; c. in 1,4-dioxane, the arene modified by polyethylene glycol and hexadecanoic acid benzene ether are stirred to dissolve, deionized water is dripped during stirring, deionized water dripping is stopped when sky-blue opalescence appears in the solution, and a stable assembly body is achieved. The invention takes advantages of the interaction between the calyx arene subject and object to prepare nano vesicles with controllable sizes, and the vesicle varies between 200 nanometers and 600 nanometers.
Description
Technical field
The present invention relates to a kind of preparation method of chemical technology field, specifically is a kind of preparation method of cup [4] arene-based supermolecule self-assembly vesicle.
Background technology
Vesica is a kind of form of the orderly assembly of amphipathic molecule, and it has very big specific surface area and internal space, can adsorb more guest molecule and particle.The vesica film that is made of double-deck amphipathic molecule is that the duplicature of vesica has very strong rigidity, has the characteristic of lipoid plastid.The vesica that amphipathic molecule is assembled into has great application prospect in fields such as pharmaceutical carrier and release, genetically engineered, micropore reactor catalysis.
Find that through literature search the work that utilizes calixarene to prepare vesica at present mainly is divided into two big classes to prior art.One class is to modify close and distant water base group respectively at the decorating site of calixarene, utilize amphipathic nano vesicle: the Tanaka etc. that in selective solvent, are assembled into of calixarene in " Angew.Chem.Int.Ed. " (German applied chemistry then, 1999, the 38th volume, 504～506 pages) on delivered " Selective VesicleFormation from Calixarenes by Self-Assembly " (based on selectivity vesica preparation of calixarene self-assembly), this article is modified the calixarene of hydroquinone type and is gone up the octane long-chain, thereby makes hydrophilic hydroquinone type calixarene have amphipathic.With tetrahydrofuran (THF) dissolving back solution is slowly added in the buffered soln of pH=7.0, thereby obtained stable vesica shape assembly.Another kind ofly be by utilizing the calixarene molecule to the recognition function of metal ion control vesica size: Ritter etc. are at " Langmuir " (Langmuir, 2007, the 23rd volume, 4849～4855 pages) on delivered " Architecture Controlled " SMART " Calix[6] Arene Self-Assemblies in Aqueous Solution " (intelligent cup [6] aromatic hydrocarbons self-assembly in the aqueous solution of controllable structure), this article utilizes six hydroxyl group sites of cup [6] aromatic hydrocarbons to modify three imidazolyl and three sulfonic groups, obtain amphipathic calixarene, self-assembly obtains vesica in the aqueous solution.By cup [6] aromatic hydrocarbons and the silver ions effect that imidazoles is modified, can control the size of assembly.
Calixarene except metal ion is had the recognition function, equally has identification and compound effect to neutral organic molecule as third generation supermolecule main block compound.Utilize calixarene that the host and guest of neutral molecule is interacted, can form two block molecules, make it have the characteristic of close and distant water, this supramolecular complex is expected to be self-assembled into vesica in the aqueous solution, and can control the size of vesica by regulating the compound ratio, yet this part work does not appear in the newspapers so far.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of preparation method of cup [4] arene-based supermolecule self-assembly vesicle is provided, make it utilize the calixarene host and guest controlled nano vesicle of preparation size that interacts, by changing the amount of substance that the Subjective and Objective molecule adds, the vesica size changes between 600 nanometers in 200 nanometers.
The present invention is achieved by the following technical solutions, the principle of the present invention's utilization " assembling of earlier compound back ", earlier with two hydrophilic peg molecules on cup [4] the aromatic hydrocarbons lower edge contraposition hydroxyl modified, add modified calixarene subject and object palmitinic acid phenyl ester then in the cosolvent dioxane, slowly adding the compound and further simultaneously assembling of deionized water driving Subjective and Objective becomes vesica.The vesica size can be controlled by regulating the Subjective and Objective mol ratio.
The present invention includes following steps:
Step a: under nitrogen protection, as alkali, cup [4] aromatic hydrocarbons and terminal methyl polyoxyethylene glycol p-methyl benzenesulfonic acid ester react in anhydrous acetonitrile with salt of wormwood.Reaction finishes the aqueous solution stirring that the back adds sodium hydroxide, revolves to steam and removes acetonitrile, with the extraction of ethyl acetate water.Product is crossed post with silica gel column chromatography and is separated purification.
Step b: palmityl chloride, phenol, salt of wormwood reacting by heating in anhydrous acetonitrile.Crude product obtains white crystal with the mixed solvent recrystallization of methylene dichloride and sherwood oil.
Step c:, with polyethyleneglycol modified calixarene and the abundant stirring and dissolving of palmitinic acid phenyl ester, dropwise adding deionized water under the agitation condition fast in the 4-dioxane 1.Stop to add deionized water when occurring light blue opalescence in the solution, obtain stable assembly.
Described calixarene is to tertiary butyl cup [4] aromatic hydrocarbons or removes tertiary butyl cup [4] aromatic hydrocarbons.
Among the step a, the amount of substance of described adding terminal methyl polyoxyethylene glycol p-methyl benzenesulfonic acid ester is 2.1 times of cup [4] aromatic hydrocarbons.
Among the step a, calixarene is modified the product that obtains and is the dibasic cup of symmetry [4] aromatic hydrocarbons polyethyleneglycol derivative.
Among the step a, reaction finishes the aqueous solution stirring that the back adds sodium hydroxide, is to be used for the terminal methyl polyoxyethylene glycol p-methyl benzenesulfonic acid ester of hydrolysis as raw material, can remove the unreacting material of part in the water extraction.
Among the step a, described column chromatography is purified and is meant and uses silicon-dioxide chromatography post, methylene dichloride and methyl alcohol with the 10:1-10:3 ratio as the elutriant gradient elution.
Among the step b, described with methylene dichloride and sherwood oil mixing solutions recrystallization, wherein methylene dichloride and sherwood oil volume ratio are 1:10.
Among the step c, described 1, with polyethyleneglycol modified calixarene and the abundant stirring and dissolving of palmitinic acid phenyl ester, be meant in the 4-dioxane:, add 5 milligrams of polyethyleneglycol modified calixarene, 0.1-5 milligram palmitinic acid phenyl ester in the 4-dioxane at 10 milliliter 1.
Among the step c, described adding deionized water be meant with the 2-10 milliliter/hour speed splash into deionized water.
Can analyze by transmission electron microscope by the interact pattern of the nano vesicle obtain of calixarene host and guest, and dynamic light scattering, nucleus magnetic resonance etc. can be used as the assistant analysis means.
Utilize the calixarene host and guest assemble nanometer vesica that interacts according to the present invention, can be by changing mol ratio control vesica size, technology is simple, controllability good.The big I of nano vesicle changes between 600 nanometers in 200 nanometers.Nano vesicle can be used for fields such as drug conveying, genetically engineered, microreactor catalysis.
Description of drawings
Fig. 1: cup [4] aromatic hydrocarbons polyethyleneglycol derivative building-up process.
Fig. 2: based on the interactional nano vesicle assembling process of calixarene host and guest synoptic diagram.
Fig. 3: cup [4] the aromatic hydrocarbons nucleus magnetic resonance figure that terminal methyl polyoxyethylene glycol 550 is modified.
Fig. 4: based on the transmission electron microscope figure of the interactional nano vesicle of calixarene host and guest.
Fig. 5: the nucleus magnetic resonance titration figure of calixarene polyethyleneglycol derivative and palmitinic acid phenyl ester.
Fig. 6: the dynamic light scattering figure of calixarene supramolecule self-assembled nanometer vesica.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
The implementation process of following examples, as shown in Figure 1, 2, wherein Fig. 1 is tertiary butyl calixarene polyethyleneglycol derivative and removes tertiary butyl calixarene polyethyleneglycol derivative building-up process synoptic diagram, and Fig. 2 is based on the nano vesicle assembling process synoptic diagram of the polyethyleneglycol derivative of cup [4] aromatic hydrocarbons.
Step a: in 250 milliliters of there-necked flasks, add 1.29 grams to tertiary butyl cup [4] aromatic hydrocarbons 3.67 gram terminal methyl polyoxyethylene glycol 550 p-methyl benzenesulfonic acid esters, 559 milligrams of salt of wormwood, 70 milliliters of anhydrous acetonitriles.Stir dissolving fully, refluxed three days under the nitrogen protection condition.Add less water and 0.4 gram sodium hydroxide stirring two hours.Acetonitrile is removed in underpressure distillation, adds 100 milliliters of ethyl acetate extractions.Evaporate to dryness ethyl acetate after product becomes faint yellow oily thing, and crude product has 3.2 grams, productive rate 87%.Cross post through silica gel column chromatography, methylene chloride=20:1 is an eluent, obtains product 2.6 grams after the purification, productive rate 70%.
Step b: in 100 milliliters of round-bottomed flasks, add 1.87 gram palmityl chlorides, 0.4 gram phenol, 845 milligrams of salt of wormwood, 50 milliliters of anhydrous acetonitriles.Stir fully dissolving, refluxed 12 hours.With Rotary Evaporators evaporate to dryness acetonitrile, dichloromethane extraction obtains crude product.Add a small amount of sherwood oil recrystallization, obtaining product is white crystal, productive rate 93%.
Step c: in 50 milliliters of Erlenmeyer flasks, add 5 milligrams of polyethyleneglycol modified calixarene, 0.1 milligram of palmitinic acid phenyl ester, 10 milliliter 1, the 4-dioxane, fully stirring and dissolving is mixed with 10
-3The solution of mol.Under quick agitation condition, dropwise add deionized water with the speed of 5 of per minute kinds with microsyringe.At this moment the light blue opalescent formation that the nanometer assembly occurs indicating stop the adding of deionized water in the solution, continues at normal temperatures to stir and stablized 1 hour.
Step a: with example 1 step a
Step b: with example 1 step b
Step c: in 50 milliliters of Erlenmeyer flasks, add 5 milligrams of polyethyleneglycol modified calixarene, 2.0 milligrams of palmitinic acid phenyl esters, 10 milliliter 1, the 4-dioxane, fully stirring and dissolving is mixed with 10
-3The solution of mol.Under quick agitation condition, dropwise add deionized water with the speed of 5 of per minute kinds with microsyringe.At this moment the light blue opalescent formation that the nanometer assembly occurs indicating stop the adding of deionized water in the solution, continues at normal temperatures to stir and stablized 1 hour.
Embodiment 3
Step a: with example 1 step a
Step b: with example 1 step b
Step c: in 50 milliliters of Erlenmeyer flasks, add 5 milligrams of polyethyleneglycol modified calixarene, 4.0 milligrams of palmitinic acid phenyl esters, 10 milliliter 1, the 4-dioxane, fully stirring and dissolving is mixed with 10
-3The solution of mol.Under quick agitation condition, dropwise add deionized water with the speed of 5 of per minute kinds with microsyringe.At this moment the light blue opalescent formation that the nanometer assembly occurs indicating stop the adding of deionized water in the solution, continues at normal temperatures to stir and stablized 1 hour.
Embodiment 4
Step a: in 250 milliliters of there-necked flasks, add 0.85 gram and remove tertiary butyl cup [4] aromatic hydrocarbons, 550,559 milligrams of salt of wormwood of 2.65 gram terminal methyl polyoxyethylene glycol, 70 milliliters of anhydrous acetonitriles.Stir dissolving fully, the nitrogen protection condition refluxes and disappeared to thin-layer chromatographic analysis calixarene raw material in two days.Add the sodium hydroxide solution of 20 milliliter of 0.1 mol, stirred two hours.Acetonitrile is removed in underpressure distillation, adds 100 milliliters of ethyl acetate extractions then.Evaporate to dryness ethyl acetate after product becomes faint yellow oily thing, crude product 2.8 grams, productive rate 80%.Cross post through silica gel column chromatography, methylene chloride=35:1 to 5:1 gradient elution obtains product 2.2 grams after the purification, and productive rate is 61%.
Step b: with example 1 step b
Step c: in 50 milliliters of Erlenmeyer flasks, add 4.8 milligrams of polyethyleneglycol modified calixarene, 2.0 milligrams of palmitinic acid phenyl esters, 10 milliliter 1, the 4-dioxane, fully stirring and dissolving is mixed with 10
-3The solution of mol.Under quick agitation condition, dropwise add deionized water with the speed of 5 of per minute kinds with microsyringe.At this moment the light blue opalescent formation that the nanometer assembly occurs indicating stop the adding of deionized water in the solution, continues at normal temperatures to stir and stablized 1 hour.
Embodiment the results are shown in accompanying drawing.Fig. 3 is the one dimension nucleus magnetic hydrogen spectrum figure of the amphipathic calixarene main body of embodiment 1 preparation, the methylene radical of bridging has the branch of splitting between the phenyl ring, at 4.36ppm and 3.28ppm place two doublets are arranged, this is that two relative phenolic hydroxyl groups replace the symmetrical structures that form according to bibliographical information, also is the product that symmetry replaces as can be seen from the peak 1.27ppm and the 0.95ppm of two groups of tertiary butyls.The ratio of the integral area of the peak area of phenyl ring and ethylene glycol unit also meets a calixarene molecule and connects two peg molecules in addition.
Fig. 4 is based on the interactional nano vesicle transmission electron microscope of calixarene host and guest figure, the figure shows modified calixarene main body and palmitinic acid phenyl ester and be assembled into regular nano vesicle in solution.
Fig. 5 is the nuclear-magnetism titration results.Show that calixarene main body and palmitinic acid phenyl ester are can 1:1 compound.
Fig. 6 is respectively the result of dynamic light scattering test nano vesicle particle diameter among embodiment 1, embodiment 2, the embodiment 3.Show that the nano vesicle particle diameter that obtains can be controlled by changing reinforced mol ratio.
Claims (8)
1. the preparation method of a cup [4] arene-based supermolecule self-assembly vesicle is characterized in that, may further comprise the steps:
Step a: under nitrogen protection, with salt of wormwood as alkali, cup [4] aromatic hydrocarbons and terminal methyl polyoxyethylene glycol p-methyl benzenesulfonic acid ester react in anhydrous acetonitrile, reaction finishes the back and adds the aqueous sodium hydroxide solution stirring, revolve to steam and remove acetonitrile, with the extraction of ethyl acetate water, product is crossed post with silica gel column chromatography and is separated purification;
Step b: palmityl chloride, phenol, salt of wormwood reacting by heating in anhydrous acetonitrile, crude product obtains white crystal with the mixed solvent recrystallization of methylene dichloride and sherwood oil;
Step c: 1, with polyethyleneglycol modified calixarene and palmitinic acid phenyl ester stirring and dissolving, under agitation condition, dropwise add deionized water in the 4-dioxane, stop to add deionized water when occurring light blue opalescence in the solution, obtain stable assembly.
2. the preparation method of the interactional nano vesicle of calixarene host and guest according to claim 1 is characterized in that, described calixarene is to tertiary butyl cup [4] aromatic hydrocarbons or removes tertiary butyl cup [4] aromatic hydrocarbons.
3. the preparation method of cup [4] arene-based supermolecule self-assembly vesicle according to claim 1 is characterized in that, among the step a, the amount of substance of described adding terminal methyl polyoxyethylene glycol p-methyl benzenesulfonic acid ester is 2.1 times of cup [4] aromatic hydrocarbons.
4. the preparation method of cup [4] arene-based supermolecule self-assembly vesicle according to claim 1 is characterized in that, among the step a, calixarene is modified the product that obtains and is the dibasic cup of symmetry [4] aromatic hydrocarbons polyethyleneglycol derivative.
5. the preparation method of cup [4] arene-based supermolecule self-assembly vesicle according to claim 1, it is characterized in that, among the step a, described column chromatography is purified and is meant: use silicon-dioxide chromatography post, methylene dichloride and methyl alcohol with the 10:1-10:3 ratio as the elutriant gradient elution.
6. the preparation method of cup [4] arene-based supermolecule self-assembly vesicle according to claim 1 is characterized in that, among the step b, described with methylene dichloride and sherwood oil mixing solutions recrystallization, wherein methylene dichloride and sherwood oil volume ratio are 1:10.
7. the preparation method of cup [4] arene-based supermolecule self-assembly vesicle according to claim 1, it is characterized in that, among the step c, described 1, in the 4-dioxane with polyethyleneglycol modified calixarene and the abundant stirring and dissolving of palmitinic acid phenyl ester, be meant:, add 5 milligrams of polyethyleneglycol modified calixarene, 0.1-5 milligram palmitinic acid phenyl ester in the 4-dioxane at 10 milliliter 1.
8. the preparation method of cup according to claim 1 [4] arene-based supermolecule self-assembly vesicle is characterized in that, among the step c, described adding deionized water be meant with the 2-10 milliliter/hour speed splash into deionized water.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102258471A (en) * | 2011-04-22 | 2011-11-30 | 南开大学 | Preparation and application of sulfonated calix [4] arene-based nano supramolecular vesicles |
| CN104473902A (en) * | 2014-11-21 | 2015-04-01 | 南开大学 | Light and thermal controlled nano supermolecule vesicle as well as preparation method and application thereof |
| CN110157005A (en) * | 2019-05-29 | 2019-08-23 | 西南林业大学 | A kind of biological based supermolecular polyester and its synthetic method containing unsaturated chain alkyl |
| CN113092642A (en) * | 2021-03-30 | 2021-07-09 | 苏州爱宝德生物科技有限公司 | A quick extraction element for extracellular vesicles |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102258471A (en) * | 2011-04-22 | 2011-11-30 | 南开大学 | Preparation and application of sulfonated calix [4] arene-based nano supramolecular vesicles |
| CN102258471B (en) * | 2011-04-22 | 2012-12-26 | 南开大学 | Preparation and application of sulfonated calix [4] arene-based nano supramolecular vesicles |
| CN104473902A (en) * | 2014-11-21 | 2015-04-01 | 南开大学 | Light and thermal controlled nano supermolecule vesicle as well as preparation method and application thereof |
| CN104473902B (en) * | 2014-11-21 | 2017-03-22 | 南开大学 | Light and thermal controlled nano supermolecule vesicle as well as preparation method and application thereof |
| CN110157005A (en) * | 2019-05-29 | 2019-08-23 | 西南林业大学 | A kind of biological based supermolecular polyester and its synthetic method containing unsaturated chain alkyl |
| CN110157005B (en) * | 2019-05-29 | 2021-06-15 | 西南林业大学 | Bio-based supramolecular polyester containing unsaturated long-chain alkyl and synthetic method thereof |
| CN113092642A (en) * | 2021-03-30 | 2021-07-09 | 苏州爱宝德生物科技有限公司 | A quick extraction element for extracellular vesicles |
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