CN1736367A - Water solublity supermolecule capsule and its production and use - Google Patents
Water solublity supermolecule capsule and its production and use Download PDFInfo
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Abstract
The invention belongs to the supermolecule polymer chemical field, particularly cyclodextrin and block copolymer self assembly form and have water solublity supermolecule capsule of biocompatibility and its production and use.Obtain the sphere and/or the tubulose supermolecule capsule of hollow structure by cyclodextrin and two blocks or triblock copolymer self assembly, block copolymer wherein one section be can with the polymer segment of cyclodextrin generation clathration, another section or two sections be not with the hydrophilic segment of cyclodextrin effect, for triblock copolymer then hydrophilic segment be positioned at two ends; The capsular wall of this supermolecule is made of the bar-shaped complex that part segment in the cyclodextrin inclusion compound block copolymer forms, and is stable by the segmental hydrophilic interaction of enclose in water.This material not only production technology is simple, with low cost, and composition is nontoxic, good biocompatibility, can be used as containing, load, the sustained release material of biology, medical science, medicine, health, cosmetics, food, daily or field of fine chemical.
Description
Technical field
The invention belongs to the supermolecule polymer chemical field, also belong to the supermolecule polymer material science, particularly cyclodextrin and block copolymer self assembly form and have water solublity supermolecule capsule of biocompatibility and its production and use.
Background technology
Block copolymer relies on the difference of hydrophilic and hydrophobic, the difference of firm rod-ball of string chain conformation and the gathering that the crystallinity segment causes, self assembly forms specific pattern in specific dicyandiamide solution, in these patterns especially vesicle, capsule and the pipe with hollow structure using value is arranged most, (Amphiphilic Block Copolymers:Self-assemblyand Application is applied in the material field that containing, carrier, sustained release are correlated with, Elsevier, 2000).But, the particle of most of hollow structures because contain the biocompatible component and water solublity bad, thereby limited its application in fields such as biology, medicine, cosmetics, food.In addition, some particle also needs by covalent bond pattern to be fixed, and has therefore lacked the characteristic of supramolecular system dynamic reversible.Cyclodextrin is as host molecule, can with multiple guest molecule generation clathration, help improving guest molecule to external world stability and have the function of sustained release, therefore be widely used in fields such as medicine, food, fine chemistry industry (cyclodextrin chemistry-basis and application, Science Press, 2001; Chemical Review, 1998, Vol.98, Issue 5).Polymer and cyclodextrin formed the supramolecular structure of many rotaxanes and studied (Russian Chemical Reviews, 2001,70,23-44 widely since the nineties in last century by clathration; Advancein Polymer Science, 1997,133,141-191).Therefore, utilize block copolymer and cyclodextrin can assemble the bar structure of the ball of string of formation-just and have crystallization excellent segmental novel block polymer just, it has obtained biodegradable medical high polymer aggregation (the international monopoly WO9609073 of supramolecular structure under the just excellent effect of crystallinity cyclodextrin, Chinese patent CN95190936.3), injectable drug transmits hydrogel (U.S. Pat 2002019369, international monopoly WO02094324) and Biodegradable hydrogel biomaterial (U.S. Pat 2004072799, international monopoly WO2004009664), realize biology, medicine, the application of aspects such as food.Simultaneously, these many rotaxanes have supermolecule dynamic reversible character, under certain condition sustained release and retainer ring dextrin and block copolymer.
Summary of the invention
One of purpose of the present invention provide a kind of can be in aqueous solution stable existence and water solublity supermolecule capsule with stimulus-response characteristic, this water solublity supermolecule capsule has no side effect and has excellent biological compatibility.
A further object of the present invention provides the capsular preparation method of water solublity supermolecule, and mainly by the principle of molecular recognition and self assembly, products obtained therefrom has dynamic reversible character to this method.
An also purpose of the present invention provides the capsular purposes of water solublity supermolecule.
Water solublity supermolecule capsule of the present invention is that cyclodextrin (CD) and two blocks or triblock copolymer are pressed certain concentration and mixed in molar ratio at aqueous phase, and self assembly obtains the sphere and/or the tubulose supermolecule capsule of hollow structure.One section of block copolymer can with cyclodextrin generation clathration.
Water solublity supermolecule capsule of the present invention is obtained the sphere and/or the tubulose supermolecule capsule of hollow structure by cyclodextrin and two blocks or triblock copolymer self assembly, block copolymer wherein one section be can with the polymer segment of cyclodextrin generation clathration, another section or two sections are the hydrophilic segment of discord cyclodextrin effect, for triblock copolymer then two sections hydrophilic segment be positioned at two ends; The bar-shaped complex assembly that the capsular wall of this supermolecule forms after by the cyclodextrin inclusion compound polymer segment constitutes.
Can it be 1: 1～10: 1 by the mol ratio of segment monomeric unit of cyclodextrin inclusion compound (propylene oxide (PO), ethylene oxide (EO), methyl vinyl ether, lactic acid, caprolactone, siloxanes) and cyclodextrin molecular in two blocks or the triblock copolymer in the water solublity supermolecule capsule of the present invention, and the molecular weight of the polymer segment of cyclodextrin generation clathration is between 400～4000, preferred 800～3000, simultaneously sub-thread hydrophilic segment unit with can be 2.5～5.0 with the unitary mol ratio of the polymer segment of cyclodextrin inclusion compound.
The supermolecule capsule size is measured by dynamic light scattering, and its hydrodynamic radius is between 40nm～5 μ m.Transmission electron microscope observes its pattern present spherical hollow vesicle or hollow tubular structure, the diameter range 60～250nm of spherical vesicles, and the capsule diameter of hollow tubular structure and length range are respectively 60～250nm and 250nm～5 μ m.The capsular wall of this supermolecule is made of the bar-shaped complex that polymer segment enclose cyclodextrin forms, and is stable by the segmental hydrophilic interaction of enclose in water.
The block copolymer that adopts be by can forming with bonded segment of cyclodextrin and hydrophilic segment, sub-thread hydrophilic segment unit and can be 2.5～5.0 by the unitary mol ratio of the polymer segment of cyclodextrin inclusion compound.With the polymer segment of cyclodextrin generation clathration can be polypropylene oxide (PPO), polyethylene glycol oxide (PEO), polyisobutylene, polymethyl vinyl ether, polylactic acid, polycaprolactone or polysiloxanes; And hydrophilic segment can be polyethylene glycol oxide (PEO) or polyacrylic acid.And when polyethylene glycol oxide (PEO) as with the segment of alpha-cyclodextrin generation enclose the time, can not be simultaneously as hydrophilic segment.
Adopt in the block copolymer not the unit of the hydrophilic segment of enclose far more than can with the unit of the bonded polymer segment of cyclodextrin, usually sub-thread hydrophilic segment unit be 2.5～5.0 by the unitary mol ratio of cyclodextrin inclusion compound polymer segment, simultaneously and the bonded polymer segment molecular weight of cyclodextrin between 400～4000, preferred 600～2000.
Adopt the cyclodextrin can be according to the cyclodextrin of being selected to be fit to internal diameter by the segmental cross-sectional area of inclusion polymerization thing, can for α-, β-or gamma-cyclodextrin.
The capsular preparation method of water solublity supermolecule of the present invention: in container,, obtain water solublity supermolecule capsule behind the certain hour with the aqueous solution of aqueous solution and commercially available or the homemade block copolymer of cyclodextrin (CD).The concentration range of block copolymer is 0.01～0.50mM in the mixed solution, then according to the quality of the required adding cyclodextrin of mol ratio (scope is 10: 1～1: 1) setting of polymer chain segment unit and the cyclodextrin of cyclodextrin inclusion compound, the concentration range of cyclodextrin solution is 0.03～24mM in the mixed solution.
In said method, composition that can be by changing block copolymer, can be with the mol ratio of the polymer chain segment unit of cyclodextrin inclusion compound and cyclodextrin, mix time and system concentration, control forms the capsular particle diameter of supermolecule to a certain extent, can satisfy actual needs more widely.
Described water solublity supermolecule capsule, has stimulus-response character, can be by changing the external condition control capsular formation of supermolecule and untiing, controllably bring into play cyclodextrin molecular to the Subjective and Objective effect of other material and block copolymer in emulsifying, effect aspect medical.
Water solublity supermolecule capsule of the present invention can be by being widely used for numerous materials fields such as biology, medical science, medicine, health, cosmetics, food, daily and fine chemistry industry to segmental selection and collocation.Particularly adopt can biocompatible block copolymer after, can be as biological medicine with the containing of guest molecule (as protein, polypeptide, polysaccharide, DNA etc.), load, sustained release material etc.
The present invention obtains having the water solublity supermolecule capsule of biocompatibility and dynamic reversible characteristic by the principle of molecular recognition and self assembly.Supermolecule capsule of the present invention is with respect to other hollow-particle, and its particle scale wider distribution and controlled is to a certain extent assembled the crystallization wall that forms simultaneously and had advantages of higher stability.In addition, this supermolecule capsule also can carry out reversibly fixing and release to cyclodextrin and block copolymer by changing external condition, controllably brings into play the function of cyclodextrin or block copolymer.
Water solublity supermolecule capsule of the present invention has no side effect and has excellent biological compatibility, can be used in material fields such as biology, medical science, medicine, health, cosmetics, food, daily and fine chemistry industry, and practicality is given prominence to, had to performance.Water solublity supermolecule capsule of the present invention is with respect to the product of other similar structures, and its particle scale wider distribution has advantages of higher stability, can reversibly assemble and untie by the influence of external condition, therefore has significant technological progress.
Description of drawings
Fig. 1. triblock copolymer and cyclodextrin form the capsular sketch map of supermolecule in the embodiment of the invention 1～6, and wherein A represent the hydrophilic polyoxyethylene segments, B represent can with the bonded polypropylene oxide segment of beta-schardinger dextrin-.
Fig. 2. di-block copolymer and cyclodextrin form the capsular sketch map of supermolecule in the embodiment of the invention 7, and wherein A represent the hydrophilic polyacrylic segment, B represent can with the bonded polyoxyethylene segments of alpha-cyclodextrin.
Fig. 3 .EO
137PO
44EO
137Triblock copolymer and beta-schardinger dextrin-(mixed back EO
137PO
44EO
137Concentration is 0.2mM, PO: β-CD mol ratio is 2: 1) transmission electron microscope photo of self assembly formation supermolecule capsule pattern after mixing certain hour.
The specific embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is further described:
Embodiment 1
Adopt EO
mPO
nEO
mTriblock copolymer (commodity are called Pluronic) and beta-schardinger dextrin-(β-CD), wherein β-CD is 1: 2 with PO unit selective binding and theoretical molar ratio, and two EO segments are as two hydrophilic segments and be positioned at the segmental two ends of PO that clathration can take place with β-CD herein.With 0.1460g EO
137PO
44EO
137(number-average molecular weight is 14600, and wherein EO element quality mark is 82.5wt%, and the segmental molecular weight of PO that can clathration take place with β-CD be 2555), with water dissolution and be settled to 25mL, concentration is 0.4mM; With water dissolution and be settled to 25mL, concentration is 8.8mM with 0.2489g beta-schardinger dextrin-(molecular weight 1135.01).Above-mentioned two kinds of solution equal-volumes are mixed EO in the gained mixed solution
137PO
11EO
137Concentration be 0.2mM and PO: β-CD mol ratio is 2: 1.Observe the vesicle (size range sees attached list 1) of its hollow structure and proved that with electronic diffraction wall is polycrystalline structure (seeing accompanying drawing 3A) with transmission electron microscope.Mixing after 2 hours dynamic light scattering observes the capsular hydrodynamic radius of supermolecule and sees attached list 2.
Embodiment 2
Whole process of preparation, raw material and proportioning thereof only change the blended time with embodiment 1.Observe the long tube (mixed 28 days, structure is seen accompanying drawing 3C, and size range sees attached list 1) of short tube that the capsular pattern of supermolecule is a hollow structure (mixed 4 days, structure is seen accompanying drawing 3B, and size range sees attached list 1) and hollow structure with transmission electron microscope.After mixing, observe the capsular hydrodynamic radius of supermolecule with dynamic light scattering on the 4th and 28 day and see attached list 2.
Embodiment 3
Whole process of preparation and raw material are with embodiment 1, and fixedly the mixed solution concentration of the solution concentration of triblock copolymer and equal-volume is constant, and only the adding concentration by control β-CD solution changes PO: β-CD mol ratio.With water dissolution and be settled to 25mL, concentration is 4.4mM, with EO with the 0.1249g beta-schardinger dextrin-
137PO
44EO
137Obtain the PO of mixed solution after the solution equal-volume mixes: β-CD mol ratio is 4: 1 and EO
137PO
44EO
137Concentration be 0.2mM.See attached list 2 with the hydrodynamic radius behind the dynamic light scattering observation different time interval, consistent with accompanying drawing 3A (mixing 2 hours) and 3B (mixing 4 days～28 days) after the different incorporation times with the pattern of transmission electron microscope observation.With water dissolution and be settled to 25mL, concentration is 2.2mM, with EO with the 0.0625g beta-schardinger dextrin-
137PO
44EO
137Obtain the PO of mixed solution after the solution equal-volume mixes: β-CD mol ratio is 8: 1 and EO
137PO
44EO
137Concentration be 0.2mM.See attached list 2 with the hydrodynamic radius behind the dynamic light scattering observation different time interval, consistent with accompanying drawing 3A (mixing 2 hours), 3B (mixing 4 days) and 3C (mixing 28 days) after the different incorporation times with the pattern of transmission electron microscope observation.
Embodiment 4
Whole process of preparation is with embodiment 1, keep PO: β-CD mol ratio be 2: 1 constant, reduce the concentration of triblock copolymer and β-CD simultaneously.With 0.0730g EO
137PO
44EO
137With water dissolution and be settled to 25mL, concentration is 0.2mM; With water dissolution and be settled to 25mL, concentration is 4.4mM with the 0.1249g beta-schardinger dextrin-; Equal-volume mixes back EO
137PO
44EO
137Concentration be 0.1mM.See attached list 2 with the hydrodynamic radius behind the dynamic light scattering observation different time interval, consistent with accompanying drawing 3A (mixing 2 hours～4 days) and 3B (mixing 28 days) after the different incorporation times with the pattern of transmission electron microscope observation.With 0.0365gEO
137PO
44EO
137With water dissolution and be settled to 25mL, concentration is 0.1mM; With water dissolution and be settled to 25mL, concentration is 2.2mM with the 0.0625g beta-schardinger dextrin-; Equal-volume mixes back EO
137PO
44EO
137Concentration be 0.05mM.See attached list 2 with the hydrodynamic radius behind the dynamic light scattering observation different time interval, consistent with accompanying drawing 3A (mixing 2 hours～4 days) and 3B (mixing 28 days) after the different incorporation times with the pattern of transmission electron microscope observation.
Embodiment 5
Whole process of preparation adopts block than different Pluronic products with embodiment 1.With 0.0875gEO
76PO
30EO
76(number-average molecular weight is 8750, and wherein EO element quality mark is 80wt%, can be 1750 with the segmental molecular weight of PO of β-CD generation clathration) is with water dissolution and be settled to 25mL, and concentration is 0.4mM.With water dissolution and be settled to 25mL, concentration is 6.0mM with 0.1697g β-CD.Above-mentioned two kinds of solution equal-volumes are mixed EO in the gained mixed solution
76PO
30EO
76Concentration be 0.2mM and PO: β-CD mol ratio is 2: 1.The pattern of transmission electron microscope observation is consistent with accompanying drawing 3.
Embodiment 6
EO
137PO
44EO
137And the quality that feeds intake of β-CD is with embodiment 1, and preparation method has change slightly.Be about to EO
137PO
44EO
137And the pressed powder of β-CD is dissolved in water after mixed and is settled to 50mL, obtains EO
137PO
44EO
137Concentration be 0.2mM and PO: β-CD mol ratio is 2: 1 a solution, and the pattern with transmission electron microscope observation after the different incorporation times is consistent with accompanying drawing 3A (mixing 2 hours), 3B (mixing 4 days) and 3C (mixing 28 days).
Embodiment 7
Preparation method is with embodiment 1, the di-block copolymer of employing acrylic acid (AA) and EO and alpha-cyclodextrin (α-CD), herein the AA segment as hydrophilic segment and the EO segment as with the segment of α-CD enclose, and α-CD is 1: 2 with EO unit selective binding and theoretical molar ratio.With 0.1280g AA
150EO
45(number-average molecular weight is 12800, and wherein the segmental molecular weight of EO that can clathration take place with α-CD be 2000), with water dissolution and be settled to 25mL, concentration is 0.4mM; With water dissolution and be settled to 25mL, concentration is 8.8mM with 0.2140g alpha-cyclodextrin (molecular weight 972.86).Above-mentioned two kinds of solution equal-volumes are mixed AA in the gained mixed solution
150EO
45Concentration be 0.2mM and E0: α-CD mol ratio is 2: 1.The pattern of transmission electron microscope observation is consistent with accompanying drawing 3.
EO among the subordinate list 1. transmission electron microscopes observation embodiment 1
137PO
44EO
137With β-CD self assembly forms in aqueous solution capsular shape characteristic of supermolecule and size range
| Incorporation time | Shape characteristic | Diameter (sphere) | Hollow tubular structure | |
| Diameter | Length | |||
| 2 hours | Spherical vesicles | 60～200nm | - | - |
| 4 days | Hollow short pipe | - | 60～ | 250～1000nm |
| 28 days | Hollow elongated tubular | - | 60～250nm | 1000～5000nm |
The EO that subordinate list 2. dynamic light scatterings are measured
137PO
44EO
137With β-CD capsular hydrodynamic radius of supermolecule that self assembly forms under different condition.Though hydrodynamic radius can not accurately provide the capsular size of corresponding supermolecule, can reflect that transmission electron microscope observes the capsular range scale of the supermolecule with identical pattern herein.
| Mixed back EO 137PO 44EO 137Concentration | PO: β-CD mol ratio | Hydrodynamic radius (nm) | |||
| 2 hours | 4 days | 28 days | |||
| Embodiment 1 and 2 | 0.2mM | 2∶1 | 40～200 | 80～1100 | 200～4500 |
| Embodiment 3 | 0.2mM | 4∶1 | 40～200 | 80～1200 | 80～1200 |
| Embodiment 3 | 0.2mM | 8∶1 | 40～200 | 80～1100 | 80～2500 |
| Embodiment 4 | 0.1mM | 2∶1 | 40～200 | 60～200 | 80～1100 |
| Embodiment 4 | 0.05mM | 2∶1 | 40～200 | 60～200 | 80～600 |
Claims (10)
1. water solublity supermolecule capsule, it is characterized in that: the sphere and/or the tubulose supermolecule capsule that obtain hollow structure by cyclodextrin and two blocks or triblock copolymer self assembly, block copolymer wherein one section be can with the polymer segment of cyclodextrin generation clathration, another the section or two sections be hydrophilic segment, for triblock copolymer then two sections hydrophilic segment be positioned at two ends; The capsular wall of this supermolecule is made of the bar-shaped complex that the cyclodextrin inclusion compound polymer segment forms;
Described can be polypropylene oxide, polyethylene glycol oxide, polymethyl vinyl ether, polylactic acid, polycaprolactone or polysiloxanes with the polymer segment of cyclodextrin generation clathration;
Described hydrophilic segment is polyethylene glycol oxide or polyacrylic acid.
2. water solublity supermolecule capsule according to claim 1, it is characterized in that: the mol ratio of the propylene oxide in the described block copolymer segments, ethylene oxide, methyl vinyl ether, lactic acid, caprolactone or siloxanyl monomers unit and cyclodextrin molecular is 1: 1～10: 1, the ethylene oxide of sub-thread hydrophilic segment or acrylic acid units and can be 2.5～5.0 with the unitary mol ratio of polymer segment of cyclodextrin generation clathration.
3. water solublity supermolecule capsule according to claim 1 is characterized in that: the diameter range 60～250nm of described spherical vesicles; The diameter of hollow tubular structure and length range are respectively 60～250nm and 250nm～5 μ m.
4. water solublity supermolecule capsule according to claim 1 and 2 is characterized in that: the molecular weight of the polymer segment of described and cyclodextrin generation clathration is between 400～4000.
5. water solublity supermolecule capsule according to claim 4 is characterized in that: the molecular weight of the polymer segment of described and cyclodextrin generation clathration is between 800～3000.
6. water solublity supermolecule capsule according to claim 1 and 2 is characterized in that: described cyclodextrin be α-, β-or gamma-cyclodextrin.
7. one kind according to the capsular preparation method of each described water solublity supermolecule of claim 1～6, it is characterized in that: with the aqueous solution of the aqueous solution and the block copolymer of cyclodextrin, obtain water solublity supermolecule capsule in container; Wherein the concentration of block copolymer is 0.01～0.50mM in the mixed liquor, and the concentration of cyclodextrin solution is 0.03～24mM; Described block copolymer wherein one section be can with the polymer segment of cyclodextrin generation clathration, another the section or two sections be hydrophilic segment, for triblock copolymer then hydrophilic segment be positioned at two ends;
Described can be polypropylene oxide, polyethylene glycol oxide, polymethyl vinyl ether, polylactic acid, polycaprolactone or polysiloxanes with the polymer segment of cyclodextrin generation clathration;
Described hydrophilic segment is polyethylene glycol oxide or polyacrylic acid.
8. method according to claim 7, it is characterized in that: the mol ratio of the propylene oxide in the described block copolymer segments, ethylene oxide, methyl vinyl ether, lactic acid, caprolactone or siloxanyl monomers unit and cyclodextrin molecular is 1: 1～10: 1, and the unitary mol ratio of ethylene oxide or acrylic acid units and polymer segment is 2.5～5.0 in the sub-thread hydrophilic segment.
9. water solublity supermolecule capsule according to claim 7 is characterized in that: the molecular weight of the polymer segment of described and cyclodextrin generation clathration is between 400～4000.
10. one kind according to the capsular purposes of each described water solublity supermolecule of claim 1～6, it is characterized in that: described water solublity supermolecule capsule is used for containing, load, the sustained release material of biology, medical science, medicine, health, cosmetics, food, daily or field of fine chemical.
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| CN 200410009473 CN1736367A (en) | 2004-08-20 | 2004-08-20 | Water solublity supermolecule capsule and its production and use |
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|---|---|---|---|
| CN 200410009473 CN1736367A (en) | 2004-08-20 | 2004-08-20 | Water solublity supermolecule capsule and its production and use |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101298504B (en) * | 2008-07-02 | 2011-01-05 | 武汉大学 | Supermolecule polymer micelle and preparation thereof |
| CN101314644B (en) * | 2008-07-22 | 2011-09-21 | 四川大学 | Host-guest complex type supermolecule hollow microsphere, preparation and application thereof |
| CN102911326A (en) * | 2012-07-05 | 2013-02-06 | 苏州大学 | Acid-sensitive degradable polymer vesicle and preparation and application thereof |
| CN103827178A (en) * | 2011-07-26 | 2014-05-28 | 剑桥实业有限公司 | Supramolecular capsules |
| CN104968712A (en) * | 2013-01-30 | 2015-10-07 | 剑桥实业有限公司 | Nested supramolecular capsules |
| CN106511276A (en) * | 2016-12-13 | 2017-03-22 | 云南师范大学 | Water-soluble coagulant drug vitamin k2 solid-state complex and preparation method thereof |
| CN110876378A (en) * | 2019-12-11 | 2020-03-13 | 利民化学有限责任公司 | Intelligent microcapsule suspending agent and preparation method thereof |
-
2004
- 2004-08-20 CN CN 200410009473 patent/CN1736367A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101298504B (en) * | 2008-07-02 | 2011-01-05 | 武汉大学 | Supermolecule polymer micelle and preparation thereof |
| CN101314644B (en) * | 2008-07-22 | 2011-09-21 | 四川大学 | Host-guest complex type supermolecule hollow microsphere, preparation and application thereof |
| CN103827178A (en) * | 2011-07-26 | 2014-05-28 | 剑桥实业有限公司 | Supramolecular capsules |
| CN103827178B (en) * | 2011-07-26 | 2016-10-05 | 剑桥实业有限公司 | Supermolecule capsule |
| CN102911326A (en) * | 2012-07-05 | 2013-02-06 | 苏州大学 | Acid-sensitive degradable polymer vesicle and preparation and application thereof |
| CN102911326B (en) * | 2012-07-05 | 2014-12-10 | 苏州大学 | Acid-sensitive degradable polymer vesicle and preparation and application thereof |
| CN104968712A (en) * | 2013-01-30 | 2015-10-07 | 剑桥实业有限公司 | Nested supramolecular capsules |
| CN104968712B (en) * | 2013-01-30 | 2017-06-09 | 剑桥实业有限公司 | Nested supermolecule capsule |
| US10189955B2 (en) | 2013-01-30 | 2019-01-29 | Cambridge Enterprise Limited | Nested supramolecular capsules |
| CN106511276A (en) * | 2016-12-13 | 2017-03-22 | 云南师范大学 | Water-soluble coagulant drug vitamin k2 solid-state complex and preparation method thereof |
| CN110876378A (en) * | 2019-12-11 | 2020-03-13 | 利民化学有限责任公司 | Intelligent microcapsule suspending agent and preparation method thereof |
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