CN109172536A - The preparation of hollow capsules with Dagwood structure and obtained hollow capsules - Google Patents
The preparation of hollow capsules with Dagwood structure and obtained hollow capsules Download PDFInfo
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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Abstract
The invention discloses a kind of preparation of hollow capsules with Dagwood structure and obtained hollow capsules, wherein, certain density chitosan oligosaccharide is added dropwise in certain density high molecular weight polyelectrolyte polysaccharide/graphene oxide mixed solution, hollow capsules can be formed under oscillation；The preparation method is simple, it is at low cost, be suitable for large-scale production, meanwhile, obtained hollow capsules have unique sandwich structure, controllability, good compression strength, medicament slow release performance, absorption property.
Description
Technical field
The present invention relates to field of capsules, and in particular to hollow capsules particularly are related to having in Dagwood structure
The preparation of capsulae vacuus and obtained hollow capsules.
Background technique
Hollow capsules have been widely used for the industrial circles such as food, drug, cosmetics, bioengineering and organizational project,
With the continuous improvement to product structure and performance indicator requirement, in the prior art, the emulsion method and template legal system generallyd use
Standby technology, more or less encounters different problems or technical bottleneck.
For example, template in the prior art, use using particle as template, using layer-by-layer in template
Particle over-assemble polymer ultra-thin film, after removing removing template, structure and performance are controllable, easily assign various unique functions to obtain, and accord with
It closes end product and uses the microcapsules needed.
But since template material is generally CaCO3, gold, silicon or other inorganic material, template fabrication is complicated, at
This height is restricted by factors such as shape of template, sizes, can not carry out Flexible Production.
The problem of emulsion method and deficiency are mainly manifested in, first is that, due to preparation process to be added exhibiting high surface activating agent or
Inevitably, more or less residual toxic chemicals exist certain congenital for other chemical stabilizers, capsule product
Property it is insufficient.Second is that the relatively high complex treatment process of production cost.In addition, side reaction has capsule property in synthesis process
It significantly affects.
Summary of the invention
In order to overcome the above problem, present inventor has performed sharp study, the middle hungry area of a kind of simple process, environmental protection is provided
The preparation method of capsule, preparation cost is low and is suitable for large-scale production；Meanwhile obtained hollow capsules have number of plies controllability,
Good compression strength, medicament slow release performance, absorption property, and there is unique sandwich structure, while containing there are many groups
Point.
One aspect of the present invention is to provide a kind of preparation method of hollow capsules with Dagwood structure, specific body
Present the following aspects:
(1) a kind of preparation method of the hollow capsules with Dagwood structure, wherein the method includes following steps
It is rapid:
Chitosan oligosaccharide is added to the water by step 1, obtains solution A；
High molecular weight polyelectrolyte polysaccharide is added to the water by step 2, obtains solution B；
Step 3 adds graphene oxide into water, and ultrasonic disperse obtains solution C；
Solution B is added in solution C by step 4, is stirred, is obtained solution D；
Solution A is added dropwise in solution D step 5, then vibrates, and obtains the middle hungry area of the sandwich unique texture
Capsule.
(2) preparation method according to above-mentioned (1), wherein in step 1, the molecular weight of the chitosan oligosaccharide is 2000
~10000Da, preferably 2000~6000Da.
(3) preparation method according to above-mentioned (1) or (2), wherein in step 2,
The molecular weight of the high molecular weight polyelectrolyte polysaccharide be 100000~800000Da, preferably 300000~
700000Da, more preferably 400000~600000Da；And/or
The high molecular weight polyelectrolyte polysaccharide is selected from sodium alginate, xanthan gum or carragheen.
(4) preparation method according to one of above-mentioned (1) to (3), wherein in step 1, in the solution A, shell
The mass percent concentration of oligosaccharides is 5~60%, preferably 10~40%, more preferably 20~40%, such as 30~40%；
And/or
In step 2, in the solution B, the mass percent concentration of high molecular weight polyelectrolyte polysaccharide is 0.5~
5%, preferably 1~3%, such as 1%；And/or
In step 3, in the solution C, the mass percent concentration of graphene oxide is 1~3%, such as 1%；
(5) preparation method according to one of above-mentioned (1) to (4), wherein in step 4,
By volume (0.8~1.5): (such as volume ratio is 1:1) is added in solution C in solution B by 1, obtains solution D；
(6) preparation method according to one of above-mentioned (1) to (5), wherein in steps of 5,
1:(10~500 by volume) solution A is added in solution D, preferred 1:(10~200), more preferable 1:50；With/
Or
The oscillation carries out 1~for 24 hours, preferably 2~8h of progress, more preferably 4~6h of progress.
(7) a kind of hollow capsules are obtained preferably by preparation method described in one of above-mentioned (1) to (6), more preferably described
The diameter of hollow capsules is 500 μm~10cm.
(8) hollow capsules according to above-mentioned (7), wherein the cyst wall of the hollow capsules is in Dagwood structure,
Preferably, the structure of adjacent layer is different, and every alternating floor structure is identical.
Detailed description of the invention
Fig. 1 show chitosan oligosaccharide obtained by embodiment 1 (sodium alginate/graphene oxide) capsule electron micrograph it
One (mainly showing the cross section of capsule-wall)；
Fig. 2 is two of chitosan oligosaccharide (sodium alginate/graphene oxide) capsule electron micrograph obtained by embodiment 1
(cross section of the adjacent layer of capsule-wall is mainly shown)；
Fig. 3 is three of chitosan oligosaccharide (sodium alginate/graphene oxide) capsule electron micrograph obtained by comparative example 1
(cross section of the adjacent layer of capsule-wall is mainly shown).
Specific embodiment
Below by embodiment and experimental example, the present invention is described in more detail.Illustrated by these, spy of the invention
Point and advantage will become more apparent from clear.The present invention provides a kind of preparation side of hollow capsules with Dagwood structure
Method the described method comprises the following steps:
Chitosan oligosaccharide is added to the water by step 1, obtains solution A；
High molecular weight polysaccharide is added to the water by step 2, obtains solution B；
Step 3 adds graphene oxide into water, and ultrasonic disperse obtains solution C；
Solution B is added in solution C by step 4, is stirred, is obtained solution D；
Solution A is added dropwise in solution D step 5, then vibrates, and obtains the hollow capsules with sandwich structure.
Wherein, it (is respectively provided with opposite using chitosan oligosaccharide and high molecular weight polyelectrolyte polysaccharide/graphene oxide mixture
Positive and negative charge) between electrostatic interaction so that three be complexed, formed complexing film.
A kind of preferred embodiment according to the present invention, in step 1, the molecular weight of the chitosan oligosaccharide is 2000~
10000Da。
In further preferred embodiment, in step 1, the molecular weight of the chitosan oligosaccharide is 2000~6000Da.
Wherein, if the number-average molecular weight of chitosan oligosaccharide is less than 2000Da, when complex reaction occurs with sodium alginate, due to
The binding site of chitosan oligosaccharide and sodium alginate or graphene oxide is few, tangles not enough, is not enough to that film forming is supported especially to have
The film of certain curvature will finally form complex precipitate particle.Meanwhile if the number-average molecular weight of the chitosan oligosaccharide is greater than
When 10000Da, chitosan oligosaccharide occurs Electrostatic complexation with sodium alginate or graphene oxide and reacts the complexing layer close structure to be formed,
Chitosan oligosaccharide cannot pass through, and diffusion process is prevented, and cannot finally form hollow structure.
A kind of preferred embodiment according to the present invention, in step 2, point of the high molecular weight polyelectrolyte polysaccharide
Son amount is 100000~800000Da.
In further preferred embodiment, in step 2, the molecular weight of the high molecular weight polyelectrolyte polysaccharide is
300000~700000Da.
In embodiment still more preferably, in step 2, the high molecular weight polyelectrolyte polysaccharide is
400000~600000Da.
Wherein, if the molecular weight of high molecular weight polyelectrolyte polysaccharide is complexed more than after above range with chitosan oligosaccharide
Reaction is formed by polyelectrolyte membrane will be excessively fine and close, this, which would potentially result in chitosan oligosaccharide, cannot pass through polyelectrolyte membrane, from
And the further diffusion of chitosan oligosaccharide is hindered, it not can be carried out the process that complexing-diffusion-is complexed again, finally, one layer of cause will be can only obtain
The film of close structure.
A kind of preferred embodiment according to the present invention, the high molecular weight polyelectrolyte polysaccharide are selected from sodium alginate, Huang
Virgin rubber or carragheen.
A kind of preferred embodiment according to the present invention, in step 1, in the solution A, the quality percentage of chitosan oligosaccharide
Specific concentration is 5~60%.
In further preferred embodiment, in step 1, in the solution A, the mass percent of chitosan oligosaccharide is dense
Degree is 10~40%.
In embodiment still more preferably, in step 1, in the solution A, the mass percent of chitosan oligosaccharide
Concentration is 20~40%, such as 30~40%.A kind of preferred embodiment according to the present invention, in the solution B, macromolecule
The mass percent concentration for measuring polyelectrolyte polysaccharide is 0.5~5%.
In further preferred embodiment, in the solution B, the quality percentage of high molecular weight polyelectrolyte polysaccharide
Specific concentration is 1~3%, such as 1%.
A kind of preferred embodiment according to the present invention, in the solution C, the mass percent concentration of graphene oxide
It is 0.5~5%%.
In further preferred embodiment, in the solution C, the mass percent concentration of graphene oxide is 1
~3%, such as 1%.
Wherein, control chitosan oligosaccharide at higher concentrations, and high molecular weight polyelectrolyte polysaccharide and graphene oxide control
At relatively low concentration, in this way, the two is since ion concentration difference forms osmotic pressure, chitosan oligosaccharide is to sodium alginate under osmotic pressure
It spreads with graphene oxide, is then combined using electrostatic interaction, form film.
Specifically, different with the diffusion rate of graphene oxide due to high molecular weight polyelectrolyte polysaccharide, with chitosan oligosaccharide knot
The rate of conjunction is different, and chitosan oligosaccharide first reacts that form chitosan oligosaccharide/high molecular weight polyelectrolyte more with high molecular weight polyelectrolyte polysaccharide
Sugar complexing film, continues diffusion and is complexed to form new complexing film with graphene oxide.Under the driving effect of osmotic pressure, solution is spontaneous
Ground constantly repeats the process that above-mentioned complexing-diffusion-is complexed again, i.e., controllable to obtain the different capsules with unique sandwich structure
The capsule of parietal layer number.
A kind of preferred embodiment according to the present invention, in step 4, by volume (0.8~1.5): 1 adds solution B
Enter in solution C, obtains solution D.
In further preferred embodiment, in step 4, solution B is added in solution C 1:1 by volume, obtains
Solution D.
A kind of preferred embodiment according to the present invention, in steps of 5,1:(10~500 by volume) solution A is added
In solution D.
In further preferred embodiment, in step 3,1:(10~200 by volume) solution is added in solution A
In D.
In embodiment still more preferably, in step 3,1:(10~100 by volume) solution A is added it is molten
In liquid D, such as 1:50.
A kind of preferred embodiment according to the present invention, in steps of 5, the oscillation carries out 1~for 24 hours.
In further preferred embodiment, in steps of 5, the oscillation carries out 2~8h.
In embodiment still more preferably, in steps of 5, the oscillation carries out 4~6h.
Wherein, the purpose of oscillation is to advantageously promote molecule diffusion, prevents capsule adherent.
Another aspect of the present invention provides the hollow capsules that preparation method described in a kind of first aspect present invention obtains.
A kind of preferred embodiment according to the present invention, the hollow capsules be hollow structure, the hollow capsules it is straight
Diameter is 500 μm~10cm.
In further preferred embodiment, the cyst wall of the hollow capsules is sandwich structure, it is preferable that adjacent layer
Difference, every alternating floor structure are identical.
Beneficial effect possessed by the present invention includes:
(1) preparation method of the present invention is simple, and the preparation of capsule, and preparation process can be completed under room temperature, normal pressure
Parameter is easily controllable, production efficiency with higher；
(2) capsule with special Dagwood structure can be made using preparation method of the present invention.
(3) every layer of capsule obtained of the invention is closed sphere, and therefore, obtained capsule product is particularly suitable for making
For pharmaceutical carrier；
(4) preparation method obtains through the invention capsule compression strength with higher, good absorption property,
Suitable for the sewage treatment containing chemical components such as finish, organic solvent or organic dyestuff.
Embodiment
The present invention is further described below by way of specific embodiment.But these embodiments are only exemplary, not
Any restrictions are constituted to protection scope of the present invention.
Embodiment 1
40:1:1 in mass ratio weighs the chitosan oligosaccharide that molecular weight is 2000Da, the alginic acid that molecular weight is 300,000 Da respectively
Sodium and thickness is about 1.1nm, 1~6 μm of graphene oxide of size, spare；
Taken chitosan oligosaccharide is added into deionized water dissolving, obtains the solution A that mass percent concentration is 40%；
Taken sodium alginate is added in deionized water and is dissolved, the solution B that mass percent concentration is 1% is configured to；
Taken graphene oxide is added in deionized water and is dissolved, the solution C that mass percent concentration is 1% is configured to；
Solution B is added in solution C in the ratio of 1:1, is stirred, solution D is obtained；
Above-mentioned solution A is immersed in solution D by 1:50 dropwise by volume under oscillation, sustained oscillation for 24 hours after, obtain glue
Capsule.
Electron microscopy is carried out to obtained capsule, as a result shown in 1~2, it is known that, obtained capsule is special
Sandwich structure, adjacent layer structure is different, and one layer is cyst wall close structure, and one layer is open structure.
Embodiment 2
Repeat the process of embodiment 1, difference is: the mass percent concentration of solution A is 20%, the quality hundred of solution B
Dividing specific concentration is 3%, and the mass percent concentration of solution C is 3%.
Electron microscopy is carried out to obtained hollow capsules, learning capsule-wall equally has special sandwich knot
Structure.
Embodiment 3
Repeat the process of embodiment 1, difference is: (1) molecular weight of the chitosan oligosaccharide is 6000Da, (2) described seaweed
The molecular weight of sour sodium is 700,000 Da, and (3) solution B is added in solution C 0.8:1 by volume.
Electron microscopy is carried out to obtained hollow capsules, learning capsule-wall equally has special sandwich knot
Structure.
Embodiment 4
40:1:1 in mass ratio weighs the chitosan oligosaccharide that molecular weight is 2000Da, the xanthan gum that molecular weight is 300,000 Da respectively
And thickness is about 1.1nm, 1~6 μm of graphene oxide of size, it is spare；
Taken chitosan oligosaccharide is added into deionized water dissolving, obtains the solution A that mass percent concentration is 40%；
Taken xanthan gum is added in deionized water and is dissolved, the solution B that mass percent concentration is 1% is configured to；
Taken graphene oxide is added in deionized water and is dissolved, the solution C that mass percent concentration is 1% is configured to；
Solution B is added in solution C in the ratio of 1:1, is stirred, solution D is obtained；
Above-mentioned solution A is immersed in solution D by 1:50 dropwise by volume under oscillation, sustained oscillation for 24 hours after, obtain glue
Capsule.
Electron microscopy is carried out to obtained capsule, it is known that, obtained capsule is special sandwich structure, phase
Adjacent bed structure is different, and one layer is cyst wall close structure, and one layer is open structure.
Embodiment 5
40:1:1 in mass ratio weighs the chitosan oligosaccharide that molecular weight is 2000Da, the carragheen that molecular weight is 300,000 Da respectively
And thickness is about 1.1nm, 1~6 μm of graphene oxide of size, it is spare；
Taken chitosan oligosaccharide is added into deionized water dissolving, obtains the solution A that mass percent concentration is 40%；
Taken carragheen is added in deionized water and is dissolved, the solution B that mass percent concentration is 1% is configured to；
Taken graphene oxide is added in deionized water and is dissolved, the solution C that mass percent concentration is 1% is configured to；
Solution B is added in solution C in the ratio of 1:1, is stirred, solution D is obtained；
Above-mentioned solution A is immersed in solution D by 1:50 dropwise by volume under oscillation, sustained oscillation for 24 hours after, obtain glue
Capsule.
Electron microscopy is carried out to obtained capsule, it is known that, obtained capsule is special sandwich structure, phase
Adjacent bed structure is different, and one layer is cyst wall close structure, and one layer is open structure.
Comparative example
Comparative example 1
The process of embodiment 1 is repeated, difference is: the quality of sodium alginate and graphene oxide mixed solution in solution D
Percent concentration is very low, and respectively 0.1%.
As a result, it has been found that (as shown in Figure 3) will form when sodium alginate and very low graphene oxide mixed solution concentration
Precipitating.Since the binding site between chitosan oligosaccharide and sodium alginate and sodium alginate and graphene oxide mixed solution is insufficient, only
Precipitating is formed, support membrane is not enough to, especially forms the film of certain curvature.
Comparative example 2
The process of embodiment 1 is repeated, difference is: solution A being directly added into solution D and is mixed, rather than is added dropwise.
It was found that the hollow capsules cannot be formed at all, but the whole state in similar " sticky ".
Comparative example 3
The process of embodiment 1 is repeated, difference is: 40:1.32:0.66 in mass ratio, weighing molecular weight respectively is
The chitosan oligosaccharide of 2000Da, the sodium alginate that molecular weight is 300,000 Da and thickness are about 1.1nm, 1~6 μm of oxidation stone of size
Black alkene, it is spare；
Taken chitosan oligosaccharide is added into deionized water dissolving, obtains the solution A that mass percent concentration is 40%；
Taken sodium alginate is added in deionized water and is dissolved, the solution B that mass percent concentration is 1.32% is configured to；
Taken graphene oxide is added in deionized water and is dissolved, the solution that mass percent concentration is 0.66% is configured to
C；
Solution B is added in solution C in the ratio of 1:1, is stirred, solution D is obtained；
It was found that the sandwich structure that the hollow capsules cyst wall formed is not special at all, whole cyst wall presents loose
Porous form.The reason is that by the concentration for changing sodium alginate and graphene oxide, so that the diffusion coefficient of the two is changed,
So finally obtained structure is also changed.
Preferred embodiment and exemplary example is combined to describe the invention in detail above.But need to state
It is that these specific embodiments are only not constitute any limit to protection scope of the present invention to illustrative explanations of the invention
System.Without departing from spirit of that invention and protection scope, the technology of the present invention content and embodiments thereof can be carried out
Various improvement, equivalencing or modification, these fall within the protection scope of the present invention.Protection scope of the present invention is with appended power
Subject to benefit requires.
Claims (8)
1. a kind of preparation method of the hollow capsules with Dagwood structure, which is characterized in that the method includes following
Step:
Chitosan oligosaccharide is added to the water by step 1, obtains solution A；
High molecular weight polyelectrolyte polysaccharide is added to the water by step 2, obtains solution B；
Step 3 adds graphene oxide into water, and ultrasonic disperse obtains solution C；
Solution B is added in solution C by step 4, is stirred, is obtained solution D；
Solution A is added dropwise in solution D step 5, then vibrates, and obtains the hollow capsules with sandwich structure.
2. preparation method according to claim 1, which is characterized in that in step 1,
The molecular weight of the chitosan oligosaccharide is 2000~10000Da, preferably 2000~6000Da.
3. preparation method according to claim 1 or 2, which is characterized in that in step 2,
The molecular weight of the high molecular weight polyelectrolyte polysaccharide be 100000~800000Da, preferably 300000~
700000Da, more preferably 400000~600000Da；And/or
The high molecular weight polyelectrolyte polysaccharide is selected from sodium alginate, xanthan gum or carragheen.
4. according to claim 1 to preparation method described in one of 3, which is characterized in that
In the solution A described in step 1, the mass percent concentration of chitosan oligosaccharide is 5~60%, preferably 10~40%, more preferably
It is 20~40%, such as 30~40%；And/or
In the solution B described in step 2, the mass percent concentration of high molecular weight polyelectrolyte polysaccharide is 0.5~5%, preferably 1
~3%, such as 1%；And/or in the solution C described in step 3, the mass percent concentration of graphene oxide is 1~3%, such as
1%.
5. according to claim 1 to preparation method described in one of 4, which is characterized in that in step 4,
By volume (0.8~1.5): (such as volume ratio is 1:1) is added in solution C in solution B by 1, obtains solution D.
6. preparation method according to one of claims 1 to 5, which is characterized in that in steps of 5,
1:(10~500 by volume) solution A is added in solution D, preferred 1:(10~200), more preferable 1:50；And/or
The oscillation carries out 1~for 24 hours, preferably 2~8h of progress, more preferably 4~6h of progress.
7. a kind of hollow capsules are obtained preferably by preparation method described in one of claim 1 to 6, more preferably described hollow
The diameter of capsule is 500 μm~10cm.
8. hollow capsules according to claim 7, wherein the cyst wall of the hollow capsules is in Dagwood structure, excellent
The structure of selection of land, adjacent layer is different, and every alternating floor structure is identical.
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Cited By (1)
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| WO2020221361A1 (en) * | 2019-04-30 | 2020-11-05 | 青岛大学 | Preparation method for graphene oxide fiber, and fiber obtained thereby |
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