CN103113626B - A kind of oversized hole polysaccharide microsphere and preparation method thereof - Google Patents
A kind of oversized hole polysaccharide microsphere and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of oversized hole polysaccharide microsphere product and preparation method thereof.The median size of microballoon is 1-500 μm, and mean pore size is controlled within the scope of 90-800nm.This microballoon is the water soluble surfactant active by adding high-content in aqueous phase, by the Aqueous dispersions containing tensio-active agent in oil phase, the oil suction swelling action of the micelle formed by tensio-active agent, obtains large duct, prepares oversized hole microballoon after crosslinking curing.This product can be used as separation and purification medium, fixed enzyme vector, support of the catalyst or high-efficiency adsorbent, is especially suitable for use as the separating medium of biomacromolecule.
Description
Technical field
The present invention relates to biological chemical field, be specifically related to a kind of oversized hole polysaccharide microsphere particularly oversized hole Konjac Glucomannan Granules, oversized hole dextran microspheres or oversized hole Rhizoma amorphophalli glucomannan-dextran microspheres and preparation method thereof.
Background technology
In recent years, along with developing rapidly of Life Sci-Tech, a large amount of biological products are introduced to the market, and biological products comprise, and the needs such as protein, polypeptide, nucleic acid carry out analyzing, are separated, purifying, just can reach specification of quality.But, because the aperture of conventional polysaccharide microsphere is less, for conventional agarose medium, its aperture is greatly about 20-30nm, make biomacromolecule with diffusion way by medium, thus can only occur that rate of mass transfer is slow, cause the problems such as long, the easy inactivation of disengaging time.Therefore, prepare the polysaccharide microsphere with oversized hole structure and receive very big concern.
Rhizoma amorphophalli glucomannan (KGM) is a kind of linear macromolecule polysaccharide, is to be made up of the glucose of β-Isosorbide-5-Nitrae-glycosidic link connection and seminose.Rhizoma amorphophalli glucomannan has very high viscosity, good thickening property, gelling, wetting ability, film-forming properties, easily gelatinization, and Rhizoma amorphophalli glucomannan good biocompatibility, can not with the characteristics such as biomacromolecule generation non-specific adsorption, may be used for further derivative activation containing a large amount of hydroxyls, make it, as novel biomaterial, there is good application prospect.
At present, the application of Rhizoma amorphophalli glucomannan in food is comparatively extensive, but does not obtain enough attention as a kind of novel biomaterial.If particularly Rhizoma amorphophalli glucomannan is prepared into microspheric material can be used as bio-chemistry separation medium, fixed enzyme vector and medicine controlled releasing aspect, effectively can promote the value added of Rhizoma amorphophalli glucomannan, but the Measures compare at present Rhizoma amorphophalli glucomannan being prepared into microspheric material is few, mainly contains following 2 kinds of methods.
(1) people such as Xiao Xu, Wang Jiaxing is by water-soluble by konjac glucomanna, with water-fast organic compound for dispersion medium, dispersion agent is added in dispersion medium, by konjac glucomanna aqueous dispersion in dispersion medium, obtain water-in-oil-type suspension, then evaporate the water in drop, obtain pearl konjac glucomanna particle, again through crosslinked, finally obtain pearl and be cross-linked portuguese gansu polyose gel.Microballoon prepared by this method is that gel-type structure only contains the chemical hole formed by chemically crosslinked, and duct is little, and the separation making molecular weight be greater than the biomacromolecule of 100,000 is restricted.Such as CN102492178A discloses a kind of preparation method of Konjac Glucomannan Granules of size uniformity, comprising: first Rhizoma amorphophalli glucomannan degraded is obtained konjak portuguese gansu polyose sugar aqueous solution as aqueous phase (W); Be dissolved with oil-soluble emulsifier and with the immiscible solution of water as oil phase (O); Aqueous phase is pressed into oil phase and obtains w/o type emulsion; In emulsion, drip linking agent, stir and react; After crosslinked balling-up, through washing, collect, the Konjac Glucomannan Granules of size uniformity can be obtained.
(2) Wang Jiaxing, Ge Jiali etc. propose to have prepared a kind of Rhizoma amorphophalli glucomannan macroporous microsphere by the method adding pore-creating agent in konjak portuguese gansu polyose sugar aqueous solution further, by the macroporous type konjak portuguese gansu polyose gel microsphere regulating the consumption of pore-creating agent to prepare different pore volume, the preparation method that this invention provides adopts balling-up, crosslinked single step reaction, shorten the production cycle, simplify balling technique step, only 5-12h and simple reaction device can be produced; And the macroporous type konjak portuguese gansu polyose gel microsphere that provides of this invention more can be widely used in the separation and purification of protein.But this patent has selected the method for perforating agent drilling, the consumption of perforating agent is 2%-20%, consumption due to perforating agent is difficult to improve, therefore, although the pearl body aperture obtained can reach the level (20-30nm) close with agarose, still there is the problems such as mass transfer is slow, velocity of separation is low in the separation and purification for macromolecular biomacromolecule.Such as CN101113180A discloses a kind of preparation method of konjak portuguese gansu polyose gel microsphere, comprising: konjac glucomanna Rhizoma amorphophalli glucomannan being degraded into small molecules chain, and impurity screening obtains konjak portuguese gansu polyose sugar aqueous solution; The konjak portuguese gansu polyose sugar aqueous solution of gained is joined at 50 DEG C ~ 95 DEG C temperature in the oily matter containing oil phase emulsifier, drip linking agent simultaneously, while stirring balling-up, crosslinking reaction occurs; One step is cross-linked into the gel micro-ball that ball is formed, and through washing, collects, can obtain konjak portuguese gansu polyose gel microsphere.Also can add pore-creating agent in konjak portuguese gansu polyose sugar aqueous solution, to prepare macroporosity konjak portuguese gansu polyose gel microsphere.
Dextran is also a kind of linear polysaccharide molecule, and the gel micro-ball prepared by dextran is widely used in biochemical separation processes, and because duct is less, dextrane gel is particularly suitable as separation of small molecuies medium and desalination medium.
In order to expand the range of application of Konjac Glucomannan Granules and dextran microspheres, and effectively solve the little mass transfer problem caused in duct, we propose to adopt micelle swelling method to prepare the method for oversized hole polysaccharide microsphere, prepare the larger Konjac Glucomannan Granules in aperture, dextran microspheres or Rhizoma amorphophalli glucomannan-dextran microspheres, can effectively solve the problems such as mass-transfer efficiency is low, velocity of separation is slow, improve the separation and purification effect of biomacromolecule.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of oversized hole polysaccharide microsphere, it is characterized in that, the mean pore size of described oversized hole polysaccharide microsphere is 90 ~ 800nm, and described polysaccharide is that Rhizoma amorphophalli glucomannan is degraded the small molecules konjac glucomanna and/or dextran that obtain, the aqueous solution of described small molecules konjac glucomanna has good mobility, its weight-average molecular weight is 1,000-500,000, be preferably 5000-100,000.
Preferably, the median size of described oversized hole polysaccharide microsphere is 1 ~ 500 μm, is particularly preferably 50 ~ 300 μm.
Preferably, the mean pore size of described oversized hole polysaccharide microsphere is 100 ~ 300nm.
Rhizoma amorphophalli glucomannan is a kind of natural polysaccharide macro-molecular, and molecular weight is 80 ~ about 1,000,000, and under normal circumstances, the konjac glucomanna of 1% is dissolved in and is namely formed gelatin in water, without any mobility, can not disperse balling-up in oil phase.Therefore, need the konjac glucomanna molecule of macromolecule to degrade, small molecules konjak portuguese gansu polyose sugar aqueous solution that obtain molecular weight, that be easy to flowing and dispersion.The method of usual degraded macromolecular polysaccharide mainly contains irradiation technique (such as adopting radioactive source Co 60 gamma-radiation), acidolysis and enzymolysis three kinds of methods.
Preferably, of the present inventionly acid hydrolyzation is degraded to, preferably, the acid used in described acidolysis is organic acid and/or mineral acid, more preferably hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, carbonic acid, 1 kind in propionic acid or acetic acid or the combination of at least 2 kinds, the typical but non-limiting example of described combination comprises: the combination of hydrochloric acid and sulfuric acid, the combination of nitric acid and phosphoric acid, oxalic acid, the combination of carbonic acid and propionic acid, hydrochloric acid, carbonic acid, the combination of propionic acid and acetic acid, sulfuric acid, nitric acid, phosphoric acid, the combination of oxalic acid and carbonic acid, nitric acid, phosphoric acid, oxalic acid, carbonic acid, the combination etc. of propionic acid and acetic acid, be particularly preferably hydrochloric acid, nitric acid, 1 kind in propionic acid or acetic acid or the combination of at least 2 kinds.Described acid hydrolyzation comprises: be dissolved in by a certain amount of konjaku powder in the acid solution of a certain amount of suitable concn, abundant stirring is formed gelatin, then autoclave high temperature degradation is put into, again degradation product is taken out and be down to room temperature, add alkali lye and dissolve degradation product, abundant stirring makes gelatin material all dissolve, and then impurity screening obtains yellow clarified liq and konjak portuguese gansu polyose sugar soln.Described acid hydrolyzation is affiliated field known technology, and one of ordinary skill in the art can select concrete acidolysis condition as required.
Oversized hole polysaccharide microsphere of the present invention can be used as separation and purification medium, fixed enzyme vector, support of the catalyst or high-efficiency adsorbent, is especially suitable for use as the separating medium of biomacromolecule.
An object of the present invention is the preparation method providing a kind of described oversized hole polysaccharide microsphere.For the shortcoming that prior art exists, propose to adopt micelle swelling method to prepare oversized hole polysaccharide microsphere.In aqueous phase, add the water soluble surfactant active of high level, tensio-active agent forms a large amount of micelles in aqueous phase.After Aqueous dispersions to oil phase, micelle is spontaneous to be sucked oil phase in its polarity kernel, the duct that swelling formation is large, and then adds cross-linking agents, can obtain oversized hole KGM microballoon.
The preparation method of described oversized hole polysaccharide microsphere comprises: the aqueous phase containing water soluble surfactant active and polysaccharide and the oil phase immiscible with water are mixed, add linking agent, obtain oversized hole polysaccharide microsphere, wherein said polysaccharide is that Rhizoma amorphophalli glucomannan is degraded the small molecules konjac glucomanna and/or dextran that obtain.
Preferably, described oil phase contains oil-soluble emulsifier.
Preferably, described method comprises:
(1) polysaccharide and water soluble surfactant active soluble in water, be mixed with aqueous phase (W); Oil-soluble emulsifier will be dissolved with and with the immiscible solution of water as oil phase (O); Wherein said polysaccharide is that Rhizoma amorphophalli glucomannan is degraded the small molecules konjac glucomanna and/or dextran that obtain;
(2) mix oil phase and aqueous phase, obtain w/o type emulsion;
(3) add linking agent in the emulsion obtained in step (2), be cross-linked;
(4), after crosslinked balling-up, removal of impurities, can obtain oversized hole polysaccharide microsphere.
Preferably, step (3) described linking agent is dropping to the feed postition of described emulsion.
Preferably, described being cross-linked of step (3) is under agitation carried out.
Preferably, described small molecules konjac glucomanna adopts irradiation method, acid hydrolyzation and/or enzymolysis process to degrade by Rhizoma amorphophalli glucomannan and obtains, and particularly preferably adopts acidolysis to obtain, preferably, the acid that described acidolysis uses is organic acid and/or mineral acid, more preferably hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, carbonic acid, 1 kind in propionic acid or acetic acid or the combination of at least 2 kinds, the typical but non-limiting example of described combination comprises: the combination of hydrochloric acid and sulfuric acid, the combination of nitric acid and phosphoric acid, oxalic acid, the combination of carbonic acid and propionic acid, hydrochloric acid, carbonic acid, the combination of propionic acid and acetic acid, sulfuric acid, nitric acid, phosphoric acid, the combination of oxalic acid and carbonic acid, nitric acid, phosphoric acid, oxalic acid, carbonic acid, the combination etc. of propionic acid and acetic acid, be particularly preferably hydrochloric acid, nitric acid, 1 kind in propionic acid or acetic acid or the combination of at least 2 kinds.Described acid hydrolyzation comprises: be dissolved in by a certain amount of konjaku powder in the acid solution of a certain amount of suitable concn, abundant stirring is formed gelatin, then autoclave high temperature degradation is put into, again degradation product is taken out and be down to room temperature, add alkali lye and dissolve degradation product, abundant stirring makes gelatin material all dissolve, and then impurity screening obtains yellow clarified liq and konjak portuguese gansu polyose sugar soln.Described acid hydrolyzation is affiliated field known technology, and one of ordinary skill in the art can select concrete acidolysis condition as required.
Described aqueous phase small molecular konjac glucomanna can mix with arbitrary proportion with dextran.
The preparation method of described aqueous phase comprises: in polysaccharide soln, add water soluble surfactant active, obtains aqueous phase; Preferably, in described polysaccharide soln, the concentration of polysaccharide is 0.05wt% ~ 60wt%, such as: 0.06wt%, 0.07wt%, 0.09wt%, 0.11wt%, 0.2wt%, 0.3wt%, 0.5wt%, 1wt%, 3wt%, 5wt%, 10wt%, 19wt%, 21wt%, 30wt%, 39wt%, 41wt%, 50wt%, 54wt%, 56wt%, 57wt%, 58wt%, 59wt% etc., more preferably 0.1wt% ~ 40wt%, is particularly preferably 2wt% ~ 20wt%.
Preferably, described water soluble surfactant active is polyoxyethylene sorbitan fatty acid ester (such as polyoxyethylene 20 sorbitan monostearate, polyoxyethylene 20 sorbitan tristearate, polyoxyethylene 20 sorbitan trioleate or polyoxyethylene 20 sorbitan monolaurate etc.), octyl phenyl polyoxyethylene ether, polyoxyethylene glycol, alkyl glycoside, 1 kind in lauric acid amide of ethanol or sodium lauryl sulphate or the combination of at least 2 kinds, the typical but non-limiting example of described combination comprises the combination of polyoxyethylene 20 sorbitan monostearate and polyoxyethylene 20 sorbitan tristearate, the combination of polyoxyethylene 20 sorbitan trioleate and polyoxyethylene 20 sorbitan monolaurate, polyoxyethylene 20 sorbitan monolaurate, the combination of octyl phenyl polyoxyethylene ether and polyoxyethylene glycol, polyoxyethylene glycol, alkyl glycoside, the combination of lauric acid amide of ethanol and sodium lauryl sulphate, polyoxyethylene 20 sorbitan tristearate, polyoxyethylene 20 sorbitan trioleate, polyoxyethylene glycol, the combination etc. of alkyl glycoside and lauric acid amide of ethanol, the effect of water soluble surfactant active is in aqueous phase, form a large amount of micelles, and when after Aqueous dispersions to oil phase, the micelle in aqueous phase droplets by the polarity kernel of spontaneous for oil phase suction micelle, can carry out formation continuous print passage.After crosslinking curing, these continuous print passages just form large duct.
Preferably, the mass ratio of described water soluble surfactant active and polysaccharide soln is 10:100 ~ 60:100, such as: 11:100,12:100,15:100,19:100,21:100,30:100,40:100,49:100,51:100,54:100,56:100,57:100,58:100,59:100 etc., more preferably 10:100 ~ 55:100, particularly preferably 20:100 ~ 50:100.
Preferably, the solvent of described oil phase is the combination of in ester, heterocycloalkane, heterocycloalkane halides, hydro carbons or halogenated hydrocarbon a kind or at least 2 kinds, such as, in N-BUTYL ACETATE, polychlorinated dibenzo-furans, machine oil, kerosene, turbine oil, methylene dichloride, sherwood oil, tetracol phenixin, whiteruss, aromatics or aromatics halides (as toluene, dichlorobenzene, dimethylbenzene etc.) a kind or the combination of at least 2 kinds.
The effect of the oil-soluble emulsifier added in oil phase is stable water-oil interface, improves the stability of drop, drop well can be disperseed in oil phase, and the gathering that can reduce between microballoon and adhesion phenomenon.Preferably, described oil-soluble emulsifier is the combination of in sorbitan fatty acid ester, polyglycerol fatty acid ester, polyoxyethylene fatty acid ester or alkylphenol polyoxyethylene class a kind or at least 2 kinds.
Preferably, the concentration of described oil-soluble emulsifier in oil phase is 0.05wt% ~ 25wt%, such as: 0.06wt%, 0.07wt%, 0.09wt%, 0.11wt%, 0.15wt%, 0.2wt%, 0.5wt%, 1wt%, 2wt%, 4wt%, 6wt%, 9wt%, 11wt%, 14wt%, 16wt%, 18wt%, 20wt%, 23wt%, 24wt% etc., more preferably 0.1wt% ~ 15wt%, is particularly preferably 3wt% ~ 10wt%.
Preferably, described aqueous phase mixes with oil phase and under agitation carries out, and reaction unit should provide suitable shearing force, can control size by adjusting rotary speed; Preferably, described stirring velocity is regulate within the scope of 50 ~ 1000rpm, is particularly preferably 100 ~ 500rpm.Aqueous phase containing polysaccharide and water soluble surfactant active is separated into small droplets by being stirred in oil phase, the micelle that water soluble surfactant active is formed in aqueous phase is by the polarity kernel of spontaneous for oil phase suction micelle, carry out formation continuous print passage, after adding linking agent, linking agent is diffused into microballoon inside, crosslinking reaction is carried out with polysaccharide chain, thus the physical strength of adjustment microballoon, removal of impurities (such as washing) is removed in aqueous phase and is not participated in the compositions such as the tensio-active agent of reaction, remaining oil phase solvent and oil-soluble emulsifier, obtains wide-aperture polysaccharide microsphere.
Preferably, the mass ratio of described oil phase and aqueous phase is more than 2:1, such as 2.1:1,2.2:1,2.5:1,2.9:1,3.1:1,3.5:1,3.9:1,4.1:1,4.5:1,5:1,10:1,14:1,16:1,19:1,21:1,25:1,30:1 etc., more preferably 3:1 ~ 20:1, is particularly preferably 4:1 ~ 15:1.
Preferably, described linking agent is polyfunctional compound containing epoxide group and/or the polyfunctional compound containing epoxide group and halogenic substituent, is particularly preferably the combination of in butane diepoxide, epoxy chloropropane-polyol derivative or epoxy chloropropane a kind or at least 2 kinds.Linking agent is diffused into microballoon inside, carries out crosslinking reaction, can be controlled the physical strength of microballoon by the add-on adjusting linking agent under suitable temperature and time with polysaccharide chain.
Preferably, described crosslinking temperature is 15 ~ 100 DEG C, such as: 16 DEG C, 17 DEG C, 18 DEG C, 19 DEG C, 21 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 39 DEG C, 41 DEG C, 45 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 79 DEG C, 81 DEG C, 85 DEG C, 90 DEG C, 95 DEG C, 97 DEG C, 8 DEG C, 99 DEG C etc., more preferably 20 ~ 90 DEG C, be particularly preferably 40 ~ 80 DEG C.
Preferably, described crosslinking time is at least 2 hours, such as: 2.1 hours, 2.2 hours, 2.5 hours, 3 hours, 5 hours, 6 hours, 10 hours, 11 hours, 13 hours, 15 hours, 20 hours, 21 hours, 22 hours, 23 hours, 25 hours, 30 hours etc., more preferably 2 ~ 24 hours, be particularly preferably 4 ~ 12 hours.
After being cross-linked, need to carry out removal of impurities to product, to remove in aqueous phase the tensio-active agent not participating in reaction, and the composition such as emulsifying agent in remaining whiteruss, sherwood oil and oil phase.Preferably, step (4) described removal of impurities is washing; Preferably, described washing adopts ethanol and/or deionized water; Preferably, described washing times is at least 2 times, such as 3 times, 4 times, 5 times, 6 times, 8 times, 10 times, 15 times, 20 inferior, particularly preferably at least 3 times.
The configuration of surface, skeleton structure, internal pore structure, aperture, specific surface area, porosity etc. of the microballoon obtained by the inventive method can by regulating the add-on, water oil ratio, emulsification times etc. of tensio-active agent and polysaccharide in aqueous phase because usually carrying out regulation and control.
The method of the invention utilizes the swelling of water soluble surfactant active to prepare polysaccharide microsphere, its mean pore size is larger, 90 ~ 800nm can be reached, median size is 1 ~ 500 μm, by regulating the consumption of tensio-active agent in aqueous phase, the maximum oil number of polysaccharide drop can be controlled easily, and then realize the regulation and control to product aperture, in conjunction with being cross-linked polysaccharide, thus ensure the physical strength of product.
Compared with prior art, advantage of the present invention is:
(1) the polysaccharide microsphere mean pore size prepared of the method for the invention is comparatively large and aperture is controlled, can reach 90 ~ 800nm, can effectively solve the problems such as biomacromolecule mass-transfer efficiency is low, velocity of separation is slow, improve the separation and purification effect of biomacromolecule;
(2) preparation method's technique is simple, can be used for suitability for industrialized production;
(3) particle diameter can be controlled by stirring velocity when oil phase and aqueous phase mixing, easy to operate.
Accompanying drawing explanation
Fig. 1 is oversized hole Konjac Glucomannan Granules prepared by embodiment 2.
Fig. 2 is oversized hole Konjac Glucomannan Granules prepared by embodiment 3.
Fig. 3 is oversized hole Konjac Glucomannan Granules prepared by embodiment 4.
Fig. 4 is oversized hole Konjac Glucomannan Granules internal structure prepared by embodiment 4.
Fig. 5 is oversized hole Konjac Glucomannan Granules prepared by embodiment 5.
Fig. 6 is oversized hole dextran microspheres prepared by embodiment 6.
Fig. 7 is oversized hole Rhizoma amorphophalli glucomannan-dextran microspheres prepared by embodiment 7.
Fig. 8 is oversized hole Konjac Glucomannan Granules prepared by embodiment 8.
Fig. 9 is oversized hole Konjac Glucomannan Granules surface tissue prepared by embodiment 8.
Figure 10 is oversized hole Rhizoma amorphophalli glucomannan-dextran microspheres prepared by embodiment 9.
Figure 11 is the internal structure of oversized hole Rhizoma amorphophalli glucomannan-dextran microspheres prepared by embodiment 9.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1: the preparation of small molecules konjac glucomanna
In the beaker of 1L, HCl and the 200g of 25ml0.1M deionized water is mixed, konjak glucomannan fine powder 50g is poured in mixed solution, stirs, in gelatin after swelling 10min.Put into autoclave, degrade 40min at 120 DEG C.Take out reactor after degraded, be placed to room temperature.Add the NaOH solution of 125g40%, stir and make gelatin substance dissolves, the konjak portuguese gansu polyose sugar aqueous solution of the desired concn clarified after impurity screening, can be obtained.The konjak portuguese gansu polyose sugar aqueous solution can preparing the solid content such as 0.1%, 4%, 15%, 20%, 40% with method is for subsequent use.
Embodiment 2
(molecular weight is 50 accurately to take the Rhizoma amorphophalli glucomannan that 30g concentration is 0.05wt%, 000) aqueous solution, add polyoxyethylene 20 sorbitan monooleate and 2g sodium lauryl sulphate that quality is 6g in aqueous in beaker, at 50 DEG C, be uniformly mixed 1h under water bath with thermostatic control condition.Accurately take the polyglycerol fatty acid ester of 20g, 15g methylene dichloride and 45g kerosene in there-necked flask, as oil phase, stir in thermostat water bath at 50 DEG C, regulate suitable rotational speed.The aqueous phase mixed is joined in oil phase, dispersion and emulsion 40min, then take 15g epichlorohydrin crosslinker, drop in mixed system, after being added dropwise to complete, be warming up to 90 DEG C, at this temperature crosslinked 6h.After reaction terminates, filter, with industrial alcohol and distilled water cleaning products several, the components such as methylene dichloride, kerosene, tensio-active agent are cleaned, obtains product.The outward appearance of thus obtained microsphere as shown in Figure 1.The median size of microballoon is 62 μm, and mean pore size is 106nm.
Embodiment 3
Accurately take 20g concentration be 20% Rhizoma amorphophalli glucomannan (molecular weight is 150, the 000) aqueous solution, 2g polyoxyethylene 20 sorbitan tristearate in beaker, under 30 DEG C of water bath with thermostatic control conditions, be uniformly mixed 1h.Accurately take 15g polyoxyethylene fatty acid ester, 50g sherwood oil and 200g turbine oil in there-necked flask, as oil phase, stir in thermostat water bath at 30 DEG C, regulate suitable rotational speed.The aqueous phase mixed is joined in oil phase, dispersion and emulsion 1h, then take 30g epichlorohydrin crosslinker, drop in mixed system, after being added dropwise to complete, be warming up to 60 DEG C, at this temperature crosslinking curing 10h.After reaction terminates, filter, with industrial alcohol and distilled water cleaning products several, after the component cleaning, drying such as sherwood oil, turbine oil, tensio-active agent, obtain product.The electromicroscopic photograph of thus obtained microsphere as shown in Figure 2.The median size of microballoon is 45 μm, and mean pore size is 90nm.
Embodiment 4
The concentration accurately taking 30g be the Rhizoma amorphophalli glucomannan of 8% (molecular weight is 220, the 000) aqueous solution, 18g alkyl glycoside in beaker, be uniformly mixed under 60 DEG C of water bath with thermostatic control conditions.Accurately take 0.3g polyglycerol fatty acid ester, 600g machine oil in there-necked flask, as oil phase, stir in thermostat water bath at 60 DEG C, regulate suitable rotational speed.The aqueous phase mixed is joined in oil phase, dispersion and emulsion 20min, then take 15g epichlorohydrin crosslinker, drop in mixed system, after being added dropwise to complete, be warming up to 80 DEG C, at this temperature crosslinked 4h.After reaction terminates, filter, with industrial alcohol and distilled water cleaning products several, after the cleaning, drying such as machine oil, tensio-active agent, obtain product.Electromicroscopic photograph such as Fig. 3, Fig. 4 of thus obtained microsphere show.The median size of microballoon is 96 μm, and mean pore size is 210nm.
Embodiment 5
The octyl phenyl polyoxyethylene ether that the concentration accurately taking 25g is the Rhizoma amorphophalli glucomannan of 60% (molecular weight the is 1000) aqueous solution, quality is 8g and the alkyl glycoside of 1g, in beaker, are uniformly mixed under 40 DEG C of water bath with thermostatic control conditions.Accurately take 15g alkylphenol polyoxyethylene, 10g polychlorinated dibenzo-furans and 120g whiteruss in there-necked flask, stir in thermostat water bath at 40 DEG C, regulate suitable rotational speed.The aqueous phase mixed is joined in oil phase, dispersion and emulsion 30min, then take 25g epichlorohydrin crosslinker, drop in mixed system, after being added dropwise to complete, be warming up to 70 DEG C, at this temperature crosslinked 15h.After reaction terminates, filter, with industrial alcohol and distilled water cleaning products several, after the component cleaning, drying such as polychlorinated dibenzo-furans, whiteruss, tensio-active agent, obtain product.The electromicroscopic photograph of thus obtained microsphere as shown in Figure 5.The median size of microballoon is 30 μm, and mean pore size is 310nm.
Embodiment 6
By weight-average molecular weight be 100,000 dextran be dissolved in deionized water, make the dextran solution that concentration is 15%.Accurately take 30g, the sodium lauryl sulphate adding polyoxyethylene 20 sorbitan monooleate that quality is 10g and 2g in aqueous, in beaker, is uniformly mixed 1h under water bath with thermostatic control condition at 20 DEG C.Accurately take the polyglycerol fatty acid ester of 20g, 100g methylene dichloride and 150g kerosene in there-necked flask, as oil phase, stir in thermostat water bath at 50 DEG C, regulate suitable rotational speed.The aqueous phase mixed is joined in oil phase, dispersion and emulsion 40min, then take 15g epichlorohydrin crosslinker, drop in mixed system, after being added dropwise to complete, constant temperature 20 DEG C, at this temperature crosslinked 2h.After reaction terminates, filter, with industrial alcohol and distilled water cleaning products several, the components such as methylene dichloride, kerosene, tensio-active agent are cleaned, obtains product.The outward appearance of thus obtained microsphere as shown in Figure 6.The median size of microballoon is 150 μm, and mean pore size is 96nm.
Embodiment 7
Accurately take 20g concentration be 0.1% Rhizoma amorphophalli glucomannan (molecular weight is 1000,000) aqueous solution, adds 1.6g dextran wherein, and total polysaccharide content is 7.5%, add 4g polyoxyethylene 20 sorbitan tristearate again, under 30 DEG C of water bath with thermostatic control conditions, be uniformly mixed 1h.Accurately take 15g polyoxyethylene fatty acid ester, 50g sherwood oil and 200g turbine oil in there-necked flask, as oil phase, stir in thermostat water bath at 30 DEG C, regulate suitable rotational speed.The aqueous phase mixed is joined in oil phase, dispersion and emulsion 1h, then take 30g epichlorohydrin crosslinker, drop in mixed system, after being added dropwise to complete, be warming up to 60 DEG C, at this temperature crosslinking curing 12h.After reaction terminates, filter, with industrial alcohol and distilled water cleaning products several, after the component cleaning, drying such as sherwood oil, turbine oil, tensio-active agent, obtain product.The electromicroscopic photograph of thus obtained microsphere as shown in Figure 7.The median size of microballoon is 220 μm, and mean pore size is 150nm.
Embodiment 8
The concentration accurately taking 25g is that (molecular weight is 10 to the Rhizoma amorphophalli glucomannan of 40%, 000) polyoxyethylene glycol of the aqueous solution, 2.5g and 6.5g polyoxyethylene 20 sorbitan monooleate are in beaker, be uniformly mixed under 40 DEG C of water bath with thermostatic control conditions, obtain aqueous phase.Accurately take 0.5g sorbitan fatty acid ester and 165.5g tetracol phenixin in there-necked flask, stir in thermostat water bath at 40 DEG C, regulate suitable rotational speed, obtain oil phase.The aqueous phase mixed is joined in oil phase, at 500 rpm dispersion and emulsion 2h, then take 10g dioxy chlorobutane linking agent, drop in mixed system, after being added dropwise to complete, be warming up to 50 DEG C, at this temperature crosslinked 24h.After reaction terminates, filter, with industrial alcohol and distilled water cleaning products several, after the cleaning, drying of the component such as tetracol phenixin, tensio-active agent, obtain product.As shown in Figure 8, Figure 9, median size is 50 μm to the electron microscopic picture of thus obtained microsphere, and mean pore size is 240nm.
Embodiment 9
Accurately take 10.9g concentration be 20% Rhizoma amorphophalli glucomannan (molecular weight is 500,000) aqueous solution, add 7.82g dextran wherein, in polysaccharide soln, the concentration of polysaccharide is 53%, add 9g polyoxyethylene 20 sorbitan monolaurate and 1g lauric acid amide of ethanol again, 1h is uniformly mixed, as aqueous phase under 30 DEG C of water bath with thermostatic control conditions.Accurately take 60g polyoxyethylene fatty acid ester, 200g toluene and 100g dichlorobenzene in there-necked flask, as oil phase, stir in thermostat water bath at 30 DEG C, regulate suitable rotational speed, obtain oil phase.The aqueous phase mixed is joined in oil phase, at 100 rpm dispersion and emulsion 1h, then take 20g epichlorohydrin crosslinker, drop in mixed system, after being added dropwise to complete, constant temperature 30 DEG C, at this temperature crosslinking curing 8h.After reaction terminates, filter, with industrial alcohol and distilled water cleaning products several, after the component cleaning, drying such as toluene, dichlorobenzene, tensio-active agent, obtain product.As shown in Figure 10, Figure 11, median size is 68 μm to the electron microscopic picture of thus obtained microsphere, and mean pore size is 800nm.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (24)
1. a preparation method for oversized hole polysaccharide microsphere, is characterized in that, the mean pore size of described oversized hole polysaccharide microsphere is 90 ~ 800nm, and described polysaccharide is that Rhizoma amorphophalli glucomannan is degraded the small molecules konjac glucomanna and/or dextran that obtain; Describedly be degraded to acid hydrolyzation; The weight-average molecular weight of described small molecules konjac glucomanna is 1,000-500,000; Described method comprises: the aqueous phase containing water soluble surfactant active and polysaccharide and the oil phase immiscible with water are mixed, add linking agent, obtain oversized hole polysaccharide microsphere.
2. the method for claim 1, is characterized in that, the median size of described oversized hole polysaccharide microsphere is 1 ~ 500 μm.
3. the method for claim 1, is characterized in that, the acid used in described acidolysis is organic acid and/or mineral acid.
4. method as claimed in claim 3, is characterized in that, the acid used in described acidolysis is hydrochloric acid, the combination of in sulfuric acid, nitric acid, phosphoric acid, oxalic acid, carbonic acid, propionic acid or acetic acid a kind or at least 2 kinds.
5. the method for claim 1, is characterized in that, the weight-average molecular weight of described small molecules konjac glucomanna is 5000-100,000.
6. the method for claim 1, is characterized in that, described oil phase contains oil-soluble emulsifier.
7. the method for claim 1, is characterized in that, described method comprises:
(1) by polysaccharide soln and water soluble surfactant active soluble in water, be mixed with aqueous phase; Oil-soluble emulsifier will be dissolved with and with the immiscible solution of water as oil phase;
(2) mix oil phase and aqueous phase, obtain w/o type emulsion;
(3) add linking agent in the emulsion obtained in step (2), be cross-linked;
(4), after crosslinked balling-up, removal of impurities, namely obtains oversized hole polysaccharide microsphere.
8. method as claimed in claim 7, is characterized in that, step (3) described linking agent is dropping to the feed postition of described emulsion.
9. method as claimed in claim 7, is characterized in that, described being cross-linked of step (3) is under agitation carried out.
10. method as claimed in claim 7, it is characterized in that, in described polysaccharide soln, the concentration of polysaccharide is 0.05wt% ~ 60wt%.
11. methods as claimed in claim 10, it is characterized in that, in described polysaccharide soln, the concentration of polysaccharide is 0.1wt% ~ 40wt%.
12. methods as claimed in claim 7, it is characterized in that, described water soluble surfactant active is the combination of in polyoxyethylene sorbitan fatty acid ester, octyl phenyl polyoxyethylene ether, polyoxyethylene glycol, alkyl glycoside, lauric acid amide of ethanol or sodium lauryl sulphate a kind or at least 2 kinds.
13. methods as claimed in claim 7, is characterized in that, the mass ratio of described water soluble surfactant active and polysaccharide soln is 10:100 ~ 60:100.
14. methods as claimed in claim 13, is characterized in that, the mass ratio of described water soluble surfactant active and polysaccharide soln is 10:100 ~ 55:100.
15. methods as claimed in claim 7, is characterized in that, the solvent of described oil phase is the combination of in ester, heterocycloalkane, heterocycloalkane halides, hydro carbons or halogenated hydrocarbon a kind or at least 2 kinds.
16. methods as claimed in claim 7, is characterized in that, described oil-soluble emulsifier is the combination of in sorbitan fatty acid ester, polyglycerol fatty acid ester, polyoxyethylene fatty acid ester or alkylphenol polyoxyethylene class a kind or at least 2 kinds.
17. methods as claimed in claim 7, it is characterized in that, the content of described oil-soluble emulsifier in oil phase is 0.05wt% ~ 25wt%.
18. methods as claimed in claim 17, it is characterized in that, the content of described oil-soluble emulsifier in oil phase is 0.1wt% ~ 15wt%.
19. methods as claimed in claim 7, is characterized in that, described aqueous phase mixes with oil phase and under agitation carries out; Described stirring velocity is 50 ~ 1000rpm.
20. methods as claimed in claim 7, is characterized in that, the mass ratio of described oil phase and aqueous phase is 3:1 ~ 20:1.
21. methods as claimed in claim 7, is characterized in that, described linking agent is the combination of in butane diepoxide, epoxy chloropropane-polyol derivative or epoxy chloropropane a kind or at least 2 kinds.
22. methods as claimed in claim 7, it is characterized in that, described crosslinked temperature is 15 ~ 100 DEG C.
23. methods as claimed in claim 7, it is characterized in that, the described crosslinked time is at least 2 hours.
24. methods as claimed in claim 7, is characterized in that, step (4) described removal of impurities is washing; Described washing adopts ethanol and/or deionized water; Described washing times is at least 2 times.
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| CN106432816B (en) * | 2016-09-07 | 2019-02-15 | 中科森辉微球技术（苏州）有限公司 | A kind of high flow rate polysaccharide microsphere and preparation method thereof |
| CN110026138B (en) * | 2018-01-11 | 2020-10-16 | 中国科学院过程工程研究所 | Polysaccharide microsphere and preparation method thereof |
| CN108949702A (en) * | 2018-08-01 | 2018-12-07 | 苏州纳微科技股份有限公司 | Application of the ultra-large aperture chromatography media in purified virus particles |
| CN110961053A (en) * | 2018-09-29 | 2020-04-07 | 泰州医药城国科化物生物医药科技有限公司 | Method for preparing polysaccharide microspheres by using emulsifying formula containing polyoxyethylene polyoxypropylene ether block copolymer |
| CN112973590A (en) * | 2021-03-12 | 2021-06-18 | 四川大学 | Novel preparation method of macroporous chitin microspheres |
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