CN102010525B - Method for preparing superparamagnetic micron starch - Google Patents
Method for preparing superparamagnetic micron starch Download PDFInfo
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- CN102010525B CN102010525B CN201010547886.3A CN201010547886A CN102010525B CN 102010525 B CN102010525 B CN 102010525B CN 201010547886 A CN201010547886 A CN 201010547886A CN 102010525 B CN102010525 B CN 102010525B
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- 229920002472 Starch Polymers 0.000 title claims abstract description 118
- 235000019698 starch Nutrition 0.000 title claims abstract description 118
- 239000008107 starch Substances 0.000 title claims abstract description 117
- 238000000034 method Methods 0.000 title claims abstract description 7
- 230000005291 magnetic effect Effects 0.000 claims abstract description 76
- 239000008367 deionised water Substances 0.000 claims abstract description 34
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 238000002360 preparation method Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000011553 magnetic fluid Substances 0.000 claims abstract description 26
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 25
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 15
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000005642 Oleic acid Substances 0.000 claims abstract description 15
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 15
- 238000001556 precipitation Methods 0.000 claims abstract description 11
- 108090000790 Enzymes Proteins 0.000 claims abstract description 10
- 102000004190 Enzymes Human genes 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000004108 freeze drying Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000010521 absorption reaction Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 238000004062 sedimentation Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 6
- 239000004382 Amylase Substances 0.000 claims description 4
- 108010065511 Amylases Proteins 0.000 claims description 4
- 102000013142 Amylases Human genes 0.000 claims description 4
- 235000019418 amylase Nutrition 0.000 claims description 4
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 3
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 3
- UGTZMIPZNRIWHX-UHFFFAOYSA-K sodium trimetaphosphate Chemical compound [Na+].[Na+].[Na+].[O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 UGTZMIPZNRIWHX-UHFFFAOYSA-K 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000007885 magnetic separation Methods 0.000 abstract description 6
- WSSMOXHYUFMBLS-UHFFFAOYSA-L iron dichloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Fe+2] WSSMOXHYUFMBLS-UHFFFAOYSA-L 0.000 abstract description 5
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- KBOPZPXVLCULAV-UHFFFAOYSA-N mesalamine Chemical compound NC1=CC=C(O)C(C(O)=O)=C1 KBOPZPXVLCULAV-UHFFFAOYSA-N 0.000 description 20
- 229960004963 mesalazine Drugs 0.000 description 20
- 239000003814 drug Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- 229940079593 drug Drugs 0.000 description 11
- 239000004005 microsphere Substances 0.000 description 8
- 239000012047 saturated solution Substances 0.000 description 8
- 240000003183 Manihot esculenta Species 0.000 description 7
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 7
- 241000209094 Oryza Species 0.000 description 7
- 235000007164 Oryza sativa Nutrition 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 235000009566 rice Nutrition 0.000 description 7
- 230000009471 action Effects 0.000 description 4
- 230000000112 colonic effect Effects 0.000 description 4
- 230000002478 diastatic effect Effects 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 235000013312 flour Nutrition 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000000338 in vitro Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 230000003902 lesion Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920001592 potato starch Polymers 0.000 description 4
- 238000002626 targeted therapy Methods 0.000 description 4
- 244000061456 Solanum tuberosum Species 0.000 description 3
- 235000002595 Solanum tuberosum Nutrition 0.000 description 3
- 240000008042 Zea mays Species 0.000 description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 3
- 235000005822 corn Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229940100486 rice starch Drugs 0.000 description 3
- 229920002085 Dialdehyde starch Polymers 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 108010073178 Glucan 1,4-alpha-Glucosidase Proteins 0.000 description 2
- 102100022624 Glucoamylase Human genes 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 108010028688 Isoamylase Proteins 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000560 biocompatible material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- Medicinal Preparation (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
Abstract
The invention discloses a method for preparing superparamagnetic micron starch, comprising the following steps: 1) dissolving the weighed FeCl3.6H2O solid and FeCl2.4H2O solid, adding stronger ammonia water, dropwise adding oleic acid, stirring and reacting to obtain a black sol substance, and separating the obtained precipitation from a reaction system by adopting an externally applied magnetic field to obtain a magnetic fluid; 2) mixing the magnetic fluid and an enzyme preparation, and performing magnetic separation to obtain magnetic nano particles absorbed with the enzyme preparation; 3) adding deionized water into insoluble raw starch, and stirring to obtain a raw starch dispersion solution; 4) adding the magnetic nanoparticles absorbed with the enzyme preparation into the raw starch dispersion solution, and performing magnetic separation after reaction to obtain magnetic starch precipitation; and 5) drying or freeze drying the magnetic starch precipitation obtained in step 4) to obtain the superparamagnetic micron starch powder. The preparation process in the invention is simple, green and environment-friendly and no toxic reagent is utilized, thus the superparamagnetic micron starch can be utilized as a medical carrier.
Description
Technical field
The present invention relates to magnetic starch, be specifically related to a kind of preparation method of superparamagnetic micron starch.
Background technology
Magnetic microsphere has that particle diameter is little, specific surface area is large, be easy to adsorb the feature such as other material, tool superparamagnetism, utilize magnetic microsphere prepared by biocompatible materials or to be adsorbed on macromolecule layer by drug encapsulation, therefore can be used as target medicine carrier and realize targeted delivery of drugs, there is important using value.Pharmaceutical carrier can enter in human body with medicine, requires carrier harmless.
The plurality of advantages such as that the magnetic microsphere of preparing with starch has is nontoxic, meta-bolites can excrete, biodegradable, easy to prepare, material is cheap, and starch can not produce the antigenicity of protein material, is more conducive to use.
Existing magnetic spherex, generally first to prepare nano level ultra paramagnetic particle, then prepare Zulkovsky starch solution, again superparamagnetic nanoparticle is dispersed in Zulkovsky starch solution, reaction certain hour makes starch molecule be adsorbed on magnetic nano particle sub-surface, makes magnetic Nano starch after oven dry.What magnetic Nano starch prepared by the method used is Zulkovsky starch, has destroyed the vesicular structure of starch inside, can the serious absorption medicine carrying capacity that reduces starch.
The people such as Wen Qibiao disclose a kind of preparation method who prepares superparamagnetic starch in patent 200610123853.X, first use starch milk absorption soluble ferrite, then utilize hydrogen peroxide oxidation to be adsorbed on starch inside and surperficial ferrous particle, obtain after drying superparamagnetic starch.Due to the ferrous particle of enough Z 250 crystal production can not be provided in preparation process of the method, thus need just can prepare superparamagnetic starch through multiple adsorb oxidation, and have more superparamagnetic starch granules in surface arrangement.
The people such as Wang Li provide a kind of preparation method of magnetic macromolecular microsphere of crosslinking dialdehyde starch in patent 200610146935.6, for only containing hydroxyl in starch magnetic microsphere, when for targeting preparation, be difficult for immobilized defect on starch magnetic microsphere containing amino medicine, starch magnetic microsphere is carried out to modification, prepared crosslinking dialdehyde starch magnetic microsphere, made hydroxyl more be converted into aldehyde radical, make it easily and medicine in-NH
2in conjunction with.
Summary of the invention
The object of this invention is to provide a kind of method of utilizing superparamagnetic micron starch prepared by various insoluble starches and starch derivative, prepared superparamagnetic micron starch has farinose structure and superparamagnetic characteristic.
In order to reach above-mentioned purpose, solution of the present invention is:
A preparation method for superparamagnetic micron starch, comprises the following steps:
1) take FeCl
36H
2o solid and FeCl
24H
2after O dissolution of solid, under intense agitation, add strong aqua, then dropwise add oleic acid, after stirring reaction, obtain the molten gelatinoid of black, utilize externally-applied magnetic field that the precipitation of gained is separated and obtained magnetic fluid from reaction system;
2) magnetic fluid obtains absorption after separating with zymin equal-volume mixing magnetic the magnetic nano-particle of zymin;
3) adopt insoluble raw starch to add deionized water and stirring and obtain raw starch dispersion liquid;
4) by step 2) in the absorption that obtains have the magnetic nano-particle of zymin to join in the raw starch dispersion liquid that step 3) obtains, after reaction, magnetic separates and obtains magnetic starch sedimentation;
5) magnetic starch sedimentation step 4) being obtained is dried or lyophilize obtains superparamagnetic micron starch powder, one or many superparamagnetic nanoparticles are contained in the superparamagnetic micron starch inside of gained, the partial starch surface nanoparticle that also may be magnetic, the original characteristic of raw starch that its structure and shape maintains are used.
FeCl in described step 1)
36H
2o solid consumption is 7-9g, is transferred in there-necked flask after being dissolved in 140-160mL deionized water; FeCl
24H
2o solid consumption is 4-5g, be dissolved in 8-12mL deionized water, filter after be also transferred in there-necked flask; Described strong aqua concentration is 25%(w/v), add-on is 15-20mL, the reaction times is 1-5min; The dripping quantity of described oleic acid is 3-6g, continues rapid stirring 30-120min at 50-80 DEG C to obtain the molten gelatinoid of black.
In described step 1), utilize externally-applied magnetic field that the precipitation of the molten gelatinoid of black of gained is separated from reaction system, utilize alcohol washing to remove unnecessary oleic acid for 2-5 times, then with deionized water wash to pH=7 left and right; Then adding 100-200 ml concentration is the KMnO of 8-12 mg/ml
4solution oxide magnetic fluid surface oleic acid forms carboxyl, and ultrasonic washing instrument sonic oscillation 8 h use deionized water wash 3 times after magnetic separates, and obtain magnetic fluid.
After described magnetic fluid process washing, vacuum lyophilization 40 h, obtaining finishing has the magnetic nano-particle of carboxyl.
Described step 2) in adopt be configured to 30-50mg/ml magnetic fluid 10ml; Adopt the zymin 10ml that concentration is 3-5mg/ml; Equal-volume reacts 2-24h after mixing at 5-20 DEG C.
In described step 3), insoluble raw starch takes 3-5g and adds in 100ml～200ml deionized water, and maintains the temperature at 20 DEG C of raw starch gelatinization temperatures below-40 DEG C, stirs raw starch to be uniformly dispersed obtain raw starch dispersion liquid.
In described step 4), magnetic nano-particle joins temperature of reaction in raw starch dispersion liquid at 10 DEG C～40 DEG C, stirring reaction 5-48h, and after having reacted, magnetic separates to obtain magnetic starch sedimentation.
In described step 5), drying temperature is below 40 DEG C.
Described insoluble raw starch comprises the various raw starch with complete grain pattern, adopt the one in W-Gum, Starch rice, potato starch, tapioca (flour), and in the raw starch dispersion liquid obtaining in step 3), adopt linking agent to be cross-linked and to maintain its complete grain pattern raw starch; Described linking agent adopt Trisodium trimetaphosphate, oxalic dialdehyde, one in epoxy chloropropane.
Described zymin adopts the one in saccharifying enzyme, amylase, isoamylase.
Beneficial effect of the present invention is: the superparamagnetic micron starch that the present invention utilizes the various raw starch such as corn, rice (rice is divided into polished rice and glutinous rice), potato, cassava to prepare maintains the original vesicular structure of raw starch and shape, and there is superparamagnetic characteristic, can be used as target medicine carrier, improve the bioavailability of medicine, reduce Side effects of pharmaceutical drugs.Compared with prior art, tool has the following advantages in the present invention: the magnetic starch that first prepared by the present invention maintains farinose complete structure, can make full use of farinose absorption property medicine carrying.Secondly the present invention adopts enzyme guiding magnetic nanoparticle to count starch inside, and the magnetic starch surface of system is containing less magnetic nanoparticle.So preparation technology of the present invention is simple, green, environmental protection, without any toxic reagent, therefore can be used as medical carrier.
Embodiment
Embodiment 1
The preparation of superparamagnetic polished rice starch
Accurately take Iron(III) chloride hexahydrate 8.1g and be dissolved in 142.5 ml deionized waters, transfer in there-necked flask, be heated with stirring to 70 DEG C.Take Iron dichloride tetrahydrate 4.4 g and be dissolved in 10ml deionized water, filter, get 7.5 ml and add there-necked flask.Under the condition of vigorous stirring, add fast 18 ml strong aquas (25%, w/v), after 1 min, dropwise add 4.66 g oleic acid, continue rapid stirring 1 h at 70 DEG C.After reaction finishes, obtain the molten gelatinoid of black, utilize externally-applied magnetic field that the precipitation of gained is separated from reaction system.Remove unnecessary oleic acid 2 times with alcohol washing, then with deionized water wash to pH=7 left and right.Then adding 160 ml concentration is the KMnO of 10 mg/ml
4solution, KMnO
4solution oxide magnetic fluid surface oleic acid forms carboxyl.Ultrasonic washing instrument sonic oscillation 8 h, use deionized water wash 3 times after magnetic separates, and obtain magnetic fluid.Also can be by after magnetic fluid washing, vacuum lyophilization 40 h, obtaining finishing has the magnetic nano-particle of carboxyl for subsequent use.
Configuration concentration is 50mg/ml magnetic fluid 10ml, and the Glucoamylase Solution 10ml that configuration concentration is 5mg/ml, by mixed 2 equal-volumes, reacts 4h at 20 DEG C, and magnetic obtains absorption after separating the magnetic nano-particle of saccharifying enzyme.
Insoluble polished rice starch 5g is added in 100ml deionized water to 20 DEG C of insulation 1h.Stirring obtains the raw starch dispersion liquid of polished rice.
Have the magnetic nano-particle of saccharifying enzyme to add in the raw starch dispersion liquid of above-mentioned polished rice absorption, holding temperature is at 40 DEG C, stirring reaction 15h, after react, magnetic separates to obtain magnetic starch sedimentation, 40 DEG C below lyophilizes obtain superparamagnetic micron starch powder.
Superparamagnetic polished rice starch load 5-aminosalicylic acid
Taking 5-aminosalicylic acid as model drug, the 5-aminosalicylic acid saturated solution of configuration 200ml, the magnetic starch 5g of preparation in embodiment 4 is added to the 5-aminosalicylic acid saturated solution of 200ml, after whip attachment 3h, magnetic separation filtration, dry, obtaining absorption has the magnetic starch of 5-aminosalicylic acid.The release in vitro performance of this drug loaded magnetic starch in colonic fluid is as shown in table 1, therefore magnetic starch displacement under additional magnetic action can be carried out to targeted therapy to lesions position.
Embodiment 2
The preparation of superparamagnetic tapioca (flour)
Accurately take Iron(III) chloride hexahydrate 8.1 g and be dissolved in 142.5 ml deionized waters, transfer in there-necked flask, be heated with stirring to 70 DEG C.Take Iron dichloride tetrahydrate 4.4 g and be dissolved in 10ml deionized water, filter, get 7.5 ml and add there-necked flask.Under the condition of vigorous stirring, add fast 18 ml strong aquas (25%, w/v), after 1 min, dropwise add 4.66 g oleic acid, continue rapid stirring 1 h at 70 DEG C.After reaction finishes, obtain the molten gelatinoid of black, utilize externally-applied magnetic field that the precipitation of gained is separated from reaction system.Remove unnecessary oleic acid 2 times with alcohol washing, then with deionized water wash to pH=7 left and right.Then adding 160 ml concentration is the KMnO of 10 mg/ml
4solution, KMnO
4solution oxide magnetic fluid surface oleic acid forms carboxyl.Ultrasonic washing instrument sonic oscillation 8 h, use deionized water wash 3 times after magnetic separates, and obtain magnetic fluid.Or after washing, vacuum lyophilization 40 h, obtaining finishing has the magnetic nano-particle of carboxyl for subsequent use.
Configuration concentration is 50mg/ml magnetic fluid 10ml, and the raw amylase solution 10ml that configuration concentration is 5mg/ml, by mixed 2 equal-volumes, reacts 4h at 20 DEG C, and magnetic obtains absorption after separating have raw diastatic magnetic nano-particle.
Insoluble tapioca (flour) 5g is added in 100ml deionized water, add linking agent Trisodium trimetaphosphate, 30 DEG C of insulation 1h.After filtration, be again scattered in 100ml deionized water, stir and obtain the raw starch dispersion liquid of cassava.
Have raw diastatic magnetic nano-particle to add in the raw starch dispersion liquid of above-mentioned cassava absorption, holding temperature is at 30 DEG C, stirring reaction 24h, after react, magnetic separates to obtain magnetic starch sedimentation, 40 DEG C below lyophilizes obtain superparamagnetic micron starch powder.
Superparamagnetic tapioca (flour) load 5-aminosalicylic acid
Taking 5-aminosalicylic acid as model drug, the 5-aminosalicylic acid saturated solution of configuration 200ml, the magnetic starch 5g of preparation in embodiment 2 is added to the 5-aminosalicylic acid saturated solution of 200ml, after whip attachment 3h, magnetic separation filtration, dry, obtaining absorption has the magnetic starch of 5-aminosalicylic acid.The release in vitro performance of this drug loaded magnetic starch in colonic fluid is as shown in table 1, therefore magnetic starch displacement under additional magnetic action can be carried out to targeted therapy to lesions position.
Embodiment 3
The preparation of superparamagnetic W-Gum
Accurately take Iron(III) chloride hexahydrate 7g and be dissolved in 140ml deionized water, transfer in there-necked flask, be heated with stirring to 50 DEG C.Take Iron dichloride tetrahydrate 4g and be dissolved in 8ml deionized water, filter, get 7ml and add there-necked flask.Under the condition of vigorous stirring, add fast 15ml strong aqua (25%, w/v), after 3 min, dropwise add 3.2g oleic acid, continue rapid stirring 30min at 50 DEG C.After reaction finishes, obtain the molten gelatinoid of black, utilize externally-applied magnetic field that the precipitation of gained is separated from reaction system.Remove unnecessary oleic acid 3 times with alcohol washing, then with deionized water wash to pH=7 left and right.Then add the KMnO that 100 ml concentration are 8mg/ml
4solution, KMnO
4solution oxide magnetic fluid surface oleic acid forms carboxyl.Ultrasonic washing instrument sonic oscillation 8 h, use deionized water wash 3 times after magnetic separates, and obtain magnetic fluid.Or after washing, vacuum lyophilization 40 h, obtaining finishing has the magnetic nano-particle of carboxyl for subsequent use.
Configuration concentration is 30mg/ml magnetic fluid 10ml, and the Glucoamylase Solution 10ml that configuration concentration is 3mg/ml, by mixed 2 equal-volumes, reacts 24h at 5 DEG C, and magnetic obtains absorption after separating the magnetic nano-particle of saccharifying enzyme.
Insoluble W-Gum 3g is added in 150ml deionized water, add linking agent oxalic dialdehyde, 20 DEG C of insulation 1h.After filtration, be again scattered in 150ml deionized water, stir and obtain the raw starch dispersion liquid of corn.
Have the magnetic nano-particle of saccharifying enzyme to add in the raw starch dispersion liquid of above-mentioned corn absorption, holding temperature is at 10 DEG C, stirring reaction 48h, after react, magnetic separates to obtain magnetic starch sedimentation, 40 DEG C below lyophilizes obtain superparamagnetic micron starch powder.
Superparamagnetic W-Gum load 5-aminosalicylic acid
Taking 5-aminosalicylic acid as model drug, the 5-aminosalicylic acid saturated solution of configuration 200ml, the magnetic starch 5g of preparation in embodiment 3 is added to the 5-aminosalicylic acid saturated solution of 200ml, after whip attachment 3h, magnetic separation filtration, dry, obtaining absorption has the magnetic starch of 5-aminosalicylic acid.The release in vitro performance of this drug loaded magnetic starch in colonic fluid is as shown in table 3, therefore magnetic starch displacement under additional magnetic action can be carried out to targeted therapy to lesions position.
Embodiment 4
The preparation of superparamagnetic potato starch
Accurately take Iron(III) chloride hexahydrate 9g and be dissolved in 150ml deionized water, transfer in there-necked flask, be heated with stirring to 80 DEG C.Take Iron dichloride tetrahydrate 5g and be dissolved in 12ml deionized water, filter, get 9.5 ml and add there-necked flask.Under the condition of vigorous stirring, add fast 20 ml strong aquas (25%, w/v), after 5min, dropwise add 6g oleic acid, continue rapid stirring 120min at 80 DEG C.After reaction finishes, obtain the molten gelatinoid of black, utilize externally-applied magnetic field that the precipitation of gained is separated from reaction system.Remove unnecessary oleic acid 5 times with alcohol washing, then with deionized water wash to pH=7 left and right.Then adding 200 ml concentration is the KMnO of 12 mg/ml
4solution, KMnO
4solution oxide magnetic fluid surface oleic acid forms carboxyl.Ultrasonic washing instrument sonic oscillation 8 h, use deionized water wash 3 times after magnetic separates, and obtain magnetic fluid.Or after washing, vacuum lyophilization 40 h, obtaining finishing has the magnetic nano-particle of carboxyl for subsequent use.
Configuration concentration is 40mg/ml magnetic fluid 10ml, and the raw amylase solution 10ml that configuration concentration is 4mg/ml, by mixed 2 equal-volumes, reacts 12h at 15 DEG C, and magnetic obtains absorption after separating have raw diastatic magnetic nano-particle.
Insoluble potato starch 4g is added in 200ml deionized water, add linking agent epoxy chloropropane, 40 DEG C of insulation 1h.After filtration, be again scattered in 200ml deionized water, stir and obtain the raw starch dispersion liquid of potato.
Have raw diastatic magnetic nano-particle to add in the raw starch dispersion liquid of above-mentioned potato absorption, holding temperature is at 40 DEG C, stirring reaction 12h, after react, magnetic separates to obtain magnetic starch sedimentation, 40 DEG C below lyophilizes obtain superparamagnetic micron starch powder.
Superparamagnetic potato starch load 5-aminosalicylic acid
Taking 5-aminosalicylic acid as model drug, the 5-aminosalicylic acid saturated solution of configuration 200ml, the magnetic starch 5g of preparation in embodiment 4 is added to the 5-aminosalicylic acid saturated solution of 200ml, after whip attachment 3h, magnetic separation filtration, dry, obtaining absorption has the magnetic starch of 5-aminosalicylic acid.The release in vitro performance of this drug loaded magnetic starch in colonic fluid is as shown in table 4, therefore magnetic starch displacement under additional magnetic action can be carried out to targeted therapy to lesions position.
Claims (9)
1. a preparation method for superparamagnetic micron starch, is characterized in that: comprise the following steps:
1) take FeCl
36H
2o solid and FeCl
24H
2after O dissolution of solid, under intense agitation, add strong aqua, then dropwise add oleic acid, after stirring reaction, obtain the molten gelatinoid of black, utilize externally-applied magnetic field that the precipitation of gained is separated and obtained magnetic fluid from reaction system;
2) magnetic fluid mixes with enzymes soln, and magnetic obtains absorption after separating the magnetic nano-particle of zymin;
3) adopt insoluble raw starch to add deionized water and stirring and obtain raw starch dispersion liquid;
4) by step 2) in the absorption that obtains have the magnetic nano-particle of zymin to join in the raw starch dispersion liquid that step 3) obtains, after reaction, magnetic separates and obtains magnetic starch sedimentation;
5) magnetic starch sedimentation step 4) being obtained is dried or lyophilize obtains superparamagnetic micron starch powder;
In described step 1), utilize externally-applied magnetic field that the precipitation of the molten gelatinoid of black of gained is separated from reaction system, utilize alcohol washing to remove unnecessary oleic acid for 2-5 times, then with deionized water wash to pH=7; Then adding 100-200 ml concentration is the KMnO of 8-12 mg/ml
4solution oxide surface oleic acid forms carboxyl, and ultrasonic washing instrument sonic oscillation 8 h use deionized water wash 3 times after magnetic separates, and obtain magnetic fluid.
2. the preparation method of a kind of superparamagnetic micron starch as claimed in claim 1, is characterized in that: FeCl in described step 1)
36H
2o solid consumption is 7-9g, is transferred in there-necked flask after being dissolved in 140-160mL deionized water; FeCl
24H
2o solid consumption is 4-5g, be dissolved in 8-12mL deionized water, filter after be also transferred in there-necked flask; Described strong aqua concentration is 25%(w/v), add-on is 15-20mL, the reaction times is 1-5min; The dripping quantity of described oleic acid is 3-6g, continues rapid stirring 30-120min at 50-80 DEG C to obtain the molten gelatinoid of black.
3. the preparation method of a kind of superparamagnetic micron starch as claimed in claim 1, is characterized in that: after described magnetic fluid process washing, and vacuum lyophilization 40 h, obtaining finishing has the magnetic nano-particle of carboxyl.
4. the preparation method of a kind of superparamagnetic micron starch as claimed in claim 1, is characterized in that: described step 2) the middle magnetic fluid 10ml that is configured to 30-50mg/ml that adopts; Adopt the zymin 10ml that concentration is 3-5mg/ml; Equal-volume reacts 2-24h after mixing at 5-20 DEG C.
5. the preparation method of a kind of superparamagnetic micron starch as claimed in claim 1, it is characterized in that: in described step 3), insoluble raw starch takes 3-5g and adds in 100ml～200ml deionized water, and maintain the temperature at 20 DEG C-40 DEG C of raw starch gelatinization temperatures, stirring is uniformly dispersed raw starch and obtains raw starch dispersion liquid.
6. the preparation method of a kind of superparamagnetic micron starch as claimed in claim 1, it is characterized in that: in described step 4), magnetic nano-particle joins temperature of reaction in raw starch dispersion liquid at 10 DEG C～40 DEG C, stirring reaction 5-48h, after having reacted, magnetic separates to obtain magnetic starch sedimentation.
7. the preparation method of a kind of superparamagnetic micron starch as claimed in claim 1, is characterized in that: described drying temperature is below 40 DEG C.
8. the preparation method of a kind of superparamagnetic micron starch as claimed in claim 1, it is characterized in that: described insoluble raw starch comprises the various raw starch with complete grain pattern, and in the raw starch dispersion liquid obtaining in step 3), adopt linking agent to be cross-linked and to maintain its complete grain pattern raw starch; Described linking agent adopt Trisodium trimetaphosphate, oxalic dialdehyde, one in epoxy chloropropane.
9. the preparation method of a kind of superparamagnetic micron starch as claimed in claim 1, is characterized in that: described step 2) middle zymin employing amylase.
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| CN103804699B (en) * | 2014-02-10 | 2016-03-30 | 广西民族大学 | A kind of tapioca (flour) magnetic microsphere and preparation method thereof |
| CN104307480A (en) * | 2014-11-18 | 2015-01-28 | 成都理想财富投资咨询有限公司 | Preparing method for printing and dyeing sewage treatment magnetic particles |
| CN105581294A (en) * | 2016-02-18 | 2016-05-18 | 安徽徽风生态农业开发有限公司 | Preparation method of potato food with long guarantee period and convenience in eating |
| CN107008573B (en) * | 2017-06-19 | 2019-05-03 | 中南大学 | A kind of preparation method and application of magnetism starch beneficiation reagent |
| CN111665361B (en) * | 2020-04-29 | 2023-02-28 | 中南林业科技大学 | Lysosome-labeled magnetic fluorescent starch nanoparticle and preparation method thereof |
| CN112891613A (en) * | 2021-01-28 | 2021-06-04 | 西南大学 | Directional driving targeted hemostasis micromotor and preparation method thereof |
| CN113866073A (en) * | 2021-09-24 | 2021-12-31 | 致慧医疗科技(上海)有限公司 | Enzyme-sensitive nano material for efficiently capturing cancer cells, and preparation method and application thereof |
| CN113980951A (en) * | 2021-11-23 | 2022-01-28 | 东北农业大学 | Immobilized CALB preparation method based on nano dialdehyde starch carrier |
| CN114014418B (en) * | 2021-11-28 | 2023-07-07 | 贵州省分析测试研究院 | Preparation method of magnetic flocculant and application of magnetic flocculant in removal of microcystis aeruginosa |
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