CN102010525A - Method for preparing superparamagnetic micron starch - Google Patents
Method for preparing superparamagnetic micron starch Download PDFInfo
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- CN102010525A CN102010525A CN2010105478863A CN201010547886A CN102010525A CN 102010525 A CN102010525 A CN 102010525A CN 2010105478863 A CN2010105478863 A CN 2010105478863A CN 201010547886 A CN201010547886 A CN 201010547886A CN 102010525 A CN102010525 A CN 102010525A
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- superparamagnetism
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- 229920002472 Starch Polymers 0.000 title claims abstract description 120
- 235000019698 starch Nutrition 0.000 title claims abstract description 120
- 239000008107 starch Substances 0.000 title claims abstract description 119
- 238000000034 method Methods 0.000 title abstract description 5
- 230000005291 magnetic effect Effects 0.000 claims abstract description 75
- 238000002360 preparation method Methods 0.000 claims abstract description 36
- 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
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 239000011553 magnetic fluid Substances 0.000 claims abstract description 26
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 26
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 15
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 13
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 13
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005642 Oleic acid Substances 0.000 claims abstract description 13
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 108090000790 Enzymes Proteins 0.000 claims abstract description 11
- 102000004190 Enzymes Human genes 0.000 claims abstract description 11
- 238000001556 precipitation Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 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
- 239000007788 liquid Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 12
- 238000004062 sedimentation Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 240000003183 Manihot esculenta Species 0.000 claims description 8
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 8
- 235000007164 Oryza sativa Nutrition 0.000 claims description 8
- 235000009566 rice Nutrition 0.000 claims description 8
- 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
- 235000013312 flour Nutrition 0.000 claims description 5
- 229920001592 potato starch Polymers 0.000 claims description 5
- 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
- 235000013339 cereals Nutrition 0.000 claims description 4
- 230000032696 parturition Effects 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
- 108010028688 Isoamylase Proteins 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 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
- 238000002156 mixing Methods 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
- 230000005298 paramagnetic effect Effects 0.000 description 23
- 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
- 241000209094 Oryza Species 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
- 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
- 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
- 238000010521 absorption reaction Methods 0.000 description 3
- 235000005822 corn Nutrition 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
- 230000008901 benefit Effects 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
- 239000002105 nanoparticle Substances 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
- 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
- 230000002950 deficient 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
- 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 superparamagnetism micron starch.
Background technology
Magnetic microsphere has that particle diameter is little, specific surface area is big, be easy to adsorb characteristics such as other material, tool superparamagnetism, utilize the magnetic microsphere of biocompatible materials preparation or to be adsorbed on macromolecule layer with drug encapsulation, therefore can be used as target medicine carrier and realize targeted delivery of drugs, have important use and be worth.Pharmaceutical carrier can enter in the human body with medicine, requires carrier harmless.
With the magnetic microsphere of starch preparation have nontoxic, meta-bolites can excrete, biodegradable, easy to prepare, plurality of advantages such as material is cheap, and starch can not produce the antigenicity of protein material, is more conducive to use.
Existing magnetic spherex, generally be to prepare the nano level ultra paramagnetic particle earlier, prepare Zulkovsky starch solution then, to surpass the paramagnetic nano particle again is dispersed in the Zulkovsky starch solution, the reaction certain hour makes starch molecule be adsorbed on the magnetic nano particle sub-surface, makes magnetic Nano starch after the oven dry.What the magnetic Nano starch of this method preparation used is Zulkovsky starch, has destroyed the vesicular structure of starch inside, can the serious absorption medicine carrying capacity that reduces starch.
People such as Wen Qibiao disclose a kind of preparation method who prepares superparamagnetic starch in patent 200610123853.X, at first use starch milk absorption soluble ferrite, utilize hydrogen peroxide oxidation to be adsorbed on the inner and surperficial ferrous particle of starch then, obtain super paramagnetic starch after drying.Since the ferrous particle of enough Z 250 crystal production can not be provided in preparation process of this method, thus need could prepare excess of export paramagnetic starch through the multiple adsorb oxidation, and more super paramagnetic starch granules is arranged in surface arrangement.
People such as Wang Li provide a kind of preparation method of magnetic macromolecular microsphere of crosslinking dialdehyde starch in patent 200610146935.6, at only containing hydroxyl in the starch magnetic microsphere, when being used for targeting preparation, contain amino medicine and be difficult for immobilized defective on the starch magnetic microsphere, the starch magnetic microsphere is carried out modification, prepared the 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 purpose of this invention is to provide a kind of method of utilizing the super paramagnetic micron starch of various insoluble starches and starch derivative preparation, prepared super paramagnetic micron starch has farinose structure and super paramagnetic characteristic.
In order to reach above-mentioned purpose, solution of the present invention is:
A kind of preparation method of superparamagnetism micron starch may further comprise the steps:
1) takes by weighing FeCl
36H
2O solid and FeCl
24H
2Under the intense agitation of O solid dissolving back, add strong aqua, dropwise add oleic acid then, obtain black colloidal sol shape material behind the stirring reaction, utilize externally-applied magnetic field that the precipitation of gained is separated from reaction system and obtain magnetic fluid;
2) magnetic fluid and the magnetic nano-particle that obtains being adsorbed with zymin after zymin equal-volume mixing magnetic separates;
3) adopt insoluble living starch to add deionized water and stirring and obtain giving birth to starch dispersion liquid;
4) with step 2) in the magnetic nano-particle that is adsorbed with zymin that obtains join in the resulting living starch dispersion liquid of step 3), reaction back magnetic separates and obtains the magnetic starch sedimentation;
5) magnetic starch sedimentation drying that step 4) is obtained or lyophilize promptly get superparamagnetism micron starch powder, one or many super paramagnetic nano particles are contained in the superparamagnetism micron starch inside of gained, the partial starch surface also has magnetic nano-particle, the original characteristic of the employed living starch of its structure and shape maintains.
FeCl in the described step 1)
36H
2O solid consumption is 7-9g, is transferred in the there-necked flask after being dissolved in the 140-160mL deionized water; FeCl
24H
2O solid consumption is 4-5g, is dissolved in the 8-12mL deionized water, also is transferred in the there-necked flask after filtering; Described strong aqua concentration is 25%(w/v), add-on is 15-20mL, the reaction times is 1-5min; Described oleic dripping quantity is 3-6g, and 50-80 ℃ is continued to stir fast 30-120min down and obtain black colloidal sol shape material.
Utilize externally-applied magnetic field that the precipitation of the black colloidal sol shape material of gained is separated from reaction system in the described step 1), utilize alcohol washing to remove unnecessary oleic acid 2-5 times, again with deionized water wash to the pH=7; Adding 100-200 ml concentration then 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, magnetic separate back deionized water wash 3 times, obtain magnetic fluid.
Described magnetic fluid is through after the washing, and vacuum lyophilization 40 h obtain the magnetic nano-particle that finishing has carboxyl.
Described step 2) adopt in be configured to 30-50mg/ml magnetic fluid 10ml; Adopting concentration is the zymin 10ml of 3-5mg/ml; Equal-volume mixes the back and reacts 2-24h down at 5-20 ℃.
Insoluble living starch takes by weighing 3-5g and adds in 100ml～200ml deionized water in the described step 3), and maintains the temperature at 20 ℃ of living starch gelatinization temperatures below-40 ℃, stirs living starch to be uniformly dispersed obtain giving birth to starch dispersion liquid.
Magnetic nano-particle joins temperature of reaction in the living starch dispersion liquid at 10 ℃～40 ℃ in the described step 4), stirring reaction 5-48h, after reaction is finished, magnetic separate the magnetic starch sedimentation.
Drying temperature is below 40 ℃ in the described step 5).
Described insoluble living starch comprises the various living starch with complete grain pattern, adopt a kind of in W-Gum, Starch rice, potato starch, the tapioca (flour), and adopt linking agent that life starch is carried out crosslinked its complete grain pattern of keeping in the livings starch dispersion liquid that obtains in the step 3); Described linking agent adopt Trisodium trimetaphosphate, oxalic dialdehyde, a kind of in the epoxy chloropropane.
Described zymin adopts a kind of in saccharifying enzyme, amylase, the isoamylase.
Beneficial effect of the present invention is: the present invention utilizes the super paramagnetic micron starch of various living starch preparations such as corn, rice (rice is divided into polished rice and glutinous rice), potato, cassava to keep original vesicular structure of living starch and shape, and has super paramagnetic characteristic, can be used as target medicine carrier, improve bioavailability of medicament, reduce Side effects of pharmaceutical drugs.The present invention compared with prior art has following advantage: at first the magnetic starch of the present invention's preparation is kept 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 contains less magnetic nanoparticle.So preparation technology of the present invention is simple, green, environmental protection, does not have any toxic reagent, therefore can be used as medical carrier.
Embodiment
Embodiment 1
The preparation of super paramagnetic polished rice starch
Accurately take by weighing Iron(III) chloride hexahydrate 8.1g and be dissolved in 142.5 ml deionized waters, transfer in the there-necked flask, be heated with stirring to 70 ℃.Take by weighing Iron dichloride tetrahydrate 4.4 g and be dissolved in the 10ml deionized water, filter, get 7.5 ml and add there-necked flask.Under intense stirring condition, add fast 18 ml strong aquas (25%, w/v), behind 1 min, dropwise add 4.66 g oleic acid, 70 ℃ are continued down to stir fast 1 h.Reaction obtains black colloidal sol shape material after finishing, and utilizes externally-applied magnetic field that the precipitation of gained is separated from reaction system.Remove unnecessary oleic acid 2 times with alcohol washing, again with deionized water wash to the pH=7.Adding 160 ml concentration then 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, magnetic separate back deionized water wash 3 times, obtain magnetic fluid.Also can be with after the magnetic fluid washing, vacuum lyophilization 40 h, obtaining finishing has the magnetic nano-particle of carboxyl standby.
Configuration concentration is 50mg/ml magnetic fluid 10ml, and configuration concentration is the Glucoamylase Solution 10ml of 5mg/ml, and 2 equal-volumes are mixed, and 20 ℃ are reacted 4h down, obtain being adsorbed with the magnetic nano-particle of saccharifying enzyme after magnetic separates.
Insoluble polished rice starch 5g is added in the 100ml deionized water 20 ℃ of insulation 1h.Stirring obtains polished rice and gives birth to starch dispersion liquid.
The magnetic nano-particle that is adsorbed with saccharifying enzyme is added above-mentioned polished rice give birth in the starch dispersion liquid, holding temperature is at 40 ℃, stirring reaction 15h, after reaction is finished, magnetic separate the magnetic starch sedimentation, lyophilize below 40 ℃ obtains super paramagnetic micron starch powder.
Super paramagnetic polished rice starch load 5-aminosalicylic acid
With the 5-aminosalicylic acid is model drug, the 5-aminosalicylic acid saturated solution of configuration 200ml, the 5-aminosalicylic acid saturated solution that the magnetic starch 5g of preparation among the embodiment 4 is added 200ml, behind the whip attachment 3h, magnetic separation filtration, drying obtain being adsorbed with the magnetic starch of 5-aminosalicylic acid.Therefore the release in vitro performance of this drug loaded magnetic starch in colonic fluid is as shown in table 1, magnetic starch can be moved to lesions position and carries out targeted therapy adding under the magnetic action orientation.
Embodiment 2
The preparation of super paramagnetic tapioca (flour)
Accurately take by weighing Iron(III) chloride hexahydrate 8.1 g and be dissolved in 142.5 ml deionized waters, transfer in the there-necked flask, be heated with stirring to 70 ℃.Take by weighing Iron dichloride tetrahydrate 4.4 g and be dissolved in the 10ml deionized water, filter, get 7.5 ml and add there-necked flask.Under intense stirring condition, add fast 18 ml strong aquas (25%, w/v), behind 1 min, dropwise add 4.66 g oleic acid, 70 ℃ are continued down to stir fast 1 h.Reaction obtains black colloidal sol shape material after finishing, and utilizes externally-applied magnetic field that the precipitation of gained is separated from reaction system.Remove unnecessary oleic acid 2 times with alcohol washing, again with deionized water wash to the pH=7.Adding 160 ml concentration then 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, magnetic separate back deionized water wash 3 times, obtain magnetic fluid.Perhaps the washing after, vacuum lyophilization 40 h, obtaining finishing has the magnetic nano-particle of carboxyl standby.
Configuration concentration is 50mg/ml magnetic fluid 10ml, and configuration concentration is the living amylase solution 10ml of 5mg/ml, and 2 equal-volumes are mixed, and 20 ℃ are reacted 4h down, obtains being adsorbed with living diastatic magnetic nano-particle after magnetic separates.
Insoluble tapioca (flour) 5g is added in the 100ml deionized water, add the linking agent Trisodium trimetaphosphate, 30 ℃ of insulation 1h.Again be scattered in after the filtration in the 100ml deionized water, stir and obtain the living starch dispersion liquid of cassava.
To be adsorbed with and give birth to diastatic magnetic nano-particle and add above-mentioned cassava and give birth in the starch dispersion liquid, holding temperature is at 30 ℃, stirring reaction 24h, after reaction is finished, magnetic separate the magnetic starch sedimentation, lyophilize below 40 ℃ obtains super paramagnetic micron starch powder.
Super paramagnetic tapioca (flour) load 5-aminosalicylic acid
With the 5-aminosalicylic acid is model drug, the 5-aminosalicylic acid saturated solution of configuration 200ml, the 5-aminosalicylic acid saturated solution that the magnetic starch 5g of preparation among the embodiment 2 is added 200ml, behind the whip attachment 3h, magnetic separation filtration, drying obtain being adsorbed with the magnetic starch of 5-aminosalicylic acid.Therefore the release in vitro performance of this drug loaded magnetic starch in colonic fluid is as shown in table 1, magnetic starch can be moved to lesions position and carries out targeted therapy adding under the magnetic action orientation.
Embodiment 3
The preparation of super paramagnetic W-Gum
Accurately take by weighing Iron(III) chloride hexahydrate 7g and be dissolved in the 140ml deionized water, transfer in the there-necked flask, be heated with stirring to 50 ℃.Take by weighing Iron dichloride tetrahydrate 4g and be dissolved in the 8ml deionized water, filter, get 7ml and add there-necked flask.Under intense stirring condition, add fast the 15ml strong aqua (25%, w/v), behind 3 min, dropwise add 3.2g oleic acid, 50 ℃ are continued down to stir fast 30min.Reaction obtains black colloidal sol shape material after finishing, and utilizes externally-applied magnetic field that the precipitation of gained is separated from reaction system.Remove unnecessary oleic acid 3 times with alcohol washing, again with deionized water wash to the pH=7.Adding 100 ml concentration then is the KMnO of 8mg/ml
4Solution, KMnO
4Solution oxide magnetic fluid surface oleic acid forms carboxyl.Ultrasonic washing instrument sonic oscillation 8 h, magnetic separate back deionized water wash 3 times, obtain magnetic fluid.Perhaps the washing after, vacuum lyophilization 40 h, obtaining finishing has the magnetic nano-particle of carboxyl standby.
Configuration concentration is 30mg/ml magnetic fluid 10ml, and configuration concentration is the Glucoamylase Solution 10ml of 3mg/ml, and 2 equal-volumes are mixed, and 5 ℃ are reacted 24h down, obtain being adsorbed with the magnetic nano-particle of saccharifying enzyme after magnetic separates.
Insoluble W-Gum 3g is added in the 150ml deionized water, add the linking agent oxalic dialdehyde, 20 ℃ of insulation 1h.Again be scattered in after the filtration in the 150ml deionized water, stir and obtain the living starch dispersion liquid of corn.
The magnetic nano-particle that is adsorbed with saccharifying enzyme is added above-mentioned corn give birth in the starch dispersion liquid, holding temperature is at 10 ℃, stirring reaction 48h, after reaction is finished, magnetic separate the magnetic starch sedimentation, lyophilize below 40 ℃ obtains super paramagnetic micron starch powder.
Super paramagnetic W-Gum load 5-aminosalicylic acid
With the 5-aminosalicylic acid is model drug, the 5-aminosalicylic acid saturated solution of configuration 200ml, the 5-aminosalicylic acid saturated solution that the magnetic starch 5g of preparation among the embodiment 3 is added 200ml, behind the whip attachment 3h, magnetic separation filtration, drying obtain being adsorbed with the magnetic starch of 5-aminosalicylic acid.Therefore the release in vitro performance of this drug loaded magnetic starch in colonic fluid is as shown in table 3, magnetic starch can be moved to lesions position and carries out targeted therapy adding under the magnetic action orientation.
Embodiment 4
The preparation of super paramagnetic potato starch
Accurately take by weighing Iron(III) chloride hexahydrate 9g and be dissolved in the 150ml deionized water, transfer in the there-necked flask, be heated with stirring to 80 ℃.Take by weighing Iron dichloride tetrahydrate 5g and be dissolved in the 12ml deionized water, filter, get 9.5 ml and add there-necked flask.Under intense stirring condition, add fast 20 ml strong aquas (25%, w/v), behind the 5min, dropwise add 6g oleic acid, 80 ℃ are continued down to stir fast 120min.Reaction obtains black colloidal sol shape material after finishing, and utilizes externally-applied magnetic field that the precipitation of gained is separated from reaction system.Remove unnecessary oleic acid 5 times with alcohol washing, again with deionized water wash to the pH=7.Adding 200 ml concentration then 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, magnetic separate back deionized water wash 3 times, obtain magnetic fluid.Perhaps the washing after, vacuum lyophilization 40 h, obtaining finishing has the magnetic nano-particle of carboxyl standby.
Configuration concentration is 40mg/ml magnetic fluid 10ml, and configuration concentration is the living amylase solution 10ml of 4mg/ml, and 2 equal-volumes are mixed, and 15 ℃ are reacted 12h down, obtains being adsorbed with living diastatic magnetic nano-particle after magnetic separates.
Insoluble potato starch 4g is added in the 200ml deionized water, add the linking agent epoxy chloropropane, 40 ℃ of insulation 1h.Again be scattered in after the filtration in the 200ml deionized water, stir and obtain the living starch dispersion liquid of potato.
To be adsorbed with and give birth to diastatic magnetic nano-particle and add above-mentioned potato and give birth in the starch dispersion liquid, holding temperature is at 40 ℃, stirring reaction 12h, after reaction is finished, magnetic separate the magnetic starch sedimentation, lyophilize below 40 ℃ obtains super paramagnetic micron starch powder.
Super paramagnetic potato starch load 5-aminosalicylic acid
With the 5-aminosalicylic acid is model drug, the 5-aminosalicylic acid saturated solution of configuration 200ml, the 5-aminosalicylic acid saturated solution that the magnetic starch 5g of preparation among the embodiment 4 is added 200ml, behind the whip attachment 3h, magnetic separation filtration, drying obtain being adsorbed with the magnetic starch of 5-aminosalicylic acid.Therefore the release in vitro performance of this drug loaded magnetic starch in colonic fluid is as shown in table 4, magnetic starch can be moved to lesions position and carries out targeted therapy adding under the magnetic action orientation.
Claims (10)
1. the preparation method of a superparamagnetism micron starch is characterized in that: may further comprise the steps:
1) takes by weighing FeCl
36H
2O solid and FeCl
24H
2Under the intense agitation of O solid dissolving back, add strong aqua, dropwise add oleic acid then, obtain black colloidal sol shape material behind the stirring reaction, utilize externally-applied magnetic field that the precipitation of gained is separated from reaction system and obtain magnetic fluid;
2) magnetic fluid mixes with enzymes soln, obtains being adsorbed with the magnetic nano-particle of zymin after magnetic separates;
3) adopt insoluble living starch to add deionized water and stirring and obtain giving birth to starch dispersion liquid;
4) with step 2) in the magnetic nano-particle that is adsorbed with zymin that obtains join in the resulting living starch dispersion liquid of step 3), reaction back magnetic separates and obtains the magnetic starch sedimentation;
5) magnetic starch sedimentation drying that step 4) is obtained or lyophilize promptly get superparamagnetism micron starch powder.
2. the preparation method of a kind of superparamagnetism micron starch as claimed in claim 1 is characterized in that: FeCl in the described step 1)
36H
2O solid consumption is 7-9g, is transferred in the there-necked flask after being dissolved in the 140-160mL deionized water; FeCl
24H
2O solid consumption is 4-5g, is dissolved in the 8-12mL deionized water, also is transferred in the there-necked flask after filtering; Described strong aqua concentration is 25%(w/v), add-on is 15-20mL, the reaction times is 1-5min; Described oleic dripping quantity is 3-6g, and 50-80 ℃ is continued to stir fast 30-120min down and obtain black colloidal sol shape material.
3. the preparation method of a kind of superparamagnetism micron starch as claimed in claim 1, it is characterized in that: utilize externally-applied magnetic field that the precipitation of the black colloidal sol shape material of gained is separated from reaction system in the described step 1), utilize alcohol washing to remove unnecessary oleic acid 2-5 times, again with deionized water wash to the pH=7; Adding 100-200 ml concentration then is the KMnO of 8-12 mg/ml
4Solution oxide surface oleic acid forms carboxyl, and ultrasonic washing instrument sonic oscillation 8 h, magnetic separate back deionized water wash 3 times, obtain magnetic fluid.
4. the preparation method of a kind of superparamagnetism micron starch as claimed in claim 3 is characterized in that: described magnetic fluid is through after the washing, and vacuum lyophilization 40 h obtain the magnetic nano-particle that finishing has carboxyl.
5. the preparation method of a kind of superparamagnetism micron starch as claimed in claim 1 is characterized in that: adopt described step 2) be configured to 30-50mg/ml magnetic fluid 10ml; Adopting concentration is the zymin 10ml of 3-5mg/ml; Equal-volume mixes the back and reacts 2-24h down at 5-20 ℃.
6. the preparation method of a kind of superparamagnetism micron starch as claimed in claim 1, it is characterized in that: insoluble living starch takes by weighing in 3-5g adding 100ml～200ml deionized water in the described step 3), and maintain the temperature at 20 ℃ of living starch gelatinization temperatures below-40 ℃, stir and living starch is uniformly dispersed obtain giving birth to starch dispersion liquid.
7. the preparation method of a kind of superparamagnetism micron starch as claimed in claim 1, it is characterized in that: magnetic nano-particle joins temperature of reaction in the living starch dispersion liquid at 10 ℃～40 ℃ in the described step 4), stirring reaction 5-48h, the reaction finish after, magnetic separate the magnetic starch sedimentation.
8. the preparation method of a kind of superparamagnetism micron starch as claimed in claim 1 is characterized in that: described drying temperature is below 40 ℃.
9. the preparation method of a kind of superparamagnetism micron starch as claimed in claim 1, it is characterized in that: described insoluble living starch comprises the various living starch with complete grain pattern, adopt a kind of in W-Gum, Starch rice, potato starch, the tapioca (flour), and adopt linking agent that life starch is carried out crosslinked its complete grain pattern of keeping in the livings starch dispersion liquid that obtains in the step 3); Described linking agent adopt Trisodium trimetaphosphate, oxalic dialdehyde, a kind of in the epoxy chloropropane.
10. the preparation method of a kind of superparamagnetism micron starch as claimed in claim 1 is characterized in that: zymin adopts a kind of in saccharifying enzyme, amylase, the isoamylase in the described step 5).
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