CN100577747C - Method for preparing biocompatible helix-shaped amylose functionalized carbon nano-tubes - Google Patents
Method for preparing biocompatible helix-shaped amylose functionalized carbon nano-tubes Download PDFInfo
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- CN100577747C CN100577747C CN200710047938A CN200710047938A CN100577747C CN 100577747 C CN100577747 C CN 100577747C CN 200710047938 A CN200710047938 A CN 200710047938A CN 200710047938 A CN200710047938 A CN 200710047938A CN 100577747 C CN100577747 C CN 100577747C
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Abstract
The invention relates to a preparation method of amylose functionalized carbon nanotube of biocompatibility and spiral shape in the field of chemical technology. With the non-covalent physical influence, the natural amylose is used for functionalizing a carbon nanotube; the rest of amylose is washed away so that the surface of composition of the amylose and the carbon nanotube is of spiral shape; the final product has good biocompatibility; thus the final product is the amylose functionalized carbon nanotube of biocompatibility and spiral shape. The preparation method is simple and easy to be controlled; the product can be dispersed in water for a long time and has good biocompatibility; the product can be used as substrate for cell culture and can be widely used in the biological field.
Description
Technical field
The present invention relates to a kind of preparation method's of field of nanometer technology, particularly a kind of biocompatible helix-shaped amylose functionalized carbon nano-tubes preparation method.
Background technology
Carbon nanotube (being called for short CNT) is found in recent years a kind of novel carbon structure, it is the seamless hollow carbon pipe that curls and form by the Graphene lamella that carbon atom forms, two ends respectively have the fullerene molecule end-blocking half, are a kind of One-dimensional Quantum materials with height delocalization πDian Zi conjugated system.Carbon nanotube is divided into Single Walled Carbon Nanotube (SWNT) and multi-walled carbon nano-tubes (MWNT).Its preparation method mainly contains catalyse pyrolysis, arc-over, template, chemical Vapor deposition process etc.
Carbon nanotube (CNT) has been worth with its unique electronics and mechanical property and accurate one dimension tracheary element structure and potential huge applications since coming out, and becomes the focus of physics, chemistry, material and even biological study rapidly.Because the carbon nanotube tube wall is smooth and highly polarizable, easy reunion bunchy under strong Van der Waals force effect, water-soluble hardly and various organic solvents are difficult to disperse, and the application in a lot of fields is greatly limited.Therefore, carbon nanotube being carried out functional modification is in recent years by the research focus of extensive concern to improve its solubility property and dispersing property.Different with the mode of connection of functional decorative material according to carbon nanotube, functional method can be divided into two kinds of covalent modification and non covalent bond modifications.Covalent modification is by changing the sp of carbon atom on the carbon nanotube tube wall
2Configuration is realized the covalent bonding between decorative material and the carbon nanotube, so the electronic structure of destroying carbon nanometer tube and mechanical property to a certain extent.But not covalent modification then is to utilize the water repellent surface of carbon nanotube or πDian Zi structure to combine by weak interactions such as hydrophobic force, pi-pi accumulations with other molecule, can keep perfect electronic structure of carbon nanotube and mechanical property that considerable change does not take place.On the other hand, amylose starch is the research focus of natural polymer research field in recent years, it is with α-1 by glucose, the chain compound of 4-glycosidic link be combined into, in specific solvent, present helical conformation, owing to living things system good consistency and relative being easy to get are arranged, very big application prospect must be arranged.
Find through literature search prior art, " solvability of helical conformation amylose starch coated single-walled carbon nano tube " that Kim etc. delivered on 4426～4427 pages of " JACS " 2003 the 125th 15 phases of volume, proposing concrete grammar in this article is: be scattered in the water SWNT ultrasonic in advance earlier, then amylose starch and scattered carbon nanotube are put into the certain density methyl-sulphoxide and the aqueous solution, through ultrasonic, washing preparation amylose starch functionalized carbon nanotube.Its deficiency is: aftertreatment is difficult to unnecessary amylose starch flush away, thereby can't obtain trickleer surface topography.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of preparation method of biocompatible helix-shaped amylose functionalized carbon nano-tubes is provided, making it carry out non-covalent physics with amylose starch to carbon nanotube coats, preparation biocompatibility amylose starch functionalized carbon nano-tube, fully unnecessary starch on the flush away carbon nanotube has obtained regular helical surface pattern.
The present invention is achieved by the following technical solutions, the present invention is by non-covalent physical action, utilize natural amylose starch that carbon nanotube is carried out functionalization, the unnecessary amylose starch of flush away makes amylose starch and carbon mano-tube composite surface present the spiral pattern, final product has excellent biological compatibility, just biocompatible helix-shaped amylose functionalized carbon nano-tubes.
The present invention includes following steps:
Step a: starch material is mixed with deionized water with 0.01～1 weight ratio, stir, centrifugal, leave standstill, isolate upper strata amylose starch crude extract, to wherein adding ethanol, leave standstill, centrifugal, isolate lower floor's amylose starch, add ethanol drip washing repeatedly, filter, vacuum-drying obtains amylose starch;
Step b: the oxidizing acid of 1 weight part carbon nanometer tube material and 50～5000 weight parts is mixed, ultrasonication, stirring reaction, suction filtration repeatedly is neutral to solution with the deionized water repetitive scrubbing, obtains the carbon nanotube of purifying after the vacuum-drying;
Step c: with 1～100mg/mL step b gained purifying carbon nano-tube aqueous solution, 1 parts by volume with ultrasonication after, the dimethyl sulfoxide solution that adds 0.1～1 parts by volume amylose starch, ultrasonication, leave standstill, after filtration, solvent wash, washing, vacuum-drying obtains amylose starch and the carbon mano-tube composite that there be the spiral pattern on the surface.
Among the above-mentioned steps a, described starch material is a kind of in W-Gum, yam starch, the wheat starch.
Among the above-mentioned steps a, described stirring, centrifugal, leave standstill, be meant: churning time is 0.5h～10h, whipping temp is 20 ℃～100 ℃, is centrifugal 15min under the 3000g at centrifugal force, leaves standstill 1min～100min.
Among the above-mentioned steps a, describedly leave standstill to wherein adding ethanol, centrifugal, be meant: adding volume ratio and be 0.1～0.5 ethanol in the amylose starch crude extract of upper strata, leave standstill 1min～200min, is centrifugal 15min under the 3000g at centrifugal force.
Among the above-mentioned steps b, described carbon nanotube is the single wall or the multi-walled carbon nano-tubes of catalyse pyrolysis, arc-over, template, the preparation of chemical Vapor deposition process method.
Among the above-mentioned steps b, described oxidizing acid comprises nitric acid, 0.1～100% weight acid concentration sulfuric acid, 1/100 ~ 100/1 mol ratio nitric acid and sulfuric acid mixed solution, 1/100 ~ 100/1 mol ratio potassium permanganate and sulfuric acid mixed solution, 1/100 ~ 100/1 mol ratio H of 1～5mol/L
2O
2A kind of with in the sulfuric acid mixed solution.
Among the above-mentioned steps b, described ultrasonication, stirring reaction is meant: with 0kHz～100kHz ultrasonication 1min～100min, 20 ℃～200 ℃ are stirred reaction 1h～50h down.
Among the above-mentioned steps c, described solvent wash, its used solvent are methyl-sulphoxide, chloroform, tetrahydrofuran (THF), acetone, acetonitrile, butanone, pyridine or the mixed solvent that contains these solvents.
Among the above-mentioned steps c, the described ultrasonication of using is meant: with 0kHz～100kHz ultrasonication 1min～100min.
Among the above-mentioned steps c, described ultrasonication leaves standstill, and is meant: with 0kHz～100kHz ultrasonication 1min～100min, leave standstill 1h～50h.
The present invention utilizes perfect structure of carbon nanotube and excellent performance, and exploitation is that the biotype nano material of matrix is wanted with the carbon nanotube.Utilize the natural polymer amylose starch, carbon nanotube is carried out non-covalent physics to coat, the exclusive characteristic of amylose molecule excellent biological compatibility and carbon nanotube is organically combined, thereby can prepare nano composite material with biocompatibility.This has not only expanded the application of natural polymer and carbon nano-tube material greatly, has also promoted the development in nanoscale science and technology field simultaneously.
Preparation method provided by the invention is simple, and controllability is strong; Products obtained therefrom has the spiral pattern of rule, and pitch is 14-15nm; As the cell cultures substrate, mtt assay detects cell survival rate, and to be about primary carbon nanotube be 4 times of substrate sample with it.Because its excellent biological compatibility can be used as biomaterial and uses, and can widely be applied in all many-sides such as nano science, Materials science and biomedicine.
Description of drawings
Fig. 1: the electron scanning micrograph of biocompatible helix-shaped amylose functionalized carbon nano-tubes;
Fig. 2: the cytoactive check figure of biocompatible helix-shaped amylose functionalized carbon nano-tubes;
Fig. 3: the atomic force microscope photo of biocompatible helix-shaped amylose functionalized carbon nano-tubes.
Concrete embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
Single Walled Carbon Nanotube with chemical Vapor deposition process preparation is an initial raw material, through behind the purifying, coats the amylose starch functionalization to the Single Walled Carbon Nanotube surface by non-covalent physics, obtains biocompatible helix-shaped amylose functionalized carbon nano-tubes.
Step a: in single neck round-bottomed flask of magnetic agitation rotor is housed, add 5g W-Gum and 150mL deionized water, be heated to 80 ℃, stirring 60min, is centrifugal 15min under the 3000g at centrifugal force, leaves standstill 90min, isolate upper strata amylose starch crude extract,, leave standstill 90min to wherein adding 80mL ethanol, centrifugal 15min under centrifugal force 3000g isolates lower floor's amylose starch slurries, adds a large amount of washing with alcohol, filter, repeat 8 times, 50 ℃ of vacuum-dryings obtain amylose starch;
Step b: in single neck round-bottomed flask of magnetic agitation rotor is housed, the nitric acid that adds 40mg carbon nanometer tube material and 120mL 2.6mol/L, with 40kHz ultrasonication 30min post-heating to 120 ℃, reaction 48h down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain the carbon nanotube of purifying with a large amount of deionized water repetitive scrubbings behind 50 ℃ of vacuum-drying 24h;
Step c: in single neck round-bottomed flask of magnetic agitation rotor is housed, add the 85mL 2mg/mL step b gained purifying carbon nano-tube aqueous solution, behind 40kHz ultrasonication 30min, the dimethyl sulfoxide solution that adds 15mL 15mg/mL amylose starch, behind 40kHz ultrasonication 60min, after leaving standstill 48h, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, with the washing of 50mL methyl-sulphoxide, use φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration again, with a large amount of deionized water repetitive scrubbings, filter, repeat 5 times, 50 ℃ of vacuum-dryings obtain biocompatible helix-shaped amylose functionalized carbon nano-tubes.
Fig. 1 has provided the electron scanning micrograph of biocompatible helix-shaped amylose functionalized carbon nano-tubes, and photo presents uniform amylose starch of big area and carbon mano-tube composite mixture, pattern of well-regulated spiral type cycle of composite surface.
From cytoactive check data (Fig. 2) as can be seen, carbon nanotube after the amylose starch functionalization has better biological activity, being embodied in amylose starch and carbon mano-tube composite serves as to cultivate the substrate sample cell to cultivate 24h, it is comparative sample at the bottom of the substratum that 48h, 72h activity index all are higher than with simple carbon nanotube.
Embodiment 2
Single Walled Carbon Nanotube with catalytic pyrolysis method preparation is an initial raw material, through behind the purifying, coats the amylose starch functionalization to the Single Walled Carbon Nanotube surface by non-covalent physics, obtains biocompatible helix-shaped amylose functionalized carbon nano-tubes.
Step a: in single neck round-bottomed flask of magnetic agitation rotor is housed, add 10g yam starch and 200mL deionized water, be heated to 100 ℃, stirring 180min, is centrifugal 15min under the 3000g at centrifugal force, leaves standstill 75min, isolate upper strata amylose starch crude extract,, leave standstill 60min to wherein adding 100mL ethanol, centrifugal 15min under centrifugal force 3000g isolates lower floor's amylose starch slurries, adds a large amount of washing with alcohol, filter, repeat 8 times, 50 ℃ of vacuum-dryings obtain amylose starch;
Step b: in single neck round-bottomed flask of magnetic agitation rotor is housed, the sulfuric acid that adds 20mg carbon nanometer tube material and 80mL 20%, with 40kHz ultrasonication 15min post-heating to 110 ℃, reaction 24h down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain the carbon nanotube of purifying with a large amount of deionized water repetitive scrubbings behind 50 ℃ of vacuum-drying 24h;
Step c: in single neck round-bottomed flask of magnetic agitation rotor is housed, add the 170mL 3mg/mL step b gained purifying carbon nano-tube aqueous solution, behind 40kHz ultrasonication 30min, the dimethyl sulfoxide solution that adds 30mL 10mg/mL amylose starch, behind 40kHz ultrasonication 90min, after leaving standstill 24h, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, with the washing of 50mL pyridine, use φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration again, with a large amount of deionized water repetitive scrubbings, filter, repeat 5 times, 50 ℃ of vacuum-dryings obtain biocompatible helix-shaped amylose functionalized carbon nano-tubes.
Fig. 3 has provided the atomic force microscope photo of biocompatible helix-shaped amylose functionalized carbon nano-tubes, and photo can know that the surface of seeing the amylose starch functionalized carbon nano-tube has the spiral type cycle pattern of rule, and pitch is 14-15nm after measured.
Single Walled Carbon Nanotube with the preparation of chemical Vapor deposition process method is an initial raw material, through behind the purifying, coat the amylose starch functionalization to the Single Walled Carbon Nanotube surface by non-covalent physics, obtain biocompatible helix-shaped amylose functionalized carbon nano-tubes.
Step a: in single neck round-bottomed flask of magnetic agitation rotor is housed, add 7.5 wheat starches and 175mL deionized water, be heated to 90 ℃, stirring 120min, is centrifugal 15min under the 3000g at centrifugal force, leaves standstill 45min, isolate upper strata amylose starch crude extract,, leave standstill 45min to wherein adding 75mL ethanol, centrifugal 15min under centrifugal force 3000g isolates lower floor's amylose starch slurries, adds a large amount of washing with alcohol, filter, repeat 8 times, 50 ℃ of vacuum-dryings obtain amylose starch;
Step b: in single neck round-bottomed flask of magnetic agitation rotor is housed, the nitric acid that adds 30mg carbon nanometer tube material and 100mL 4mol/L, with 40kHz ultrasonication 20min post-heating to 95 ℃, reaction 12h down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain the carbon nanotube of purifying with a large amount of deionized water repetitive scrubbings behind 50 ℃ of vacuum-drying 24h;
Step c: in single neck round-bottomed flask of magnetic agitation rotor is housed, add the 255mL 4mg/mL step b gained purifying carbon nano-tube aqueous solution, behind 40kHz ultrasonication 20min, the dimethyl sulfoxide solution that adds 45mL 23mg/mL amylose starch, behind 40kHz ultrasonication 75min, after leaving standstill 12h, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, acetone and the washing of pyridine mixed solvent with 50mL 1/1 volume ratio, use φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration again,, filter with a large amount of deionized water repetitive scrubbings, repeat 5 times, 50 ℃ of vacuum-dryings obtain biocompatible helix-shaped amylose functionalized carbon nano-tubes, with it as the cell cultures substrate, it is 140% that mtt assay detects cell survival rate, and being higher than primary carbon nanotube is the cell survival rate 40% of substrate sample.
Single Walled Carbon Nanotube with catalytic pyrolysis method preparation is an initial raw material, through behind the purifying, coats the amylose starch functionalization to the Single Walled Carbon Nanotube surface by non-covalent physics, obtains biocompatible helix-shaped amylose functionalized carbon nano-tubes.
Step a: in single neck round-bottomed flask of magnetic agitation rotor is housed, add 3g W-Gum and 100mL deionized water, be heated to 105 ℃, stirring 90min, is centrifugal 15min under the 3000g at centrifugal force, leaves standstill 55min, isolate upper strata amylose starch crude extract,, leave standstill 60min to wherein adding 80mL ethanol, centrifugal 15min under centrifugal force 3000g isolates lower floor's amylose starch slurries, adds a large amount of washing with alcohol, filter, repeat 8 times, 50 ℃ of vacuum-dryings obtain amylose starch;
Step b: in single neck round-bottomed flask of magnetic agitation rotor is housed, the sulfuric acid that adds 50mg carbon nanometer tube material and 150mL 40%, with 40kHz ultrasonication 25min post-heating to 90 ℃, reaction 24h down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain the carbon nanotube of purifying with a large amount of deionized water repetitive scrubbings behind 50 ℃ of vacuum-drying 24h;
Step c: in single neck round-bottomed flask of magnetic agitation rotor is housed, add the 90mL 1mg/mL step b gained purifying carbon nano-tube aqueous solution, behind 40kHz ultrasonication 30min, the dimethyl sulfoxide solution that adds 16mL 10mg/mL amylose starch, behind 40kHz ultrasonication 25min, after leaving standstill 16h, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, mixed solvent washing with 50mL 1/1 volume ratio methyl-sulphoxide and acetone, use φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration again, with a large amount of deionized water repetitive scrubbings, filter, repeat 5 times, 50 ℃ of vacuum-dryings, obtain biocompatible helix-shaped amylose functionalized carbon nano-tubes, as the cell cultures substrate, it is 150% that mtt assay detects cell survival rate with it.
Claims (8)
1. the preparation method of a biocompatible helix-shaped amylose functionalized carbon nano-tubes is characterized in that, may further comprise the steps:
Step a: starch material is mixed with deionized water with 0.01～1 weight ratio, stir, centrifugal, leave standstill, isolate upper strata amylose starch crude extract, to wherein adding ethanol, leave standstill, centrifugal, isolate lower floor's amylose starch, add ethanol drip washing repeatedly, filter, vacuum-drying obtains amylose starch;
Step b: the oxidizing acid of 1 weight part carbon nanometer tube material and 1～100 weight part is mixed, ultrasonication, stirring reaction, suction filtration repeatedly is neutral to solution with the deionized water repetitive scrubbing, obtains the carbon nanotube of purifying after the vacuum-drying;
Step c: with 1～100mg/mL step b gained purifying carbon nano-tube aqueous solution, 1 parts by volume with ultrasonication after, the dimethyl sulfoxide solution that adds 0.1～1 parts by volume amylose starch, ultrasonication, leave standstill, after filtration, solvent wash, washing, vacuum-drying obtains amylose starch and the carbon mano-tube composite that there be the spiral pattern on the surface;
Described solvent wash, its used solvent are methyl-sulphoxide, chloroform, tetrahydrofuran (THF), acetone, acetonitrile, butanone, pyridine or the mixed solvent that contains these solvents;
The described ultrasonication of using is meant: with 0kHz～100kHz ultrasonication 1min～100min.
2. the preparation method of biocompatible helix-shaped amylose functionalized carbon nano-tubes according to claim 1 is characterized in that, among the step a, described starch material is a kind of in W-Gum, yam starch, the wheat starch.
3. the preparation method of biocompatible helix-shaped amylose functionalized carbon nano-tubes according to claim 1 and 2, among the step a, described stirring, centrifugal, leave standstill, be meant: churning time is 0.5h～10h, and whipping temp is 20 ℃～100 ℃, at centrifugal force is centrifugal 15min under the 3000g, leaves standstill 1min～100min.
4. the preparation method of biocompatible helix-shaped amylose functionalized carbon nano-tubes according to claim 1 and 2, among the step a, described to wherein adding ethanol, leave standstill, centrifugal, be meant: the adding volume ratio is 0.1～0.5 ethanol in the amylose starch crude extract of upper strata, leaves standstill 1min～100min, is centrifugal 15min under the 3000g at centrifugal force.
5. the preparation method of biocompatible helix-shaped amylose functionalized carbon nano-tubes according to claim 1, it is characterized in that, among the step b, described carbon nanotube is the single wall or the multi-walled carbon nano-tubes of catalyse pyrolysis, arc-over, template, the preparation of chemical Vapor deposition process method.
6. the preparation method of biocompatible helix-shaped amylose functionalized carbon nano-tubes according to claim 1 or 5, it is characterized in that, among the step b, described ultrasonication, stirring reaction, be meant: with 0kHz～100kHz ultrasonication 1min～100min, 20 ℃～200 ℃ are stirred reaction 1h～50h down.
7. the preparation method of biocompatible helix-shaped amylose functionalized carbon nano-tubes according to claim 1 or 5, it is characterized in that, among the step b, described oxidizing acid comprises nitric acid, sulfuric acid, 1/100 ~ 100/1 mol ratio nitric acid and sulfuric acid mixed solution, 1/100 ~ 100/1 mol ratio potassium permanganate and the sulfuric acid mixed solution of 0.1～100% weight percent concentration, 1/100 ~ 100/1 mol ratio H of 1～5mol/L
2O
2A kind of with in the sulfuric acid mixed solution.
8. the preparation method of biocompatible helix-shaped amylose functionalized carbon nano-tubes according to claim 1 is characterized in that, among the step c, described ultrasonication, leave standstill, be meant:, leave standstill 1h～50h with 0kHz～100kHz ultrasonication 1min～100min.
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| CN101353430B (en) * | 2008-07-15 | 2011-03-30 | 中山大学 | Method for preparing amylose water solution |
| CN102992301A (en) * | 2012-12-28 | 2013-03-27 | 江南大学 | Method for enhancing solubility of single-walled carbon nanotube in water by utilizing spring dextrin |
| CN104548126B (en) * | 2015-01-16 | 2017-08-25 | 中山大学 | A kind of coiled strand polysaccharide derivates load compound and its preparation and application of single-walled carbon nanotube and nucleic acid altogether |
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Non-Patent Citations (4)
| Title |
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| Solubilization of Single-Wall Carbon Nanotubes bySupramolecular Encapsulation of Helical Amylose. Oh-Kil Kim,Jongtae Je等.Journal of the American Chemical Society,Vol.125 No.15. 2003 |
| Solubilization of Single-Wall Carbon Nanotubes bySupramolecular Encapsulation of Helical Amylose. Oh-Kil Kim,Jongtae Je等.Journal of the American Chemical Society,Vol.125 No.15. 2003 * |
| 减压化学气相沉积法制备规则螺旋状纳米碳管. 陆梅.郭新勇.力虎林等.高等学校化学学报，第25卷第8期. 2004 |
| 减压化学气相沉积法制备规则螺旋状纳米碳管. 陆梅.郭新勇.力虎林等.高等学校化学学报，第25卷第8期. 2004 * |
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