CN103007285A - Preparation method for folic acid-decorated and rare earth-modified carbon nano tube - Google Patents
Preparation method for folic acid-decorated and rare earth-modified carbon nano tube Download PDFInfo
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Abstract
The invention relates to a preparation method for a folic acid-decorated and rare earth-modified carbon nano tube. The method comprises the following steps: 1, soaking a carbon nano tube after functionalization processing into a rare earth modifying agent for 2-4 hours at room temperature, performing ultrasonic dispersion for 1-3 hours, filtering and drying; 2, using thionyl chloride to process the rare earth modified carbon nano tube obtained in step 1, so as to enable the functional group carboxyl on the rare earth modified carbon nano tube to be converted into acyl chloride, and grafting the obtained acylating chlorination carbon nano tube on a polymer polyethyleneglycol through an esterification reaction; and 3, adopting folic acid to perform decoration processing on the product obtained in step 2, so as to enable the product to have biocompatibility. Compared with the prior art, the preparation method has the advantages of no toxicity, excellent sensibilization performance, favorable dispersivity, biocompatibility and targeting performance and the like.
Description
Technical field
The present invention relates to a kind of modified carbon nano-tube that is applied to cancer therapy drug, especially relate to a kind of preparation method of modified with folic acid rare earth modified carbon nanotube.
Background technology
CNT is applied in the biomedical particularly research on pharmaceutical carrier becomes new focus gradually.CNT has unique one-dimentional structure, have unique character such as physical chemistry, electricity and optics, its outer surface is except adsorbing various molecules by noncovalent force, all right bonding number of chemical group is to realize solubilising and targeting, its inner space then can embedded ion and micromolecule, and can pass through cell membrane with the toxicity of minimum, CNT comprises that in biomedicine the aspects such as drug delivery, molecular image, gene therapy have preferably application prospect.
But CNT radially has nano-grade size and higher surface energy, easily is under normal conditions aggregating state, bad dispersibility; Be insoluble to most solvents, wet performance is poor.In order to strengthen the dispersibility of CNT, must modify and modification carbon nano tube surface.Utilize the defective of CNT itself, make its fault location oxidation by certain method, form the functional group with certain function, such as hydroxyl, carboxyl etc.
In addition, at present most of research concentrates on CNT is transmitted the bioactive molecule of contrast agent, medicine and tool as a kind of effective tumor cell carrier, and CNT can absorb special laser and ray and then change into heat and destroy tumor cell simultaneously.But, for the specific Clinics and Practices for tumor cell of CNT, also need to improve the targeting of carbon pipe.
Summary of the invention
Purpose of the present invention is exactly a kind of nontoxic, enhanced sensitivity excellent performance is provided in order to overcome the defective that above-mentioned prior art exists, has the preparation method of the modified with folic acid rare earth modified carbon nanotube of good dispersion, biocompatibility and targeting.
Purpose of the present invention can be achieved through the following technical solutions: a kind of preparation method of modified with folic acid rare earth modified carbon nanotube is characterized in that the method may further comprise the steps:
(1) CNT after the functionalization is at room temperature immersed soak 2～4 hours in the rare-earth modifier first, ultrasound wave disperseed 1～3 hour, filtered post-drying;
(2) with thionyl chloride treatment step (1) gained rare earth modified carbon nanotube, make the functional group's carboxyl on the rare earth modified carbon nanotube be converted to acyl chlorides, the chloride CNT that obtains is grafted on the polymer poly ethylene glycol by esterification;
(3) adopt folic acid that above-mentioned steps (2) products therefrom is modified processing, make it have biocompatibility.
The described functionalized carbon nanotube of step (1) is treated to: CNT is ground to form carbon nanotube powder, then mix with salpeter solution, place ultrasonator to vibrate again; The mass volume ratio of described carbon nanotube powder and salpeter solution is 20mg/ml.
The concentration of described salpeter solution is 3.0mol/L.
The mass volume ratio of the described CNT of step (1) and rare-earth modifier is 2mg/mL.
The weight percentages of components of the described rare-earth modifier of step (1) is: rare earth compound 1～2%, alcohol 95 .5～96.5%, ethylenediaminetetraacetic acid 0.2%, ammonium chloride 0.8%, nitric acid 0.5%, carbamide 1%.
Described rare earth compound is a kind of in lanthanum chloride, cerium chloride, lanthana or the cerium oxide.
The described CNT of step (1) comprises single wall, double-walled or multi-walled carbon nano-tubes.
The described thionyl chloride of step (2) is treated to: with rare earth modified carbon nanotube and thionyl chloride mixing post-heating backflow 24h, reactant liquor is chilled to room temperature, revolves with Rotary Evaporators and steam excessive SOCl
2, wherein the mass volume ratio of rare earth modified carbon nanotube and thionyl chloride is 1g/200ml.
The described esterification of step (2) is: the chloride CNT is added anhydrous N, in the dinethylformamide, after ultra-sonic dispersion is even, add the diaminourea Polyethylene Glycol through dried, ultra-sonic dispersion 10min, mix homogeneously, then at 110～130 ℃ of lower heated and stirred backflow 24h, mixture is chilled to room temperature, revolves with Rotary Evaporators to steam anhydrous N, the N-METHYLFORMAMIDE solvent; Wherein the mass ratio of chloride CNT and diaminourea Polyethylene Glycol is 1: 10; The mass volume ratio of chloride CNT and anhydrous DMF is 1g/100ml.
The modification of the described folic acid of step (3) is treated to: with grafting CNT and the N of Polyethylene Glycol, N '-two cyclohexyl carbimide, DMAP add dmso solution, stir, add folic acid, make the rate of charge of folic acid and diaminourea Polyethylene Glycol greater than 2: 1, shake up and make it dissolving, in 40 ℃ of reaction 48～72h;
Described grafting CNT and the N of Polyethylene Glycol, the quality mol ratio of N '-dicyclohexyl carbimide, DMAP is: 20g: 1mmol: 1mmol; Described grafting the CNT of Polyethylene Glycol and the mass volume ratio of dimethyl sulfoxide be 2g/5ml.
Compared with prior art, technique of the present invention is simple, and CNT is carried out functionalization and rare earth modified, and utilizes esterification to be grafted on the polymer poly ethylene glycol, adopts folic acid that it is modified, and makes it have biocompatibility.The modified with folic acid rare earth modified carbon nanotube that prepare a kind of nontoxic, enhanced sensitivity excellent performance, has good dispersion, biocompatibility and targeting is as desirable radiosensitizer.
Description of drawings
Fig. 1 is transmission electron microscope (TEM) figure of CNT after rare earth modified of single functionalization;
Fig. 2 is transmission electron microscope (TEM) figure of CNT after rare earth modified of functionalization, as seen from the figure, and being dispersed in the solution of even carbon nanotube.
The specific embodiment
The below elaborates to embodiments of the invention, and present embodiment has provided detailed embodiment and concrete operating process take technical solution of the present invention as prerequisite, and embodiment is the support to the technology of the present invention feature, rather than limits.
Embodiment 1:
CNT: the multi-walled carbon nano-tubes that Chengdu organic material institute is produced.The weight percentages of components of the rare-earth modifier that adopts is: rare earth compound lanthanum chloride 1%, ethanol 96.5%, ethylenediaminetetraacetic acid 0.2%, ammonium chloride 0.8%, nitric acid 0.5%, carbamide 1%.
(1) at first with the 1g CNT in grinding in ball grinder.Configuration concentration is the salpeter solution 50ml of 3.0mol/L in beaker.The carbon nanotube powder that takes by weighing after a certain amount of grinding is positioned over the 500ml conical flask, with the rare HNO of 50ml
3Mixed liquor is poured in the conical flask, places ultrasonator to vibrate conical flask.Described carbon nanotube powder and rare HNO
3The mass volume ratio of mixed liquor is 20mg/ml.Under 100 ℃ temperature conditions, oxidation backflow 0.5h refluxes and finishes, and reactant liquor naturally cools to room temperature.CNT is washed and is positioned in the baking oven 60 ℃ of lower oven dry.
Be that 2mg/ml immerses in the rare-earth modifier and soaked 2 hours by concentration at room temperature with the CNT after the functionalization, ultrasound wave disperseed (100W) 1 hour, filtered post-drying;
(2) with the thionyl chloride processing functional group's carboxyl on the CNT is converted to acyl chlorides, is grafted on the polymer poly ethylene glycol by esterification, concrete steps are:
Get 1g functionalized carbon nano-tube (being the rare earth modified carbon nanotube that step 1 makes) and 200ml thionyl chloride reflux 24h, reactant liquor is chilled to room temperature, revolve with Rotary Evaporators and steam excessive SOCl
2Then in 1g chloride CNT, add anhydrous N, dinethylformamide (DMF) 100ml, ultra-sonic dispersion is even, add 10g in the suspension through the diaminourea Polyethylene Glycol of dried, ultrasonic 10min, with PEG and CNT mix homogeneously, at about 120 ℃ of lower heated and stirred backflow 24h, mixture is chilled to room temperature, revolves with Rotary Evaporators to steam the DMF solvent, after evaporating, in flask, add the 40ml distilled water, after the dissolving fully, again with centrifuge high speed (11900r/min) centrifugal above-mentioned black liquor, discard the precipitation in the centrifuge tube and collect the upper strata black liquor, filter black liquor with the microfiltration funnel, repeatedly wash the atrament on the filter membrane in the funnel with distilled water, filter membrane and atrament are together put into 60 ℃ of dryings of vacuum drying oven, scrape gently the CNT on the filter membrane after drying is complete.
(3) adopt folic acid that above-mentioned product is modified, make it have biocompatibility.CNT and the 0.1mmol N of Polyethylene Glycol that taken by weighing the 2g grafting, N '-two cyclohexyl carbimide (DCC), 0.1mmol4-dimethylamino naphthyridine (DMAP) places round-bottomed flask, add 5mL dimethyl sulfoxide (DMSO) dissolving, stir, add 0.3mmol folic acid, make the rate of charge of folic acid and diaminourea Polyethylene Glycol greater than 2: 1, shake up and make it dissolving, in 40 ℃ of reaction 60h.Pour 10mL distilled water (about 0 ℃) into the reactant liquor cessation reaction, be cooled to room temperature and obtain yellow jelly, the centrifugal 15min of 4000r obtains yellow solution.Get its supernatant with 5mmol Na
2CO
3Solution dialysis 3 days, distill water dialysis 1 day, solution gets pale yellow powder through lyophilizing, is the modified with folic acid rare earth modified carbon nanotube, as described in Fig. 1～2, as seen from the figure, being dispersed in the solution of even carbon nanotube.
Embodiment 2:
CNT: the multi-walled carbon nano-tubes that Chengdu organic material institute is produced.The weight percentages of components of the rare-earth modifier that adopts is: rare earth compound chlorination metal plate 1.5%, ethanol 96%, ethylenediaminetetraacetic acid 0.2%, ammonium chloride 0.8%, nitric acid 0.5%, carbamide 1%.
(1) at first with the 1g CNT in grinding in ball grinder.Configuration concentration is the salpeter solution 50ml of 3.0mol/L in beaker.The carbon nanotube powder that takes by weighing after a certain amount of grinding is positioned over the 500ml conical flask, with the rare HNO of 50ml
3Mixed liquor is poured in the conical flask, places ultrasonator to vibrate conical flask.The mass volume ratio of described carbon nanotube powder and mixed acid is 20mg/ml.Under 100 ℃ temperature conditions, oxidation backflow 0.5h refluxes and finishes, and reactant liquor naturally cools to room temperature.CNT is washed and is positioned in the baking oven 60 ℃ of lower oven dry.
Be that 2mg/ml immerses in the rare-earth modifier and soaked 3 hours by concentration at room temperature with the CNT after the functionalization, ultrasound wave disperseed (100W) 1.5 hours, filtered post-drying;
(2) with the thionyl chloride processing functional group's carboxyl on the CNT is converted to acyl chlorides.Get 1g functionalized carbon nano-tube and 200ml thionyl chloride reflux 24h, reactant liquor is chilled to room temperature, revolve with Rotary Evaporators and steam excessive SOCl
2Then in 1g chloride CNT, add anhydrous N, dinethylformamide (DMF) 100ml, ultra-sonic dispersion is even, add 10g in the suspension through the diaminourea Polyethylene Glycol of dried, ultrasonic 10min, with PEG and CNT mix homogeneously, at about 120 ℃ of lower heated and stirred backflow 24h, mixture is chilled to room temperature, revolves with Rotary Evaporators to steam the DMF solvent, after evaporating, in flask, add the 40ml distilled water, after the dissolving fully, again with centrifuge high speed (11900r/min) centrifugal above-mentioned black liquor, discard the precipitation in the centrifuge tube and collect the upper strata black liquor, filter black liquor with the microfiltration funnel, repeatedly wash the atrament on the filter membrane in the funnel with distilled water, filter membrane and atrament are together put into 60 ℃ of dryings of vacuum drying oven, scrape gently the CNT on the filter membrane after drying is complete.
(3) adopt folic acid that above-mentioned product is modified, make it have biocompatibility.CNT and the 0.1mmol N of Polyethylene Glycol that taken by weighing the 2g grafting, N ' two cyclohexyl carbimides (DCC), 0.1mmol4-dimethylamino naphthyridine (DMAP) places round-bottomed flask, add 5mL dimethyl sulfoxide (DMSO) dissolving, stir, add 0.3mmol folic acid, make the rate of charge of folic acid and diaminourea Polyethylene Glycol greater than 2: 1, shake up and make it dissolving, in 40 ℃ of reaction 72h.Pour 10mL distilled water (about 0 ℃) into the reactant liquor cessation reaction, be cooled to room temperature and obtain yellow jelly, the centrifugal 15min of 4000r obtains yellow solution.Get its supernatant with 5mmol Na
2CO
3Solution dialysis 3 days, distill water dialysis 1 day, solution gets pale yellow powder through lyophilizing, is the modified with folic acid rare earth modified carbon nanotube.
Embodiment 3:
CNT: the multi-walled carbon nano-tubes that Chengdu organic material institute is produced.The weight percentages of components of the rare-earth modifier that adopts is: rare earth compound cerium chloride 1%, alcohol 95 .5%, ethylenediaminetetraacetic acid 0.2%, ammonium chloride 0.8%, nitric acid 0.5%, carbamide 1%.
(1) at first with the 1g CNT in grinding in ball grinder.Configuration concentration is the salpeter solution 50ml of 3.0mol/L in beaker.The carbon nanotube powder that takes by weighing after a certain amount of grinding is positioned over the 500ml conical flask, with the rare HNO of 50ml
3Mixed liquor is poured in the conical flask, places ultrasonator to vibrate conical flask.The mass volume ratio of described carbon nanotube powder and mixed acid is 20mg/ml.Under 100 ℃ temperature conditions, oxidation backflow 0.5h refluxes and finishes, and reactant liquor naturally cools to room temperature.From ultrasonator, take out conical flask, in conical flask, add about 300ml deionized water, solution is diluted.Leave standstill a period of time, after the CNT precipitation in solution, pour out the upper transparent liquid in the conical flask, remaining dirty solution is filtered with microporous filter membrane.The filter paper that deposits CNT is positioned in the beaker of deionized water, in ultrasonator, uses sonic oscillation, peel CNT, again solution is poured in the conical flask.With the CNT cyclic washing, until pH value is neutral.CNT is washed and is positioned in the baking oven 60 ℃ of lower oven dry.
Be that 2mg/ml immerses in the rare-earth modifier and soaked 4 hours by concentration at room temperature with the CNT after the functionalization, ultrasound wave disperseed (100W) 3 hours, filtered post-drying;
(2) with the thionyl chloride processing functional group's carboxyl on the CNT is converted to acyl chlorides.Get 1g functionalized carbon nano-tube and 200ml thionyl chloride reflux 24h, reactant liquor is chilled to room temperature, revolve with Rotary Evaporators and steam excessive SOCl
2Then in 1g chloride CNT, add anhydrous N, dinethylformamide (DMF) 100ml, ultra-sonic dispersion is even, add 10g in the suspension through the diaminourea Polyethylene Glycol of dried, ultrasonic 10min, with PEG and CNT mix homogeneously, at about 120 ℃ of lower heated and stirred backflow 24h, mixture is chilled to room temperature, revolves with Rotary Evaporators to steam the DMF solvent, after evaporating, in flask, add the 40ml distilled water, after the dissolving fully, again with centrifuge high speed (11900r/min) centrifugal above-mentioned black liquor, discard the precipitation in the centrifuge tube and collect the upper strata black liquor, filter black liquor with the microfiltration funnel, repeatedly wash the atrament on the filter membrane in the funnel with distilled water, filter membrane and atrament are together put into 60 ℃ of dryings of vacuum drying oven, scrape gently the CNT on the filter membrane after drying is complete.
(3) adopt folic acid that above-mentioned product is modified, make it have biocompatibility.CNT and the 0.1mmolN of Polyethylene Glycol that taken by weighing the 2g grafting, N '-two cyclohexyl carbimide (DCC), 0.1mmol4-dimethylamino naphthyridine (DMAP) places round-bottomed flask, add 5mL dimethyl sulfoxide (DMSO) dissolving, stir, add 0.3mmol folic acid, make the rate of charge of folic acid and diaminourea Polyethylene Glycol greater than 2: 1, shake up and make it dissolving, in 40 ℃ of reaction 72h.Pour 10mL distilled water (about 0 ℃) into the reactant liquor cessation reaction, be cooled to room temperature and obtain yellow jelly, the centrifugal 15min of 4000r obtains yellow solution.Get its supernatant with 5mmol Na
2CO
3Solution dialysis 3 days, distill water dialysis 1 day, solution gets pale yellow powder through lyophilizing, is the modified with folic acid rare earth modified carbon nanotube.
Claims (10)
1. the preparation method of a modified with folic acid rare earth modified carbon nanotube is characterized in that, the method may further comprise the steps:
(1) CNT after the functionalization is at room temperature immersed soak 2～4 hours in the rare-earth modifier first, ultrasound wave disperseed 1～3 hour, filtered post-drying;
(2) with thionyl chloride treatment step (1) gained rare earth modified carbon nanotube, make the functional group's carboxyl on the rare earth modified carbon nanotube be converted to acyl chlorides, the chloride CNT that obtains is grafted on the polymer poly ethylene glycol by esterification;
(3) adopt folic acid that above-mentioned steps (2) products therefrom is modified processing, make it have biocompatibility.
2. the preparation method of a kind of modified with folic acid rare earth modified carbon nanotube according to claim 1 is characterized in that, the described functionalized carbon nanotube of step (1) is treated to; CNT is ground to form carbon nanotube powder, then mix with salpeter solution, place again ultrasonator to vibrate; The mass volume ratio of described carbon nanotube powder and salpeter solution is 20mg/ml.
3. the preparation method of a kind of modified with folic acid rare earth modified carbon nanotube according to claim 2 is characterized in that, the concentration of described salpeter solution is 3.0mol/L.
4. the preparation method of a kind of modified with folic acid rare earth modified carbon nanotube according to claim 1 is characterized in that, the mass volume ratio of the described CNT of step (1) and rare-earth modifier is 2mg/mL.
5. according to claim 1 or the preparation method of 4 described a kind of modified with folic acid rare earth modified carbon nanotubes, it is characterized in that, the weight percentages of components of the described rare-earth modifier of step (1) is: rare earth compound 1～2%, alcohol 95 .5～96.5%, ethylenediaminetetraacetic acid 0.2%, ammonium chloride 0.8%, nitric acid 0.5%, carbamide 1%.
6. the preparation method of a kind of modified with folic acid rare earth modified carbon nanotube according to claim 5 is characterized in that, described rare earth compound is a kind of in lanthanum chloride, cerium chloride, lanthana or the cerium oxide.
7. the preparation method of a kind of modified with folic acid rare earth modified carbon nanotube according to claim 1 is characterized in that, the described CNT of step (1) comprises single wall, double-walled or multi-walled carbon nano-tubes.
8. the preparation method of a kind of modified with folic acid rare earth modified carbon nanotube according to claim 1, it is characterized in that, the described thionyl chloride of step (2) is treated to: with rare earth modified carbon nanotube and thionyl chloride mixing post-heating backflow 24h, reactant liquor is chilled to room temperature, revolves with Rotary Evaporators and steam excessive SOCl
2, wherein the mass volume ratio of rare earth modified carbon nanotube and thionyl chloride is 1g/200ml.
9. the preparation method of a kind of modified with folic acid rare earth modified carbon nanotube according to claim 1, it is characterized in that, the described esterification of step (2) is: the chloride CNT is added anhydrous N, in the dinethylformamide, after ultra-sonic dispersion is even, add the diaminourea Polyethylene Glycol through dried, ultra-sonic dispersion 10min, mix homogeneously, then at 110～130 ℃ of lower heated and stirred backflow 24h, mixture is chilled to room temperature, revolves with Rotary Evaporators to steam anhydrous DMF solvent; Wherein the mass ratio of chloride CNT and diaminourea Polyethylene Glycol is 1: 10; The mass volume ratio of chloride CNT and anhydrous DMF is 1g/100ml.
10. the preparation method of a kind of modified with folic acid rare earth modified carbon nanotube according to claim 9 is characterized in that, the modification of the described folic acid of step (3) is treated to; With grafting CNT and the N of Polyethylene Glycol, N '-two cyclohexyl carbimide, DMAP add dmso solution, stir, add folic acid, make the rate of charge of folic acid and diaminourea Polyethylene Glycol greater than 2: 1, shake up and make it dissolving, in 40 ℃ of reaction 48～72h;
Described grafting CNT and the N of Polyethylene Glycol, the quality mol ratio of N '-two cyclohexyl carbimide, DMAP is: 20g: 1mmol: 1mmol; Described grafting the CNT of Polyethylene Glycol and the mass volume ratio of dimethyl sulfoxide be 2g/5ml.
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| CN105949475A (en) * | 2016-06-16 | 2016-09-21 | 中国药科大学 | Antineoplastic folic acid-cobalt coordination polymer nanotubes and preparation method thereof |
| CN116370705A (en) * | 2023-04-14 | 2023-07-04 | 洛兮生命科技(杭州)有限公司 | Folic acid modified noble metal-based carbon nanotube composite hydroxyapatite bone repair stent material and preparation method thereof |
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| CN116370705B (en) * | 2023-04-14 | 2023-11-03 | 洛兮生命科技(杭州)有限公司 | Folic acid modified noble metal-based carbon nanotube composite hydroxyapatite bone repair stent material and preparation method thereof |
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