CN102743753A - Preparation method of rare earth-modified oxygen-carrying carbon nanotube - Google Patents
Preparation method of rare earth-modified oxygen-carrying carbon nanotube Download PDFInfo
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- CN102743753A CN102743753A CN2012102603822A CN201210260382A CN102743753A CN 102743753 A CN102743753 A CN 102743753A CN 2012102603822 A CN2012102603822 A CN 2012102603822A CN 201210260382 A CN201210260382 A CN 201210260382A CN 102743753 A CN102743753 A CN 102743753A
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Abstract
The invention relates to a preparation method of a rare earth-modified oxygen-carrying carbon nanotube. The method comprises the following steps of: (1) submerging a functionally-treated carbon nanotube into a rare earth modifier at the room temperature for 2-4 hours, ultrasonically dispersing for 1-3 hours, filtering and drying; (2) putting the dried carbon nanotube into a sample room, heating the sample room to 300-400 DEG C, vacuumizing till the vacuum degree is over 10<-3>Pa, keeping the sample room in a vacuum state, and introducing high-purity oxygen of 9-10MPa after the sample room is naturally cooled to the room temperature; and (3) recording the pressure intensity change in the sample room simultaneously to obtain a product 2-3 hours after the pressure intensity stops falling. Compared with the prior art, the rare earth-modified oxygen-carrying carbon nanotube has the advantages of nontoxicity, excellent sensitivity enhancing performance, high dispersivity and the like.
Description
Technical field
The present invention relates to a kind of CNT as the application of carrier in cancer therapy drug, particularly in the research of new type anticancer medicine, have a wide range of applications.
Background technology
Cancer is the disease of contemporary serious harm human health.At present, be main still to tumor treatment clinically, but owing in solid tumor, exist 10%～50% anoxic cell, these anoxic cells are higher 2.5～3 times than aerobic cell to the toleration of ray and chemotherapeutics with operation and radiotherapy, chemotherapy.Weary oxygen is the of paramount importance characteristic of tumor microenvironment, and the weary oxygen of tumor inner cell is the key factor that influences tumor efficiency, and the existence of anoxic cell has increased the aggressive of tumor to radiocurable negation and tumor self significantly.
Oxygen is the best sensitizer of radiotherapy, but attempts to improve the method for cell oxygen content in the past, and like hyperbaric oxygen, blood transfusion etc., its effect is all undesirable.The radiation sensitization research of attaching most importance to anoxic cell enhanced sensitivity (improving the content of tumor cell oxygen) is the important topic of radiation oncology research always.The anoxic cell sensitizer is a kind of content that can improve tumor cell oxygen; Reduce the effective ways that anoxic cell produces; Can in the process of fixing irradiation damage, act on; The potential advantages of this type material are need not get into Normocellular metabolism, but only increase the sensitivity of anoxic cell to irradiation.Chinese scholars is attached great importance to the research of radiosensitizer, has synthesized a large amount of dissimilar enhanced sensitivity preparations, but all undesirable at clinical application effect so far.The hypoxic cell radiation sensitizer of seeking high-efficiency low-toxicity is one of method that improves the effectiveness of curing tumor patient.
CNT is a kind of quasi-one-dimensional nanometer material; The tube that the hexagonal mesh of similar graphite is formed; Have unique character such as physical chemistry, electricity and optics, its outer surface is except adsorbing various molecules by noncovalent force, and 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,, comprise that aspects such as drug delivery, molecular image, gene therapy have application promise in clinical practice therefore in biomedicine.
Summary of the invention
The object of the 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 method for preparing of the rare earth modified oxygen carrier CNT of good dispersion.
The object of the invention can be realized through following technical scheme: a kind of method for preparing of rare earth modified oxygen carrier CNT is characterized in that this method may further comprise the steps:
(1) elder generation at room temperature immerses the CNT after the functionalization and soaks 2～4 hours in the rare-earth modifier, and ultrasonic dispersing 1～3 hour is filtered the back oven dry;
(2) CNT of oven dry is put into the sample room, the sample room is heated to 300～400 ℃, be evacuated to vacuum and reach 10
-3More than the Pa, keep the sample vacuum chamber state, treat that the sample room naturally cools to room temperature after, charge into 9～10MPa high purity oxygen gas;
(3) write down pressure change in the sample room simultaneously, when pressure stop to descend reach 2～3 hours after, promptly get product.
The functionalization of the described CNT of step (1) is: with purity is that 98% concentrated sulphuric acid and purity are that 3: 1 by volume ratio of 78% nitric acid is formulated as mixed acid; Carbon nanotube powder is positioned in the mixed acid; Then 100 ℃ of following reflux 0.5 hour; The hydrochloric acid of reuse 2mol/L is 100 ℃ of following reflux 2 hours, reuse deionized water rinsing, oven dry; The mass volume ratio of described carbon nanotube powder and mixed acid is 20mg/mL.
The weight percentages of components of the described rare-earth modifier of step (1) is: rare earth compound 1.5%, ethanol 96%, 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 mass volume ratio of described CNT of step (1) and rare-earth modifier is 2mg/mL.
Described CNT comprises single wall, double-walled or multi-walled carbon nano-tubes.
The described evacuation of step (2) is earlier with mechanical pump evacuation 3～5 hours, and the reuse molecular pump was taken out 2～3 hours, made vacuum reach 10
-3More than the Pa.
The oxygen carrier amount of described rare earth modified oxygen carrier CNT calculates through following method: after the pressure change in the record sample room stops, getting 2g/cm
3As the density of CNT, deduct the shared volume of sample with the volume of sample room, the pressure that reduces of chamber per sample calculates the weight of oxygen that sample absorbs, and obtains the percentage by weight of sample oxygen uptake subsequently.
Compared with prior art; Technology of the present invention is simple; CNT is carried out functionalization and rare earth modified; And the storage oxygen experimental provision that utilizes design carries out the oxygen carrier experiment, and the rare earth modified oxygen carrier CNT that prepare a kind of nontoxic, enhanced sensitivity excellent performance, has good dispersion is as ideal radiosensitizer.
Description of drawings
Fig. 1 stores up the structural representation of oxygen experimental provision for the present invention;
Wherein: 1-high pressure high purity oxygen source of the gas, 2-first control valve, 3-sample room, 4-volume measurement device, 5-pressure transducer, 6-record computer, 7-second control valve, 8-vacuum system.
The specific embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated, present embodiment is a prerequisite with technical scheme of the present invention, has provided detailed embodiment and concrete operating process, and embodiment is the support to technical characterictic of the present invention, rather than limits.
Adopt storage oxygen experimental provision shown in Figure 1 to store up oxygen in following examples, this storage oxygen experimental provision comprises high pressure high purity oxygen source of the gas 1, first control valve 2, sample room 3, volume measurement device 4, pressure transducer 5, write down computer 6, second control valve 7, vacuum system 8; The gas outlet of high pressure high purity oxygen source of the gas 1 links to each other with the air inlet of sample room 3, and sample room 3 links to each other with vacuum system 8, and volume measurement device 4 and pressure transducer 5 all link to each other with sample room 3, and pressure transducer 5 links to each other with record computer 6.Comprise that also first control valve 2, second control valve, 7, the first control valves 2 are installed on the escape pipe of said high pressure high purity oxygen source of the gas 1, second control valve 7 is installed on the connection tube of said vacuum system 8.Described vacuum system comprises mechanical pump and molecular pump.
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 is adopted is: rare earth compound 1.5%, ethanol 96%, ethylenediaminetetraacetic acid 0.2%, ammonium chloride 0.8%, nitric acid 0.5%, carbamide 1%.
1, functionalization is handled: with purity be 98% concentrated sulphuric acid and purity be 78% nitric acid by volume (V (sulphuric acid): V (nitric acid)) be that 3: 1 ratio is formulated as mixed liquor.Take by weighing the 2g carbon nanotube powder and be positioned in the mixed acid, then 100 ℃ of following reflux 0.5 hour, the hydrochloric acid of reuse 2mol/L is in 100 ℃ of following reflux 2 hours, reuse deionized water rinsing, oven dry;
2, be to soak 2 hours in the 2mg/mL immersion rare-earth modifier by concentration at room temperature with CNT, ultrasonic dispersing (100W) 1 hour is filtered the back oven dry;
3, the CNT of oven dry is put into the sample room after with scales/electronic balance weighing, and the sample room is heated to 300 ℃, and with mechanical pump evacuation 3 hours, the reuse molecular pump was taken out 2 hours, made vacuum reach 10 earlier
-3More than the Pa.Keep the sample vacuum chamber state, treat that the sample room naturally cools to room temperature after, charge into the 9MPa high purity oxygen gas;
4, the pressure change of record in the sample room after pressure stops decline and reaches 2 hours, stops record.Get 2g/cm
3Density as CNT.Volume with the sample room deducts the shared volume of sample, and the pressure that reduces of chamber per sample calculates the weight of oxygen that sample absorbs, and the percentage by weight that obtains the sample oxygen uptake subsequently is 1.3wt%.
Embodiment 2:
CNT: the SWCN that Chengdu organic material institute is produced.The weight percentages of components of the rare-earth modifier that is adopted is: rare earth compound 1.5%, ethanol 96%, ethylenediaminetetraacetic acid 0.2%, ammonium chloride 0.8%, nitric acid 0.5%, carbamide 1%.
1, functionalization is handled: with purity be 98% concentrated sulphuric acid and purity be 78% nitric acid by volume (V (sulphuric acid): V (nitric acid)) be that 3: 1 ratio is formulated as mixed liquor.Take by weighing the 2g carbon nanotube powder and be positioned in the mixed acid, then 100 ℃ of following reflux 0.5 hour, the hydrochloric acid of reuse 2mol/L is in 100 ℃ of following reflux 2 hours, reuse deionized water rinsing, oven dry;
2, be to soak 4 hours in the 2mg/mL immersion rare-earth modifier by concentration at room temperature with CNT, ultrasonic dispersing (100W) 3 hours is filtered the back oven dry;
3, the CNT of oven dry is put into the sample room after with scales/electronic balance weighing, and the sample room is heated to 400 ℃, and with mechanical pump evacuation 5 hours, the reuse molecular pump was taken out 3 hours, made vacuum reach 10 earlier
-3More than the Pa.Keep the sample vacuum chamber state, treat that the sample room naturally cools to room temperature after, charge into the 10MPa high purity oxygen gas;
4, simultaneously the pressure measurement system writes down the pressure change the sample room in automatically, after pressure stops decline and reaches 3 hours, stops record.Get 2g/cm
3Density as CNT.Volume with the sample room deducts the shared volume of sample, and the pressure that reduces of chamber per sample calculates the weight of oxygen that sample absorbs, and obtains the percentage by weight 1.1wt% of sample oxygen uptake subsequently.
Claims (8)
1. the method for preparing of a rare earth modified oxygen carrier CNT is characterized in that, this method may further comprise the steps:
(1) elder generation at room temperature immerses the CNT after the functionalization and soaks 2～4 hours in the rare-earth modifier, and ultrasonic dispersing 1～3 hour is filtered the back oven dry;
(2) CNT of oven dry is put into the sample room, the sample room is heated to 300～400 ℃, be evacuated to vacuum and reach 10
-3More than the Pa, keep the sample vacuum chamber state, treat that the sample room naturally cools to room temperature after, charge into 9～10MPa high purity oxygen gas;
(3) write down pressure change in the sample room simultaneously, when pressure stop to descend reach 2～3 hours after, promptly get product.
2. the method for preparing of a kind of rare earth modified oxygen carrier CNT according to claim 1; It is characterized in that the functionalization of the described CNT of step (1) is: with purity is that 98% concentrated sulphuric acid and purity are that 3: 1 by volume ratio of 78% nitric acid is formulated as mixed acid, and carbon nanotube powder is positioned in the mixed acid; Then 100 ℃ of following reflux 0.5 hour; The hydrochloric acid of reuse 2mol/L is 100 ℃ of following reflux 2 hours, reuse deionized water rinsing, oven dry; The mass volume ratio of described carbon nanotube powder and mixed acid is 20mg/mL.
3. the method for preparing of a kind of rare earth modified oxygen carrier CNT according to claim 1; It is characterized in that the weight percentages of components of the described rare-earth modifier of step (1) is: rare earth compound 1.5%, ethanol 96%; Ethylenediaminetetraacetic acid 0.2%; Ammonium chloride 0.8%, nitric acid 0.5%, carbamide 1%.
4. the method for preparing of a kind of rare earth modified oxygen carrier CNT according to claim 3 is characterized in that, described rare earth compound is a kind of in lanthanum chloride, cerium chloride, lanthana or the cerium oxide.
5. the method for preparing of a kind of rare earth modified oxygen carrier CNT according to claim 1 is characterized in that, the mass volume ratio of described CNT of step (1) and rare-earth modifier is 2mg/mL.
6. the method for preparing of a kind of rare earth modified oxygen carrier CNT according to claim 1 is characterized in that, described CNT comprises single wall, double-walled or multi-walled carbon nano-tubes.
7. the method for preparing of a kind of rare earth modified oxygen carrier CNT according to claim 1 is characterized in that, the described evacuation of step (2) is earlier with mechanical pump evacuation 3～5 hours, and the reuse molecular pump was taken out 2～3 hours, made vacuum reach 10
-3More than the Pa.
8. the method for preparing of a kind of rare earth modified oxygen carrier CNT according to claim 1 is characterized in that, the oxygen carrier amount of described rare earth modified oxygen carrier CNT calculates through following method: after the pressure change in the record sample room stops, getting 2g/cm
3As the density of CNT, deduct the shared volume of sample with the volume of sample room, the pressure that reduces of chamber per sample calculates the weight of oxygen that sample absorbs, and obtains the percentage by weight of sample oxygen uptake subsequently.
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Cited By (7)
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| CN103232848A (en) * | 2013-04-18 | 2013-08-07 | 上海交通大学 | Preparation method of rare earth fluoride/carbon nano tube composite luminescent material |
| CN105585785A (en) * | 2016-02-18 | 2016-05-18 | 合肥市再德高分子材料有限公司 | High-flame-retardancy chlorinated polyethylene cable material |
| CN105602023A (en) * | 2016-02-18 | 2016-05-25 | 合肥市再德高分子材料有限公司 | Heat-resistant and flame-retardant modified natural rubber cable sheath material |
| CN106892427A (en) * | 2017-04-10 | 2017-06-27 | 河南科技大学 | A kind of method of rare-earth surface modification Graphene |
| CN108658595A (en) * | 2018-08-13 | 2018-10-16 | 合肥汉甲陶瓷科技有限公司 | A kind of coloring stabilized, high-strength ceramic preparation method |
| CN108727052A (en) * | 2018-08-13 | 2018-11-02 | 合肥汉甲陶瓷科技有限公司 | A kind of new ceramics of high strength easy coloring |
| CN108863355A (en) * | 2018-08-13 | 2018-11-23 | 合肥汉甲陶瓷科技有限公司 | A kind of preparation method for the modified Nano zirconium oxide being used to prepare high-strength ceramic |
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| CN2808112Y (en) * | 2005-05-10 | 2006-08-23 | 朱戈 | Ozone anti-cancer sensitization therapeutic instrument |
| CN1844222A (en) * | 2006-05-11 | 2006-10-11 | 上海交通大学 | Process for preparing rare earth modified carbon nanotube/polypropylene composite materials |
| CN100400423C (en) * | 2006-09-21 | 2008-07-09 | 上海大学 | Preparation method of rare-earth oxide nano tubular structure |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN2808112Y (en) * | 2005-05-10 | 2006-08-23 | 朱戈 | Ozone anti-cancer sensitization therapeutic instrument |
| CN1844222A (en) * | 2006-05-11 | 2006-10-11 | 上海交通大学 | Process for preparing rare earth modified carbon nanotube/polypropylene composite materials |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232848A (en) * | 2013-04-18 | 2013-08-07 | 上海交通大学 | Preparation method of rare earth fluoride/carbon nano tube composite luminescent material |
| CN103232848B (en) * | 2013-04-18 | 2014-07-09 | 上海交通大学 | Preparation method of rare earth fluoride/carbon nano tube composite luminescent material |
| CN105585785A (en) * | 2016-02-18 | 2016-05-18 | 合肥市再德高分子材料有限公司 | High-flame-retardancy chlorinated polyethylene cable material |
| CN105602023A (en) * | 2016-02-18 | 2016-05-25 | 合肥市再德高分子材料有限公司 | Heat-resistant and flame-retardant modified natural rubber cable sheath material |
| CN106892427A (en) * | 2017-04-10 | 2017-06-27 | 河南科技大学 | A kind of method of rare-earth surface modification Graphene |
| CN108658595A (en) * | 2018-08-13 | 2018-10-16 | 合肥汉甲陶瓷科技有限公司 | A kind of coloring stabilized, high-strength ceramic preparation method |
| CN108727052A (en) * | 2018-08-13 | 2018-11-02 | 合肥汉甲陶瓷科技有限公司 | A kind of new ceramics of high strength easy coloring |
| CN108863355A (en) * | 2018-08-13 | 2018-11-23 | 合肥汉甲陶瓷科技有限公司 | A kind of preparation method for the modified Nano zirconium oxide being used to prepare high-strength ceramic |
| CN108727052B (en) * | 2018-08-13 | 2019-11-01 | 潮州市礼升陶瓷有限公司 | A kind of ceramics of high strength easy coloring |
| CN108658595B (en) * | 2018-08-13 | 2021-06-15 | 临沂市银雪瓷业有限公司 | Preparation method of high-strength ceramic with stable coloring |
| CN108863355B (en) * | 2018-08-13 | 2021-10-08 | 青岛欧维斯节能材料有限公司 | Preparation method of modified nano-zirconia for preparing high-strength ceramic |
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