CN104208725A - Activated carbon nanosphere and application thereof to tumor boundary and lymph gland tracing - Google Patents
Activated carbon nanosphere and application thereof to tumor boundary and lymph gland tracing Download PDFInfo
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- CN104208725A CN104208725A CN201410468300.2A CN201410468300A CN104208725A CN 104208725 A CN104208725 A CN 104208725A CN 201410468300 A CN201410468300 A CN 201410468300A CN 104208725 A CN104208725 A CN 104208725A
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Abstract
The invention discloses an activated carbon nanosphere which is prepared by taking activated carbon particles with the particle sizes of 10-100nm as carriers, and the surfaces of the activated carbon particles are compounded with an organic dyestuff. The activated carbon nanosphere disclosed by the invention is rather strong in dyeing property, remarkable in tracing effect and capable of remarkably showing a lymph tracing effect for a tested living body within half a hour, realizing multi-mode imaging and directly observing the trace of the nanosphere from tumors, tissues or organs through naked eyes.
Description
Technical field
The present invention relates to a kind of nano-particle, particularly relating to a kind of take active carbon as composite nanometer particle prepared by carrier, and the application in the determination of this nanoparticles tumor boundaries and lymphatic metastasis spike.
Background technology
Current China is every year because of nearly 3,000,000 examples of cancer mortality case, and surgical operation is still first-selection and the most effective Therapeutic Method.But survival rates rests on reduced levels both at home and abroad, and for gastric cancer, within postoperative 5 years, survival rate great majority are hovered 20 ~ 30% always.When a very large reason is exactly tumor resection, lymph node is removed thorough, and the tumor cell of infiltration, through lymph tube wall, with lymph fluid shifts along lymphatic vessel, to make after operation in patients recurrence in a short time or transfer and dead.
Chinese invention patent application 201110045024.5 discloses a kind of stomach lymph node and knows method, comprise and first cut hepatogastric ligament, clean the 12nd group of lymph node of hepatodudenal ligament, district's lymph node on the 5th group of pylorus is cleaned again by above pylorus, and cut off, the ligation stomach right side is dynamic, vein, again along diaphram foot, omentum minus internal film tissue cuts by caudate lobe of liver lower edge, along clockwise direction on the right side of cardia district, clean the 1st group of right lymph node of cardia and the 3rd group of lymph node of lesser curvature of stomach, capsula pancreatis is cut again along pancreas upper limb place, to pylorus, clean the 6th group of subpyloric lymph nodes, join with district on pylorus, do that surface is cleaned by the 7th group of left gastric artery, by the 8th group of common hepatic artery successively, the 9th group of coeliac artery is taken up the dry lymph node of splenic artery, thus completed the removing of lymph node again along common hepatic artery.This technology proposes the lymph node dissection method with " surrounding and annihilating formula " first, and takes more reasonably to remove approach, and simplify the operation step greatly, improves operability, reduces reset procedure to the damage of surrounding tissue, significantly reduces wound surface, improve the safety of operation.
Therefore, removing thoroughly the lymph node of tumor region, is tumor key at least, seems particularly important.As a rule, lymph node and lymphatic vessel are not easily gone out by discernable by eye.Utilizing some material to carry out spike to lymph, is very helpful for lymph cleaning.
Active carbon coloring is excellent, and good biocompatibility, has no side effect, and is desirable lymphatic tracer.There is two large problems and constrain its application on clinical medicine in common active carbon, one is that particle diameter is comparatively large, and two is hydrophobic properties.Therefore, active carbon is applied to tracer as carrier and still has larger technical difficulty.
Summary of the invention
One object of the present invention is to provide a kind of active carbon composite nano-microsphere, is carrier with activated carbon granule, Compound partition wall agent on it.
Another object of the present invention is the preparation method providing a kind of active carbon composite nano-microsphere, and technique is simple, and obtained microsphere can realize multi-modal imaging.
Another object of the present invention is to provide a kind of active carbon composite nano-microsphere, as tracer, for the confirmation of tumor boundaries.
Another object of the present invention is to provide a kind of active carbon composite nano-microsphere, as tracer, for lymphatic metastasis spike.
A kind of active carbon composite nano-microsphere provided by the invention, with particle diameter 10nm ~ 100nm activated carbon granule for carrier, at its surface recombination organic dyestuff.
A kind of active carbon composite nano-microsphere provided by the invention, with particle diameter 10nm ~ 100nm activated carbon granule for carrier, coated material is compound in activated carbon granule surface, and organic dyestuff is compound in coated material.
In the present invention, compound comprises: but be not limited only to chemical coupling, Electrostatic Absorption and embedding etc., and such as: organic dyestuff chemical coupling is in coated material.
The preparation method of a kind of active carbon composite nano-microsphere provided by the invention, its step is as follows:
First active carbon is positioned over grinding in ball grinder, is put in water and leaves standstill two days, get upper strata suspension after taking-up, obtain active carbon Nano microsphere, its particle diameter is at 10nm ~ 100nm;
Then, add activator, stir 20 minutes ~ 40 minutes, to activate further the carboxyl of activated carbon surface, and the activated carbon microballon of obtained surface active;
Then, add coated material, stir 6 hours ~ 10 hours, the obtained active carbon complex microsphere with water-wet behavior;
Finally, add organic dyestuff, with the obtained further compound of active carbon composite nano-microsphere with water-wet behavior, and obtained active carbon composite nano-microsphere.
The preparation method of active carbon composite nano-microsphere of the present invention, its active carbon Nano microsphere and activator are mol ratio 20:1 ~ 80:1, prioritizing selection 30:1 ~ 50:1, as: but be not limited only to 30:1,31:1,32:1,33:1,34:1,35:1,36:1,37:1,38:1,39:1,40:1,41:1,42:1,43:1,44:1,45:1,46:1,47:1,48:1,49:1 and 50:1.
The preparation method of active carbon composite nano-microsphere of the present invention, the active carbon Nano microsphere of its surface active and coated material are mass ratio 20:1 ~ 80:1, prioritizing selection 20:1 ~ 40:1, as: but be not limited only to 20:1,21:1,22:1,23:1,24:1,25:1,26:1,27:1,28:1,29:1,30:1,31:1,32:1,33:1,34:1,35:1,36:1,37:1,38:1,39:1 and 40:1.
The preparation method of active carbon composite nano-microsphere of the present invention, it has the active carbon composite nano-microsphere of water-wet behavior and organic dyestuff is mass ratio 20:1 ~ 80:1, prioritizing selection 40:1 ~ 60:1, as: but be not limited only to 40:1,41:1,42:1,43:1,44:1,45:1,46:1,47:1,48:1,49:1,50:1,51:1,52:1,53:1,54:1,55:1,56:1,57:1,58:1,59:1 and 60:1.
The preparation method of active carbon Nano microsphere of the present invention, activator as: but be not limited only to carbodiimide, dicyclohexylcarbodiimide, N-hydroxy-succinamide, maleimide, succimide, DMAP and DMF.These activators can independent or any several application and the present invention.
The invention provides in various technical scheme, coated material as: but be not limited only to chitosan, hyaluronic acid, Polyethylene Glycol, 3-aminopropyl triethoxysilane and ethyl orthosilicate.These coated materials can independent or any several application and the present invention.
The invention provides in various technical scheme, organic dyestuff as: but be not limited only to indocyanine green, isosulfan blue, methylene blue and patent blue.These organic dyestuff can independent or any several application and the present invention.
Various active carbon composite nano-microsphere provided by the invention, after being given biological subject body, can realize the confirmation of tumor boundaries, and lymphatic metastasis spike.Therefore, these active carbon Nano microspheres can be used as tracer, for the confirmation of tumor boundaries, and lymphatic metastasis spike.
The beneficial effect that technical solution of the present invention realizes:
Various active carbon composite nano-microsphere provided by the invention, there is very strong coloring, can multi-modal imaging be realized, and observe directly the trace of Nano microsphere from tumor, tissue or organ by naked eyes, its surface, also by being loaded with fluorescent dye, can realize fluorescence detection.
Various active carbon composite nano-microsphere provided by the invention, spike Be very effective, gives at once to represent obvious lymphatic tracer effect in biological subject body half an hour.
Various active carbon composite nano-microsphere provided by the invention, only need to adopt a small amount of reagent to obtain, method is easy, quick and efficient.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope figure of active carbon composite nano-microsphere of the present invention;
Fig. 2 is the electronogram of active carbon composite nano-microsphere of the present invention;
Fig. 3 is the mouse peritoneal position ordinary optical photo taken after nude mice omentum majus activated carbon injection composite nano-microsphere half an hour;
Fig. 4 is the fluorescence photo taken after nude mice omentum majus activated carbon injection composite nano-microsphere half an hour;
Fig. 5 behaves position, the abdominal cavity ordinary optical photo that omentum majus activated carbon injection composite nano-microsphere was taken after 20 minutes.
Detailed description of the invention
Technical scheme of the present invention is described in detail below in conjunction with accompanying drawing.The embodiment of the present invention is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to the technical scheme of invention or equivalent replacement, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in right of the present invention.
Active carbon composite nano-microsphere involved by the present embodiment is produced all as follows
First active carbon is positioned over grinding in ball grinder, is put in water and leaves standstill two days, get upper strata suspension after taking-up, obtain active carbon Nano microsphere, its particle diameter is at 10nm ~ 100nm;
Then, with reference to the active carbon Nano microsphere obtained, 30:1 ~ 50:1 adds activator in molar ratio, stirs 20 minutes ~ 40 minutes, to activate further the carboxyl of activated carbon surface, and the active carbon Nano microsphere of obtained surface active;
Then, with reference to the activated carbon microballon obtaining surface active, 20:1 ~ 40:1 adds coated material in mass ratio, stirs 6 hours ~ 10 hours, the obtained active carbon composite nano-microsphere with water-wet behavior;
Finally, with reference to the active carbon complex microsphere with water-wet behavior, 40:1 ~ 60:1 adds organic dyestuff in mass ratio, with the obtained further compound of active carbon complex microsphere, and obtained active carbon composite nano-microsphere.
Wherein, activator is selected from one or more of carbodiimide, dicyclohexylcarbodiimide, N-hydroxy-succinamide, maleimide, succimide, DMAP and DMF.
Coated material is selected from one or more of chitosan, hyaluronic acid, Polyethylene Glycol, 3-aminopropyl triethoxysilane and ethyl orthosilicate.
Organic dyestuff is selected from one or more of indocyanine green, isosulfan blue, methylene blue and patent blue.
Obtained active carbon composite nano-microsphere is see Fig. 1 and Fig. 2.Indicated by Fig. 1 arrow, active carbon composite nano-microsphere is of a size of ~ 10nm, present comparatively rule spherical.As seen from Figure 2, diffraction spot is clear, and view picture figure is a set of diffraction spot, proves the single crystal characteristics of active carbon composite nano-microsphere.
Active carbon composite nano-microsphere is used for lymph node spike, specific as follows:
Gastric cancer situ tumor model is set up in advance to nude mice, gets the active carbon Nano microsphere solution of 10mg/mL, be injected in the omentum majus under gastric cancer tumor.As shown in Figure 3, after half an hour, clearly can find that lymph node becomes black (in figure arrow mark), spike successful.As indicated at 4, excite at 710nm wavelength laser, under the condition of 750nm wavelength absorption, except injection site, can also find that all there is fluorescence at omentum majus and other positions.Illustrate that active carbon Nano microsphere successfully spreads along lymphatic vessel.
Active carbon composite nano-microsphere is used for the lymphatic tracer of people, specific as follows:
Choose a Patients with Gastric Cancer, get the active carbon composite nano-microsphere solution of 10mg/mL, be injected in the omentum majus under gastric cancer tumor, as shown in Figure 5, after 20 minutes, clearly can find that lymph node becomes black (in figure arrow mark), illustrate that active carbon Nano microsphere successfully achieves spreading along lymphatic vessel in human body.
Claims (10)
1. an active carbon composite nano-microsphere, is characterized in that with particle diameter 10nm ~ 100nm activated carbon granule for carrier, at its surface recombination organic dyestuff.
2. an active carbon composite nano-microsphere, is characterized in that with particle diameter 10nm ~ 100nm activated carbon granule for carrier, and coated material is compound in described activated carbon granule surface, and organic dyestuff is compound in described coated material.
3. produce a method for the active carbon composite nano-microsphere described in claim 1 or 2, its step is as follows:
First active carbon is positioned over grinding in ball grinder, is put in water and leaves standstill two days, get upper strata suspension after taking-up, obtain active carbon Nano microsphere, its particle diameter is at 10nm ~ 100nm;
Then, add activator, stir 20 minutes ~ 40 minutes, to activate further the carboxyl of activated carbon surface, and the activated carbon microballon of obtained surface active;
Then, add coated material, stir 6 hours ~ 10 hours, the obtained active carbon complex microsphere with water-wet behavior;
Finally, add organic dyestuff, with the obtained further compound of active carbon composite nano-microsphere with water-wet behavior, and obtained active carbon composite nano-microsphere;
Described coated material is selected from one or more of chitosan, hyaluronic acid, Polyethylene Glycol, 3-aminopropyl triethoxysilane and ethyl orthosilicate.
4. the method producing active carbon composite nano-microsphere according to claim 3, is characterized in that described active carbon Nano microsphere and described activator are mol ratio 20:1 ~ 80:1.
5. the method producing active carbon composite nano-microsphere according to claim 3, is characterized in that the active carbon Nano microsphere of described surface active and coated material are mass ratio 20:1 ~ 80:1.
6. the method producing active carbon composite nano-microsphere according to claim 3, is characterized in that the described active carbon composite nano-microsphere with water-wet behavior and organic dyestuff are mass ratio 20:1 ~ 80:1.
7. the method producing active carbon composite nano-microsphere according to claim 3, it is characterized in that described activator is selected from one or more of carbodiimide, dicyclohexylcarbodiimide, N-hydroxy-succinamide, maleimide, succimide, DMAP and DMF.
8. the method producing active carbon composite nano-microsphere according to claim 3, is characterized in that organic dyestuff is selected from one or more of indocyanine green, isosulfan blue, methylene blue and patent blue.
9. the application of active carbon composite nano-microsphere as claimed in claim 1 or 2 in tumor boundaries confirms.
10. the application of an active carbon composite nano-microsphere as claimed in claim 1 or 2 in lymphatic metastasis spike.
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Cited By (5)
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CN106822906A (en) * | 2016-12-30 | 2017-06-13 | 四川大学 | Water soluble acid responds lympha targeted slow-released carrier Nano carbon, preparation method and application |
CN107260137A (en) * | 2017-07-31 | 2017-10-20 | 济南显微智能科技有限公司 | It is a kind of to detect ICG and double Tracing detection device and methods of methylenum careuleum simultaneously |
CN108452323A (en) * | 2017-02-21 | 2018-08-28 | 中国科学院宁波材料技术与工程研究所 | A kind of nanocomposite and its application in tracer lymph node |
CN111218127A (en) * | 2020-01-07 | 2020-06-02 | 山东大学齐鲁医院 | Near-infrared fluorescent dye and preparation method and application thereof |
WO2022041802A1 (en) * | 2020-08-26 | 2022-03-03 | 成都纽瑞特医疗科技股份有限公司 | Zirconium carbon microsphere suspension, preparation method therefor and use thereof |
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Cited By (7)
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CN106822906A (en) * | 2016-12-30 | 2017-06-13 | 四川大学 | Water soluble acid responds lympha targeted slow-released carrier Nano carbon, preparation method and application |
CN106822906B (en) * | 2016-12-30 | 2020-08-04 | 四川大学 | Water-dispersible acid-responsive lymph-targeting slow-release carrier nano-carbon, preparation method and application |
CN108452323A (en) * | 2017-02-21 | 2018-08-28 | 中国科学院宁波材料技术与工程研究所 | A kind of nanocomposite and its application in tracer lymph node |
CN107260137A (en) * | 2017-07-31 | 2017-10-20 | 济南显微智能科技有限公司 | It is a kind of to detect ICG and double Tracing detection device and methods of methylenum careuleum simultaneously |
CN111218127A (en) * | 2020-01-07 | 2020-06-02 | 山东大学齐鲁医院 | Near-infrared fluorescent dye and preparation method and application thereof |
CN111218127B (en) * | 2020-01-07 | 2022-03-08 | 山东大学齐鲁医院 | Near-infrared fluorescent dye and preparation method and application thereof |
WO2022041802A1 (en) * | 2020-08-26 | 2022-03-03 | 成都纽瑞特医疗科技股份有限公司 | Zirconium carbon microsphere suspension, preparation method therefor and use thereof |
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