技术领域technical field
本发明涉及一种核壳结构的聚吡咯/介孔二氧化硅/石墨烯量子点纳米复合材料在药物控释中的应用，属于生物医药领域。The invention relates to the application of a polypyrrole/mesoporous silicon dioxide/graphene quantum dot nanocomposite material with a core-shell structure in drug controlled release, belonging to the field of biomedicine.
技术背景technical background
药物缓释技术出现于80年代，药物可控释放的形式可以产生适度的反应，较小的毒副作用和较长的疗效。这种给药方式可以调节药物释放速率，减少给药次数，从而增加了药物治疗的安全性、高效性和可靠性。因此，使一种药物高效的、可预计的释放，并持续较长时间的疗效在临床上是很有意义的。Drug sustained release technology appeared in the 1980s. The form of controlled release of drugs can produce moderate response, less toxic side effects and longer curative effect. This administration method can adjust the release rate of the drug and reduce the number of administrations, thereby increasing the safety, efficiency and reliability of the drug treatment. Therefore, it is clinically meaningful to make a drug release efficiently, predictably, and last for a long time.
聚吡咯具有很好的光学性能，可以将光能转化成热能。介孔二氧化硅在药物缓释中可以有效的提高药物的装载率，并且介孔二氧化硅具有很好的生物相容性和低的细胞毒性。而石墨烯量子点含有大量的羧基，可以很好的与硅羟基和氨基形成氢键，并且其具有与介孔二氧化硅孔径大小相匹配的粒径。因此合成聚吡咯/介孔二氧化硅/石墨烯量子点纳米复合材料，可以利用介孔二氧化硅提高药物的装载量，在近红外光照射下聚吡咯将光能转化成热能控制药物释放。甲氨喋呤被广泛的应用于癌症的化疗，其主要用于治疗绒毛膜上皮癌、恶性葡萄胎、各类急性白血病、乳腺癌、肺癌、头颈部癌、消化道癌、宫颈癌及恶性淋巴瘤等。但由于大量的甲氨喋呤对人体的正常细胞具有损害，因此需要控制甲氨喋呤的释放量，减少对正常细胞的损伤。Polypyrrole has good optical properties and can convert light energy into heat energy. Mesoporous silica can effectively improve the drug loading rate in drug sustained release, and mesoporous silica has good biocompatibility and low cytotoxicity. Graphene quantum dots contain a large number of carboxyl groups, which can form hydrogen bonds well with silicon hydroxyl groups and amino groups, and have a particle size that matches the pore size of mesoporous silica. Therefore, the synthesis of polypyrrole/mesoporous silica/graphene quantum dot nanocomposites can use mesoporous silica to increase the drug loading capacity, and polypyrrole converts light energy into heat energy to control drug release under near-infrared light irradiation. Methotrexate is widely used in cancer chemotherapy, mainly for the treatment of choriocarcinoma, malignant mole, various types of acute leukemia, breast cancer, lung cancer, head and neck cancer, digestive tract cancer, cervical cancer and malignant Lymphoma etc. However, since a large amount of methotrexate can damage normal cells of the human body, it is necessary to control the amount of methotrexate released to reduce damage to normal cells.
发明内容Contents of the invention
本发明的目的是在于提供一种核壳结构的聚吡咯/介孔二氧化硅/石墨烯量子点纳米复合材料在药物控释中的应用，使药物光控释放，并维持较长时间的药效。The purpose of the present invention is to provide a polypyrrole/mesoporous silica/graphene quantum dot nanocomposite material with a core-shell structure in the application of drug controlled release, so that the drug can be released by light and maintain a long-term drug release. effect.
本发明所述一种核壳结构的聚吡咯/介孔二氧化硅/石墨烯量子点纳米复合材料在药物控释中的应用，包括以下步骤：The application of a polypyrrole/mesoporous silica/graphene quantum dot nanocomposite material with a core-shell structure in the drug controlled release of the present invention comprises the following steps:
a、制备聚吡咯/介孔二氧化硅载药复合材料：将聚吡咯/介孔二氧化硅纳米粒子分散在甲氨喋呤溶液中，恒温37℃下搅拌，达到平衡状态。将载药后的样品离心分离，在60℃下干燥。a. Preparation of polypyrrole/mesoporous silica drug-loaded composite material: disperse polypyrrole/mesoporous silica nanoparticles in a methotrexate solution, stir at a constant temperature of 37° C., and reach an equilibrium state. The drug-loaded samples were centrifuged and dried at 60°C.
b、制备聚吡咯/介孔二氧化硅/石墨烯量子点复合材料：将步骤a制备的聚吡咯/介孔二氧化硅载药复合材料加入到含有石墨烯量子点的溶液中，搅拌反应12小时。将装载石墨烯量子点的材料离心分离，60℃下干燥。b. Preparation of polypyrrole/mesoporous silica/graphene quantum dot composite material: add the polypyrrole/mesoporous silica drug-loaded composite material prepared in step a to the solution containing graphene quantum dots, and stir for 12 Hour. The material loaded with graphene quantum dots was centrifuged and dried at 60°C.
c、取20mg载药复合材料，置于透析袋中，并将透析袋放于30mL磷酸盐缓冲溶液中进行磁力搅拌，在初始温度为37℃条件下进行近红外光照射控制药物释放。磷酸盐缓冲溶液的pH为7.4，释放12小时。每隔1小时取出5mL溶液，测定甲氨喋呤的含量，同时补加5mL磷酸盐缓冲溶液。甲氨喋呤的含量使用紫外分光光度计在302nm处测定，根据测定的甲氨喋呤含量计算出不同时间的释药累积百分数。c. Take 20 mg of the drug-loaded composite material, put it in a dialysis bag, put the dialysis bag in 30 mL of phosphate buffer solution for magnetic stirring, and irradiate near-infrared light at an initial temperature of 37° C. to control drug release. Phosphate buffered saline had a pH of 7.4 and was released for 12 hours. Take out 5mL of solution every 1 hour, measure the content of methotrexate, and add 5mL of phosphate buffered saline at the same time. The content of methotrexate was measured at 302nm using an ultraviolet spectrophotometer, and the cumulative percentage of drug release at different times was calculated according to the measured content of methotrexate.
进一步地，步骤a中甲氨喋呤浓度为0～1mg/mL。Further, the methotrexate concentration in step a is 0-1 mg/mL.
进一步地，步骤c中磷酸盐缓冲溶液由磷酸二氢钠和氢氧化钠配制而成，浓度为0～0.2mol/L。Further, in step c, the phosphate buffer solution is prepared from sodium dihydrogen phosphate and sodium hydroxide, and the concentration is 0-0.2 mol/L.
本发明的有益效果是：聚吡咯/介孔二氧化硅/石墨烯量子点纳米复合材料具有优良的光转热性能，在近红外光照射下将光转化成热控制药物缓慢释放，并有效利用。The beneficial effects of the present invention are: the polypyrrole/mesoporous silica/graphene quantum dot nano-composite material has excellent light-to-heat performance, converts light into heat under the irradiation of near-infrared light to control the slow release of drugs, and effectively utilizes .
附图说明Description of drawings
下面结合附图对本实验进一步说明。The experiment will be further described below in conjunction with the accompanying drawings.
图1为实施例一中近红外光照射和对比例一中未用近红外光照射复合材料的体外药物缓释性能图。Fig. 1 is a graph showing the sustained-release performance of drugs in vitro of the composite material irradiated with near-infrared light in Example 1 and in Comparative Example 1 without near-infrared light irradiation.
具体实施方式detailed description
现在结合具体实施例对本发明做进一步说明，以下实施例旨在说明本发明而不是对本发明的进一步限定。The present invention will now be further described in conjunction with specific examples, and the following examples are intended to illustrate the present invention rather than further limit the present invention.
实施例一：Embodiment one:
制备核壳结构的聚吡咯/介孔二氧化硅/石墨烯量子点纳米载药复合材料包括以下几个步骤：The preparation of polypyrrole/mesoporous silica/graphene quantum dot nano drug-loaded composite material with core-shell structure includes the following steps:
(1)将聚吡咯/介孔二氧化硅纳米粒子分散在0.05mg/mL甲氨喋呤溶液中，恒温37℃搅拌，达到平衡状态。将载药后的样品离心分离，在60℃下干燥。(1) Disperse the polypyrrole/mesoporous silica nanoparticles in a 0.05 mg/mL methotrexate solution, and stir at a constant temperature of 37° C. to reach an equilibrium state. The drug-loaded samples were centrifuged and dried at 60°C.
(2)将步骤(1)制备的聚吡咯/介孔二氧化硅载药复合材料加入到含有石墨烯量子点的溶液中，搅拌反应12小时。将装载石墨烯量子点的材料离心分离，60℃下干燥。(2) Add the polypyrrole/mesoporous silica drug-loaded composite material prepared in step (1) into the solution containing the graphene quantum dots, and stir and react for 12 hours. The material loaded with graphene quantum dots was centrifuged and dried at 60°C.
实施例二：Embodiment two:
近红外光照射条件下体外药物释放行为包括以下几个步骤：The in vitro drug release behavior under near-infrared light irradiation includes the following steps:
核壳结构的聚吡咯/介孔二氧化硅/石墨烯量子点纳米载药复合材料的制备过程与实施例一相同。The preparation process of the polypyrrole/mesoporous silica/graphene quantum dot nano drug-loaded composite material with core-shell structure is the same as that of Example 1.
(1)配制0.1mol/L的磷酸盐缓冲溶液用于模拟人体环境，称取20mg复合材料置于透析袋中，并将透析袋放入30mL磷酸盐缓冲溶液中，在初始温度为37℃条件下磁力搅拌。用近红外光照射复合材料，释放12小时。(1) Prepare 0.1mol/L phosphate buffer solution for simulating the human body environment, weigh 20mg of the composite material and place it in a dialysis bag, and put the dialysis bag into 30mL phosphate buffer solution, at an initial temperature of 37°C Under magnetic stirring. The composite was irradiated with near-infrared light for 12 hours of release.
(2)每隔1小时从溶液中取出5mL溶液，测定药物含量，同时补加5mL磷酸盐缓冲溶液。药物的含量使用紫外分光光度计在302nm处测定，根据测定药物含量计算出不同时间的药物累积百分数，如图1a所示。(2) Take out 5mL solution from the solution every 1 hour, measure the drug content, and add 5mL phosphate buffer solution at the same time. The drug content was measured at 302nm using an ultraviolet spectrophotometer, and the drug accumulation percentage at different times was calculated according to the measured drug content, as shown in Figure 1a.
对比例一：Comparative example one:
未用近红外光照射条件下体外药物释放行为包括以下几个步骤：The in vitro drug release behavior without near-infrared light irradiation includes the following steps:
核壳结构的聚吡咯/介孔二氧化硅/石墨烯量子点纳米载药复合材料的制备过程与实施例一相同。The preparation process of the polypyrrole/mesoporous silica/graphene quantum dot nano drug-loaded composite material with core-shell structure is the same as that of Example 1.
(1)配制0.1mol/L的磷酸盐缓冲溶液用于模拟人体环境，称取20mg复合材料置于透析袋中，并将透析袋放入30mL的磷酸盐缓冲溶液恒温37℃磁力搅拌。未用近红外光照射复合材料，释放12小时。(1) Prepare 0.1mol/L phosphate buffer solution for simulating human environment, weigh 20mg of the composite material and place it in a dialysis bag, and put the dialysis bag into 30mL phosphate buffer solution at a constant temperature of 37°C for magnetic stirring. The composite was not irradiated with near-infrared light and released for 12 hours.
(2)每隔1小时从溶液中取出5mL溶液，测定药物含量，同时补加5mL磷酸盐缓冲溶液。药物的含量使用紫外分光光度计在302nm处测定，根据测定药物含量计算出不同时间的药物累积百分数，如图1b所示。从图中可以看出，近红外光照射复合材料药物释放累积量明显高于未照射复合材料药物释放累积量。这说明了近红外光照射可以很好的控制药物的释放。(2) Take out 5mL solution from the solution every 1 hour, measure the drug content, and add 5mL phosphate buffer solution at the same time. The drug content was measured at 302nm using an ultraviolet spectrophotometer, and the drug accumulation percentage at different times was calculated according to the measured drug content, as shown in Figure 1b. It can be seen from the figure that the cumulative drug release amount of the composite material irradiated by near-infrared light is significantly higher than that of the non-irradiated composite material. This shows that near-infrared light irradiation can well control the release of drugs.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710129975.8ACN106974882A (en) | 2017-03-07 | 2017-03-07 | A kind of polypyrrole/mesoporous silicon oxide of core shell structure/application of the graphene quantum dot nano composite material in medicine controlled releasing |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710129975.8ACN106974882A (en) | 2017-03-07 | 2017-03-07 | A kind of polypyrrole/mesoporous silicon oxide of core shell structure/application of the graphene quantum dot nano composite material in medicine controlled releasing |
| Publication Number | Publication Date |
|---|---|
| CN106974882Atrue CN106974882A (en) | 2017-07-25 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710129975.8APendingCN106974882A (en) | 2017-03-07 | 2017-03-07 | A kind of polypyrrole/mesoporous silicon oxide of core shell structure/application of the graphene quantum dot nano composite material in medicine controlled releasing |
| Country | Link |
|---|---|
| CN (1) | CN106974882A (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108354897A (en)* | 2018-04-20 | 2018-08-03 | 常州大学 | A kind of silica/the polypyrrole can be used for medicament slow release/poly- (acrylamide and acrylic acid) carries the preparation of medicine plural gel |
| CN108671233A (en)* | 2018-05-25 | 2018-10-19 | 常州大学 | A kind of preparation of Poly(ethylene glycol)-Polycaprolactone-Poly(ethyleneglycol) coated silica/polypyrrole/mesoporous silicon oxide medicine carrying material |
| CN109012624A (en)* | 2018-07-14 | 2018-12-18 | 桂林理工大学 | A kind of preparation method and applications of polypyrrole/magnetic mesoporous silicon |
| CN110215179A (en)* | 2019-06-20 | 2019-09-10 | 京东方科技集团股份有限公司 | The medicament release device and capsule endoscope of capsule endoscope |
| CN111166893A (en)* | 2020-02-19 | 2020-05-19 | 常州大学 | Preparation method of gold/graphene quantum dot/mercaptopropionic acid/polyethyleneimine drug-loaded hydrogel for drug sustained release |
| CN111214655A (en)* | 2020-02-19 | 2020-06-02 | 常州大学 | A kind of preparation method of drug sustained-release system with dual response of pH and near-infrared light |
| CN114848846A (en)* | 2022-05-26 | 2022-08-05 | 深圳市世格赛思医疗科技有限公司 | Drug delivery system and preparation method and application thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1358775A (en)* | 2001-12-26 | 2002-07-17 | 河北工业大学 | Polypyrrole/silicon dioxide nano composite material and preparation process thereof |
| CN1559656A (en)* | 2004-02-19 | 2005-01-05 | 上海交通大学 | Preparation method of core-shell nanocomposite particles of magnetic particles and quantum dots |
| CN102573910A (en)* | 2009-06-12 | 2012-07-11 | 鹿特丹伊拉斯谟大学医疗中心 | Targeted Nanophotopharmaceuticals for Cancer Photodynamic Therapy |
| CN105997944A (en)* | 2016-07-07 | 2016-10-12 | 上海理工大学 | Nano-drug carrier with magnetothermal and photothermal effects and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1358775A (en)* | 2001-12-26 | 2002-07-17 | 河北工业大学 | Polypyrrole/silicon dioxide nano composite material and preparation process thereof |
| CN1247630C (en)* | 2001-12-26 | 2006-03-29 | 河北工业大学 | Polypyrrole/silicon dioxide nano composite material and preparation process thereof |
| CN1559656A (en)* | 2004-02-19 | 2005-01-05 | 上海交通大学 | Preparation method of core-shell nanocomposite particles of magnetic particles and quantum dots |
| CN102573910A (en)* | 2009-06-12 | 2012-07-11 | 鹿特丹伊拉斯谟大学医疗中心 | Targeted Nanophotopharmaceuticals for Cancer Photodynamic Therapy |
| CN105997944A (en)* | 2016-07-07 | 2016-10-12 | 上海理工大学 | Nano-drug carrier with magnetothermal and photothermal effects and preparation method thereof |
| Title |
|---|
| KARAM MOLAEI ET AL: "SiO2-coated magnetic graphene oxide modified with polypyrrole–polythiophene: A novel and efficient nanocomposite for solid phase extraction of trace amounts of heavy metals", 《TALANTA》* |
| MANJIE ZHANG ET AL: "Near-Infrared Light and pH-Responsive Polypyrrole@Polyacrylicacid/Fluorescent Mesoporous Silica Nanoparticles for Imaging and Chemo-Photothermal Cancer Therapy", 《CHEM. EUR. J》* |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108354897A (en)* | 2018-04-20 | 2018-08-03 | 常州大学 | A kind of silica/the polypyrrole can be used for medicament slow release/poly- (acrylamide and acrylic acid) carries the preparation of medicine plural gel |
| CN108354897B (en)* | 2018-04-20 | 2019-07-26 | 常州大学 | Preparation of a silica/polypyrrole/poly(acrylamide-acrylic acid) drug-loaded composite gel for sustained drug release |
| CN108671233A (en)* | 2018-05-25 | 2018-10-19 | 常州大学 | A kind of preparation of Poly(ethylene glycol)-Polycaprolactone-Poly(ethyleneglycol) coated silica/polypyrrole/mesoporous silicon oxide medicine carrying material |
| CN109012624A (en)* | 2018-07-14 | 2018-12-18 | 桂林理工大学 | A kind of preparation method and applications of polypyrrole/magnetic mesoporous silicon |
| CN110215179A (en)* | 2019-06-20 | 2019-09-10 | 京东方科技集团股份有限公司 | The medicament release device and capsule endoscope of capsule endoscope |
| CN110215179B (en)* | 2019-06-20 | 2022-02-25 | 京东方科技集团股份有限公司 | Medicine releasing device of capsule endoscope and capsule endoscope |
| CN111166893A (en)* | 2020-02-19 | 2020-05-19 | 常州大学 | Preparation method of gold/graphene quantum dot/mercaptopropionic acid/polyethyleneimine drug-loaded hydrogel for drug sustained release |
| CN111214655A (en)* | 2020-02-19 | 2020-06-02 | 常州大学 | A kind of preparation method of drug sustained-release system with dual response of pH and near-infrared light |
| CN111166893B (en)* | 2020-02-19 | 2022-06-28 | 常州大学 | A kind of preparation method of gold/graphene quantum dots/mercaptopropionic acid/polyethyleneimine drug-loaded hydrogel that can be used for drug sustained release |
| CN114848846A (en)* | 2022-05-26 | 2022-08-05 | 深圳市世格赛思医疗科技有限公司 | Drug delivery system and preparation method and application thereof |
| Publication | Publication Date | Title |
|---|---|---|
| CN106974882A (en) | A kind of polypyrrole/mesoporous silicon oxide of core shell structure/application of the graphene quantum dot nano composite material in medicine controlled releasing | |
| Teng et al. | Mesoporous organosilica hollow nanoparticles: synthesis and applications | |
| CN107412195B (en) | PH-responsive antitumor drug carrier material and preparation and application thereof | |
| Xie et al. | Layered clay minerals in cancer therapy: recent progress and prospects | |
| CN114452268B (en) | Preparation method of mesoporous polydopamine anthocyanin-carrying nanoparticle | |
| CN115192543B (en) | Preparation method of lipid-loaded soluble pigment nanoparticles | |
| Guo et al. | Organic/inorganic nanohybrids as multifunctional gene delivery systems | |
| CN107596366B (en) | A kind of diagnoses and treatment preparation and its preparation method and application with multiple stimulation response type drug controlled-releasing function | |
| Shao et al. | Facile Synthesis of Core–shell Magnetic Mesoporous Silica Nanoparticles for pH‐sensitive Anticancer Drug Delivery | |
| CN106692970B (en) | Bismuth selenide nano composite material and preparation method and application thereof | |
| CN114652841B (en) | pH, redox and near infrared triple-response type dual-drug-carrying system and preparation method and application thereof | |
| CN106727274A (en) | A kind of preparation method of the polypyrrole/mesoporous silicon oxide/graphene quantum dot nano composite material of core shell structure | |
| Xu et al. | Advanced carbon-based nanoplatforms combining drug delivery and thermal therapy for cancer treatment | |
| CN107469078A (en) | Selenium quantum dot/silica/copper sulphide nano compound particle and its preparation and application | |
| CN104940945B (en) | A kind of hyaluronic acid decorated hollow mesoporous vulcanization copper composition and preparation method and application | |
| Thirumurugan et al. | Inorganic nanoparticles for photothermal treatment of cancer | |
| CN101797387A (en) | Magnetic targeting carrier capable of carrying gene and drug, preparation method and application thereof | |
| CN104474556A (en) | Application of carbon dot as anti-tumor medicine carrier | |
| CN103768620B (en) | Fe/ mesoporous monox nanometer composite and its preparation method and application | |
| Xu et al. | A review on cancer therapy based on the photothermal effect of gold nanorod | |
| CN114081956A (en) | Polyelectrolyte multilayer film-calcium carbonate nano-drug carrier and its preparation method and application | |
| Xing et al. | Engineering mono‐chalcogen nanomaterials for omnipotent anticancer applications: Progress and challenges | |
| CN110559274A (en) | preparation method of folic acid modified nano MOF-Al responsive drug carrier with targeting function | |
| Yu et al. | Carbon nanomaterials for photothermal therapies | |
| CN111686249B (en) | Nano carrier material, preparation method thereof and application thereof in preparing anti-tumor drugs |
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | Application publication date:20170725 | |
| WD01 | Invention patent application deemed withdrawn after publication |