CN111249459A - Iodine-containing polyaniline photothermal diagnosis and treatment agent with CT (computed tomography) contrast function and preparation method thereof - Google Patents
Iodine-containing polyaniline photothermal diagnosis and treatment agent with CT (computed tomography) contrast function and preparation method thereof Download PDFInfo
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- CN111249459A CN111249459A CN202010061501.6A CN202010061501A CN111249459A CN 111249459 A CN111249459 A CN 111249459A CN 202010061501 A CN202010061501 A CN 202010061501A CN 111249459 A CN111249459 A CN 111249459A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/50—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates
- A61K47/51—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent
- A61K47/56—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent the modifying agent being an organic macromolecular compound, e.g. an oligomeric, polymeric or dendrimeric molecule
- A61K47/58—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent the modifying agent being an organic macromolecular compound, e.g. an oligomeric, polymeric or dendrimeric molecule obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. poly[meth]acrylate, polyacrylamide, polystyrene, polyvinylpyrrolidone, polyvinylalcohol or polystyrene sulfonic acid resin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/04—X-ray contrast preparations
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
Abstract
The invention relates to an iodine-containing polyaniline photothermal diagnosis and treatment agent with a CT (computed tomography) contrast function and a preparation method thereof. The method comprises the following steps: dissolving aniline, polyvinyl alcohol and ursolic acid in a solvent, adding an iodine-containing oxidant, carrying out oxidative polymerization and iodine element doping reaction, centrifuging, and washing. The method adopts a one-step method which integrates preparation and modification, has simple and convenient process, good repeatability, cheap and easily obtained raw materials, no need of expensive equipment and low preparation cost, and is suitable for large-scale mass production.
Description
Technical Field
The invention belongs to the field of photothermal diagnosis and treatment agents and preparation thereof, and particularly relates to an iodine-containing polyaniline photothermal diagnosis and treatment agent with a CT (computed tomography) contrast function and a preparation method thereof.
Background
Cancer treatment is a major problem that is difficult for human beings to overcome. Photothermal therapy is a novel tumor treatment method developed in recent years after means such as surgery, radiotherapy and chemotherapy. The main principle is that a photothermal reagent with high photothermal conversion efficiency is applied to a tumor part, and then the part is irradiated by near infrared light to generate heat to kill tumor cells.
With the vigorous development of nano science and technology, the establishment and development of nano diagnosis and treatment medicine provides a brand new platform for early diagnosis and accurate treatment of cancer. The organic conjugated polymer material has low toxicity, good biocompatibility and other excellent characteristics, and has wide application prospect in the field of tumor photothermal therapy. Researchers devote to developing novel nano preparations, can realize tumor imaging and treat tumors, and achieves the aim of diagnosis and treatment integration.
Polyaniline is the first polymeric material studied for use as a photothermal therapeutic. The preparation method generally adopts an oxidant to oxidize and polymerize aniline monomers to form the polyaniline nano-material. Researches find that the use of the oxidant plays a decisive role in the morphology of the nano material, and ferric chloride is used as the oxidant to prepare the spherical nano particles with uniform and regular size; ammonium thiosulfate is used as an oxidizing agent to prepare the slender nanofiber. However, polyaniline has disadvantages in biomedical therapy in that: it has only the function of treatment and no diagnosis. Therefore, from the perspective of an oxidant, a new preparation method is explored, so that the polyaniline nanoparticles with the photothermal conversion performance can be obtained, the CT radiography function can be endowed, and the method has a certain significance in promoting the development of tumor diagnosis and treatment.
Disclosure of Invention
The invention aims to solve the technical problem of providing an iodine-containing polyaniline photothermal diagnosis and treatment agent with a CT (computed tomography) contrast function and a preparation method thereof, so as to overcome the defects that polyaniline in the prior art does not have a diagnosis function and the like.
The invention provides an iodine-containing polyaniline photothermal diagnostic agent, aniline uses an iodine-containing oxidant to carry out oxidative polymerization and iodine element doping, and polyvinyl alcohol is modified at the same time.
The iodine-containing oxidizing agent is iodic acid or periodic acid.
The invention also provides a preparation method of the iodine-containing polyaniline photothermal diagnosis and treatment agent, which comprises the following steps:
dissolving aniline, polyvinyl alcohol and ursolic acid in a solvent, adding an iodine-containing oxidant, carrying out oxidative polymerization and iodine element doping reaction, centrifuging, and washing to obtain the iodine-containing polyaniline photothermal diagnosis and treatment agent, wherein the molar ratio of the iodine-containing oxidant to the aniline is 0.8:1-3.8:1, and the volume ratio of the aniline to the solvent is 1-1.5: 20-35.
The polyvinyl alcohol has an average molecular weight of 16000-200000.
The solvent is as follows: a mixed solvent of ethanol and water in a volume ratio of 1: 1.8-3.
The reaction temperature of the oxidative polymerization and the doping of the iodine element is 90-105 ℃, and the reaction time of the oxidative polymerization and the doping of the iodine element is 8-12 h.
The invention also provides application of the iodine-containing polyaniline photothermal diagnosis and treatment agent in preparation of a diagnosis and treatment agent for CT (computed tomography) radiography and photothermal treatment.
The oxidation polymerization and iodine element doping reaction process related by the invention simultaneously modifies polyvinyl alcohol, so that the surface of the obtained iodine-containing polyaniline is modified with polyvinyl alcohol, and the surface modified polyvinyl alcohol has good colloid stability.
Advantageous effects
(1) The one-step method adopted by the invention integrates preparation and modification, has simple and convenient process, good repeatability, cheap and easily obtained raw materials, no need of expensive equipment and low preparation cost, and is suitable for large-scale mass production;
(2) the polyaniline prepared by the method has a nanoscale size, and the hydrodynamic radius is about 180 nm;
(3) the prepared iodine-containing polyaniline nanometer surface is modified with polyvinyl alcohol, which is beneficial to the colloid stability (see figure 4) and widens the deep application of the iodine-containing polyaniline nanometer surface in the biomedical field;
(4) the iodine-containing polyaniline nano photothermal diagnosis and treatment agent prepared by the invention has good CT contrast function and photothermal conversion effect, and is beneficial to diagnosis and treatment of tumors.
Drawings
Fig. 1 shows the in vitro CT imaging effect of nano-PAN prepared in example 1. (there are 4 CT images, the first 3 are iodine-containing polyaniline solution with concentration of 1mg/L, the last one is 5mg/L)
Fig. 2 is a transmission electron micrograph of nano-PAN with CT contrast function prepared in example 1.
Fig. 3 is a graph showing photothermal effects of nano-PAN with CT contrast function prepared according to different molar ratios of iodic acid to aniline in example 1, example 2 and example 3 (the solution temperature before temperature rise is 25 ℃).
FIG. 4 shows the presence of iodine-containing polyaniline in H in example 12O, PBS and RPMI-1640 medium.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
3g of polyvinyl alcohol (molecular weight 16000) is weighed, dissolved in 20mL of deionized water, added to 10mL of ethanol, stirred vigorously until completely dissolved, and then 1.3mL of aniline is added dropwise and stirring is continued for 10 min. Subsequently, 5.8g of ursolic acid and 6.9g of HIO were added3And after vigorously stirring for 10min, transferring into a polytetrafluoroethylene mold, sealing in a stainless steel reaction kettle, maintaining at 100 ℃ for 10h, cooling to room temperature, removing the mold, sucking out reaction liquid, centrifuging at high speed, and repeatedly washing with deionized water to obtain the black iodine-containing polyaniline nano-particles.
Dispersing the obtained iodine-containing polyaniline in water to obtain 1mg/mL dispersion, and processing with near infrared laser (center wavelength 808nm, 1.5W/cm)3) Upon irradiation, a significant temperature increase effect was observed under photothermal irradiation of the detector.
CT imaging effect experiment: 4 EP tubes of 1.5mL size were prepared, and to 3 of the EP tubes, 1mg/mL iodine-containing polyaniline solution was added, and the other was added with a solution of 5 mg/mL. The 4 EP tubes were placed simultaneously at the CT imaging device for scanning.
FIG. 1 shows that: the CT contrast effect of the iodine-containing polyaniline has obvious concentration dependence.
FIG. 2 shows that: the prepared iodine-containing polyaniline has a uniform spherical shape.
FIG. 4 shows that: the prepared iodine-containing polyaniline has good colloidal stability.
Example 2
According to example 1, HIO3The mass of the black particles was changed to 4.43g, and the rest was the same as in example 1, thereby obtaining black iodine-containing polyaniline nanoparticles. Dispersing the obtained iodine-containing polyaniline in water, sequentially preparing 1mg/mL of composite iodine-containing polyaniline nano dispersion solution, and passing through near infrared laser (center wavelength of 808nm, 1.5W/cm)3) The heating effect under photo-thermal irradiation is not obvious.
Example 3
According to example 1, HIO3The mass of the black iodine-containing polyaniline nanoparticles was changed to 2.34g, and the rest was the same as in example 1. Dispersing the obtained iodine-containing polyaniline in water, sequentially preparing 1mg/mL of composite iodine-containing polyaniline nano dispersion solution, and passing through near infrared laser (center wavelength of 808nm, 1.5W/cm)3) The heating effect under photo-thermal irradiation is not obvious.
FIG. 3 shows: the temperature of the solution before warming was 25 ℃, the molar ratio of iodic acid to aniline in example 1 was 2.8: 1, the material temperature can reach approximately 50 ℃.
Claims (7)
1. The iodine-containing polyaniline photothermal diagnosis and treatment agent is characterized in that aniline is subjected to oxidative polymerization by using an iodine-containing oxidant, iodine elements are doped, and polyvinyl alcohol is modified.
2. The diagnostic and therapeutic agent according to claim 1, wherein said iodine-containing oxidizing agent is iodic acid or periodic acid.
3. A method for preparing iodine-containing polyaniline photothermal diagnosis and treatment agent comprises the following steps:
dissolving aniline, polyvinyl alcohol and ursolic acid in a solvent, adding an iodine-containing oxidant, carrying out oxidative polymerization and iodine element doping reaction, centrifuging, and washing to obtain the iodine-containing polyaniline photothermal diagnosis and treatment agent, wherein the molar ratio of the iodine-containing oxidant to the aniline is 0.8:1-3.8:1, and the volume ratio of the aniline to the solvent is 1-1.5: 20-35.
4. The method as claimed in claim 3, wherein the polyvinyl alcohol has an average molecular weight of 16000-.
5. The method of claim 3, wherein the solvent is: the volume ratio is 1:1.8-3 of a mixed solvent of ethanol and water.
6. The method as claimed in claim 3, wherein the temperature for the oxidative polymerization and iodine element doping reaction is 90-105 ℃, and the time for the oxidative polymerization and iodine element doping reaction is 8-12 h.
7. Use of the photothermal diagnostic agent of claim 1 for preparing a diagnostic agent for CT imaging and photothermal therapy.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294154A (en) * | 1999-10-26 | 2001-05-09 | 北京燕山石油化工公司研究院 | Electrically conductive aqueous latex of polyphnenylamine and its preparing process and application |
| CN101215418A (en) * | 2007-12-27 | 2008-07-09 | 江苏工业学院 | Method for preparing polyaniline/attapulgite clay nano conductive composite material |
| CN102428068A (en) * | 2009-04-21 | 2012-04-25 | 伯拉考成像股份公司 | Process for the iodination of aromatic compounds |
| CN105709243A (en) * | 2016-02-01 | 2016-06-29 | 吉林大学 | Fe (III) and Cu (II) doped polyaniline nano-compound and application thereof |
-
2020
- 2020-01-19 CN CN202010061501.6A patent/CN111249459A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294154A (en) * | 1999-10-26 | 2001-05-09 | 北京燕山石油化工公司研究院 | Electrically conductive aqueous latex of polyphnenylamine and its preparing process and application |
| CN101215418A (en) * | 2007-12-27 | 2008-07-09 | 江苏工业学院 | Method for preparing polyaniline/attapulgite clay nano conductive composite material |
| CN102428068A (en) * | 2009-04-21 | 2012-04-25 | 伯拉考成像股份公司 | Process for the iodination of aromatic compounds |
| CN105709243A (en) * | 2016-02-01 | 2016-06-29 | 吉林大学 | Fe (III) and Cu (II) doped polyaniline nano-compound and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| QUAN ZOU等: ""One-Step Synthesis of Iodinated Polypyrrole Nanoparticles for CT Imaging Guided Photothermal Therapy of Tumors"", 《SMALL》 * |
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