CN111588852A - Polypyrrole/manganese dioxide-methylene blue nano composite particle and preparation method thereof - Google Patents
Polypyrrole/manganese dioxide-methylene blue nano composite particle and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polypyrrole/manganese dioxide-methylene blue nano composite particle and a preparation method thereof, belonging to the technical field of nano composite materials. The polypyrrole/manganese dioxide-methylene blue nano composite particles are directly prepared through the in-situ redox reaction of the polypyrrole core and potassium permanganate, and are finally obtained after the photosensitizer methylene blue is loaded, wherein the particle size of the polypyrrole/manganese dioxide-methylene blue nano composite particles is 69-72 nm. The nano composite particle has better photo-thermal conversion capability and singlet oxygen generation performance, and has better killing capability on cancer cells under laser radiation, which shows that the nano composite particle can be used as an effective photo-thermal and photodynamic combined treatment material. The polypyrrole/manganese dioxide nano composite particles are prepared by directly mixing the polypyrrole nano particles with the potassium permanganate and performing rapid reaction, and no additional reducing agent is required in the process, so that the use of large-scale instruments is avoided, and the method is simple and easy to operate, rapid in reaction, green and environment-friendly.
Description
Technical Field
The invention relates to a nano composite material, and in particular belongs to polypyrrole/manganese dioxide-methylene blue nano composite particles and a preparation method and application thereof.
Background
Cancer is still one of the most fatal diseases today, causing millions of deaths each year. The development of nano medicine can improve the cancer treatment index and reduce the side effect, and opens up a new way for cancer treatment. Chemotherapy and radiation therapy are still the two leading clinical treatments at present, however both are prone to severe systemic toxicity and adverse effects. In contrast, photothermal therapy and photodynamic therapy are receiving attention because of their advantages of specific spatio-temporal selectivity, small wound, few side effects, negligible drug resistance, and rapid healing.
Various nanomaterials have been used in photothermal therapy, such as gold nanomaterials, copper sulphide nanomaterials, some polymer nanomaterials. The polypyrrole nano particles have a strong absorption peak between 700-900nm, high photo-thermal conversion rate and excellent thermal stability, are easy to synthesize by in-situ redox reaction, have excellent biocompatibility and biodegradability, and are widely used as photo-thermal conversion agents. In order to improve the effect of photodynamic therapy, some new O-compounds have been developed2Generation of photodynamic therapeutic agents, mixing conventional photosensitizers with other materials such as: catalase, CaO2And manganese dioxide is combined to realize effective photodynamic therapy under an anoxic environment. Wherein the manganese dioxide nanometer material has similar antioxidase catalysis effect and can react with H for a long time2O2And H2O2/H+In vivo metabolite action, in situ O production in tumor cells2Improving tumor hypoxia environment and improving photodynamic therapy effect. Simultaneously, manganese dioxide and H2O2/H+Mn produced after the action2+Ions, Mn which is easily cleared by liver and kidney, not easy to cause tissue accumulation and biotoxicity and released2+The ions have stronger magnetic resonance signals and can be used for magnetic resonance imaging. In addition, the manganese dioxide is easy to prepare, has no toxicity, and has better biocompatibility and biodegradabilityBut is increasingly used as O2-generating agent and H2O2-a depleting agent to enhance photodynamic therapy effect.
However, the photothermal therapy or photodynamic therapy alone still cannot achieve a good therapeutic effect, and the combination of photothermal therapy and photodynamic therapy can improve the therapeutic effect of cancer. Based on the principle, the polypyrrole and manganese dioxide are combined and loaded with methylene blue to obtain the composite nano particles, so that the effective combination of photothermal therapy and photodynamic therapy can be realized. The literature reports that a manganese dioxide shell is modified on the surface of polypyrrole through an in-situ redox reaction between polypyrrole and potassium permanganate (Sci. China chem.,2018,61:812-823), but the used method not only needs the addition of strong acid, but also has long reaction time and high reaction temperature. At present, polypyrrole is used as an inner core and a reducing agent, and is stirred with potassium permanganate at room temperature for a few minutes to perform an in-situ redox reaction to obtain polypyrrole/manganese dioxide nano composite particles, and after a photosensitizer methylene blue is loaded, the polypyrrole/manganese dioxide-methylene blue nano composite particles are obtained and used as a photo-thermal and photodynamic combined treatment material.
Disclosure of Invention
The invention aims to provide polypyrrole/manganese dioxide-methylene blue nano composite particles and a preparation method thereof, the method is simple and easy to operate, the reaction is rapid, the method is green and environment-friendly, and the obtained polypyrrole/manganese dioxide-methylene blue nano composite particles have good dispersibility and can be used as a photo-thermal and photodynamic combined treatment material.
The polypyrrole nano particles are used as the inner core and the reducing agent at the same time, and the intrinsic reducibility of the polypyrrole nano particles and potassium permanganate directly undergo in-situ redox reaction, so that manganese dioxide nanosheets are quickly formed on the surfaces of the polypyrrole inner cores, and the polypyrrole/manganese dioxide nano composite particles are obtained. The method better avoids the modification of other reducing materials, greatly shortens the reaction time and simplifies the operation flow. After the methylene blue is loaded, the obtained polypyrrole/manganese dioxide-methylene blue nano composite particles can be used as an excellent photo-thermal treatment material, and meanwhile, the modified manganese dioxide nano sheets can improve the tumor anoxic environment and enhance the capacity of the modified manganese dioxide nano sheets as a photodynamic treatment material, so that the modified manganese dioxide nano sheets can be used as a photo-thermal and photodynamic combined treatment material, and the cancer treatment effect is greatly improved.
The polypyrrole/manganese dioxide-methylene blue nano composite particles provided by the invention adopt polypyrrole nano particles as an inner core and a reducing agent at the same time, are subjected to in-situ redox reaction with potassium permanganate to directly and rapidly prepare the polypyrrole/manganese dioxide nano composite particles, and are loaded with a photosensitizer methylene blue through electrostatic interaction, so that the particle size of the prepared polypyrrole/manganese dioxide-methylene blue nano composite particles is 69-72nm, and manganese dioxide lamella is uniformly distributed on the surfaces of the polypyrrole nano particles.
The invention provides a polypyrrole/manganese dioxide-methylene blue nano composite particle and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) preparing polypyrrole nano particles: dissolving 13000-23000 polyvinyl alcohol in secondary water, stirring for 40-50 minutes at 70-80 ℃; FeCl is added after the solution is cooled to room temperature3·6H2O, stirring for 1-1.5 hours in a balanced manner; then adding pyrrole monomer, stirring for 3.5-4.5 hours at the temperature of 3-5 ℃; after the reaction is finished, centrifugally separating, repeatedly washing for 3-5 times by using hot secondary water, and freeze-drying for later use, wherein the weight ratio of polyvinyl alcohol 13000-23000: secondary water: FeCl3·6H2O: pyrrole monomer ═ 1.5-1.6 g: 18-20 mL: 1.2-1.3 g: 120-;
(2) preparing polypyrrole/manganese dioxide nano composite particles: according to the polypyrrole nano-particles: 15-20mg of secondary water: 8mL, adding the polypyrrole nano particles prepared in the step (1) into secondary water for ultrasonic dispersion for later use; dissolving 5-12.5mg potassium permanganate in 12mL secondary water, dropwise adding the dissolved potassium permanganate into the dispersed polypyrrole nanoparticles, stirring, reacting for 5-15 minutes, alternately washing with secondary water and absolute ethyl alcohol for 3-5 times, and drying to obtain polypyrrole/manganese dioxide nano composite particles (PPy/MnO)2)；
(3) Preparing polypyrrole/manganese dioxide-methylene blue nano composite particles: weighing 3-5mg of the prepared polypyrrole/manganese dioxide nano composite particles into 15-20mL of secondary water, and adding 0.3-0.5mg of the secondary waterStirring methylene blue at room temperature for 20-24 hours, and centrifugally washing to obtain polypyrrole/manganese dioxide-methylene blue nano composite particles (PPy/MnO)2-MB)。
In the step (1), the pyrrole monomer used needs to be purified by distillation under reduced pressure before the reaction.
In the step (1), the temperature of the hot secondary water used for washing the product after the reaction is finished is 75-80 ℃.
The polypyrrole/manganese dioxide-methylene blue nano composite particles prepared by the invention are applied to photo-thermal treatment and researched:
the research on the photo-thermal conversion performance of the polypyrrole/manganese dioxide-methylene blue nano composite particles comprises the following specific processes: preparing polypyrrole/manganese dioxide-methylene blue nano composite particle water solution with different concentrations, and using near infrared laser (808nm, 2W/cm)2) The solution temperature is gradually increased after the irradiation is respectively carried out for 10 minutes and 30 seconds, and the polypyrrole/manganese dioxide-methylene blue nano composite particles can be used as photo-thermal treatment materials.
The application research of the polypyrrole/manganese dioxide-methylene blue nano composite particles prepared by the invention in the preparation of photodynamic therapy materials comprises the following steps:
by using manganese dioxide and H under acidic condition2O2The polypyrrole/manganese dioxide-methylene blue nano composite particles can be used as photodynamic therapy materials.
1, 3-diphenyl isobenzofuran (DPBF) is used as a singlet oxygen indicator, the generated singlet oxygen can be used for consuming the DPBF and reducing the ultraviolet absorbance value at 410nm, and based on the above principle, the laser radiation at 635nm and the presence/absence of H are respectively carried out2O2Under the conditions, research on PPy/MnO2-effect of MB on DPBF UV absorbance.
The polypyrrole/manganese dioxide-methylene blue nano composite particle is researched in photo-thermal and photodynamic combined treatment aiming at cancer cells:
(1) obtained byPPy nanoparticles and PPy/MnO2And PPy/MnO2-the effect of MB composite nanoparticles on HeLa cancer cell activity in the absence of laser radiation to study the biocompatibility of the resulting composite nanoparticles;
(2)PPy/MnO2the influence of the MB composite nano particles on the activity of the HeLa cancer cells under the condition of 808nm laser radiation or 635nm laser radiation or the common radiation of 808nm laser and 635nm laser is respectively used for researching the photo-thermal and photodynamic combined treatment effect of the obtained polypyrrole/manganese dioxide-methylene blue composite nano particles on the cancer cells.
Compared with the prior art, the invention has the advantages that:
(1) the polypyrrole nano particles are simultaneously used as the inner core and the reducing agent and are rapidly oxidized and reduced in situ with potassium permanganate to form the manganese dioxide nanosheet layer, so that the addition or modification of other reducing materials is avoided, the preparation method is simplified, the operability is strong, and the environment is friendly.
(2) The prepared polypyrrole/manganese dioxide nano composite particles have good dispersibility, manganese dioxide lamella are uniformly dispersed on the surface of polypyrrole, and the modification of the lamella structure can greatly improve the load of the nano composite particles on a photosensitizer.
(3) In the prepared polypyrrole/manganese dioxide-methylene blue nano composite particles, polypyrrole can be used as a better photo-thermal treatment material, and a manganese dioxide shell can react with H under an acidic condition2O2The oxygen is generated to improve the tumor oxygen-deficient environment and improve the capability of the tumor oxygen-deficient environment as a photodynamic therapy material; after the polypyrrole and the manganese dioxide are combined and loaded with the photosensitizer methylene blue, the obtained nano composite material can be used as a photo-thermal and photodynamic combined treatment material, and the cancer treatment effect is better improved.
Drawings
FIG. 1 is a transmission electron micrograph of polypyrrole nanoparticles of example 1, with a scale of 200 nm.
FIG. 2 is an X-ray photoelectron spectrum of the polypyrrole nanoparticles of example 1. Wherein (A) is a full spectrogram, (B) is a carbon spectrogram, and (C) is a nitrogen spectrogram.
FIG. 3 is a transmission electron micrograph of the polypyrrole/manganese dioxide nanocomposite particles of example 1, with a 50nm scale.
FIG. 4 is a full spectrum diagram of X-ray photoelectron spectroscopy of the polypyrrole/manganese dioxide nano composite particles of example 1.
FIG. 5 is an X-ray photoelectron spectroscopy spectrum of the polypyrrole/manganese dioxide nanocomposite particles of example 1. Wherein (A) is a manganese spectrogram, (B) is an oxygen spectrogram, (C) is a carbon spectrogram, and (D) is a nitrogen spectrogram.
FIG. 6 is a graph showing the UV-VIS absorption spectrum of the polypyrrole nanoparticle, polypyrrole/manganese dioxide nanocomposite particles of example 1. Wherein (A) is polypyrrole nano particles, and (B) is polypyrrole/manganese dioxide nano composite particles.
FIG. 7 is a graph showing the UV-VIS absorption spectrum of the polypyrrole/manganese dioxide-methylene blue nanocomposite particles of example 1.
FIG. 8 is a thermogram of the polypyrrole nanoparticles, polypyrrole/manganese dioxide nanocomposite particles and polypyrrole/manganese dioxide-methylene blue nanocomposite particles of example 1.
FIG. 9 is a transmission electron micrograph of the polypyrrole/manganese dioxide nanocomposite particles of example 2, with a 200nm scale.
FIG. 10 is a transmission electron micrograph of the polypyrrole/manganese dioxide nanocomposite particles of example 3, with a 50nm scale.
FIG. 11 shows the near infrared laser (808nm, 2W/cm) of the aqueous solutions of different concentrations of polypyrrole/manganese dioxide-methylene blue nanocomposite particles of example 42) Temperature time profile under irradiation.
FIG. 12 shows the polypyrrole/manganese dioxide-methylene blue nanocomposite particle in example 4 in water (50. mu.g/mL) under five near infrared lasers (808nm, 2W/cm)2) Temperature time profile at on/off cycle.
FIG. 13 shows the polypyrrole/manganese dioxide-methylene blue nanocomposite particle in example 4 in water (50. mu.g/mL) under different power near infrared laser (808nm, 1W/cm)2，1.5W/cm2，2W/cm2) Temperature time profile under irradiation.
FIG. 14 shows polypyrrole/manganese dioxide-methylene blue nanocomposite particles (PPy) of example 5/MnO2MB) consumption of DPBF over time under different conditions, PPy/MnO at pH 7.42-MB nanocomposite particles without addition/addition of H2O2No laser radiation and DPBF, PPy/MnO2-MB nanocomposite particles without addition/addition of H, respectively2O2Under the condition of using laser with wavelength of 635 nm.
FIG. 15 shows polypyrrole/manganese dioxide-methylene blue nanocomposite particles (PPy/MnO) of example 52MB) curves of consumption of DPBF over time at different pH values, PPy/MnO respectively2-MB nanocomposite particles at pH 7.4 and PPy/MnO2-MB nanocomposite particles with H2O2The samples were irradiated with a laser beam having a wavelength of 635nm at pH 7.4, 6.0 and 5.0, respectively.
FIG. 16 is a graph showing the relative cell viability of HeLa cancer cells after 24 hours of treatment with different concentrations of polypyrrole nanoparticles, polypyrrole/manganese dioxide, and polypyrrole/manganese dioxide-methylene blue nanocomposite particles.
Fig. 17 is a graph showing the effect of the polypyrrole/manganese dioxide-methylene blue nanocomposite particles with different concentrations in example 6 in preparing photothermal therapy, photodynamic therapy and photothermal and photodynamic combined therapy materials for HeLa cancer cells.
Detailed Description
Example 1
Preparation and characterization of polypyrrole/manganese dioxide-methylene blue nano composite particles:
(1) dissolving 1.5g of polyvinyl alcohol 13000-23000 in 18mL of secondary water, and stirring for 40 minutes at 80 ℃; after the solution was cooled to room temperature, 1.25g FeCl was added3·6H2O, stirring for 1 hour in a balanced manner; then 135 mu L of pyrrole monomer is added and stirred for 4 hours at 4 ℃; after the reaction is finished, centrifugally separating, repeatedly washing with hot secondary water for 5 times to prepare polypyrrole nano particles, and freeze-drying for later use.
FIG. 1 shows the morphology of the polypyrrole nanoparticles obtained by transmission electron microscopy, with a scale of 200 nm. The result shows that the obtained polypyrrole nano material is spherical, has better dispersibility and has an average size of 68.18 nm.
FIG. 2 shows the results of characterization of the obtained polypyrrole nanoparticles by X-ray photoelectron spectroscopy, where (A) shows XPS full spectrum of the obtained nanoparticles, (B) shows C1 s spectrum, and (C) shows N1 s spectrum. The results show that the nano-particle contains elements such as O1 s, N1 s, C1 s and the like, the peaks at 288.6, 286.0 and 284.6eV in the C1 s spectrum are respectively the combined forms of C-O, C-N/C-O and C-C/C-C, and the peaks at 401.2, 399.8 and 397.6eV in the N1 s spectrum are respectively-N+A combination of-N-H and-N-.
(2) Putting 18mg of polypyrrole nano particles prepared in the step (1) into 8mL of secondary water, and performing ultrasonic dispersion for later use; dissolving 10mg potassium permanganate in 12mL secondary water, dropwise adding the dissolved potassium permanganate into the dispersed polypyrrole nanoparticles, stirring, reacting for 12 minutes, alternately washing with secondary water and absolute ethyl alcohol for 4 times, and drying to obtain the polypyrrole/manganese dioxide nano composite particles.
FIG. 3 is a transmission electron microscope used for the morphology characterization of the polypyrrole/manganese dioxide nanocomposite particles obtained, with a scale of 50 nm. The result shows that the manganese dioxide lamella in the obtained polypyrrole/manganese dioxide nano composite particle is uniformly distributed on the surface of polypyrrole, no obvious aggregation phenomenon exists, and the size is about 71 nm.
FIG. 4 is an XPS full spectrum of the prepared polypyrrole/manganese dioxide nano composite particles characterized by an X-ray photoelectron spectrometer, and the results show that the nano particles contain Mn 2p, O1 s, N1 s, C1 s and other elements.
Fig. 5 shows the results of characterization of the obtained nanocomposite particles by an X-ray photoelectron spectrometer, wherein (a) is a Mn 2p spectrum, (B) is an O1 s spectrum, (C) is a C1 s spectrum, and (D) is an N1 s spectrum. The peaks at 653.6 and 641.9eV in the Mn 2p chromatogram are Mn 2p1/2And Mn 2p3/2And the difference between the two peaks was 11.7eV, it was confirmed that the valence of manganese element was +4, the peaks at 532.5, 530.96 and 529.8eV in the O1 s spectrum were respectively the combination of H-OH/C-O-H, Mn-O-H and Mn-O-Mn, the peaks at 288.5, 286.2 and 284.8eV in the C1 s spectrum were respectively the combination of C ═ O, C-N/C-O and C-C/C ═ C, and the peaks at 401.6, 399.9 and 397.9eV in the N1 s spectrumIs other than-N+A combination of-N-H and-N-.
Fig. 6 shows the results of characterization of the polypyrrole nanoparticles and polypyrrole/manganese dioxide nanocomposite particles obtained by the above method using an ultraviolet-visible spectrophotometer. Wherein (A) is polypyrrole nano particles, and (B) is polypyrrole/manganese dioxide nano composite particles. In both the curve (A) and the curve (B), wide absorption peaks exist between 700 and 900nm, which correspond to the absorption of polypyrrole; in comparison to curve (A), a new broad absorption peak occurs between 300 and 500nm in curve (B), indicating successful modification of manganese dioxide.
(3) And (3) adding 0.5mg of methylene blue into 5mg of the polypyrrole/manganese dioxide nano composite particles prepared in the step (2) in 20mL of secondary water, stirring at room temperature for 23 hours, and centrifugally washing to obtain the polypyrrole/manganese dioxide-methylene blue nano composite particles.
Fig. 7 shows the result of characterization of the polypyrrole/manganese dioxide-methylene blue nanocomposite particles obtained above using an ultraviolet-visible spectrophotometer. The successful loading of methylene blue is indicated by the appearance of a new absorption peak at 667nm compared to the uv-vis absorption spectrum of the polypyrrole/manganese dioxide nanocomposite particles of example 1.
Fig. 8 shows the results of characterization of the polypyrrole nanoparticles, the polypyrrole/manganese dioxide nanocomposite particles, and the polypyrrole/manganese dioxide-methylene blue nanocomposite particles obtained in the above manner using a thermogravimetric analyzer. Compared with polypyrrole nano particles, the weight loss of the polypyrrole/manganese dioxide nano composite particles is reduced, which indicates that the manganese dioxide layer with good thermal stability is successfully modified. Compared with polypyrrole/manganese dioxide nano composite particles, after the methylene blue is loaded, the weight loss of the polypyrrole/manganese dioxide-methylene blue nano composite particles is increased, and the successful loading of the methylene blue which is an organic matter with thermal instability is shown.
Example 2
Preparation and characterization of polypyrrole/manganese dioxide-methylene blue nano composite particles:
(1) dissolving 1.6g of polyvinyl alcohol 13000-23000 in 20mL of secondary water, and stirring for 50 minutes at 75 ℃; after the solution was cooled to room temperature, 1.3g FeCl was added3·6H2O, stirring for 1.5 hours in a balanced manner; then 140 mul of pyrrole monomer is added and stirred for 4.5 hours at 3 ℃; after the reaction is finished, centrifugally separating, repeatedly washing for 4 times by using hot secondary water to prepare polypyrrole nano particles, and freeze-drying for later use;
(2) putting 20mg of polypyrrole nano particles prepared in the step (1) into 8mL of secondary water, and performing ultrasonic dispersion for later use; dissolving 12.5mg potassium permanganate in 12mL secondary water, dropwise adding the dissolved potassium permanganate into the dispersed polypyrrole nanoparticles, stirring, reacting for 15 minutes, alternately washing with secondary water and absolute ethyl alcohol for 3 times, and drying to obtain the polypyrrole/manganese dioxide nano composite particles.
FIG. 9 is a transmission electron microscope image of the polypyrrole/manganese dioxide nanocomposite particles prepared above, with a scale of 200 nm. The result shows that the manganese dioxide sheet layer is uniformly distributed on the surface of the polypyrrole to obtain the polypyrrole/manganese dioxide nano composite particles.
(3) And (3) putting 4mg of the polypyrrole/manganese dioxide nano composite particles prepared in the step (2) into 18mL of secondary water, adding 0.4mg of methylene blue, stirring at room temperature for 18 hours, and centrifugally washing to obtain the polypyrrole/manganese dioxide-methylene blue nano composite particles.
Example 3
Preparation and characterization of polypyrrole/manganese dioxide-methylene blue nano composite particles:
(1) dissolving 1.55g of polyvinyl alcohol 13000-23000 in 19mL of secondary water, and stirring for 45 minutes at 70 ℃; after the solution was cooled to room temperature, 1.2g FeCl was added3·6H2O, stirring for 1 hour in a balanced manner; then 138 mu L of pyrrole monomer is added and stirred for 3.5 hours at the temperature of 5 ℃; after the reaction is finished, centrifugally separating, repeatedly washing for 3 times by using hot secondary water to prepare polypyrrole nano particles, and freeze-drying for later use;
(2) placing 17mg of polypyrrole nano particles prepared in the step (1) in 8mL of secondary water, and performing ultrasonic dispersion for later use; dissolving 5mg potassium permanganate in 12mL secondary water, dropwise adding the dissolved potassium permanganate into the dispersed polypyrrole nanoparticles, stirring, reacting for 5 minutes, alternately washing with secondary water and absolute ethyl alcohol for 4 times, and drying to obtain the polypyrrole/manganese dioxide nano composite particles.
FIG. 10 is a transmission electron microscope image of the polypyrrole/manganese dioxide nanocomposite particles prepared as described above, with a scale of 50 nm. The results show that manganese dioxide lamella are uniformly distributed on the surface of polypyrrole.
(3) And (3) adding 0.3mg of methylene blue into 15mL of secondary water of the polypyrrole/manganese dioxide nano composite particles prepared in the step (2), stirring at room temperature for 23 hours, and centrifugally washing to obtain the polypyrrole/manganese dioxide-methylene blue nano composite particles.
Example 4
The application of the polypyrrole/manganese dioxide-methylene blue nano composite particles in photothermal therapy comprises the following steps:
(1) to investigate the use of the obtained nanocomposite particles in the preparation of photothermal therapeutic materials, the polypyrrole/manganese dioxide-methylene blue nanocomposite particles obtained in example 1 were formulated into aqueous solutions of various concentrations (0. mu.g/mL, 10. mu.g/mL, 20. mu.g/mL, 30. mu.g/mL, 50. mu.g/mL, 100. mu.g/mL) using near-infrared laser (808nm, 2W/cm, respectively)2) The solution was irradiated for 10 minutes and the temperature of the solution was measured with a thermocouple thermometer at intervals of 30 seconds, and a temperature-time curve was obtained as shown in FIG. 11. The result shows that the polypyrrole/manganese dioxide-methylene blue nano composite particle has better photo-thermal conversion capability, and the highest temperature can rise to 83.1 ℃ along with the continuous rise of the concentration.
(2) To test the photostability of the polypyrrole/manganese dioxide-methylene blue nanocomposite particles obtained in example 1, the resulting nanocomposite particles were formulated into an aqueous solution (50 μ g/mL) using a near infrared laser (808nm, 2W/cm)2) After 10 minutes of irradiation, the laser was turned off, and after the temperature was decreased to the initial temperature, the cycle was repeated five times, and the temperature of the solution was measured with a thermocouple thermometer every 30 seconds, and the temperature-time curve obtained during the cycle was as shown in fig. 12. The results show that after five laser on/off cycles, the nano composite particles still have good photo-thermal conversion capability, which shows that the nano composite particles have excellent photo-stability.
(3) To test the effect of the near-infrared laser power on photothermal therapy materials, the polypyrrole/manganese dioxide-methylene blue nanocomposite particles obtained in example 1 were formulated into aqueous solutions (50 μ g/mL) and respectively irradiated with near-infrared lasers (808 nm) of different powers，2W/cm2，1.5W/cm2，1W/cm2) The solution was irradiated for 10 minutes and the temperature of the solution was measured with a thermocouple thermometer at intervals of 30 seconds, and a temperature-time curve was obtained as shown in FIG. 13. The result shows that the highest temperature gradually rises with the continuous rise of the near-infrared laser power, and the photo-thermal effect is improved.
Example 5
The application of the polypyrrole/manganese dioxide-methylene blue nano composite particles in photodynamic therapy comprises the following steps:
using 1, 3-diphenyl isobenzofuran (DPBF) as indicator of singlet oxygen, DPBF can be consumed by the generated singlet oxygen and its ultraviolet absorbance value at 410nm can be reduced, based on the above principle, in the presence/absence of laser radiation and in the presence/absence of H, respectively2O2Under the condition, for the obtained PPy/MnO2The ability of the-MB composite nanoparticles as photodynamic therapy material was analyzed. 2mL of 20. mu.g/mL PPy/MnO2mixing-MB nanometer composite particle-PBS buffer solution (pH 7.4) with 15 μ L10mmoL/L DPBF dimethyl sulfoxide solution, and adding/not adding H2O2Transferring into cuvette, irradiating with laser with wavelength of 635nm for 10 min (20 mW/cm)2) And testing the ultraviolet-visible light spectrum at intervals of 2 minutes to obtain a consumption curve of the DPBF along with time, wherein the consumption curve is obtained without adding the nano-composite particles as a control group, as shown in FIG. 14.
The results show that DPBF was not added/added with H2O2After laser radiation, the consumption of DPBF is respectively 2.1% and 1.6%, which can be ignored; at the same time, PPy/MnO2-MB composite nanoparticles without addition/addition of H2O2When no laser radiation exists, the loss of DPBF is respectively 0.55 percent and 1.13 percent, and can be ignored; when for PPy/MnO2After the MB composite nanoparticles are subjected to laser radiation, the consumption of DPBF is obviously increased to 23.13%, which indicates that the composite nanoparticles can be used as an effective photodynamic therapy material under the laser radiation; when H is added2O2Then PPy/MnO2The consumption of DPBF by the MB composite nano-particles is further increased to 35.64%, which shows that the composite nano-particles can effectively accelerate H2O2Decompose, promote the generation of singlet oxygen, and improve the photodynamic therapy effect.
The same DPBF was used as a singlet oxygen indicator to study PPy/MnO at different pH values2-MB nanocomposite particles with H2O2Ability to generate singlet oxygen under laser irradiation after mixing, 2mL of 20. mu.g/mL of PPy/MnO2mixing-MB nanometer composite particle-PBS buffer solution (pH 7.4, 6.0, 5.0) with 15 μ L10mmoL/L DPBF dimethyl sulfoxide solution, adding H2O2Transferring into a cuvette, and irradiating with laser light having a wavelength of 635nm for 10 minutes (20 mW/cm)2) The uv-vis spectra were measured at 2 minute intervals to obtain a DPBF consumption curve over time, as shown in fig. 15. The results show that the consumption of DPBF is 35.64%, 39.16% and 48.44% respectively with the decrease of pH value, which shows that the carrier and H are further accelerated under the acidic condition2O2The oxygen is generated by the action, so that the generation of singlet oxygen is increased, and the consumption of DPBF is increased.
Example 6
The application of the polypyrrole/manganese dioxide-methylene blue nano composite particles in the photo-thermal and photo-dynamic combined treatment aiming at cancer cells comprises the following steps:
(1) research on the thus-obtained PPy nanoparticles and PPy/MnO2And PPy/MnO2Biocompatibility of MB composite nanoparticles on HeLa cancer cells: respectively adding the PPy nano particles and PPy/MnO prepared in different concentrations2And PPy/MnO2-MB composite nanoparticles (0. mu.g/mL, 6.25. mu.g/mL, 12.5. mu.g/mL, 25. mu.g/mL, 50. mu.g/mL, 100. mu.g/mL, 150. mu.g/mL, 200. mu.g/mL) were allowed to act on HeLa cancer cells, and after 24 hours of culture, the survival rate of cells was examined using the MTT method to investigate PPy nanoparticles, PPy/MnO2And PPy/MnO2-biocompatibility of the MB composite nanoparticles. The results show that when PPy nanoparticles, PPy/MnO2And PPy/MnO2When the concentration of the-MB composite nanoparticles is increased from 0 mug/mL to 200 mug/mL, the HeLa cells still have better cell activity, as shown in FIG. 16, which indicates that the materials have better biocompatibility.
(2) Investigation of the PPy/MnO obtained above2Preparation of-MB composite nano-particles for cancer cellsThe application of cellular photothermal, photodynamic and photothermal and photodynamic combined treatment materials: using PPy/MnO prepared as described above at different concentrations2-MB composite nanoparticles (0. mu.g/mL, 12.5. mu.g/mL, 25. mu.g/mL, 50. mu.g/mL, 100. mu.g/mL, 150. mu.g/mL, 200. mu.g/mL) after culturing HeLa cancer cells for 4 hours, respectively irradiating with 808nm laser for 5 minutes (2W/cm)2) Or 635nm laser radiation for 5 minutes (20 mW/cm)2) Or irradiating with 808nm laser for 5 min (2W/cm)2) Further radiating with 635nm laser for 5 minutes (20 mW/cm)2) Then culturing for 24 hours, detecting the relative activity of the cells by using MTT to respectively obtain PPy/MnO2Application of-MB composite nanoparticles in preparation of photothermal, photodynamic and photothermal and photodynamic combined treatment materials for cancer cells. As shown in FIG. 17, with PPy/MnO under laser irradiation2The concentration of the-MB composite nano particles is increased, the cell activity is continuously reduced, and the photo-thermal-photo-dynamic combined treatment material group has higher cytotoxicity compared with a single photo-thermal treatment and photo-dynamic treatment material group, which shows that the combined treatment effect is better, and PPy/MnO (phospho/MnO)2the-MB composite nano particle is expected to be used as a photo-thermal-photodynamic combined treatment material for tumor elimination.
Claims (8)
1. The polypyrrole/manganese dioxide-methylene blue nano composite particles are characterized in that polypyrrole nano particles are used as an inner core and a reducing agent at the same time, the polypyrrole/manganese dioxide nano composite particles are directly prepared through in-situ redox reaction with potassium permanganate, then photosensitizer methylene blue is loaded through electrostatic interaction, the particle size of the finally prepared nano composite particles is 69-72nm, and manganese dioxide lamella is uniformly distributed on the surfaces of the polypyrrole nano particles.
2. The method for preparing polypyrrole/manganese dioxide-methylene blue nanocomposite particles according to claim 1, comprising the steps of:
(1) preparing polypyrrole nano particles: dissolving 13000-23000 polyvinyl alcohol in secondary water, stirring for 40-50 minutes at 70-80 ℃; FeCl is added after the solution is cooled to room temperature3·6H2O, balanced stirring for 1-1.5 hours(ii) a Then adding pyrrole monomer, stirring for 3.5-4.5 hours at the temperature of 3-5 ℃; after the reaction is finished, centrifugally separating, repeatedly washing for 3-5 times by using hot secondary water, and freeze-drying for later use, wherein the weight ratio of polyvinyl alcohol 13000-23000: secondary water: FeCl3·6H2O: pyrrole monomer ═ 1.5-1.6 g: 18-20 mL: 1.2-1.3 g: 120-;
(2) preparing polypyrrole/manganese dioxide nano composite particles: according to the polypyrrole nano-particles: 15-20mg of secondary water: 8mL, adding the polypyrrole nano particles prepared in the step (1) into secondary water for ultrasonic dispersion for 1-1.5 hours for later use; dissolving 5-12.5mg of potassium permanganate in 12mL of secondary water, dropwise adding the dissolved potassium permanganate into the dispersed polypyrrole nanoparticles, stirring, reacting for 5-15 minutes, alternately washing for 3-5 times by using secondary water and absolute ethyl alcohol, and drying to obtain polypyrrole/manganese dioxide nano composite particles;
(3) preparing polypyrrole/manganese dioxide-methylene blue nano composite particles: weighing 3-5mg of the prepared polypyrrole/manganese dioxide nano composite particles into 15-20mL of secondary water, adding 0.3-0.5mg of methylene blue, stirring at room temperature for 20-24 hours, and centrifugally washing to obtain the polypyrrole/manganese dioxide-methylene blue nano composite particles.
3. The method of preparing polypyrrole/manganese dioxide-methylene blue nanocomposite particles of claim 2, wherein: the pyrrole monomer in the step (1) needs to be purified by reduced pressure distillation before reaction.
4. The method for preparing polypyrrole/manganese dioxide nano-methylene blue composite particles according to claim 2, wherein: the temperature of the hot secondary water in the step (1) is 75-80 ℃.
5. Polypyrrole/manganese dioxide-methylene blue nanocomposite particles made by the method of claim 2.
6. Use of the polypyrrole/manganese dioxide-methylene blue nanocomposite particles of claim 5 in the preparation of photothermal therapy materials.
7. Use of polypyrrole/manganese dioxide-methylene blue nanocomposite particles according to claim 5 in the preparation of photodynamic therapy materials.
8. Use of polypyrrole/manganese dioxide-methylene blue nanocomposite particles according to claim 5 in the preparation of photothermal and photodynamic combined treatment materials for cancer cells.
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