CN111407889B - Composite material for simultaneously generating oxygen and active oxygen under near infrared light excitation and preparation method and application thereof - Google Patents
Composite material for simultaneously generating oxygen and active oxygen under near infrared light excitation and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a composite material for simultaneously generating oxygen and active oxygen under the excitation of near infrared light, a preparation method and application thereof, belonging to the technical field of composite materials. The method solves the technical problems that in the prior art, the oxygen generation mode can not realize accurate matching of oxygen and photosensitizer in space and time at the same time during tumor photodynamic therapy, and PDT efficiency is greatly influenced by fast oxygen consumption and slow space transmission. The composite material consists of up-conversion nano particles and a thylakoid membrane. The invention also provides a preparation method and application of the composite material. The composite material can convert near infrared light (808 plus 980nm) into red light (660 nm) in the up-conversion nano material, and is used for exciting a light system I and a light system II in a thylakoid membrane, a photoproduction cavity generated by the light system I is used for reacting with water to generate oxygen, and the light systems I and II transfer energy to oxygen molecules and generate singlet oxygen, so that the tumor photodynamic treatment efficiency is improved.
Description
Technical Field
The invention relates to a composite material, in particular to a composite material which is used for simultaneously generating oxygen and active oxygen under the excitation of near infrared light, and a preparation method and application thereof.
Background
Photodynamic therapy (PDT), as a non-invasive medical technique, has the advantages of low toxicity, small side effect, broad-spectrum anticancer, high targeting, and the like, compared with conventional treatment means such as surgery, chemotherapy, radiotherapy, and the like. However, due to the rapid proliferation of tumor cells, incomplete blood vessel development and uneven distribution, insufficient supply of oxygen and the like in the tumor cells is easily caused, a hypoxia state is formed, the generation of Reactive Oxygen Species (ROS) in the PDT process is greatly limited, and the PDT efficiency is reduced. The current oxygen generation mode can not realize accurate matching of oxygen and photosensitizer in space and time, and the PDT efficiency is greatly influenced by the problems of fast oxygen consumption and slow space transfer. Photosynthesis generally occurs in green plants (including algae), and is highly efficient in producing oxygen because of the complex Z-type catalytic system present on the thylakoid membrane within chloroplasts. Under the excitation of sunlight, electrons generated by the photosystem II are transferred to the photosystem I through a series of complex processes, and the electrons are transmitted in a Z shape, so that the electrons and holes generated by the photosystem I and the photosystem II are effectively separated, and the separated electrons and holes have higher reduction and oxidation potentials. The cavities remaining on photosystem II cleave water to produce oxygen due to their potential being greater than the potential at which water is decomposed to produce oxygen, while photosystems I and II transfer the energy released to the oxygen produced under excitation of light to produce singlet oxygen for PDT treatment.
Disclosure of Invention
The invention aims to solve the technical problems that the oxygen generation mode in the prior art cannot realize accurate matching of oxygen and photosensitizer in space and time at the same time, and the PDT efficiency is greatly influenced by fast oxygen consumption and slow space transmission in the photodynamic tumor treatment process, and provides a composite material for simultaneously generating oxygen and active oxygen under the excitation of near infrared light, and a preparation method and application thereof. The up-conversion nano material in the composite material can convert near infrared light (808-.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the invention provides a composite material for simultaneously generating oxygen and active oxygen under the excitation of near infrared light, which consists of up-conversion nano particles and a thylakoid membrane for modifying the surfaces of the up-conversion nano particles.
In the above technical scheme, the mass percentage of the total chlorophyll in the upconversion nanoparticles and the thylakoid membrane is (90-98)%: (2-10)%.
In the above technical scheme, the mass percentage of the total chlorophyll in the upconversion nanoparticles and the thylakoid membrane is 96%: 4 percent.
In the above technical solution, the upconversion nanoparticles are upconversion nanoparticles capable of converting near-infrared light into red light.
In the above technical solution, the upconversion nanoparticles are upconversion nanoparticles with an excitation wavelength of 808-.
In the above technical scheme, the upconversion nanoparticles are upconversion nanoparticles with an excitation wavelength of 980 nm.
The invention provides a preparation method of a composite material for simultaneously generating oxygen and active oxygen under the excitation of near infrared light, which comprises the following steps:
and (3) uniformly mixing the water solution of the up-conversion nano particles with the water solution of the thylakoid membrane, and obtaining the up-conversion nano particles and the thylakoid membrane composite material by an ultrasonic method.
In the technical scheme, the upconversion nanoparticles are prepared by the following method:
weighing 1mM of rare earth acetate respectively, wherein Y: yb: er is 78: 20: 20, and 10mM sodium fluoride were added to a three-necked flask containing 10mL oleylamine and 10mL octadecene, and nitrogen was continuously introduced and heated to 120 ℃ for 1 hour; then slowly heating to 320 ℃, stirring for 1h, and naturally cooling to room temperature; adding absolute ethyl alcohol, centrifuging to obtain a precipitate, repeatedly washing with water and ethanol for three times respectively to finally obtain up-conversion nanoparticles, and dispersing in chloroform; and finally, adding 1mL of 0.1M hexadecyl trimethyl bromide solution into the chloroform solution of the upconversion nanoparticles, stirring for 4 hours at 70 ℃, centrifuging, washing with water, and drying to obtain the aqueous phase upconversion nanoparticles.
In the above technical solution, the thylakoid membrane can be extracted from a plant leaf having photosynthesis or a bacterium having photosynthesis.
The invention also provides application of the composite material for simultaneously generating oxygen and active oxygen under the excitation of near infrared light in tumor photodynamic therapy.
The invention has the beneficial effects that:
(1) according to the up-conversion nano particle and thylakoid membrane composite material provided by the invention, near infrared light (808-.
(2) The upconversion nano particle and thylakoid membrane composite material prepared by the invention has the capability of simultaneously generating oxygen and active oxygen under the excitation of near infrared light, and can be applied to the photodynamic therapy of hypoxic tumors.
(3) The killing degree of the up-conversion nano particle and thylakoid membrane composite material provided by the invention to 4T1 cells is more than 80%.
(4) The upconversion nano particle and thylakoid membrane composite material provided by the invention is injected into a mouse tumor model through tail vein, and the tumor can be completely eliminated and does not relapse within 14 days after NIR irradiation.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a TEM micrograph of the composite material of example 1.
FIG. 2 is a SDS-PAGE staining of the thylakoid membrane and composite of example 1.
Fig. 3 is a fluorescence emission profile of the upconversion nanoparticles of example 1 and an absorption profile of the thylakoid membrane.
FIG. 4 is a graph showing the oxygen generating capacity of the composite material of example 1 under irradiation of near infrared light.
FIG. 5 is a DCF fluorescence curve of the composite material of example 1 under near infrared light irradiation.
FIG. 6 is a photograph showing the detection of oxygen and singlet oxygen generated in a cell by the composite material of example 1 under irradiation of near infrared light.
FIG. 7 shows the results of the MTT colorimetry of cell damage on the composite material of example 1 under irradiation of near infrared light for cell viability.
FIG. 8 is a plot of tumor growth in mice following tail vein injection of the composite of example 1.
FIG. 9 is a hematoxylin-eosin staining pattern of the major organs of mice after the composite treatment of example 1 was completed.
Detailed Description
The invention provides a composite material for simultaneously generating oxygen and active oxygen under the excitation of near infrared light, which consists of up-conversion nano particles and a thylakoid membrane for modifying the surfaces of the up-conversion nano particles; the up-conversion nano material in the composite material can convert near infrared light (808-. Preferably, the mass percentage of the total chlorophyll in the upconversion nanoparticles and the thylakoid membrane is (90-98)%: (2-10)%, and further preferably the mass percentage of the total chlorophyll in the upconversion nanoparticles and the thylakoid membrane is 96%: 4 percent. The up-conversion nanoparticles are up-conversion nanoparticles capable of converting near infrared light into red light. Preferably, the upconversion nanoparticles are upconversion nanoparticles with an excitation wavelength of 808-980nm, and more preferably, the upconversion nanoparticles are upconversion nanoparticles with an excitation wavelength of 980 nm.
The invention provides a preparation method of a composite material for simultaneously generating oxygen and active oxygen under the excitation of near infrared light, which comprises the following steps:
The upconversion nanoparticles are prepared by the following method:
weighing 1mM of rare earth acetate respectively, wherein Y: yb: er is 78: 20: 20, and 10mM sodium fluoride were added to a three-necked flask containing 10mL oleylamine and 10mL octadecene, and nitrogen was continuously introduced and heated to 120 ℃ for 1 hour; then slowly heating to 320 ℃, stirring for 1h, and naturally cooling to room temperature; adding absolute ethyl alcohol, centrifuging to obtain a precipitate, repeatedly washing with water and ethanol for three times respectively to finally obtain up-conversion nanoparticles, and dispersing in chloroform; and finally, adding 1mL of 0.1M hexadecyl trimethyl bromide solution into the chloroform solution of the upconversion nanoparticles, stirring for 4 hours at 70 ℃, centrifuging, washing with water, and drying to obtain the aqueous phase upconversion nanoparticles.
Step 2, preparation of thylakoid membranes
The thylakoid membrane can be extracted from plant leaves with photosynthesis or bacteria with photosynthesis, and the thylakoid membrane is preferably extracted from the plant leaves with photosynthesis;
the following provides a method for extracting thylakoid membranes from plant leaves:
weighing plant leaves with photosynthesis, cleaning, and storing at 4 deg.C overnight; then homogenizing in a precooled mortar and filtering; the pellet was then collected by centrifugation and washed twice with 10mM HEPES buffer; finally, the obtained pellet was suspended in water, sonicated at 4 ℃ for 5 minutes, centrifuged at 16000rpm for 15 minutes, and lyophilized to obtain a thylakoid membrane.
Step 3, preparation of composite material
And (3) uniformly mixing the water solution of the up-conversion nano particles with the water solution of the thylakoid membrane, and obtaining the up-conversion nano particles and the thylakoid membrane composite material by an ultrasonic method.
The invention also provides application of the composite material for simultaneously generating oxygen and active oxygen under the excitation of near infrared light in tumor photodynamic therapy.
Example 1
The invention provides a preparation method of a composite material for simultaneously generating oxygen and active oxygen under near infrared light excitation, which comprises the following specific steps:
1. synthesis of upconversion nanoparticles:
1mM of rare earth acetate (Y: Yb: Er ═ 78: 20: 20) and 10mM of sodium fluoride were weighed into a three-necked flask containing 10mL of oleylamine and 10mL of octadecene, respectively, and nitrogen was continuously introduced thereto and heated to 120 ℃ for 1 hour. Then slowly heating to 320 ℃ and stirring for 1h, and naturally cooling to room temperature. Adding absolute ethyl alcohol, centrifuging to obtain precipitate, repeatedly washing with water and ethanol for three times respectively to obtain upconversion nanoparticles, and dispersing in chloroform. And finally, adding 1mL of hexadecyl trimethyl bromide solution (0.1M) into the chloroform solution of the upconversion nanoparticles, stirring for 4 hours at 70 ℃, centrifuging, washing with water, and drying to obtain the aqueous phase upconversion nanoparticles.
2. Extraction of thylakoid membranes:
weighing 100g of fresh spinach leaves, cleaning, and storing at 4 ℃ overnight. Then homogenized in a precooled mortar and filtered. The pellet was then collected by centrifugation and washed twice with 10mM HEPES buffer. Finally, the obtained pellet was suspended in water, sonicated at 4 ℃ for 5 minutes, centrifuged at 16000rpm for 15 minutes, and lyophilized to obtain a thylakoid membrane.
3. Synthesis of composite materials
1mL of the aqueous solution of upconverting nanoparticles (1mg mL)-1) With 1mL aqueous solution of thylakoid membrane (1mg mL)-1) After being mixed evenly, the composite material of the up-conversion nano particles and the thylakoid membrane is obtained by an ultrasonic method, the ultrasonic frequency is 42kHz, and the power is 100W. The mass percentage of the total chlorophyll in the up-conversion nano particles and the thylakoid membrane in the composite material is 96%: 4 percent.
Fig. 1 is a transmission electron microscope photograph of the composite material of example 1, which shows that the synthesized upconversion nanoparticle-thylakoid membrane composite material has better dispersibility and the thylakoid membrane is successfully modified on the surface of the upconversion nanoparticle.
FIG. 2 is a SDS-PAGE staining of the thylakoid membrane and composite of example 1, showing that photosystem I and photosystem II are present in the synthesized upconversion nanoparticle-thylakoid membrane composite.
Fig. 3 is a fluorescence emission profile of the upconversion nanoparticles of example 1 and an absorption profile of the thylakoid membrane, showing that the upconversion fluorescence emission peak corresponds to the absorption peak of the thylakoid membrane, indicating that the fluorescence emitted by the upconversion can excite the thylakoid membrane.
4. Oxygen and reactive oxygen species generating capability test of composite materials
Evaluation of oxygen production capacity: the composite material is firstly prepared into 2mL concentration by PBS buffer solution200. mu.g mL of-1Adding an electronic sacrificial agent (silver nitrate); then, deoxidizing by using a nitrogen bubbling solution until the content of dissolved oxygen in the solution reaches below a detection limit, and adding 1mL of liquid paraffin to seal the PBS solution so as to isolate air; finally, the oxygen generation capacity is detected by using an oxygen dissolving instrument after 980nm laser irradiation is carried out for 10 minutes.
And (3) detecting the active oxygen generating capacity: detecting the total singlet oxygen of the composite material by using SOSG. Adding 80 mu L of SOSG PBS solution into 20 mu L of composite material PBS solution, uniformly mixing, irradiating for 10 minutes by 980nm laser, then incubating for 6 hours, and finally detecting the SOSG fluorescence curve by a microplate reader. Wherein the final concentration of SOSG is 10 μ M, and the final concentration of nanoparticles is 200 μ g mL-1。
FIG. 4 is a graph of the oxygen generating capacity of the composite material of example 1 under near infrared light irradiation, which shows that the composite material has better oxygen generating capacity under near infrared light excitation.
FIG. 5 is a DCF fluorescence curve under near-infrared light irradiation of the composite material of example 1, which shows that the composite material has better singlet oxygen generation capability under near-infrared light excitation.
The up-conversion nano particle and thylakoid membrane composite material which is used for simultaneously generating oxygen and active oxygen under the excitation of near infrared light and used for tumor photodynamic therapy is used for the photodynamic therapy of hypoxic tumors.
Performance evaluation test of the above composite material:
1. experiment for generating oxygen and singlet oxygen in cells under near infrared light irradiation
The logarithmic phase 4T1 cells were digested with trypsin to prepare a cell suspension of 105 cells/mL, and then seeded into a 96-well plate at 100. mu.L per well. After 24 hours, the composite material is added, the mixture is incubated for 6 hours, and then the experiment is carried out by using 980nm near infrared light for irradiation, wherein the power density is 0.5W/cm2And irradiating for 10 min. Then, the culture box is incubated for 2 hours at 37 ℃, an oxygen detection reagent and a singlet detection reagent are respectively added, the culture box is incubated for 6 hours, redundant detection reagents are washed away by PBS, and the fluorescence microscope imaging observation is carried out.
2. Cell damage experiment under near infrared light irradiation
The logarithmic phase 4T1 cells were digested with trypsin to prepare a cell suspension of 105 cells/mL, and then seeded into a 96-well plate at 100. mu.L per well. After 24 hours, a series of different concentrations (wherein the total chlorophyll mass is 4.27 and 8.54. mu.g mL) were added-1) The composite material is incubated for 6 hours and then irradiated by 980nm near infrared light for experiment, and the power density is 0.5W/cm2And irradiating for 10 min. Then, the incubation was continued at 37 ℃ for 18 hours in an incubator, and the cell survival rate (%) (test well OD value/control well OD value) × 100%) was measured by thiazole blue (MTT) colorimetry, and the experiment was repeated three times.
3. Photothermal and photodynamic therapy of tumors in animals under near infrared illumination
Iodine/ethanol disinfection in the right dorsal side of female mice, subcutaneous transplantation of 0.1mL (1-2). times.1074T1 cell in PBS until the tumor grows in a volume close to that of the solid tumor under the skin of the mouse to a volume of about 70mm3At the time, the mice were randomly divided into 2 groups of 6 mice each. Mice were anesthetized and injected with PBS or composite via tail vein, with a final injection concentration of 20mg/kg mice. Irradiating mouse with 980nm near infrared light for 10min after 24 hr injection with power of 0.5W/cm2Tumor changes were recorded daily for 14 consecutive days and tumor growth curves were plotted. After the experiment, the mice were sacrificed to obtain the major organs, and the pathological changes of the tumor and the major organs were observed after hematoxylin-eosin staining, so as to study the influence of the composite material on the tumor and other organs.
FIG. 6 is a photograph showing the detection of oxygen and singlet oxygen generated in the cell by the composite material of example 1 under the irradiation of near infrared light, which indicates that the composite material can generate oxygen and singlet oxygen in the cell under the irradiation of near infrared light.
FIG. 7 is a graph of the results of the cell viability of the composite material of example 1 measured by the MTT colorimetry of cell damage under the irradiation of near infrared light, which shows that the composite material can kill 4T1 cells by more than 80% under the excitation of near infrared light.
FIG. 8 is a plot of tumor growth of mice after tail vein injection of the composite material of example 1, showing that the composite material is effective in inhibiting tumor growth under near infrared light excitation, substantially eliminating the tumor 6 days after injection, and that the tumor does not recur within 14 days.
FIG. 9 is a hematoxylin-eosin staining pattern of the major organs of mice after the treatment with the composite material of example 1, which shows that the composite material has better biocompatibility.
Example 2
And (3) synthesizing the up-conversion nano material with the excitation wavelength of 808nm and the thylakoid membrane composite material.
1. Synthesis of upconversion nanoparticles:
0.1mM of a rare earth acetate (Y: Yb: Er: Nd: 38: 10: 1: 1) and 10mM of sodium fluoride were each weighed into a three-necked flask containing 10mL of oleylamine and 10mL of octadecene, and nitrogen was continuously introduced thereto and heated to 120 ℃ for 1 hour. Then slowly heating to 340 ℃ and stirring for 1h, and naturally cooling to room temperature. Adding absolute ethyl alcohol, centrifuging to obtain precipitate, repeatedly washing with water and ethanol for three times respectively to obtain upconversion nanoparticles, and dispersing in chloroform. And finally, adding 1mL of hexadecyl trimethyl bromide solution (0.1M) into the chloroform solution of the upconversion nanoparticles, stirring for 4 hours at 70 ℃, centrifuging, washing with water, and drying to obtain the aqueous phase upconversion nanoparticles.
2. Extraction of thylakoid membranes:
weighing 100g of fresh spinach leaves, cleaning, and storing at 4 ℃ overnight. Then homogenized in a precooled mortar and filtered. The pellet was then collected by centrifugation and washed twice with 10mM HEPES buffer. Finally, the obtained pellet was suspended in water, sonicated at 4 ℃ for 5 minutes, centrifuged at 16000rpm for 15 minutes, and lyophilized to obtain a thylakoid membrane.
3. Synthesis of composite materials
1mL of the aqueous solution of upconverting nanoparticles (1mg mL)-1) With 1mL aqueous solution of thylakoid membrane (1mg mL)-1) After being mixed evenly, the composite material of the up-conversion nano particles and the thylakoid membrane is obtained by an ultrasonic method, the ultrasonic frequency is 42kHz, and the power is 100W. The mass percentage of the total chlorophyll in the up-conversion nano particles and the thylakoid membrane in the composite material is 96%: 4 percent.
Example 3
The mass percentage of the total chlorophyll in the upconversion nanoparticles and the thylakoid membrane is 90%: synthesis of 10% composite material.
1. Synthesis of upconversion nanoparticles:
1mM of rare earth acetate (Y: Yb: Er ═ 78: 20: 20) and 10mM of sodium fluoride were weighed into a three-necked flask containing 10mL of oleylamine and 10mL of octadecene, respectively, and nitrogen was continuously introduced thereto and heated to 120 ℃ for 1 hour. Then slowly heating to 320 ℃ and stirring for 1h, and naturally cooling to room temperature. Adding absolute ethyl alcohol, centrifuging to obtain precipitate, repeatedly washing with water and ethanol for three times respectively to obtain upconversion nanoparticles, and dispersing in chloroform. And finally, adding 1mL of hexadecyl trimethyl bromide solution (0.1M) into the chloroform solution of the upconversion nanoparticles, stirring for 4 hours at 70 ℃, centrifuging, washing with water, and drying to obtain the aqueous phase upconversion nanoparticles.
2. Extraction of thylakoid membranes:
weighing 100g of fresh spinach leaves, cleaning, and storing at 4 ℃ overnight. Then homogenized in a precooled mortar and filtered. The pellet was then collected by centrifugation and washed twice with 10mM HEPES buffer. Finally, the obtained pellet was suspended in water, sonicated at 4 ℃ for 5 minutes, centrifuged at 16000rpm for 15 minutes, and lyophilized to obtain a thylakoid membrane.
3. Synthesis of composite materials
1mL of the aqueous solution of upconverting nanoparticles (1mg mL)-1) With 3mL aqueous solution of thylakoid membrane (1mg mL)-1) After being mixed evenly, the composite material of the up-conversion nano particles and the thylakoid membrane is obtained by an ultrasonic method, the ultrasonic frequency is 42kHz, and the power is 100W. The mass percentage of the total chlorophyll in the up-conversion nano particles and the thylakoid membrane in the composite material is 90%: 10 percent.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (7)
1. A composite material for simultaneously generating oxygen and active oxygen under the excitation of near infrared light is characterized by consisting of up-conversion nanoparticles and a thylakoid membrane for modifying the surfaces of the up-conversion nanoparticles;
the up-conversion nano particles are up-conversion nano particles capable of converting near infrared light into red light, and the excitation wavelength is 808-;
the mass percentage of the total chlorophyll in the upconversion nanoparticles and the thylakoid membrane is (90-98)%: (2-10)%.
2. The composite material for simultaneously generating oxygen and active oxygen under near-infrared light excitation according to claim 1, wherein the mass percentage of total chlorophyll in the up-conversion nanoparticles and the thylakoid membrane is 96%: 4 percent.
3. The composite material for simultaneously generating oxygen and active oxygen under near-infrared light excitation according to claim 1, wherein the upconversion nanoparticles are upconversion nanoparticles having an excitation wavelength of 980 nm.
4. A method for preparing the composite material for simultaneously generating oxygen and active oxygen under near infrared light excitation according to any one of claims 1 to 3, comprising the steps of:
and (3) uniformly mixing the water solution of the up-conversion nano particles with the water solution of the thylakoid membrane, and obtaining the up-conversion nano particles and the thylakoid membrane composite material by an ultrasonic method.
5. The method for preparing the composite material capable of simultaneously generating oxygen and active oxygen under the excitation of near infrared light according to claim 4, wherein the upconversion nanoparticles are prepared by the following method:
weighing 1mM of rare earth acetate respectively, wherein Y: yb: er is 78: 20: 20, and 10mM sodium fluoride were added to a three-necked flask containing 10mL oleylamine and 10mL octadecene, and nitrogen was continuously introduced and heated to 120 ℃ for 1 hour; then heating to 320 ℃, stirring for 1h, and naturally cooling to room temperature; adding absolute ethyl alcohol, centrifuging to obtain a precipitate, repeatedly washing with water and ethanol for three times respectively to finally obtain up-conversion nanoparticles, and dispersing in chloroform; and finally, adding 1mL of 0.1M hexadecyl trimethyl bromide solution into the chloroform solution of the upconversion nanoparticles, stirring for 4 hours at 70 ℃, centrifuging, washing with water, and drying to obtain the aqueous phase upconversion nanoparticles.
6. The method according to claim 4, wherein the thylakoid membrane is extracted from photosynthetic plant leaves or photosynthetic bacteria.
7. Use of a composite material according to any one of claims 1 to 3 for simultaneously generating oxygen and reactive oxygen species under excitation by near infrared light for the manufacture of a medicament for photodynamic therapy of tumors.
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