An apparatus and method for preparing a photosensitizer

Abstract

The present application relates to the field of material preparation, and is a device and method for preparing photosensitizer. The device comprises reaction cavity, passivation cavity and drying cavity connected in sequence. The reaction cavity is provided with storage chamber I and storage chamber II above, and storage chamber III below. The passivation cavity is provided with storage chamber IV above. Each storage chamber is provided with solution spray gun. The outer layer of the reaction cavity, passivation cavity and drying cavity is provided with temperature control layer. The outer layer of each storage chamber is provided with temperature control sleeve. The reaction cavity, passivation cavity and drying cavity are provided with temperature sensor. The left end of the reaction cavity is provided with air gate I and air inlet. The reaction cavity and passivation cavity are provided with air gate II. The passivation cavity and drying cavity are provided with air gate III. The outlet of the drying cavity is connected with collection cavity. The collection cavity, reaction cavity and passivation cavity are provided with pressure controller. The present application integrates preparation, passivation modification, drying and collection, and obtains solid nanoparticle photosensitizer. The photosensitizer is prepared in medical place, and is directly made into spray for photodynamic therapy through respiratory tract.

Description

Technical Field

[0001] This invention relates to the field of materials preparation, specifically to an apparatus and method for preparing photosensitizers. Background Technology

[0002] The preparation process of photosensitizers used in photodynamic therapy is complex, typically requiring multiple solution reactions in a chemical laboratory. Various equipment is needed to control reaction conditions, thus the process generally requires specialized laboratories and a high level of expertise. Colloidal photosensitizers prepared using this solution method are often administered intravenously, which can easily damage normal tissues, causing side effects such as bone marrow suppression and gastrointestinal reactions. Furthermore, colloidal photosensitizers are difficult to preserve and cannot be prepared immediately before use. During long-term transportation and storage, they are prone to clustering and precipitation, directly affecting their efficacy. The diverse molecular compositions of photosensitizers often require rapid adjustments to their composition and structure to align with the treatment plan, highlighting the time-consuming laboratory preparation process and the potential for delays in treatment. If solid-state photosensitizers could be prepared directly at the treatment site, overcoming the limitations of laboratory facilities and specialized technicians, it would offer several advantages. Firstly, it would allow for timely optimization of components and functions based on treatment needs, enabling on-site preparation of photosensitizers and saving preparation time without requiring specialized technicians. Secondly, without compromising treatment efficacy, solid-state photosensitizers are easier to handle and store, and can be directly formulated into aerosol formulations for inhalation, avoiding the side effects of intravenous injection. Furthermore, traditional photosensitizers often use quantum dots containing organic polymers, Cd-based quantum dots, and other components that are difficult to degrade in vivo, posing a potential toxicity threat. There is an urgent need for quantum dot materials that can be designed with completely non-toxic components. Currently, there is no device that can prepare solid-state photosensitizers under conventional indoor conditions with a simple, controllable method, compatible with multiple components, and directly. Summary of the Invention

[0003] This invention provides a novel apparatus for preparing photosensitizers, and a method for preparing photosensitizers using this apparatus.

[0004] The photosensitizer prepared by this invention can have an inorganic semiconductor quantum dot core (such as II-VI and III-V group semiconductor quantum dots) or a core containing AMX3, (RNH3)2A... n-1 MX 3n+1 R(NH3)2A n-1 MX 3n+1 A(1)A(2) n–1 MX 3n+1, A2M(I)M(III)X6, A2M(IV)X6, A2M(I)M(II)X5, A3M(III)2X9, A4BM(II)M(III)2X 12 A4M(III)M(V)X 12 A4M(I)M(III)X8, A2B(I)B(III)MX8, and similar to (C9NH 20 )6[Pb3Br 12 ] and (C9NH 20 )9[ZnBr4]2[Pb3Br 11 Perovskite quantum dots in the form of [etc.] also include hybrid quantum dots in the above series in the form of component mixing and element doping. A, A(1), A(2) are monovalent cations, which can be inorganic elements or smaller organic groups; R is a larger organic cation; M is a metal cation; X is a halide anion; NH3 is an ammonium ion.

[0005] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:

[0006] This invention provides a photosensitizer preparation apparatus, comprising a reaction chamber, a passivation chamber, and a drying chamber connected in sequence; storage chamber I and storage chamber II are located above the reaction chamber, storage chamber III is located below the reaction chamber, and storage chamber IV is located above the passivation chamber; solution spray gun I, solution spray gun II, and solution spray gun IV are respectively located below storage chamber I, storage chamber II, and storage chamber IV, and solution spray gun III is located above storage chamber III; the nozzles of solution spray gun I, solution spray gun II, and solution spray gun III extend into the reaction chamber, and the nozzle of solution spray gun IV extends into the passivation chamber; a temperature control layer is provided on the outer layer of both the reaction chamber and the passivation chamber; the drying chamber is equipped with an infrared heating device, and drying is completed in 1-10 seconds; storage chamber I and storage chamber II... Temperature control sleeves are installed on the outer layers of storage chambers III and IV; temperature sensors are installed in the reaction chamber, passivation chamber, and drying chamber to monitor the temperature of each chamber; a vent gate I and a vent are installed at the left end of the reaction chamber, and a vent gate II is installed between the reaction chamber and the passivation chamber. Ventilation gates I and II are opened or closed as needed for the reaction, thus connecting or closing the reaction chamber and the passivation chamber; a vent gate III is installed between the passivation chamber and the drying chamber, and the opening or closing of the vent gate III controls the connection or closure between the passivation chamber and the drying chamber; the outlet of the drying chamber is connected to the collection chamber; pressure controllers are installed in the collection chamber, reaction chamber, and passivation chamber to control the pressure balance in each chamber.

[0007] In the above technical solution, a filter I is further provided at one end of the passivation chamber opposite to the gate II; a filter II and a particle sieve are provided between the outlet of the drying chamber and the collection chamber.

[0008] In the above technical solution, the pore size of the particle sieve is nanometer-scale, preferably 10-800nm.

[0009] In the above technical solution, filter I and filter II are filter sheets with built-in filtered water or organic reagents.

[0010] In the above technical solution, the temperature control layer is further provided with heating elements and cooling elements to control the temperature inside the chamber to rise or fall. Preferably, the temperature range of the temperature control layer is 0 to 25°C. The temperature sensor is connected to the heating element and the cooling element respectively. The temperature control sleeve is provided with heating elements to control the temperature inside the storage chamber to rise.

[0011] In the above technical solution, the probe of the temperature sensor is further placed inside the reaction chamber, the passivation chamber, and the drying chamber.

[0012] In the above technical solution, the pressure controller further includes a pressure sensor, a controller, and a regulating valve; the probe of the pressure sensor is placed in the reaction chamber, the passivation chamber, and the collection chamber.

[0013] The present invention also provides a method for preparing quantum dots, the method using the apparatus according to any one of claims 1-7, comprising the following steps:

[0014] Reaction solution I is injected into storage chamber I, and reaction solution II is injected into storage chamber II. The temperature of storage chambers I and II is adjusted by the temperature control sleeve to raise reaction solutions I and II to the required temperature. The temperature inside the reaction chamber is adjusted to the required temperature by the temperature control layer and maintained at a constant temperature. Ventilation gates I and II are closed, and reaction solutions I and II are sprayed into the reaction chamber through solution spray chamber I and solution spray gun II, respectively, to carry out the reaction. After the reaction is completed, the temperature control layer stops heating and lowers the temperature of the reaction chamber to allow the reactants to cool and condense. Ventilation gates I and II are opened, and the ventilation gate is closed. Indoor valve III is used to introduce inert gas through the vent. The cooled reactants are then blown into the passivation chamber through vent valve II. Vent valve II is then closed, and the passivation modification solution is injected into storage chamber IV. The solution is then sprayed out in a mist form through solution spray gun IV to modify and coat the reactants. After passivation and coating, vent valves II and III are opened, and inert gas is introduced through the vent. The inert gas is blown into the passivation chamber, and the passivated and coated reactants are blown into the drying chamber through a filter. Drying is completed in 1-10 seconds. After drying, the reactants are blown into the collection chamber through a filter and a particle sieve to collect quantum dots. During the preparation process, the pressure controller in each chamber maintains the pressure balance in each chamber.

[0015] In the above technical solution, when doping is required during preparation, the dopant is injected into storage chamber III and sprayed out in a mist state into the reaction chamber through a solution spray gun.

[0016] In the above technical solution, further, when the reaction in the reaction chamber is completed and rapid cooling is required, the antisolvent can be injected into the storage chamber III and cooled to a low temperature, and then sprayed into the reaction chamber in a mist state through a solution spray gun to promote the crystallization of the product.

[0017] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0018] This invention provides a novel apparatus for preparing photosensitizers, avoiding the drawbacks of traditional methods that require specialized laboratories, multiple pieces of equipment, specialized personnel, and complex operations to prepare photosensitizers, and cannot readily obtain photosensitizers with adjustable compositions according to treatment needs. It also avoids the inevitable performance changes and reduced therapeutic efficacy that occur during the transfer of traditionally prepared photosensitizer solutions from the laboratory to the hospital. This invention's apparatus integrates preparation, passivation modification, drying, and collection, requiring no location restrictions and allowing preparation by non-chemical professionals. It directly prepares solid nanoparticle photosensitizers, which are easy to store and use, and can be directly used to prepare spray formulations for inhalation administration, avoiding delays in diagnosis and treatment due to transportation and transit. This invention's apparatus is suitable for various indoor environments, has a compact structure, and is easy to operate, even for non-professionals. When the molecular composition and function of the photosensitizer need adjustment, this invention's apparatus can be used to promptly synthesize and modify the solid photosensitizer according to the adjusted scheme, improving treatment efficiency. Furthermore, the infrared rapid heating mode is used in the photosensitizer collection process, which can complete the drying step in a few seconds, maximizing the preservation of photosensitizer properties and avoiding potential degradation caused by traditional thermal resistance heating. This device can achieve the design and preparation of completely non-toxic photosensitizer components. Synthesis can be achieved by setting the solutions in storage chambers I, II, III, and IV and adjusting the reaction temperature, allowing the photosensitizer to achieve therapeutic effects under the premise of easy metabolism and safety without toxicity. Attached Figure Description

[0019] Figure 1 Structural diagram of the device of the present invention.

[0020] Figure 2 Spectral diagram of the quantum dots prepared in Example 2.

[0021] Figure 3 Scanning electron microscope image of the quantum dots prepared in Example 2.

[0022] Figure 4 Scanning electron microscope image of the quantum dots prepared in Example 3.

[0023] Figure 5 A schematic diagram illustrating the application scenario of the photosensitizer prepared by the device of this invention.

[0024] Figure 6 A schematic diagram of the photosensitizer prepared by the device of the present invention for photodynamic therapy.

[0025] In the diagram, 1. Temperature control sleeve, 2. Storage chamber I, 3. Reaction solution A spray, 4. Storage chamber II, 5. Reaction solution B spray, 6. Storage chamber IV, 71. Solution spray gun I, 72. Solution spray gun II, 73. Solution spray gun IV, 74. Solution spray gun III, 8. Temperature sensor, 9. Vent, 10. Storage chamber III, 11. Reaction chamber, 12. Modification chamber, 13. Temperature control layer, 141. Vent gate I, 142. Vent gate II, 143. Vent gate III, 15. 16. Passivated and coated photosensitizer aerosol, 17. Filter I, 18. Drying chamber, 19. Infrared heating device, 20. Dried photosensitizer particles, 21. Filter II, 22. Particle sieve, 23. Quantum dot collector, 24. Pressure controller, 25. Filter booster, 26. Atomizing nozzle, 27. Quantum dot photosensitizer aerosol, 28. Schematic diagram of human respiratory system, 29. Excitation light source, 20. Photosensitizer attached to tumor cells, 20. Photosensitizer solution storage tank. Detailed Implementation

[0026] The present invention will be further described below with reference to specific embodiments, but this does not limit the invention in any way. In this disclosure, unless otherwise stated, directional terms such as "upper," "lower," "left," and "right" generally refer to those defined based on the drawing surface of the corresponding figure, and "inner" and "outer" refer to the inner and outer contours of the corresponding components. The terms "first," "second," etc., are used to distinguish one element from another and do not have sequential or importance implications. Furthermore, when the following description relates to the figures, unless otherwise indicated, the same numbers in different figures represent the same or similar elements.

[0027] Example 1

[0028] An apparatus for preparing a photosensitizer includes a reaction chamber 11, a passivation chamber 12, and a drying chamber 17 connected in sequence. Storage chambers I2 and II4 are located above the reaction chamber, and storage chamber III10 is located below the reaction chamber. Storage chamber IV6 is located above the passivation chamber 12. Solution spray guns I71, II72, and IV73 are located below storage chambers I2, II4, and IV6, respectively, and solution spray gun III74 is located above storage chamber III. The nozzles of solution spray guns I71, II72, and III74 are... The solution spray gun IV73 nozzle is inserted into the passivation chamber 12, and the reaction chamber 11 and passivation chamber 12 are both equipped with a temperature control layer 13 on their outer layers. An infrared heating device 171 is installed on the outer side of the drying chamber 17. Temperature control sleeves 1 are installed on the outer layers of storage chambers I2, II4, III10, and IV6. Temperature sensors 8 are installed in the reaction chamber 11, passivation chamber 12, and drying chamber 17 to monitor the temperature of each chamber. A vent gate I141 and a vent 9 are installed at the left end of the reaction chamber 11. A ventilation channel is provided between the reaction chamber and the passivation chamber. Ventilation gates II 142, I 141, and II 142 open or close as needed for the reaction, simultaneously connecting or closing the reaction chamber 11 and the passivation chamber 12. A gate III 143 is installed between the passivation chamber 12 and the drying chamber 17. The opening or closing of gate III 143 controls the connection or closure between the two chambers. Alternatively, slides can be installed on the inner walls of the reaction chamber, passivation chamber 12, and drying chamber to match the ventilation gates. The ventilation gates slide along the slides to close or connect the chambers, while ventilation gate I opens. Afterwards, inert gas can be introduced through the vent; the outlet of the drying chamber 17 is connected to the collection chamber 21; pressure controllers 22 are installed in the collection chamber 21, reaction chamber 11, and passivation chamber 12 to control the pressure balance in each chamber; ventilation pipes are provided between the reaction chamber and the passivation chamber, between the passivation chamber and the drying chamber, and between the drying chamber and the collection chamber. After each ventilation gate is opened, the reaction chamber, passivation chamber, drying chamber, and collection chamber are connected, and inert gas is introduced through the ventilation pipes; ventilation gate II can be set at the left end of the passivation chamber, and ventilation gate III can be set at the left end of the drying chamber.

[0029] To improve the purity of quantum dots, optionally, a filter I 16 is provided at one end of the passivation chamber 12 opposite to the gate II 142 to filter out unreacted reactants, solvents, etc.; a filter II 19 and a particle sieve 20 are provided between the outlet of the drying chamber 17 and the collection chamber 21 to further remove residual reagents and impurities. The pore size of the particle sieve is nanoscale, which meets the requirement of directly preparing the photosensitizer into an aerosol.

[0030] Optionally, filters I and II are filter elements with built-in filters for filtering water or organic reagents to filter residual reagents or impurities.

[0031] Optionally, the temperature control layer is equipped with heating and cooling elements to control the temperature rise or fall within the chamber. The temperature range of the temperature control layer is 0–25°C. Temperature sensors are connected to the heating and cooling elements respectively, and the probes of the temperature sensors are placed in the reaction chamber, passivation chamber, and drying chamber respectively. After a set value is set, the temperature within the chamber is sensed by the temperature sensors. When the temperature does not meet the requirements, the temperature sensors feed back commands to the heating or cooling elements, causing them to work together to bring the temperature in the corresponding chamber to the required value. The temperature control sleeve is equipped with heating elements for heating the storage chamber.

[0032] Optionally, the pressure controller includes a pressure sensor, a controller, and a regulating valve; the probe of the pressure sensor is placed in the reaction chamber 11, the passivation chamber 12, and the collection chamber 21, and the pressure in the chamber is transmitted to the controller through the pressure sensor, and then the pressure in the chamber is balanced through the regulating valve.

[0033] Optionally, the drying chamber is equipped with an infrared heating device 171, which completes drying in 1-10 seconds, effectively reducing the damage to the properties of the photosensitizer caused by prolonged heating and drying, and ensuring the performance of the photosensitizer to the greatest extent.

[0034] The preparation of quantum dots using the above-described apparatus includes the following steps:

[0035] Reaction solution I is injected into storage chamber I, and reaction solution II is injected into storage chamber II. The temperature of storage chambers I and II is adjusted by the temperature control sleeve to raise reaction solutions I and II to the required temperature. The temperature inside the reaction chamber is raised to the required temperature by the temperature control layer and maintained at a constant temperature. Ventilation gates I and II are closed, and reaction solutions I and II are sprayed into the reaction chamber as mists through solution spray chamber I and solution spray gun II, respectively, to carry out the reaction. After the reaction is completed, the temperature control layer stops heating and lowers the temperature of the reaction chamber to allow the reactants to cool and condense. Ventilation gates I and II are then opened. Ventilation gate II is closed, and ventilation gate III is shut off. Inert gas is introduced through the vent, and the cooled reactants are blown into the passivation chamber through ventilation gate II. Ventilation gate II is then closed, and the passivation modification solution is injected into storage chamber IV and sprayed out in a mist state through solution spray gun IV to modify and coat the reactants. After passivation and coating, ventilation gates II and III are opened, and inert gas is introduced through the vent. The inert gas is blown into the passivation chamber, and the passivated and coated reactants are filtered and enter the drying chamber. The infrared heating device is set to complete the drying in 7 seconds. After drying, the reactants are filtered and blown into the collection chamber through a particle sieve to collect the photosensitizer. When doping is required during preparation, the dopant is injected into storage chamber III and sprayed out in a mist state through solution spray gun into the reaction chamber. The anions and cations in the molecules are exchanged using ion exchange (e.g., replacing I ions with Br ions, replacing Pb ions with Mn ions, etc.) to prepare the desired perovskite quantum dots. During the preparation process, the pressure controller in each chamber maintains the pressure balance in each chamber.

[0036] The solid photosensitizer prepared by this invention, when needed, is redispersed in a solvent, placed in the photosensitizer solution storage tank 29 of the spray device, and connected to a stainless steel spray nozzle 24 via a filter booster 23. Figure 5 The spray device includes a storage tank 29, a filter booster 23, and a nozzle 24. The storage tank 29 is connected to the filter booster 23, and the filter booster 23 is connected to the nozzle 24. The atomization pressure and spray pressure are typically 0.01-3 MPa, and the distance between the nozzle and the human mouth and nose is approximately 5-25 cm. The sprayed aerosol is an aerosol 25 containing quantum dot photosensitizers, where the photosensitizers are on the order of micrometers, with typical sizes of 10-800 nm. The nozzle velocity is approximately 1-20 mm / s. The photosensitizer 28, modified with targeted molecules, reaches the human respiratory tract through respiration and binds to tumor cells. Subsequently, a light source 27 is introduced to irradiate the tumor site for photodynamic therapy, such as... Figure 6 As shown. The inhalation volume of the photosensitizer solution can be adjusted according to the patient's specific condition.

[0037] Example 2

[0038] Preparation of completely non-toxic elemental photosensitizers using the apparatus of this invention:

[0039] 0.4 mmol of tin bromide was dissolved in 10 ml of N,N-dimethylformamide (DMF, 99.8%), and 1.6 mmol of N,N′-dimethylethylene-1,2-dibromide was dissolved in 20 ml of DMF. After forming clear precursor solutions, these solutions were injected into storage chambers I2 and II4, respectively. 600 ml of dichloromethane (DCM, 99.9%) was placed in storage chamber III10. Temperature control sleeve 1 heated the solution to 45°C, while simultaneously maintaining the temperature of reaction chamber 11 at 45°C, with temperature sensor 8 controlling the temperature to remain constant. Vent gates I141 and II142 were closed. The solutions in storage chambers I2 and II4 were sprayed out through solution spray guns I71 and II72, forming sprays 3 and 5, which reacted in reaction chamber 11. After the reaction, the temperature in reaction chamber 11 was adjusted to 0°C, and the DCM solution in storage chamber Ⅲ10 was cooled to 0°C. After being rapidly sprayed out by solution spray gun Ⅲ74, the reaction product was cooled and condensed to form C. 16 H 56 N8SnBr 10Crystals. Open vent gates I 141 and II 142, close vent gate III, and introduce inert gas N2 into reaction chamber 11 through vent 9. Use the N2 gas flow to purge the generated quantum dots into passivation modification chamber 12. Close vent gate II 142, and spray the solution in passivation modification solution storage chamber IV 6 in a mist state through solution spray gun IV 73 to further modify and coat the quantum dots, forming a passivated and coated photosensitizer mist 15. Open vent gates I, II, and III. As N2 purges, the reactants and solvents are filtered out through reactant filter I 16, and the particles enter drying chamber 17. Infrared heating device completes drying in 10 seconds, obtaining dried photosensitizer particles 18. Then, passing through filter II 19 and particle sieve 20, residual reagents and impurities are removed again. A 150nm pore size particle sieve is used for sieving to control the photosensitizer size below 150nm, finally reaching quantum dot collector 21. Filters I and II are used to remove residual reagents or impurities from the reaction process to improve the purity of the photosensitizer. The filters can contain activated carbon membranes, dried membranes, or a combination of both. Alternatively, different membranes capable of removing these substances can be selected based on the different residual reagents or impurities generated during different reactions. Throughout the reaction, a pressure controller maintains pressure balance in each chamber. The reaction yield is approximately ~72%. The quantum dots synthesized using the above method, under 350nm laser irradiation, have an emission peak centered around 570nm, a full width at half maximum (FWHM) of approximately 105nm, and a fluorescence quantum yield of approximately 90%. Figure 2 As shown. The scale is between 25-300 nm, such as... Figure 3 As shown in the scanning electron microscope image.

[0040] Collected solid C 16 H 56 N8SnBr 10 The quantum dot photosensitizer is redispersed in a solvent and placed into the photosensitizer solution storage tank 29 of the spray device, which is then connected to a stainless steel spray nozzle 24 via a filter booster 23. The atomization and spray pressure are typically 0.01-3 MPa, and the distance between the nozzle and the human mouth and nose is approximately 5-25 cm. The sprayed aerosol 25 contains the quantum dot photosensitizer, with a photosensitizer size below 150 nm, and the nozzle velocity is approximately 1-10 mm / s. The photosensitizer 28, modified with targeted molecules, reaches the human respiratory tract through respiration and binds to nasopharyngeal carcinoma tumor cells. Subsequently, a light source 27 is introduced to irradiate the tumor site for photodynamic therapy, such as... Figure 6 As shown. The course of treatment and the inhalation volume of the photosensitizer solution can be adjusted according to the patient's specific condition.

[0041] Example 3

[0042] Preparation of completely non-toxic elemental photosensitizers using the apparatus of this invention:

[0043] 0.1 mmol Ag(ac), Na(ac) (200 μL sodium oleate stock solution), 0.2 mmol In(ac)3, 40 μL Bi(ac)3, 100 μL HCl, 2.0 mL degassed oleylamine (OLAM), 1.76 mL degassed oleic acid (OA), and 8 mL ODE were mixed and dissolved. The solution was heated to 110 °C under vacuum to remove residual air and water, and then injected into storage chamber I2, with the temperature controlled at room temperature. 1 mL of cesium oleate solution was injected into storage chamber II4, and the temperature of reaction chamber 11 was controlled at room temperature. Vent gates I141 and II142 were closed. According to the chemical formula ratio, the solutions in storage chambers I2 and II4 were sprayed out through solution spray guns I71 and II72 to form sprays 3 and 5, which reacted in reaction chamber 11. After 10 min at room temperature, the system was heated to 210 °C at a rate of 0.5 °C / s using a temperature controller. After the reaction has proceeded for 15-45 minutes, the temperature control layer 13 is lowered to room temperature, allowing the reactants to cool and condense to form Cs2Ag. 0.5 Na 0.5 InCl6 crystals. Ventilation gates I141 and II142 are opened, and inert gas N2 is introduced through vent 9. The generated quantum dots are then blown into the passivation modification chamber 12 using the N2 gas flow. Ventilation gates I141 and II142 are closed, and the solution in the passivation modification solution storage chamber 6 is sprayed out in a mist state through solution spray gun IV73 to further modify and coat the quantum dots, forming a passivated and coated photosensitizer mist 15. Subsequently, ventilation gates I141, II142, and III143 are opened, and N2 is introduced. The reactants and solvents are filtered out through reactant filter I16, and the mixture enters the drying chamber 17. Drying is completed by an infrared heating device in 9 seconds, yielding dried photosensitizer particles 18. The photosensitizer particles are then screened through filter II 19 and particle sieve 20. A 300nm pore size particle sieve is used to control the size of the photosensitizer below 300nm. After removing residual reagents and impurities, the particles finally reach quantum dot collector 21. Throughout the reaction process, the pressure balance in each chamber is controlled by a pressure controller.

[0044] The preparation methods for the various solutions involved are as follows:

[0045] Preparation of cesium oleate stock solution:

[0046] 1304 mg of Cs2CO3 and 20 mL of OA were placed in a glass container and heated to 110 °C. The mixture was degassed under vacuum until Cs2CO3 was completely dissolved to form a colorless and transparent reaction solution.

[0047] Preparation of bismuth oleate stock solution:

[0048] 309 mg Bi(ac)3 and 8 ml OA were placed in a glass container and heated to 110 °C. The mixture was degassed under vacuum until it dissolved to form a colorless and transparent reaction solution.

[0049] Preparation of sodium oleate stock solution:

[0050] 164 mg Na(ac) and 4 ml OA were placed in a glass container, heated to 110 °C, and the mixture was degassed under vacuum until it dissolved to form a colorless and transparent reaction solution.

[0051] Cs2Ag synthesized by the above method 0.5 Na 0.5 InCl6 quantum dots, observed by scanning electron microscopy, have a scale of approximately 150-650 nm, such as... Figure 4 The scanning electron microscope image shows that under 340 nm laser irradiation, the center of the emission peak is around 550 nm, the full width at half maximum (FWHM) is about 150 nm, and the fluorescence quantum yield is about 95%.

[0052] Collected solid Cs2Ag 0.5 Na 0.5 The InCl6 quantum dot photosensitizer is redispersed in the solvent and placed into the photosensitizer solution storage tank 29 of the spray device. It is then connected to the stainless steel spray nozzle 24 via a filter pressurizer 23. Figure 5 The atomization and spray pressure are typically 0.01-3 MPa, and the distance between the nozzle and the patient's mouth and nose is approximately 5-25 cm. The sprayed aerosol is an aerosol 25 containing quantum dot photosensitizers, with the photosensitizers having a size of approximately 200 nm. The nozzle velocity is approximately 5-20 mm / s. The photosensitizer 28, modified with targeted molecules, reaches the lung tumor tissue through the respiratory tract. Subsequently, a light source 27 is introduced to irradiate the tumor site, performing photodynamic therapy for squamous cell carcinoma of the lung. Figure 6 As shown. The course of treatment and the inhalation volume of the photosensitizer solution can be adjusted according to the patient's specific condition.

[0053] The device of this invention can be used to prepare photosensitizers synthesized from different components. It is suitable for preparation under various reaction conditions and integrates particle preparation, modification and coating, purification and drying into one unit. It can directly prepare photosensitizers that meet the treatment requirements in terms of composition and structure, thus satisfying subsequent treatment needs. The device is simple to operate, requires no professional technicians, and can be prepared directly on the treatment site, meeting the need for timely preparation of photosensitizer components that can be adjusted at any time.

[0054] For anyone skilled in the art, many possible variations and modifications can be made to the technical solutions of this invention, or equivalent embodiments can be modified based on the disclosed technical content, without departing from the scope of the technical solutions of this invention. Therefore, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of this invention without departing from the content of the technical solutions of this invention should still fall within the protection scope of the technical solutions of this invention.

Claims

1. An apparatus for preparing a photosensitizer, characterized in that, The system includes a reaction chamber (11), a passivation chamber (12), and a drying chamber (17) connected in sequence. Above the reaction chamber are storage chambers I (2) and II (4), below the reaction chamber is storage chamber III (10), and above the passivation chamber (12) is storage chamber IV (6). Below storage chambers I (2), II (4), and IV (6) are solution spray guns I (71), II (72), and IV (73), respectively. Above storage chamber III (10)... The room is equipped with a solution spray gun III (74); the nozzles of solution spray gun I (71), solution spray gun II (72), and solution spray gun III (74) are connected to the reaction chamber, and the nozzle of solution spray gun IV (73) is connected to the passivation chamber (12); the outer layers of the reaction chamber (11) and the passivation chamber (12) are both equipped with a temperature control layer (13); the drying chamber (17) is equipped with an infrared heating device (171); the outer layers of storage chamber I (2), storage chamber II (4), storage chamber III (10), and storage chamber IV (6) are also equipped with a solution spray gun III (74 ...71), storage chamber II (72), and storage chamber III (74) are also equipped with a solution spray gun III (74); the nozzles of solution spray gun I (71), solution spray gun II (72), and solution spray gun III (74) are connected to the reaction chamber, and the nozzles of solution spray gun IV (73) are connected to the passivation chamber (12); the outer layers of storage chamber I (2), storage chamber II (4), storage chamber III (10), and storage chamber IV (6) are also equipped with a solution spray gun III (74); the outer layers of storage chamber I (71), storage chamber II (74), storage chamber III (74), and storage chamber IV (6) are also equipped with a solution spray gun III (74); the nozzles of solution spray gun I (71), solution spray gun II (72), and solution spray gun III (74) are connected to the reaction chamber, and the nozzles of solution spray gun IV (73) are connected to the passivation chamber (12); the outer layers of storage chamber I Each chamber is equipped with a temperature control sleeve (1); the reaction chamber (11), passivation chamber (12), and drying chamber (17) are all equipped with temperature sensors (8) to meet the temperature monitoring of each chamber; the left end of the reaction chamber (11) is provided with a ventilation gate I (141) and a ventilation port (9), and a ventilation gate II (142) is provided between the reaction chamber (11) and the passivation chamber (12). The ventilation gate I (141) and the ventilation gate II (142) are opened or closed according to the reaction needs, so as to realize the reaction chamber (11) and the passivation chamber (12) are connected or closed; a ventilation gate III (143) is provided between the passivation chamber (12) and the drying chamber (17), and the connection or closure between the passivation chamber (12) and the drying chamber (17) is controlled by opening or closing the ventilation gate III (143); the outlet of the drying chamber (17) is connected to the collection chamber (21); a pressure controller (22) is provided in the collection chamber (21), the reaction chamber (11) and the passivation chamber (12) to control the pressure balance in each chamber; The passivation chamber (12) is provided with a filter I (16) at one end opposite to the ventilation gate II (142); the drying chamber (17) is provided with a filter II (19) and a particle sieve (20) between the outlet and the collection chamber (21).

2. The apparatus for preparing a photosensitizer according to claim 1, characterized in that, The pore size of the particle sieve is in the nanometer range.

3. The apparatus for preparing a photosensitizer according to claim 1, characterized in that, The filters I and II are filter elements with built-in filters for filtering water or organic reagents.

4. The apparatus for preparing a photosensitizer according to claim 1, characterized in that, The temperature control layer is provided with heating elements and cooling elements to control the temperature inside the chamber to rise or fall. The temperature range of the temperature control layer is 0~25℃. The temperature sensor (8) is connected to the heating element and the cooling element respectively. The temperature control sleeve is provided with heating elements to control the temperature inside the storage chamber to rise.

5. The apparatus for preparing a photosensitizer according to claim 1, characterized in that, The probe of the temperature sensor (8) is placed in the reaction chamber (11), the passivation chamber (12), and the drying chamber (17).

6. The apparatus for preparing a photosensitizer according to claim 1, characterized in that, The pressure controller includes a pressure sensor, a controller, and a regulating valve; the probe of the pressure sensor is placed in the reaction chamber (11), the passivation chamber (12), and the collection chamber (21).

7. A method for preparing a photosensitizer, characterized in that, The method uses the apparatus according to any one of claims 1-6 and includes the following steps: Reaction solution I is injected into storage chamber I, and reaction solution II is injected into storage chamber II. The temperature of storage chambers I and II is adjusted by the temperature control sleeve to raise reaction solutions I and II to the required temperature. The temperature inside the reaction chamber is raised to the required temperature by the temperature control layer and maintained at a constant temperature. Ventilation gates I and II are closed, and reaction solutions I and II are sprayed into the reaction chamber as mists through solution spray chamber I and solution spray gun II, respectively, to carry out the reaction. After the reaction is completed, the temperature control layer stops heating and lowers the temperature of the reaction chamber to allow the reactants to cool and condense. Ventilation gates I and II are opened, and the ventilation gate is closed. III. Inert gas is introduced through the vent, and the cooled reactants are blown into the passivation chamber through the vent gate II. The vent gate II is closed, and the passivation modification solution is injected into the storage chamber IV. It is then sprayed out in a mist form through the solution spray gun IV to modify and coat the reactants. After passivation and coating, the vent gates II and III are opened, and inert gas is introduced through the vent. The inert gas is blown into the passivation chamber, and the passivated and coated reactants are blown into the drying chamber through the filter. Drying is completed in 1-10 seconds. After drying, the reactants are blown into the collection chamber through the filter and particle sieve to collect quantum dots. During the preparation process, the pressure controller of each chamber maintains the pressure balance in each chamber.

8. The method for preparing the photosensitizer according to claim 7, characterized in that, When doping is required during preparation, the dopant is injected into storage chamber III and sprayed out in a mist form into the reaction chamber through a solution spray gun.

Images