CN111298112B - Photoluminescent system for treating neonatal jaundice and preparation method and application thereof - Google Patents
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- A61K41/0057—Photodynamic therapy with a photosensitizer, i.e. agent able to produce reactive oxygen species upon exposure to light or radiation, e.g. UV or visible light; photocleavage of nucleic acids with an agent
- A61K41/0076—PDT with expanded (metallo)porphyrins, i.e. having more than 20 ring atoms, e.g. texaphyrins, sapphyrins, hexaphyrins, pentaphyrins, porphocyanines
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- A61P1/00—Drugs for disorders of the alimentary tract or the digestive system
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Abstract
The invention discloses a photoluminescent system for treating neonatal jaundice and a preparation method and application thereof. The invention mixes the luminescent agent (p-DHMPA) and the photosensitizer PdBrTPP, and then excites the mixture under the 532 nm semiconductor laser (500 mW/cm)2) The systematic luminescence can be applied to treat neonatal jaundice, namely, the bilirubin content in the neonatal body is reduced; the system of the invention has long-wavelength excitation, adjustable exciting light power, narrow wave band, no influence of ultraviolet light and infrared light, moderate light intensity, and 500 mW/cm illumination intensity in a 532 laser2The treatment effect is the best; the average decrease rate was 2.41mM/h, which is greater than the decrease rate of a halogen lamp as a radiation source irradiating the bilirubin solution.
Description
Technical Field
The invention relates to a neonatal jaundice treatment technology, belongs to the new field of optical treatment, and particularly relates to a photoluminescent system for treating neonatal jaundice, and a preparation method and application thereof.
Background
Hyperbilirubinemia (jaundice) in newborns is one of the common diseases in the neonatal period, with a high incidence, especially in asian race, with visible jaundice occurring in the first 1 week after birth in about 60% of term and 80% of premature infants. Bilirubinemia induced bilirubinemia seriously threatens the life and health of newborn infants, is one of the main reasons causing hearing impairment, abnormal vision and intelligence falling behind of the infants, and even dies the infants. Currently, the treatment of hyperbilirubinemia (jaundice) of newborns mainly comprises drug therapy and phototherapy (phototherapy). The phototherapy has the advantages of convenient use, little side effect, no wound, simple operation and economyThe potential is widely applied in clinic and is the 'standard' therapy of the hyperbilirubinemia of the newborn; the radiation light sources used in current phototherapy are mainly fluorescent lamps, halogen lamps and LED light sources. The fluorescent lamp has low illumination intensity and quick light attenuation, and the fluorescent lamp tube needs to be replaced at regular time, so that the use is inconvenient; the halogen lamp can provide higher illumination intensity than a fluorescent lamp, but the radiation spectrum is wide (including ultraviolet and infrared wave bands), and the radiation can generate a considerable amount of heat, so that the patient can have serious adverse reactions such as nondominant dehydration of the skin and the like; although the blue LED light source has a narrow spectrum (i.e. does not contain infrared and ultraviolet bands), the blue LED light has high intensity (the light intensity of the commercially available blue LED therapeutic apparatus is more than 100 muW/cm at a position 20cm away from the human body 2∙ nm) and is harmful to human body (Seidman DS, Moise J, Ergaz Z, Laor A. A new blue light-emitting photothermal device: A productive random controlled study. Journal of pests 2000; 136: 771-) 774).
Disclosure of Invention
The invention aims to utilize a photoluminescence system to emit blue light to decompose bilirubin causing jaundice. The light emitted by the photoluminescence system irradiates the skin surface of a human body, and the photoluminescence system has the advantages of adjustable exciting light power, narrow wave band, no influence of ultraviolet light and infrared light, moderate light intensity, greatly reduced volume of a phototherapy instrument and the like, has fewer adverse reactions to the human body compared with a conventional light source, is safer and more reliable, enhances the curative effect of phototherapy, and becomes an ideal phototherapy material due to the unique characteristics.
The invention adopts the following technical scheme:
the photoluminescence system for treating neonatal jaundice comprises a luminous agent and a photosensitizer; preferably, the photoluminescence system for treating neonatal jaundice consists of a luminous agent, a photosensitizer, an alcohol solvent or a DMSO solvent.
The invention discloses a preparation method of a photoluminescence system for treating neonatal jaundice.
The invention also discloses a photoluminescent device for treating neonatal jaundice, which comprises a transparent container and a photoluminescent system; the photoluminescence system comprises a luminescent agent and a photosensitizer; preferably, the photoluminescence system for treating neonatal jaundice consists of a luminous agent, a photosensitizer, an alcohol solvent or a DMSO solvent.
In the invention, the transparent container can be a cuvette and the like; the photoluminescent system is put into a transparent container to obtain the photoluminescent device for treating neonatal jaundice, and the photoluminescent device for treating neonatal jaundice can emit light, degrade bilirubin and treat neonatal jaundice under the irradiation of exciting light; the excitation light is emitted from an excitation light source, such as a semiconductor laser, preferably having an excitation light wavelength of 532nm and an excitation light intensity of 500mW/cm2。
In the invention, the chemical structural formula of the luminescent agent is as follows:
the chemical structural formula of the photosensitizer is as follows:
the alcohol solvent is n-propanol.
In the invention, the molar ratio of the luminescent agent to the photosensitizer is 250-400: 1, preferably 350: 1; the concentration of the photosensitizer was 4 μ M.
The invention discloses an application of the photoluminescent system for treating neonatal jaundice in preparation of a material for treating neonatal jaundice; also discloses application of the photoluminescence device for treating neonatal jaundice in preparation of equipment for treating neonatal jaundice.
In the invention, the wavelength of excitation light of the photoluminescence system is 532nm, and the intensity of the excitation light is 500mW/cm2。
The hyperbilirubinemia (jaundice) of the newborn is one of common diseases in the newborn period, the incidence rate is high, and bilirubin encephalopathy induced by the hyperbilirubinemia seriously threatens the life and health of the newborn, so that the hearing disorder, the visual abnormality and the intelligence of the newborn are lagged behind, and serious people even die. The radiation light sources used in current phototherapy are mainly fluorescent lamps, halogen lamps and LED light sources. The fluorescent lamp has low illumination intensity and quick light attenuation, and the fluorescent lamp tube needs to be replaced regularly, so that the use is inconvenient; the halogen lamp can provide higher illumination intensity than a fluorescent lamp, but has wide radiation spectrum and ultraviolet and infrared bands, and the ultraviolet light irradiates the skin; the thermal effect generated by long-time irradiation of infrared light can cause the skin of a patient to lose water without dominance; although the blue light LED light source has a narrow spectrum (i.e. does not contain infrared and ultraviolet bands), the high intensity of the blue light LED lamp is easy to cause damage to human bodies.
The invention relates to a luminescent agent (A)p-DHMPA) is mixed with photosensitizer PdBrTPP and excited by 532nm semiconductor laser (500 mW/cm)2) The systemic luminescence can be applied to treating neonatal jaundice, namely, the bilirubin content in the neonatal body is reduced; the system is excited by long wavelength, the exciting light power is adjustable, the wave band is narrow, the influence of ultraviolet light and infrared light is avoided, the light intensity is moderate, and the illumination intensity is 500mW/cm in a 532 laser 2The following therapeutic effects are the best.
Drawings
Fig. 1 is a fluorescence spectrum of a photoluminescence system for treating neonatal jaundice under excitation of a 532nm semiconductor laser (wherein, a solid line is a photoluminescence system 1, and a dotted line is a photoluminescence system 2);
FIG. 2 is a diagram of a sample in which a cuvette containing the photoluminescence system 1 is placed in a glass bottle containing a bilirubin solution;
FIG. 3 is a schematic diagram of a photoluminescent system 1 which is immersed in a bilirubin solution and irradiated with a laser at 532 nm;
FIG. 4 is a graph of the molar absorption coefficient of bilirubin as a function of time under irradiation with blue light from photoluminescent System 1 (tested every 10 minutes);
FIG. 5 is a graph of the molar absorption coefficient of bilirubin as a function of time under irradiation with blue light from photoluminescent System 2 (tested every 10 minutes);
FIG. 6 is a graph of the change in bilirubin concentration with time under irradiation by blue light from photoluminescent system 1;
FIG. 7 is a graph of the change in bilirubin concentration with time under irradiation by blue light from photoluminescent system 2;
FIG. 8 is a diagram showing molar absorption coefficient spectra of bilirubin solutions as a function of concentration;
FIG. 9 is a graph of the molar absorption coefficient as a function of absorption for bilirubin at 454nm at various concentrations.
Detailed Description
The invention is further described below with reference to the following figures and examples:
in this example, the measurement of the UV-vis absorption spectrum was performed on a SHIMADZU UV2600 type UV spectrophotometer; the fluorescence spectra were measured on an Edinburgh FLS-920 type fluorescence spectrometer, respectively. The measurement conditions for the blue light spectrum were: selecting a SpectraScan PR655 spectrometer by using a 532nm semiconductor laser, wherein the specification of a cuvette is 1cm (length) multiplied by 1cm (width) multiplied by 3cm (height); the solvent of the photoluminescence system is spectrally pure n-propanol or DMSO, wherein an argon atmosphere is required in the n-propanol system, and the DMSO system does not need to remove oxygen and can be used in an air atmosphere. The bilirubin solution uses chloroform as a solvent.
Preparation example
The preparation method of the photoluminescence system for treating neonatal jaundice comprises the following steps of adding a luminescent agent and a photosensitizer into n-propanol, and mixing to obtain the photoluminescence system for treating neonatal jaundice, wherein the photoluminescence system is a luminescence system 1: p-DHMPA (1.4 mM)/PdBrTPP (4. mu.M)/n-propanol; in which the concentration of the photosensitizer was 4. mu.M and the concentration of the luminescent agent was 1.4mM, were used in the following examples.
The preparation method of the photoluminescence system for treating neonatal jaundice comprises the following steps of adding a luminescent agent and a photosensitizer into DMSO, and mixing to obtain the photoluminescence system for treating neonatal jaundice, wherein the photoluminescence system is a luminescence system 2: p-DHMPA (1.4 mM)/PdBrTPP (4. mu.M)/DMSO; in which the concentration of the photosensitizer was 4. mu.M and the concentration of the luminescent agent was 1.4mM, were used in the following examples.
The chemical structural formula of the luminescent agent p-DHMPA is as follows:
the chemical structural formula of the photosensitizer PdBrTPP is as follows:
532nm excitation (500 mW/cm)2) The spectrograms of the two photoluminescence systems for treating neonatal jaundice are shown in figure 1.
Example 1:
respectively preparing 1-5 mu M bilirubin solution: the solvent is trichloromethane, the trichloromethane is prepared in a lightproof brown bottle, and the trichloromethane is stored at low temperature in a lightproof manner after the preparation.
Adding the luminescent system 1 into a quartz cuvette, introducing argon for 15min to remove oxygen, and then screwing a cuvette cap to obtain the photoluminescent device for treating neonatal jaundice; a bilirubin chloroform solution (5. mu.M, 3 mL) was poured into another glass vial, and the cuvette was inserted into the glass vial (physical representation shown in FIG. 2).
Using a 532nm semiconductor laser (500 mW/cm)2) The photoluminescence system 1 in the cuvette was illuminated to give blue light emission (peak position at 434 nm, see solid line in FIG. 1), conversion efficiency was 26.8%, and blue light intensity was 19.4. mu.W/cm2∙ nm, the bilirubin can be subjected to photodegradation and photooxidation reaction; the physical diagram is shown in figure 3. The change in the absorption spectrum of bilirubin was measured every 10 minutes during irradiation, however, using the molar absorptivity as ordinate and the irradiation time (-2 hours) as abscissa, a plot was made to obtain FIG. 4.
Adding the luminescent system 2 into a quartz cuvette, and directly screwing a cuvette cap (without degassing to remove oxygen and containing oxygen in the cuvette) to obtain the photoluminescent device for treating neonatal jaundice; a bilirubin chloroform solution (5. mu.M, 3 mL) was poured into another glass vial, and the above cuvette was inserted into the glass vial. Using a 532 nm semiconductor laser (500 mW/cm)2) In an illuminated cuvettePhotoluminescent system 2, which emits blue light (peak position at 440 nm, see dashed line in fig. 1, lasting more than 2 hours); the conversion efficiency is 17.1 percent, and the blue light intensity is 12.0 mu W/cm2∙ nm, and can make bilirubin produce photodegradation and photooxidation reaction. The change of the absorption spectrum of bilirubin is tested every 10 minutes during irradiation, and a plot is made to obtain 5 with the molar absorption coefficient as ordinate and the irradiation time (-2 hours) as abscissa.
As can be seen from FIGS. 4 and 5, as the irradiation time is prolonged, a very weak absorption peak appears at 600-750 nm, indicating the generation of biliverdin; meanwhile, a strong absorption peak appears at 270 nm, which indicates that bilirubin is degraded to generate small molecules; more importantly, the absorption peak at 454 nm is continuously reduced, indicating that the bilirubin concentration gradually decreases and almost disappears.
FIG. 6 shows the change of bilirubin levels with irradiation time for the photoluminescent System 1. As can be seen from fig. 6, the bilirubin concentration slowly decreased with increasing exposure time. After continuous irradiation for 40min, the bilirubin concentration was reduced from 5.00. mu.M to 3.9. mu.M (at this time, the reduction rate was 1.36. mu.M/h), and the bilirubin concentration was rapidly reduced from 3.9. mu.M to 0.6. mu.M (at this time, the reduction rate was 4.34. mu.M/h) by continuing irradiation for 100 min, with an average reduction rate of 2.41. mu.M/h, which was greater than the reduction rate (average 2.19. mu.M/h) of the bilirubin solution irradiated with a halogen lamp as a radiation source. Further analysis shows that under the condition, the degradation rate of bilirubin is 90%, and the degradation rate of the system under the unit light intensity is 4.6% cm2∙nm/μW。
FIG. 7 is a graph showing the change of bilirubin concentration with irradiation time in the case of the photoluminescence system 2. As can be seen from fig. 7, as the irradiation time was prolonged, the concentration of bilirubin was slowly decreased; after 60 min of continuous irradiation, the bilirubin concentration was reduced from 5. mu.M to 3.22. mu.M (at a reduction rate of 1.78. mu.M/h), and the bilirubin concentration was reduced from 3.22. mu.M to 0.60. mu.M (at a reduction rate of 2.62. mu.M/h) for 120 min, with an average reduction rate of 2.20. mu.M/h. Further analysis revealed that the degradation rate of bilirubin was 84% under these conditions.
The absorption spectra of bilirubin solutions at various concentrations in the absence of light and their performance curves are shown in FIGS. 8 and 9.
Comparative example
The preparation method of the photoluminescence system comprises the following steps of adding a luminescent agent and a photosensitizer into an alcohol solvent, and mixing to obtain the photoluminescence system; wherein the concentration of the photosensitizer is 4 mu M, and the concentration of the luminescent agent is 1.4 mM; the selection of specific compounds and the degradation effect of bilirubin are shown in the following table 1, and the degradation test method of bilirubin is consistent with the examples (5 μ M is taken as an example, bilirubin chloroform solution).
The chemical structural formula of the DPA is as follows:
the chemical structural formula of the luminescent agent 2 is as follows:
the chemical structural formula of the PdTPP is as follows:
the concentration of the photosensitizer in the preparation example was adjusted to 10 μ M, the concentration of the luminescent agent was 1mM, and the remainder was unchanged to obtain a luminescent system, and the degradation rate of bilirubin was 80.8% by irradiation time of 100 minutes using the bilirubin degradation test method in the examples (5 μ M is a bilirubin chloroform solution in the examples).
The technical scheme of the invention at least has the following technical effects and advantages: the blue light phototherapy of the invention has good effect, the light intensity of the emitted light basically has no harm to human body, and the irradiation lasts for 2 hours, and the temperature of bilirubin solution is not increased; the blue light phototherapy radiation has narrow spectrum, is between 400 and 500nm, and has no influence of ultraviolet and infrared wave bands; 532nm excitation with long wavelength is adopted, 440nm emission and long wavelength excitation are adopted, a high-power excitation source is not needed, and the limitation is overcome; obviously, the luminophore system of the present invention has good degradation effect on bilirubin without harm to human body.
Claims (10)
1. The photoluminescence system for treating neonatal jaundice is characterized by comprising a luminous agent and a photosensitizer; the chemical structural formula of the luminescent agent is as follows:
the chemical structural formula of the photosensitizer is as follows:
2. the photoluminescence system for treating neonatal jaundice as recited in claim 1, wherein a molar ratio of the luminescent agent to the photosensitizer is 250-400: 1.
3. The photoluminescent system for treating neonatal jaundice according to claim 1, wherein the photoluminescent system for treating neonatal jaundice is composed of a luminescent agent, a photosensitizer, an alcohol solvent or a DMSO solvent; the concentration of the photosensitizer was 4 μ M.
4. The photoluminescence system for treating neonatal jaundice, according to claim 3, wherein the alcohol solvent is n-propanol.
5. The photoluminescence system for treating neonatal jaundice as recited in claim 1, wherein the photoluminescence system has an excitation light wavelength of 532nm and an excitation light intensity of 500mW/cm2。
6. The method of claim 1, comprising the step of mixing a luminescent agent and a photosensitizer in an alcohol solvent or a DMSO solvent to obtain the photoluminescent system for treating neonatal jaundice.
7. The use of the photoluminescent system for treating neonatal jaundice of claim 1 in the preparation of a material for treating neonatal jaundice.
8. Use according to claim 7, wherein the photoluminescent system has an excitation light wavelength of 532nm and an excitation light intensity of 500mW/cm2 。
9. The use according to claim 7, characterized in that the photoluminescent system for the treatment of neonatal jaundice consists of a luminescent agent, a photosensitizer, an alcoholic solvent or a DMSO solvent; the concentration of the photosensitizer is 4 mu M; the molar ratio of the luminescent agent to the photosensitizer is 250-400: 1.
10. The method for preparing the photoluminescence system for treating neonatal jaundice as recited in claim 6, wherein the molar ratio of the luminescent agent to the photosensitizer is 250-400: 1; the concentration of the photosensitizer is 4 mu M; the alcohol solvent is n-propanol.
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| CN105368444B (en) * | 2015-10-26 | 2017-08-11 | 苏州科技学院 | Converting system on a kind of efficient green dim light based on protonic solvent |
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2019
- 2019-11-29 CN CN201911207714.9A patent/CN111298112B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
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| "9,10-Di(hydroxymethylphenyl)anthracenes: Highly efficient triplet annihilators with small singlet-triplet energy gap (ΔEST) and planar configuration";Xue Yu等;《Dyes and Pigments》;20200108;第176卷;第108166-108172页 * |
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