Soft corneal contact lens for infrared color visual imaging, preparation method and detection method

By using tricolor orthogonal multi-shelled lanthanide nanoparticles NaErF4@NaYF4 and poly(2-hydroxyethyl methacrylate) to convert near-infrared light into visible light in soft corneal contact lenses, the problem of human beings being unable to directly identify near-infrared light is solved, and infrared color visual imaging and multi-spectral near-infrared light information are realized.

CN120028965APending Publication Date: 2025-05-23UNIV OF SCI & TECH OF CHINA
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Patent Information

Application Number
CN202510035772.7
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2025-01-09
Publication Date
2025-05-23

AI Technical Summary

Technical Problem

Humans cannot directly identify near-infrared light, and the prior art is difficult to achieve near-infrared light vision of multiple spectrums and the color discrimination ability of effectively detecting near-infrared light.

Method used

A soft corneal contact lens prepared by tricolor orthogonal multi-shelled lanthanide nanoparticles NaErF4@NaYF4 and poly(2-hydroxyethyl methacrylate) absorbs near-infrared light through the nanoparticles and converts it into visible light at different wavelengths, thereby achieving infrared color visual imaging.

Benefits of technology

It enhances the wearer's perception of infrared light, improves the wavelength and color range of infrared light recognition, and realizes the identification of multi-spectral near-infrared light information, and is suitable for biomedical imaging, infrared information transmission and other fields.

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Abstract

The invention provides a soft corneal contact lens for infrared color visual imaging. The soft corneal contact lens comprises three-color orthogonal multi-shell lanthanide nanoparticles NaErF4 and NaYF4 and poly (2-hydroxyethyl methacrylate), the mass concentration of the three-color orthogonal multi-shell lanthanide nanoparticles NaErF4 and NaYF4 ranges from 0.1% to 10%. The invention further provides a detection method in infrared vision multicolor imaging of the soft corneal contact lens for infrared color vision imaging. The detection method comprises the following steps: applying a plurality of composite infrared lights with a preset coding sequence to a person to be detected wearing the soft corneal contact lens, the composite infrared light is emitted through a pre-trained visible light-infrared color vision color mapping relation, and the preset coding sequence represents the combination sequence of the emission wavelength and the emission frequency of the composite infrared light; acquiring a first detection result obtained by identifying the plurality of composite infrared lights through the soft corneal contact lens by a person to be detected; and determining the color discrimination capability of the to-be-detected person on the multicolor near-infrared light according to the first detection result.
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Description

Technical Field

[0001] The invention relates to the field of infrared color vision and visual science detection, and in particular to a soft corneal contact lens for infrared color vision imaging, a preparation method and a detection method. Background Art

[0002] Imaging vision is one of the most important ways for organisms, including humans, to obtain information from the outside world. It plays an important role in their life activities, such as obtaining food, mating, distinguishing directions, and avoiding natural enemies. In imaging vision, color perception is one of the indispensable functions. The human retina has cones that can recognize three wavelengths, so it has a perfect three-color vision function. Through the perception of color, humans can obtain more key information. Humans cannot see infrared light, which is determined by the inherent physicochemical properties of photosensitive proteins in photoreceptor cells. For infrared light >700 nm, due to its low photon energy, if the light in this band is to be perceived, the photosensitive protein must lower the energy threshold, resulting in a lot of thermodynamic noise. Therefore, this limitation means that humans do not have the ability to directly recognize near-infrared light.

[0003] In order to expand the spectral range of mammalian imaging vision, related technologies use upconversion nanoparticles to convert infrared light into visible light, thereby realizing near-infrared image vision of mammals. However, the spectral range of near-infrared is very wide, and different spectra represent different color information. Therefore, a near-infrared vision that can realize multiple spectra and effectively detect the color discrimination ability of near-infrared vision is needed. Summary of the invention

[0004] In view of this, in order to at least partially solve at least one of the above-mentioned technical problems, the present invention provides a soft corneal contact lens for infrared color vision imaging, a preparation method and a detection method.

[0005] According to an embodiment of one aspect of the present invention, there is provided a soft corneal contact lens for infrared color vision imaging, comprising:

[0006] Three-color orthogonal multi-shell lanthanide nanoparticles NaErF 4 @NaYF 4 and poly(2-hydroxyethyl methacrylate);

[0007] Among them, the three-color orthogonal multi-shell lanthanide nanoparticles NaErF 4 @NaYF 4 The mass concentration is 0.1~10%.

[0008] According to another embodiment of the present invention, there is provided a method for preparing a soft corneal contact lens for infrared color vision imaging, comprising:

[0009] The tricolor orthogonal multi-shell lanthanide nanoparticles NaErF 4 @NaYF 4 adding into a monomer solution of poly(2-hydroxyethyl methacrylate) to obtain a mixed solution;

[0010] The mixed solution is added into a mold and irradiated with ultraviolet light to obtain a soft corneal contact lens for infrared color vision imaging.

[0011] According to another embodiment of the present invention, there is provided a detection method for infrared visual multi-color imaging of a soft corneal contact lens for infrared color visual imaging, comprising:

[0012] Applying multiple composite infrared lights with a preset coding sequence to a person to be tested who wears a soft corneal contact lens, wherein the composite infrared light is emitted through a pre-trained color mapping relationship of visible light-infrared color vision, and the preset coding sequence represents a combination sequence of emission wavelengths and emission frequencies of the composite infrared light;

[0013] Acquire a first detection result obtained by the person to be tested identifying multiple composite infrared lights through a soft corneal contact lens;

[0014] The color discrimination ability of the person to be tested for multi-color near-infrared light is determined according to the first detection result.

[0015] According to an embodiment of the present invention, by using three-color orthogonal multi-shell lanthanide nanoparticles NaErF 4 @NaYF 4 , and soft corneal contact lenses made of poly (2-hydroxyethyl methacrylate) with good biocompatibility can enhance the wearer's perception of infrared light. Er³⁺ ions have a rich energy level structure corresponding to the specific energy level transitions of Er³⁺ ions, which can absorb near-infrared light and emit light of different wavelengths, converting different spectra of infrared light into visible light of different colors, thereby realizing infrared color visual imaging, and have good biological safety, safe and comfortable to wear, and can be widely used in the recognition and transmission of multi-color imaging information of infrared light, improving the wavelength and color range of infrared light recognition, and identifying multi-spectrum near-infrared light information. It can be applied to biomedical imaging, infrared information transmission such as display, anti-counterfeiting, encoding and decoding and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The above and other objects, features and advantages of the present invention will become more apparent through the following description of the embodiments of the present invention with reference to the accompanying drawings, in which:

[0017] Figure 1A schematic diagram of the conversion of a soft corneal contact lens for infrared color vision imaging according to an embodiment of the present invention;

[0018] Figure 2 The present invention is a flow chart of the preparation of a soft corneal contact lens according to an embodiment of the present invention;

[0019] Figure 3 A schematic diagram of a method for training a color mapping relationship between visible light and infrared color vision according to an embodiment of the present invention;

[0020] Figure 4 This is a diagram showing the training result of the color mapping relationship between visible light and infrared color vision according to an embodiment of the present invention;

[0021] Figure 5 This is a diagram showing the basic three-color discrimination test results of near-infrared light for a person wearing a soft corneal contact lens according to an embodiment of the present invention;

[0022] Figure 6 This is a diagram showing the detection results of six-color near-infrared light discrimination of a person wearing a soft corneal contact lens according to an embodiment of the present invention;

[0023] Figure 7 This is a diagram showing the results of near-infrared light coding sequence detection for a person wearing a soft corneal contact lens according to an embodiment of the present invention. DETAILED DESCRIPTION

[0024] Below, embodiments of the present invention will be described with reference to the accompanying drawings. However, it should be understood that these descriptions are exemplary only and are not intended to limit the scope of the present invention. In the following detailed description, for ease of explanation, many specific details are set forth to provide a comprehensive understanding of embodiments of the present invention. However, it is apparent that one or more embodiments may also be implemented without these specific details. In addition, in the following description, descriptions of known structures and technologies are omitted to avoid unnecessary confusion of concepts of the present invention.

[0025] The terms used herein are only for describing specific embodiments and are not intended to limit the present invention. The term "comprising" used herein indicates the existence of features, steps, operations, but does not exclude the existence or addition of one or more other features.

[0026] In the case of using expressions such as "at least one of A, B, and C, etc.", it should generally be interpreted in accordance with the meaning of the expression generally understood by those skilled in the art (for example, "a system having at least one of A, B, and C" should include but is not limited to a system having A alone, B alone, C alone, A and B, A and C, B and C, and / or A, B, C, etc.). In the case of using expressions such as "at least one of A, B, or C, etc.", it should generally be interpreted in accordance with the meaning of the expression generally understood by those skilled in the art (for example, "a system having at least one of A, B, or C" should include but is not limited to a system having A alone, B alone, C alone, A and B, A and C, B and C, and / or A, B, C, etc.).

[0027] In the process of realizing the concept of the present invention, it was found that the use of three-color fusion upconversion nanoparticles can convert near-infrared light of different wavelengths into three colors of visible light. Combining the characteristics of soft corneal contact lenses that are widely used and non-invasive in life, upconversion nanoparticles are integrated into the preparation materials of soft corneal contact lenses, and color imaging of near-infrared light can be achieved by wearing soft corneal contact lenses.

[0028] Specifically, according to an embodiment of one aspect of the present invention, there is provided a soft corneal contact lens for infrared color vision imaging, comprising:

[0029] Three-color orthogonal multi-shell lanthanide nanoparticles NaErF 4 @NaYF 4 and poly(2-hydroxyethyl methacrylate);

[0030] Among them, the three-color orthogonal multi-shell lanthanide nanoparticles NaErF 4 @NaYF 4 The mass concentration is 0.1~10%.

[0031] According to an embodiment of the present invention, the three-color orthogonal multi-shell lanthanide nanoparticles NaErF 4 @NaYF 4 The mass concentration can be 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0032] According to an embodiment of the present invention, by using three-color orthogonal multi-shell lanthanide nanoparticles NaErF 4 @NaYF 4, and soft corneal contact lenses made of poly (2-hydroxyethyl methacrylate) with good biocompatibility can enhance the wearer's perception of infrared light. Er³⁺ ions have a rich energy level structure corresponding to the specific energy level transitions of Er³⁺ ions, which can absorb near-infrared light and emit light of different wavelengths, converting different spectra of infrared light into visible light of different colors, thereby realizing infrared color visual imaging, and have good biological safety, safe and comfortable to wear, and can be widely used in the recognition and transmission of multi-color imaging information of infrared light, improving the wavelength and color range of infrared light recognition, and identifying multi-spectrum near-infrared light information. It can be applied to biomedical imaging, infrared information transmission such as display, anti-counterfeiting, encoding and decoding and other fields.

[0033] Specifically, the soft corneal contact lens for infrared color vision imaging of the present invention can convert near-infrared light with wavelengths of 980nm, 808nm, and 1532nm into visible light of multiple wavelengths, such as Figure 1 shown.

[0034] Figure 1 Schematic diagram of the conversion of a soft corneal contact lens for infrared color vision imaging according to an embodiment of the present invention.

[0035] According to an embodiment of the present invention, the three-color orthogonal multi-shell lanthanide nanoparticles NaErF 4 @NaYF 4 Including NaErF 4 nanoparticles, as core; and, NaYF 4 Epitaxial layer, covering the surface of the core; NaErF 4 Nanoparticles and NaYF 4 The molar ratio of the epitaxial layer is (0.8~1.2):(1.8~2.5).

[0036] According to an embodiment of the present invention, NaErF 4 Nanoparticles and NaYF 4 The molar ratio of the epitaxial layer can be 0.8:1.8, 1:1.8, 1.2:1.8, 0:8:2, 1:2, 1.2:2, 0:8:2.5, 1:2.5, 1.2:2.5, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0037] According to an embodiment of the present invention, NaErF 4 Nanoparticles can emit visible light under the stimulation of near-infrared light, and the multi-shell structure can further optimize the luminescence characteristics and achieve multi-color luminescence. The design of the core-shell structure can effectively improve the upconversion luminescence efficiency. 4 The epitaxial layer can effectively improve the NaErF 4Upconversion luminescence efficiency of nanoparticle core, NaYF 4 With lower phonon energy, non-radiative attenuation can be reduced, thereby improving luminescence efficiency. 4 and NaYF 4 By adjusting the molar ratio of 2-H-2O, the luminescent color can be precisely controlled, the luminescent performance can be optimized, and the desired color output can be achieved. The size and dispersibility of the final nanoparticles can also be optimized by controlling the molar ratio, thereby preparing uniform soft corneal contact lenses.

[0038] According to another embodiment of the present invention, there is provided a method for preparing a soft corneal contact lens for infrared color vision imaging, comprising steps S1 to S2:

[0039] Step S1: Tricolor orthogonal multi-shell lanthanide nanoparticles NaErF 4 @NaYF 4 adding into a monomer solution of poly(2-hydroxyethyl methacrylate) to obtain a mixed solution;

[0040] Step S2: adding the mixed solution into a mold and molding it by ultraviolet light to obtain a soft corneal contact lens for infrared color vision imaging.

[0041] According to an embodiment of the present invention, the three-color orthogonal multi-shell lanthanide nanoparticles NaErF 4 @NaYF 4 By adding it to the polymer monomer solution, the nanoparticles can be evenly dispersed in the polymer matrix, and then the molding method using ultraviolet light irradiation is simple, efficient, easy to control, and conducive to large-scale production and commercialization.

[0042] According to an embodiment of the present invention, lanthanide core-shell nanoparticles, tri-color orthogonal multi-shell lanthanide nanoparticles NaErF 4 @NaYF 4 The synthesis methods include:

[0043] Erbium chloride, oleic acid and octadecene are mixed, heated and then an alkali agent is added to obtain an alkali mixed solution;

[0044] Add NH 4 F was heated, stirred and cooled to obtain NaErF 4 Nanoparticles;

[0045] NaErF 4 Nanoparticles were prepared by epitaxial growth method with NaYF 4 Lanthanide core-shell nanoparticles with three-color orthogonal multi-shell lanthanide nanoparticles NaErF 4 @NaYF 4 .

[0046] According to an embodiment of the present invention, an epitaxial growth method can be used to grow NaErF 4 Uniform and continuous NaYF 4 Shell, which can improve the stability and optical properties of nanoparticles; NaYF 4 The outer shell has lower optical phonon energy, which can effectively reduce non-radiative transitions and thus improve the NaErF 4 The upconversion luminescence efficiency of the core and NaYF 4 The shell can protect the NaErF 4 The core is protected from the influence of the external environment, which improves the chemical stability of the nanoparticles and extends their service life; the use of surfactants such as oleic acid and octadecene helps to improve the dispersibility of the nanoparticles and prevent agglomeration, which is beneficial for subsequent applications; core-shell structured nanoparticles can be synthesized through a few simple steps, which simplifies the synthesis process and reduces the difficulty of operation.

[0047] According to an embodiment of the present invention, NaErF 4 Nanoparticles were prepared by epitaxial growth method with NaYF 4 Lanthanide core-shell nanoparticles with three-color orthogonal multi-shell lanthanide nanoparticles NaErF 4 @NaYF 4 include:

[0048] To NaErF 4 Sodium trifluoroacetate, yttrium trifluoroacetate, oleic acid and octadecene are added to the nanoparticles and heated to obtain a precursor solution;

[0049] Heat the precursor solution to 250-300°C and maintain for 50-70 minutes;

[0050] The heated precursor solution was cooled and centrifuged to obtain NaYF 4 Lanthanide core-shell nanoparticles with three-color orthogonal multi-shell lanthanide nanoparticles NaErF 4 @NaYF 4 .

[0051] According to an embodiment of the present invention, the precursor solution can be heated to 250°C, 260°C, 270°C, 280°C, 290°C, and 300°C, but are not limited to the listed values, and other unlisted values ​​within the numerical range are equally applicable; the holding time can be 50 minutes, 55 minutes, 60 minutes, 65 minutes, and 70 minutes, but is not limited to the listed values, and other unlisted values ​​within the numerical range are equally applicable.

[0052] According to an embodiment of the present invention, the precursor solution can be heated at a temperature range of 250-300°C to promote the synthesis of NaYF. 4 In NaErF4 The epitaxial growth of the nanoparticle surface forms a uniform and dense shell layer. By adjusting the heating time and temperature, the NaYF 4 The thickness of the outer shell layer can optimize the luminescence properties of the nanoparticles; epitaxially grown NaYF 4 The shell can reduce the core NaErF 4 Surface defects of nanoparticles, reducing non-radiative attenuation, improving upconversion luminescence efficiency, lanthanide core-shell nanoparticles, tri-color orthogonal multi-shell lanthanide nanoparticles, NaErF 4 @NaYF 4 The preparation steps are clear, the conditions are controllable, and it has good repeatability, which is conducive to large-scale production.

[0053] According to an embodiment of the present invention, a method for preparing a monomer solution of poly(2-hydroxyethyl methacrylate) comprises:

[0054] Ethylene glycol dimethacrylate is immersed in 2-hydroxyethyl methacrylate, and then 2-hydroxy-2-methylpropenone is added, and the mixture is stirred in a dark environment to obtain a monomer solution of poly(2-hydroxyethyl methacrylate).

[0055] According to an embodiment of the present invention, by immersing the cross-linking agent ethylene glycol dimethacrylate into 2-hydroxyethyl methacrylate and adding the photoinitiator 2-hydroxy-2-methylpropenone, a polymer monomer solution that can be cross-linked under ultraviolet light to form a network can be prepared, which can be used to prepare structurally stable soft corneal contact lenses subsequently; stirring the monomer solution in a dark environment can prevent the occurrence of prepolymerization and ensure that the polymerization reaction starts only when ultraviolet light is irradiated, thereby better controlling the polymerization process, and the prepared poly (2-hydroxyethyl methacrylate) has good biocompatibility and is suitable for preparing products that come into contact with the human body.

[0056] According to another embodiment of the present invention, there is provided a detection method for infrared visual multi-color imaging of a soft corneal contact lens for infrared color visual imaging, comprising:

[0057] Applying multiple composite infrared lights with a preset coding sequence to a person to be tested who wears a soft corneal contact lens, wherein the composite infrared light is emitted through a pre-trained color mapping relationship of visible light-infrared color vision, and the preset coding sequence represents a combination sequence of emission wavelengths and emission frequencies of the composite infrared light;

[0058] Acquire a first detection result obtained by the person to be tested identifying multiple composite infrared lights through a soft corneal contact lens;

[0059] The color discrimination ability of the person to be tested for multi-color near-infrared light is determined according to the first detection result.

[0060] According to an embodiment of the present invention, the pre-trained color mapping relationship of visible light-infrared color vision refers to a function or model, or can be understood as a corresponding relationship, which maps a specific wavelength or frequency of infrared light to a specific color in the visible spectrum. For example, the ratio of the three RGB colors of red, green, and blue in visible light can reflect all the colors of human visible light. Similarly, based on the corresponding three basic wavelengths RGB infrared light, adjusting the ratio of the three infrared light RGB can achieve the color expression within the infrared light wavelength range, and then converting the infrared light into visible light can achieve colorful infrared light imaging. The emission wavelength refers to the wavelength of different infrared composite light, for example, it can be 980nm, 1532nm, etc. The emission frequency refers to the emission frequency that conforms to the infrared light, such as 1 Hz, 2 Hz, 4 Hz, or once every 20 seconds, once every 5 seconds, etc. The preset coding sequence refers to the emission sequence of composite infrared light of different wavelengths or can be understood as composite infrared light of different colors. Different frequencies can be further set on the basis of the set sequence to achieve more combinations of coding sequences, i.e., composite infrared light information. For example, three composite infrared light colors are designed through the three words of subject, predicate, and object, and different emission frequencies are involved according to the specific content of the words, and then the results of the sentence formation of the subject, predicate, and object by the person under test are examined, thereby obtaining the test results of the person under test's near-infrared color recognition ability.

[0061] According to an embodiment of the present invention, by applying composite infrared light with a preset coding sequence, the wearer can identify the color of infrared light through a soft corneal contact lens, thereby realizing color visual imaging of infrared light. By using the pre-trained color mapping relationship of visible light-infrared color vision, the color discrimination ability of the person to be tested for multi-color near-infrared light is improved. By obtaining the recognition result of the person to be tested for the composite infrared light, the person's color perception ability for infrared light can be accurately and objectively evaluated. Moreover, the use of the preset coding sequence makes it possible to flexibly adjust and optimize the emission wavelength and frequency of infrared light to adapt to different detection needs and scenarios, as well as to transmit more types of color near-infrared information.

[0062] According to an embodiment of the present invention, the first detection result includes an identification code sequence. When the identification code sequence matches a preset code sequence, it is determined that the person to be tested has the ability to distinguish the colors of multi-color near-infrared light.

[0063] According to an embodiment of the present invention, the preset coding sequence includes the color of the composite infrared light converted into visible light and the emission frequency of the composite infrared light; the identification of the coding sequence also includes the color of the composite infrared light converted into visible light and the emission frequency of the composite infrared light. Therefore, the matching situation refers to the situation where both the sequence and frequency of the composite infrared light match. For example, if the color recognition is correct but the frequency recognition is wrong, it is a mismatch.

[0064] According to an embodiment of the present invention, the identification of the first detection result provides an objective method to evaluate the color discrimination ability of the person to be tested for infrared light, rather than relying on subjective description, to accurately judge the color discrimination ability of the person to be tested and reduce the possibility of misjudgment. The color recognition ability test of multi-color infrared can be standardized, so that the results between different tests are comparable, which helps to establish a unified evaluation standard.

[0065] According to an embodiment of the present invention, a method for training a color mapping relationship of visible light-infrared color vision includes:

[0066] Apply multiple monochromatic visible lights and three wavelengths of composite infrared light to the test person wearing a soft corneal contact lens;

[0067] By adjusting the light intensity ratio of the three wavelengths of infrared light in the three wavelengths of infrared mixed light to match the monochromatic visible light observed by the person to be tested, multiple infrared light color matching results are obtained;

[0068] According to the multiple infrared light color matching results, the color mapping relationship of visible light-infrared color vision is determined.

[0069] According to an embodiment of the present invention, since the color perception of different persons to be tested may differ, a personalized color mapping relationship can be established for each individual through training. By carefully adjusting the intensity ratio of infrared light, a high-precision match with the color of visible light can be achieved. The mapping relationship obtained through training can be applied to a variety of infrared imaging systems to improve their visualization effects. Moreover, based on the obtained mapping relationship, information transmission of any infrared color can be achieved through a model or functional relationship of the mapping relationship. By converting infrared information into visible light color, the range of human visual perception can be expanded, especially at night or in low light conditions.

[0070] According to an embodiment of the present invention, the plurality of monochromatic visible lights all have the same optical power.

[0071] According to an embodiment of the present invention, the brightness and intensity of each monochromatic visible light are controlled at a uniform level, ensuring that the optical power is not a variable when comparing the matching of visible light of different colors with infrared light, thereby eliminating the influence of the optical power difference on the experimental results, thereby standardizing the experimental conditions; since the optical power of all monochromatic visible lights is the same, the person being tested does not need to consider the change in light intensity when perceiving color, which helps to simplify the process of infrared light color matching; keeping the optical power consistent can reduce experimental errors, making the infrared light color matching result, that is, the established mapping relationship, more accurate and reliable.

[0072] The scheme of the present invention will be explained below with reference to specific embodiments. If there is no special explanation, conventional commercial reagents are used.

[0073] In the following embodiments, the term "resolution coefficient" refers to the resolution accuracy, which is calculated by subtracting the probability of random judgment correct events from the proportion of all correct ones. The expected accuracy of random judgment is (100 / n)%, where "n" represents the number of choices. The resolution coefficient formula is (subject response accuracy - (100 / n)%) / (100% - (100 / n)%).

[0074] Example 1 Synthesis of tricolor orthogonal multishell lanthanide nanoparticles (tUCNPs)

[0075] 1mmol of erbium chloride (ErCl 3 6H 2 O) was mixed with 6 mL of oleic acid (OA) and 15 mL of octadecene (ODE) in a 100 mL three-necked round-bottom flask equipped with a Schlenk line and a thermocouple temperature sensor. The mixture was then heated to 140 °C and maintained at this temperature for 60 min to remove the remaining water. After the mixture was cooled to room temperature, 5 mL of CH 3 2.5 mmol of NaOH (100 mg) in OH was added and stirred for 30 min, then the mixture was heated to 100 °C, the methanol was removed in vacuo, and cooled to room temperature to obtain a base mixture.

[0076] Add 10 mL CH 3 4mmol 148mg NH in OH 4 F, stirred for another 30 min, and then heated to 100 °C under vacuum to remove methanol and residual water. The transparent solution was heated to 300 °C for 60 min under a gentle argon flow at a heating rate of 10 °C / min. After the reaction system was cooled to room temperature, the synthesized nanoparticles were centrifuged, washed three times with cyclohexane / ethanol in a volume ratio of 1:1, and finally dispersed in 10 mL of cyclohexane for use to obtain NaErF 4 Nanoparticles.

[0077] 0.2 mmol NaErF in cyclohexane 4Nanoparticles were used as seeds, and 0.4 mmol Na-TFA and 0.4 mmol Y-TFA were added as precursor solutions for epitaxial growth of the NaYF4 shell. 3.2 mL OA and 4.8 mL ODE were added, heated to 100 ° C, and cyclohexane and other residues were removed in vacuo. Then, the mixture was heated to 300 ° C for 60 min under a gentle argon flow with a heating rate of 10 ° C / min. After the reaction system was cooled to room temperature, the synthesized nanoparticles were centrifuged, washed three times with cyclohexane / ethanol in a volume ratio of 1: 1, and finally dispersed in 2 ml cyclohexane for use. The lanthanide trifluoroacetate was synthesized by mixing lanthanide oxides with lanthanum trifluoroacetate, and the lanthanide core-shell nanoparticles were prepared by conventional epitaxial growth method. Three-color orthogonal multi-shell lanthanide nanoparticles NaErF 4 @NaYF 4 .

[0078] Example 2 Synthesis of poly(2-hydroxyethyl methacrylate) (pHEMA)

[0079] 0.085 g of ethylene glycol dimethacrylate was immersed in 4 mL of 2-hydroxyethyl methacrylate. Then, 3 mL of deionized water and 0.085 g of 2-hydroxy-2-methylpropenone were gradually added. Stirring was carried out in the dark for 30 minutes, and finally the pHEMA monomer suspension was sealed to avoid visible light.

[0080] Example 3 Preparation of soft corneal contact lenses

[0081] Figure 2 The present invention is a flow chart of the preparation of soft corneal contact lenses according to an embodiment of the present invention.

[0082] Preparation process Figure 2 As shown, the tUCNPs of Example 1 are added to the monomer solution of Example 2 and subjected to ultrasonic treatment. Then, it is immersed in a silicon wafer or a contact lens mold and irradiated with 365nm ultraviolet light for 20 minutes to catalyze the reaction. The film or contact lens is further peeled off from the silicon wafer or mold and washed with DI water / ethanol solution with a volume ratio of 1:1 at 50°C for 10 hours to remove the unreacted monomers, thereby obtaining a soft corneal contact lens, i.e., a trichromatic upconversion contact lens.

[0083] Example 4 Training method for color mapping relationship between visible light and infrared color vision of a person wearing soft corneal contact lenses

[0084] Figure 3 Schematic diagram of a method for training the color mapping relationship of visible light-infrared color vision according to an embodiment of the present invention.

[0085] like Figure 3As shown, the subjects were asked to observe the circular frosted plate in front of them within a visual angle of 2°, on which pHEMA material without tUCNPs and pHEMA material fused with tUCNPs (tUCLs) were adhered respectively.

[0086] Visible light color test: A round frosted plate is evenly divided into two parts by a black vertical partition. A series of monochromatic LED lights in the range of 400-700 nanometers are used to illuminate one side of the round plate, and a composite light composed of red (R), green (G), and blue (B) light is illuminated on the other side of the round plate; an integrating sphere is used to ensure uniform LED light.

[0087] Three monochromatic LED lamps are used as adjustable composite light, including three primary colors R: 654nm; G: 543 nm; B: 452 nm, which is convenient for color matching with a single monochromatic LED.

[0088] Among them, when the composite light cannot match some monochromatic LED light, a compensating primary color light, mainly red (R), is added to the monochromatic LED part. The brightness of the compensating light is displayed as a negative value on the tristimulus diagram. By slowly adjusting the brightness of the compensating light and the composite light, the colors on the two panels are matched in the eyes of the person under test.

[0089] Near-infrared color test: The composite light composed of three lasers with wavelengths of 1532 nm, 808 nm, and 980 nm is adjusted to achieve color matching with the monochromatic LED. The three types of lasers are combined into a single laser beam using a fiber beam combiner and amplified into a uniform, coherent light spot using a beam expander to ensure consistent optical performance.

[0090] The combined laser beam can be up-converted into composite light of red (R), green (G), and blue (B) through the planar tUCL. To ensure the safe use of the laser, we closely attach a near-infrared cutoff filter with visible light transmittance to the outside of the planar tUCL.

[0091] In the near-infrared color matching experiment, compensating primary color light is added to the monochromatic LED part. In order to determine the spectral tristimulus curve of the RGB color space and the color mapping of human visible light and near-infrared color vision, the light power intensity of each monochromatic LED lamp is 5 nW / mm 2 At the same time, the relevant brightness and chromaticity values ​​of a series of monochromatic and composite lights are measured using a spectrochromatic meter.

[0092] Figure 4 This is a diagram showing the training results of the color mapping relationship between visible light and infrared color vision according to an embodiment of the present invention.

[0093] according to Figure 4It can be seen that the corresponding curve of the three stimulus values ​​of the person under test when using visible light for color matching and the corresponding chromaticity diagram coordinates of the visible light identified by the person under test are close to the corresponding curve of the three stimulus values ​​of the person under test when using near-infrared light for color matching and the corresponding chromaticity diagram coordinates of the near-infrared light identified by the person under test, which proves that after wearing soft corneal contact lenses, multiple colors of composite near-infrared light can be identified and distinguished, and the color threshold range similar to visible light can be perceived. Furthermore, by establishing a good mapping relationship, the transmission of color infrared light information of more than 6 colors can be achieved.

[0094] Example 5 Testing of the Perception Ability of Near-Infrared Light Information of a Person Wearing Soft Contact Lenses

[0095] Basic identification sequence test: The test subjects are required to identify three primary colors - red, green and blue. The corresponding NIR RGB output wavelengths are 1532 nm, 808 nm and 980 nm respectively. Six groups of RGB sequences appear randomly 30 times. After 5 observations in each group, the test subjects need to make a judgment on the RGB sequence. The results are as follows: Figure 5 shown.

[0096] Six-color sequence discrimination test: According to the color matching experiment of Example 4, six colors of red, yellow, green, cyan, blue and purple are used to encode different letters. The test subject needs to distinguish the order of eight letters according to the content of near-infrared light stimulation. The results are as follows: Figure 6 shown.

[0097] Figure 5 This is a diagram showing the basic three-color discrimination test results of near-infrared light for a person wearing a soft corneal contact lens according to an embodiment of the present invention; Figure 6 This is a graph showing the test results of six-color discrimination of near-infrared light by a person wearing a soft corneal contact lens according to an embodiment of the present invention.

[0098] according to Figure 5 and Figure 6 It can be seen that the test subjects wearing soft corneal contact lenses can achieve a high accuracy rate, close to 100%, in distinguishing the basic order of near-infrared colors. Therefore, it can be proved that by wearing the soft corneal contact lenses for infrared color visual imaging of the present invention, multiple colors of infrared light can be effectively identified.

[0099] Coding order detection: In the discrimination experiment of near-infrared color and time coding information, six colors encode different words, including different types of subject and predicate words, and three colors and different time frequencies of 1 Hz, 2 Hz, and 4 Hz encode target words. The flashing time of the subject and predicate words is 1000 ms, while the flashing time of each object word is 1000 ms, with a duty cycle of 50%. The corresponding words can be used to encode a complete sentence.

[0100] The test subjects first learn the content of the coded information and make judgments. 63 sentences, each of which appears 5 times randomly, 315 times. The test results are as follows Figure 7 shown.

[0101] Figure 7 This is a diagram showing the results of near-infrared light coding sequence detection for a person wearing a soft corneal contact lens according to an embodiment of the present invention.

[0102] according to Figure 7 It can be seen that after wearing soft contact lenses, the subjects can identify and distinguish multiple colors of composite near-infrared light, and can reintegrate and retransmit information according to the order of perceived color information; in all color-related behavioral experiments, the light power intensity of the three primary colors in different composite colors is the associated light power intensity in the color matching experiment. When the subjects clearly perceive the near-infrared light, they can answer the near-infrared information corresponding to the stimulus. Therefore, the accuracy of answering when wearing soft contact lenses is extremely high, while those who do not wear soft contact lenses cannot feel the transmission of near-infrared light information and cannot give correct answers to the stimulus content. The near-infrared light power intensity on the cornea is less than 10 7 Photons / m 2 / s; the flash duration of each color was 1000 ms. Two-tailed t-test, ns indicates no significant difference; *** indicates p < 0.001.

[0103] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A soft corneal contact lens for infrared color vision imaging, comprising: tricolor orthogonal multishell lanthanide nanoparticles NaErF4@NaYF4 and poly(2-hydroxyethyl methacrylate); Wherein, the mass concentration of the three-color orthogonal multi-shell lanthanide nanoparticles NaErF4@NaYF4 is 0.1~10%.

2. The three-color orthogonal multi-shell lanthanide nanoparticles NaErF4@NaYF4 include NaErF4 nanoparticles as a core; and a NaYF4 epitaxial layer coated on the surface of the core; the molar ratio of the NaErF4 nanoparticles to the NaYF4 epitaxial layer is (0.8~1.2): (1.8~2.5).

3. A method for preparing the soft corneal contact lens for infrared color vision imaging as claimed in claim 1, comprising: adding the three-color orthogonal multi-shell lanthanide nanoparticles NaErF4@NaYF4 into a monomer solution of poly(2-hydroxyethyl methacrylate) to obtain a mixed solution; The mixed solution is added into a mold and molded by ultraviolet light irradiation to obtain the soft corneal contact lens for infrared color vision imaging.

4. The preparation method according to claim 3, wherein The synthesis method of the lanthanide core-shell nanoparticle tricolor orthogonal multi-shell lanthanide nanoparticle NaErF4@NaYF4 comprises: Erbium chloride, oleic acid and octadecene are mixed, heated and then an alkali agent is added to obtain an alkali mixed solution; Adding NH4F to the alkali mixture, heating and stirring, and then cooling to obtain NaErF4 nanoparticles; The NaErF4 nanoparticles are prepared by an epitaxial growth method to obtain lanthanide core-shell nanoparticles with NaYF4 as the shell, tricolor orthogonal multi-shell lanthanide nanoparticles NaErF4@NaYF4.

5. The preparation method according to claim 4, wherein: The method of preparing the NaErF4 nanoparticles by epitaxial growth to obtain lanthanide core-shell nanoparticles with NaYF4 as the shell and tricolor orthogonal multi-shell lanthanide nanoparticles NaErF4@NaYF4 comprises: Adding sodium trifluoroacetate, yttrium trifluoroacetate, oleic acid and octadecene to the NaErF4 nanoparticles, and heating to obtain a precursor solution; The precursor solution is heated to 250-300° C. and maintained at this temperature for 50-70 minutes; The heated precursor solution was cooled and centrifuged to obtain lanthanide core-shell nanoparticles with NaYF4 as the shell and three-color orthogonal multi-shell lanthanide nanoparticles NaErF4@NaYF4.

6. The preparation method according to claim 3, wherein: The preparation method of the monomer solution of poly(2-hydroxyethyl methacrylate) comprises: Ethylene glycol dimethacrylate is immersed in 2-hydroxyethyl methacrylate, and then 2-hydroxy-2-methylpropenone is added, and the mixture is stirred in a dark environment to obtain a monomer solution of poly(2-hydroxyethyl methacrylate).

7. A detection method in infrared visual multi-color imaging based on the soft corneal contact lens for infrared color visual imaging according to claim 1, comprising: Applying a plurality of composite infrared lights with a preset coding sequence to a person to be tested who wears the soft corneal contact lens, wherein the composite infrared lights are emitted through a pre-trained color mapping relationship of visible light-infrared color vision, and the preset coding sequence represents a combination sequence of emission wavelengths and emission frequencies of the composite infrared lights; Acquire a first detection result obtained by the person to be tested recognizing a plurality of the composite infrared lights through the soft corneal contact lens; The color discrimination ability of the person to be tested for the multi-color near-infrared light is determined according to the first detection result.

8. The detection method according to claim 7, wherein: The training method of the color mapping relationship of the visible light-infrared color vision comprises: Applying a plurality of monochromatic visible lights and composite infrared lights of three wavelengths to the person to be tested who wears the soft corneal contact lens; By adjusting the light intensity ratio of the three wavelengths of infrared light in the three wavelengths of infrared mixed light so as to match the monochromatic visible light observed by the person to be tested, a plurality of infrared light color matching results are obtained; The color mapping relationship of the visible light-infrared color vision is determined according to the multiple infrared light color matching results.

9. The detection method according to claim 8, wherein: The multiple monochromatic visible lights all have the same optical power.

10. The detection method according to claim 7, wherein: The first detection result includes an identification coding sequence. When the identification coding sequence matches the preset coding sequence, it is determined that the person to be tested has the ability to distinguish the colors of multi-color near-infrared light.