Preparation method and application of corneal contact lens

Abstract

The invention discloses a preparation method and application of a corneal contact lens. The preparation method specifically comprises the following steps: (1) preparing a high polymer material nanofiber web; (2) preparing a nano-metal modified fiber net; (3) preparing a nano-metal modified fiber mesh counter electrode, a nano-metal modified fiber mesh working electrode and a nano-metal modified fiber mesh reference electrode; (4) preparing a nano-enzyme modified nano-metal fiber mesh working electrode; (5) preparing a silver / silver chloride modified nano metal fiber mesh reference electrode; (6) preparing a hydrogel film; and (7) completing the preparation of the electrode assembly on the contact lens. And (8) the copper inductance coil, the NFC communication chip and the electrode assembly are connected and integrated on the contact lens to obtain the contact lens. According to the invention, comprehensive application of biological monitoring, wireless transmission and flexible materials is realized, an intelligent contact lens product is formed, and a novel solution is provided for real-time health monitoring.

Description

Technical Field

[0001] The present invention relates to the technical fields of material synthesis, device assembly, and human index detection, and more particularly to a preparation method and application of a contact lens. Background Art

[0002] Reactive Oxygen Species (ROS) are highly reactive molecules generated during physiological processes, commonly found in metabolic reactions, inflammatory reactions, and after ultraviolet irradiation. Ocular tissues are prone to generating ROS under the action of the external environment and their own metabolism, especially under ultraviolet exposure and oxidative stress conditions. ROS can trigger oxidative damage to ocular tissues, damaging the functions of corneal, lens, and retinal cells. Ocular ROS can directly damage corneal epithelial cells and lens proteins, leading to corneal inflammation, lens opacity, and retinal dysfunction, and in severe cases, can cause dry eye, glaucoma, cataract, macular degeneration, and even vision loss. In addition, ROS can also promote apoptosis and accelerate the aging process of the eye. Long-term accumulation of ROS may trigger chronic inflammatory reactions and even increase the risk of certain ocular tumors.

[0003] Currently, the detection methods for ocular ROS mainly include chemical fluorescence method, chemiluminescence method, electron paramagnetic resonance spectroscopy, and electrochemical detection method, etc. However, the above methods have cumbersome operation processes, require expensive and complex equipment, and cannot perform real-time non-invasive detection of the eye. When collecting tears for detection, it is impossible to ensure the accurate content of tears, which may lead to a decrease in the accuracy of the results.

[0004] Meanwhile, the elimination of ocular ROS usually adopts eye drops such as vitamins, or by ingesting carotenoids, polyphenolic compounds, etc. However, the bioavailability of vitamin eye drops is limited and it is difficult to effectively reach the ocular target. In addition, high doses of vitamins may produce side effects, causing ocular discomfort or systemic reactions. While carotenoids and polyphenolic compounds have low absorption rates, poor biological stability, and fast metabolism in the body.

[0005] In summary, the increase in ocular reactive oxygen species (ROS) is closely related to the occurrence of various ocular diseases (such as dry eye, glaucoma, cataract, macular degeneration, etc.). There is a lack of effective and convenient methods in the prior art for real-time detection of the concentration of ocular ROS and means for actively scavenging ROS under ocular oxidative stress conditions. In addition, traditional ocular treatment methods often rely on topical medications or supplements, and these methods have limitations in terms of efficacy, compliance, and safety, making it difficult to meet the growing ocular health needs.

[0006] Therefore, how to develop a safe, stable, accurate, and efficient non-invasive device for detecting and scavenging ocular ROS is an urgent problem to be solved by those skilled in the art. Summary of the Invention

[0007] In view of this, the purpose of the present invention is to provide a preparation method and application of a contact lens to solve the deficiencies in the prior art. The present invention realizes the comprehensive application of biological monitoring, wireless transmission, and flexible materials, forming an intelligent contact lens product, providing a new solution for real-time health monitoring.

[0008] To achieve the above purpose, the present invention adopts the following technical solutions:

[0009] A preparation method of a contact lens specifically includes the following steps:

[0010] (1) Add polymer material powder into dimethylformamide (DMF), stir to obtain a precursor solution, and perform electrospinning to obtain a polymer material nanofiber network;

[0011] (2) Sputter nano-metal onto the independent polymer material nanofiber network to obtain a nano-metal modified fiber network;

[0012] (3) Transfer the nano-metal modified fiber network to a polydimethylsiloxane (PDMS) film, and then perform patterned cutting to obtain a nano-metal modified fiber network counter electrode, a nano-metal modified fiber network working electrode, and a nano-metal modified fiber network reference electrode respectively;

[0013] (4) Immerse the nano-metal modified fiber network working electrode in an electrolytic solution containing nano-enzymes, and perform electrodeposition of nano-enzymes to obtain a nano-enzymes modified nano-metal fiber network working electrode for standby;

[0014] (5) Immerse the nano-metal modified fiber network reference electrode in an electrolytic solution containing silver (Ag), perform electrodeposition of silver, and then immerse it in an electrolytic solution containing silver chloride (AgCl) to perform electrodeposition of silver chloride to obtain a silver / silver chloride modified nano-metal fiber network reference electrode for standby;

[0015] (6) Dissolve the hydrogel material in an aqueous solution of ethanol, stir to obtain a hydrogel solution, and perform repeated freeze-thaw treatment to obtain a hydrogel film;

[0016] (7) Transfer the nano-metal modified fiber network counter electrode, the nano-enzymes modified nano-metal fiber network working electrode, and the silver / silver chloride modified nano-metal fiber network reference electrode to the hydrogel film respectively, lay them on the bottom of the contact lens mold, then add a polydimethylsiloxane mixture on the top for polymerization, and finally place the electrode assembly transferred to the contact lens in a water bath for heating to remove the hydrogel film, completing the preparation of the electrode assembly on the contact lens;

[0017] (8) Connect the copper inductor coil, NFC communication chip, and electrode assembly and integrate them onto the contact lens to obtain the corneal contact lens.

[0018] The specific functions, target user groups, usage scenarios, and expected effects of the corneal contact lens of the present invention are as follows:

[0019] 1. Specific functions

[0020] Detection function: It can detect the concentration or activity of ROS in the eye in real time and monitor the oxidative stress state of the eye, which can be achieved through the sensing material built into the contact lens to collect the ROS concentration signal in the eye in real time.

[0021] Scavenging function: Scavenge ROS in the ocular surface and corneal area through the platinum fiber mesh and platinum fiber mesh modified with Prussian blue contained in the lens to reduce the damage of oxidative stress to ocular tissues.

[0022] 2. Target user groups

[0023] Users who use electronic screens for a long time are prone to generate ROS due to blue light radiation.

[0024] The elderly, especially patients with age-related macular degeneration (AMD), glaucoma, or cataracts. The ROS levels in the eyes of these populations are usually high.

[0025] Patients with specific diseases, such as dry eye or diabetic retinopathy, etc., because these diseases may lead to increased oxidative stress.

[0026] People exposed to strong light or harmful environments, such as outdoor athletes, drivers, welders, etc.

[0027] 3. Usage scenarios

[0028] It can be worn for a long time in daily life and work, suitable for various light environments (such as indoors, outdoors, in front of the screen), and can monitor and scavenge ROS in the eye in real time.

[0029] In clinics and hospitals, medical staff can detect and treat the ROS level in patients' eyes through the corneal contact lens of the present invention, and at the same time provide real-time monitoring data for patients for disease tracking and intervention.

[0030] 4. Expected effects

[0031] Reduce the risk of oxidative damage to the eyes caused by ROS, and effectively prevent the progression of diseases such as retinopathy, macular degeneration, and cataracts.

[0032] Relieve discomfort symptoms such as eye fatigue and dryness caused by excessive ROS, and prolong the healthy state of the eyes.

[0033] Through real-time monitoring and early intervention, prevent or reduce the disease risk before eye problems show symptoms, so as to achieve the purpose of eye health management.

[0034] The advantages of the contact lens of the present invention are as follows:

[0035] 1. Real-time physiological data monitoring: Use an electrochemical sensing system to obtain the concentration data of ROS in the eye, and achieve real-time monitoring of physiological signals.

[0036] 2. ROS scavenging in the eye: Utilize the high redox enzyme (OHS), superoxide dismutase (SOD) and catalase (CAT) activities of platinum and Prussian blue to scavenge excessive ROS in the eye, achieve the oxidative stress balance of the eye environment, protect cell health, and reduce the occurrence of inflammatory reactions.

[0037] 3. Wireless data transmission: Transmit the detected data to an external device through an NFC communication chip, which is convenient for data collection and analysis.

[0038] 4. High sensitivity and stability: Ensure the stable detection and transmission of electrochemical signals through a multi-layer modified fibrous mesh electrode system, and enhance the responsiveness of the sensor.

[0039] 5. Comfortable wearing: The PDMS matrix and flexible nanofiber materials make the contact lens have good comfort and are suitable for long-term daily wearing.

[0040] Furthermore, in the above step (1), the polymer material is at least one of polyacrylonitrile (PAN), polyvinylpyrrolidone (PVP), polyurethane (PU) and polylactic acid (PLA), preferably polyacrylonitrile; the concentration of the polymer material powder in the precursor solution is 1 wt% - 50 wt%, preferably 10 wt%; the stirring temperature is 20 - 200 °C, preferably 60 °C; the stirring time is 1 - 24 h, preferably 12 h.

[0041] Furthermore, in the above step (1), the electrospinning is specifically: Pour the precursor solution into a 1 - 10 mL plastic syringe with a #10 - #30 needle, use a metal rotating shaft or metal collecting plate wrapped with a collecting membrane as the collector of the independent polymer nanofiber mesh, place the rotating shaft coaxially with the needle and keep a distance of 5 - 30 cm from the needle, apply a positive voltage of 5 - 20 kV to the needle, and apply a negative voltage of 5 - (-10) kV to the collector at the same time to promote the formation of nanofibers, and convey the precursor solution from the needle at a constant speed of 0.05 - 0.5 mm / min for 1 - 60 s.

[0042] Further, in the above step (1), the electrospinning is specifically as follows: Pour the precursor solution into a 5 mL plastic syringe with a flat blunt #20 needle. Use a metal rotating shaft wrapped with aluminum foil as the collector of the independent polymer nanofiber network. Place the rotating shaft coaxially with the needle and keep a distance of 15 cm from the needle. Apply a positive voltage of 13 kV to the needle, and at the same time apply a negative voltage of -2 kV to the collector to promote the formation of nanofibers. Deliver the precursor solution from the needle at a constant speed of 0.15 mm / min for 20 s.

[0043] The beneficial effect of the above is that by adjusting the electrospinning time, the density of the polymer material nanofiber network can be controlled.

[0044] Further, in the above step (2), the nano metal is at least one of gold (Au), silver (Ag) and platinum (Pt), preferably platinum; the sputtering device is a vacuum ion sputtering instrument, the time is 1 - 30 min, preferably 8 min; the thickness of the sputtered nano metal coating is 1 - 200 nm, preferably 40 nm. The nanofiber network modified with nano metal is characterized by a scanning electron microscope operating at an acceleration voltage of 1 - 5 kV. In addition, optical transmittance measurement is carried out using a UV / Vis spectrophotometer, and the sheet resistance is measured using a four-point probe.

[0045] The beneficial effect of the above is that the counter electrode modified with nano metal is composed of a polymer material nanofiber network prepared by electrospinning, and then a nano metal thin film with a thickness of about 40 nm is deposited on the surface of the nanofiber network by vacuum ion sputtering. The nano metal coating not only endows the electrode with high conductivity and excellent electrochemical performance and is used as the counter electrode in the electrochemical sensing system, but also has a significant reactive oxygen species (ROS) scavenging ability. The redox enzymes (OHS), superoxide dismutase (SOD) and catalase (CAT) of the nano metal material itself have high activities, enabling it to efficiently scavenge excessive ROS in the eye and maintain the oxidative stress balance. The design of this structure not only ensures the generation and transmission of high-sensitivity electrochemical signals, but also effectively improves the accuracy and reliability of detection, and further protects the health of eye cells.

[0046] Further, in the above step (3), the device for patterned cutting is a laser cutter.

[0047] Further, in the above step (4), the nanozyme is cerium oxide (CeO 2 ), manganese tetroxide (Mn 3 O 4 ), and Prussian blue (ferric ferrocyanide Fe 4 [Fe(CN) 6 3 ​) at least one of them, preferably Prussian blue; the electrolytic solution containing Prussian blue includes 0.25 - 25 mM iron chloride (FeCl 3 ), 0.25 - 25 mM potassium cyanide (K 3 [Fe(CN) 6 ), 0.01 - 1 M hydrochloric acid (HCl) and 0.01 - 0.5 M potassium chloride (KCl). Further, the electrolytic solution containing Prussian blue includes 2.5 mM iron chloride, 2.5 mM potassium cyanide, 0.1 M hydrochloric acid and 0.1 M potassium chloride; the electrodeposited nanozyme is specifically: within the potential range of -0.1 to 5.0 V, with a scanning rate of 10 - 1000 mV / s for 5 - 200 cycles. Further, the electrodeposited nanozyme is specifically: within the potential range of -0.2 to 1.0 V, with a scanning rate of 10 - 500 mV / s for 4 - 200 cycles.

[0048] The further beneficial effect of adopting the above is that in the present invention, a layer of nanozyme is uniformly deposited on the surface of the nanofiber network modified with nanometal by electrodeposition method to form a working electrode of a nanozyme-modified nanometal fiber network. The nanozyme not only has excellent electrochemical activity and stability, can monitor the concentration of reactive oxygen species (ROS) in the eye in real time, but also further improves the ROS scavenging performance. The nanozyme has relatively high activities of oxidoreductase, superoxide dismutase and catalase, and synergistically acts with the corresponding properties of the nanometal, greatly improving the ROS scavenging efficiency of this electrode. As a key signal sensing component, this working electrode can effectively scavenge the excess ROS in the eye while accurately collecting and conducting weak electrochemical signals, ensuring the oxidative stress balance of the eye environment and promoting eye health.

[0049] Further, in the above step (5), the electrolytic solution containing silver includes 1 - 50 mM silver nitrate (AgNO 3 ), and 1 - 50 M potassium nitrate (KNO 3 ). Further, the electrolytic solution containing silver includes 5 mM silver nitrate and 1 M potassium nitrate; the electrodeposition of silver is specifically: within the potential range of -2.0 to 2.0 V, with a scanning rate of 10 - 1000 mV / s for 5 - 100 cycles. Further, the electrodeposition of silver is specifically: within the potential range of -0.9 to 0.9 V, with a scanning rate of 20 - 500 mV / s for 5 - 50 cycles.

[0050] The further beneficial effects of the above are as follows. The silver / silver chloride modified nano-metal fiber mesh reference electrode is prepared by a two-step electrodeposition method. First, a silver layer is deposited on the surface of the nano-metal modified fiber mesh, and then a secondary deposition is carried out in a chloride solution to convert the silver layer into silver chloride (Ag / AgCl), thereby forming a reference electrode with a stable reference potential. The Ag / AgCl reference electrode provides a stable and accurate reference potential in electrochemical reactions, supports the signal sensing function of the working electrode, and ensures the accuracy and reliability of the measurement results.

[0051] Furthermore, in the above step (5), the electrolytic solution containing silver chloride includes 10 - 500 mM potassium chloride (KCl) and 1 - 100 mM hydrochloric acid (HCl). More preferably, the electrolytic solution containing silver chloride includes 100 mM potassium chloride and 10 mM hydrochloric acid. The electrodeposition of silver chloride is specifically carried out as follows: within the potential range of -1.0 to 2.0 V, with a scanning rate of 10 - 1000 mV / s for 1 - 50 cycles. More preferably, the electrodeposition of silver chloride is specifically carried out as follows: within the potential range of -0.15 to 1.05 V, with a scanning rate of 5 - 500 mV / s for 1 - 20 cycles.

[0052] Furthermore, in the above step (6), the hydrogel material is at least one of polyvinyl alcohol (PVA), polyethylene oxide (PEO), gelatin, agar, and chitosan, preferably polyvinyl alcohol. The temperature of heating and stirring is 20 - 200 °C, the rotation speed is 20 - 1000 rpm, and the time is 1 - 24 h. More preferably, the temperature of heating and stirring is 95 °C, the rotation speed is 200 rpm, and the time is 12 h. The concentration of the hydrogel material in the hydrogel solution is 1 wt% - 50 wt%, preferably 10 wt%. The number of times of repeated freeze-thaw treatment is 1 - 10 times, preferably 5 times.

[0053] The further beneficial effects of the above are as follows. The polyvinyl alcohol hydrogel film prepared by the present invention has certain viscosity and shape stability.

[0054] Furthermore, in the above step (8), the copper inductance coil is made of copper material and is precisely manufactured by reactive ion etching technology to ensure the consistency of the shape and inductance value of the coil. The copper inductance coil realizes efficient energy transmission through electromagnetic coupling with external devices.

[0055] The NFC communication chip is encapsulated in the contact lens matrix and works in cooperation with the copper inductance coil. Its working principle is to establish a short-range wireless communication channel through coupling with the copper inductance coil. The NFC communication chip is responsible for receiving and processing instructions from external devices and transmitting the data detected by the electrochemical sensor (electrode assembly) to external devices. The NFC communication chip makes it possible for wireless data transmission between the wearer and external devices, facilitating the real-time reading and feedback of data.

[0056] The present invention uses a polydimethylsiloxane (PDMS) film as the contact lens matrix, which has flexibility and transparency and is suitable for the contact lens environment. Through the die-casting and polymerization molding processes, a copper inductance coil, an NFC communication chip, and an electrode assembly are integrated into the PDMS matrix to form an overall structure, ensuring its flexibility and biocompatibility. The PDMS matrix not only supports and encapsulates all components, but also ensures comfortable wearing through its flexibility and transparency without affecting the line of sight. The PDMS matrix provides a biocompatible encapsulation structure, supports the stable operation of each component, and protects sensitive electronic components from the environment.

[0057] The present invention also claims the application of the contact lens prepared by the above preparation method in detecting and scavenging ocular reactive oxygen species.

[0058] As can be seen from the above technical solutions, compared with the prior art, the beneficial effects of the present invention are as follows:

[0059] 1. Real-time detection ability

[0060] By using advanced sensing materials, the concentration change of ocular ROS can be monitored in real time. Through the built-in detection system, users can obtain timely feedback on the oxidative stress state, which is convenient for ocular health management.

[0061] 2. Active ROS scavenging function

[0062] Utilizing the high oxidoreductase (OHS), superoxide dismutase (SOD), and catalase (CAT) activities of nanometals and nanoenzymes, ROS in the ocular surface and corneal region can be actively scavenged, reducing the damage of oxidative stress to ocular tissues. This function greatly enhances the ocular protection ability of users.

[0063] 3. Dual-function integration

[0064] Combining the detection and scavenging functions of ROS in the same product provides a more convenient and effective user experience compared with traditional separate treatment methods. Users do not need to use additional topical medications or supplements, enhancing treatment compliance.

[0065] 4. Safety and comfort

[0066] Using biocompatible materials ensures the safety and comfort of long-term wearing, reducing potential ocular discomfort and allergic reactions.

[0067] 5. Wide applicability

[0068] It is applicable to various populations, especially those who use electronic devices for a long time, the elderly, and patients at risk of ocular diseases, meeting the market demand for personalized ocular health management. Description of the drawings

[0069] Figure 1 This is the process flow chart of the preparation method of the electrode assembly in the contact lens of Embodiment 1 of the present invention;

[0070] Figure 2 This is the structural schematic diagram of the contact lens of Embodiment 1 of the present invention;

[0071] Figure 3 This is the ROS detection data chart of the contact lens electrode in Example 1;

[0072] Figure 4 This is the comparison chart of the ROS scavenging performance of the contact lens, PDMS, PAN NFs, Pt@PAN NFs, and PB@Pt@PAN NFs in Example 1;

[0073] Figure 5 This is the comparison chart of the UV light-induced cellular ROS scavenging performance of the contact lens, PDMS, PAN NFs, Pt@PAN NFs, PB@Pt@PAN NFs, and Ag / AgCl@Pt@PAN NFs in Example 1;

[0074] Figure 6 This is the biocompatibility comparison chart of the contact lens, PDMS, PAN NFs, Pt@PAN NFs, PB@Pt@PAN NFs, and Ag / AgCl@Pt@PAN NFs in Example 1. Detailed implementation manners

[0075] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Apparently, the described embodiments are only a part of the embodiments of the present invention, rather than all of them. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0076] Example 1

[0077] The preparation method of the contact lens is as Figure 1 shown, and specifically includes the following steps:

[0078] (1) Polyacrylonitrile powder was added to dimethylformamide and stirred at 60 °C for 12 h to obtain a precursor solution with a concentration of 10 wt%. Then, the precursor solution was poured into a 5 mL plastic syringe with a flat blunt #20 needle. An aluminum foil-coated metal rotating shaft was used as the collector for the independent polymer nanofiber network. The rotating shaft was placed coaxially with the needle and kept at a distance of 15 cm from the needle. A positive voltage of 13 kV was applied to the needle, and a negative voltage of -2 kV was applied to the collector to promote the formation of nanofibers. The precursor solution was delivered from the needle at a constant speed of 0.15 mm / min for 20 s to obtain a polyacrylonitrile nanofiber network (PAN NFs);

[0079] (2) Platinum was sputtered onto the independent polyacrylonitrile nanofiber network by a vacuum ion sputtering instrument for 8 min, and the platinum coating thickness was 40 nm to obtain a platinum-modified fiber network (Pt@PANNFs);

[0080] (3) The platinum-modified fiber network was transferred onto a polydimethylsiloxane film with polyethylene terephthalate (PET) as the substrate, and then patterned cutting was performed using a laser cutter to obtain a platinum-modified fiber network counter electrode, a platinum-modified fiber network working electrode, and a platinum-modified fiber network reference electrode, respectively;

[0081] (4) The platinum-modified fiber network working electrode was immersed in an electrolytic solution containing 2.5 mM ferric chloride, 2.5 mM potassium cyanide, 0.1 M hydrochloric acid, and 0.1 M potassium chloride, and then 40 cycles were performed at a scanning rate of 100 mV / s in the potential range of -0.2 to 1.0 V to complete the electrodeposition of Prussian blue, obtaining a Prussian blue-modified platinum fiber network working electrode (PB@Pt@PANNFs) for standby;

[0082] (5) The platinum-modified fiber network reference electrode was immersed in an electrolytic solution containing 5 mM silver nitrate and 1 M potassium nitrate, and then 14 cycles were performed at a scanning rate of 100 mV / s in the potential range of -0.9 to 0.9 V to complete the electrodeposition of silver. Then, it was immersed in an electrolytic solution containing 100 mM potassium chloride and 10 mM hydrochloric acid, and then 4 cycles were performed at a scanning rate of 50 mV / s in the potential range of -0.15 to 1.05 V to complete the electrodeposition of silver chloride, obtaining a silver / silver chloride-modified platinum fiber network reference electrode (Ag / AgCl@Pt@PAN NFs) for standby;

[0083] (6) Polyvinyl alcohol was dissolved in an aqueous solution of ethanol, heated to 95 °C and stirred at a rotation speed of 200 rpm for 12 h to obtain a polyvinyl alcohol solution with a concentration of 10 wt%. It was repeatedly freeze-thawed 5 times to obtain a polyvinyl alcohol hydrogel film;

[0084] (7) Transfer the platinum-modified fibrous network counter electrode, the Prussian blue-modified platinum fiber network working electrode, and the silver / silver chloride-modified platinum fiber network reference electrode to the polyvinyl alcohol hydrogel film respectively, lay them on the bottom of the contact lens mold, then add the polydimethylsiloxane mixture on the top for polymerization, and finally place the electrode assembly transferred to the contact lens in a water bath to heat and remove the polyvinyl alcohol hydrogel film, thus completing the preparation of the electrode assembly on the contact lens;

[0085] (8) Connect the copper inductance coil, the NFC communication chip and the electrode assembly and integrate them onto the contact lens, thus obtaining the Figure 2 contact lens as shown.

[0086] Performance Test

[0087] 1. Detection of ROS

[0088] Connect the electrodes of the contact lens prepared in Example 1 to an electrochemical workstation and place it in 50 mL of 0.05 M PBS buffer solution. The electrochemical workstation is at a potential of 0.6 V and the scanning rate is set at 50 mV / s. Add 5 μL of 500 μM hydrogen peroxide solution to the 50 mL PBS buffer solution in sequence to measure the I-t curve. The results are as Figure 3 shown.

[0089] As can be Figure 3 seen, the detection range of the contact lens sensor in Example 1 has extremely high accuracy and stability at the normal physiological level of the human body, and can achieve precise detection of ocular ROS.

[0090] 2. Scavenging of ROS

[0091] (1) Cut 1×1 cm square pieces of commercial contact lenses (CLs), the polydimethylsiloxane film (PDMS), polyacrylonitrile nanofiber network (PANNFs), platinum-modified fibrous network counter electrode (Pt@PANNFs), and Prussian blue-modified platinum fiber network working electrode (PB@Pt@PANNFs) prepared in Example 1 and place them in 5 mL centrifuge tubes, and then add 3 mL of 5 mM hydrogen peroxide to submerge the electrode pieces. Place the prepared centrifuge tubes on a shaker and take samples every 2 h respectively, and then use the APTS colorimetric method to measure the hydrogen peroxide concentration in the solution to evaluate the ROS scavenging performance of the materials. The results are as Figure 4 shown.

[0092] As can be Figure 4It can be seen that with the increase of the co-incubation time, the hydrogen peroxide concentration in commercial contact lenses (CLs), the polydimethylsiloxane film (PDMS) prepared in Example 1, and the polyacrylonitrile nanofiber network (PAN NFs) does not change significantly. However, the hydrogen peroxide co-incubated with the platinum-modified fiber network counter electrode (Pt@PANNFs) and the Prussian blue-modified platinum fiber network working electrode (PB@Pt@PANNFs) shows a rapid decrease in concentration over time. Among them, the platinum-modified fiber network counter electrode (Pt@PANNFs) is completely cleared within 10 h, while the Prussian blue-modified platinum fiber network working electrode (PB@Pt@PAN NFs) has a faster clearance rate and achieves complete clearance of hydrogen peroxide within 6 h.

[0093] (2) HCECs were cultured in a 96-well plate at a density of 5×10 3 cells per well. Then, commercial contact lenses (CLs) cut with a puncher, the polydimethylsiloxane film (PDMS) prepared in Example 1, the polyacrylonitrile nanofiber network (PANNFs), the platinum-modified fiber network counter electrode (Pt@PANNFs), the Prussian blue-modified platinum fiber network working electrode (PB@Pt@PAN NFs), and the silver / silver chloride-modified platinum fiber network reference electrode (Ag / AgCl@Pt@PANNFs) were added to each well plate. Subsequently, the cells were irradiated with ultraviolet light for 30 min to induce the generation of ROS. The cell counting kit-8 (CCK-8) was added to each well plate and incubated for 30 min. Finally, the ultraviolet absorption intensity signal of the well plate was collected at a wavelength of 450 nM to evaluate the cell viability and reflect the ROS scavenging performance of the materials. The results are as Figure 5 shown.

[0094] It can be Figure 5 seen that commercial contact lenses (CLs), the polydimethylsiloxane film (PDMS) prepared in Example 1, the polyacrylonitrile nanofiber network (PAN NFs), and the silver / silver chloride-modified platinum fiber network reference electrode (Ag / AgCl@Pt@PAN NFs) have no obvious scavenging effect on intracellular ROS induced by ultraviolet light irradiation, and the cell viability is low. While the platinum-modified fiber network counter electrode (Pt@PAN NFs) has a relatively high scavenging performance for intracellular ROS, and the Prussian blue-modified platinum fiber network working electrode (PB@Pt@PANNFs) has the highest scavenging performance for intracellular ROS.

[0095] 3. Biocompatibility

[0096] HCECs were cultured in a 96-well plate at a density of 5×10 3Cultivate human corneal epithelial cells (HCECs), and then add commercially available contact lenses (CLs) cut with a puncher, the polydimethylsiloxane film (PDMS) prepared in Example 1, polyacrylonitrile nanofiber network (PANNFs), platinum-modified nanofiber network counter electrode (Pt@PANNFs), Prussian blue-modified platinum nanofiber network working electrode (PB@Pt@PANNFs), and silver / silver chloride-modified platinum nanofiber network reference electrode (Ag / AgCl@Pt@PANNFs) into each well plate for co-culture with the cells for 24 h. Then, add cell counting kit-8 (CCK-8) into each well plate for incubation for 30 min. Finally, collect the ultraviolet absorption intensity signal of the well plate at a wavelength of 450 nM to evaluate the cell viability to reflect the biocompatibility of the materials. The results are as Figure 6 shown.

[0097] As Figure 6 can be seen, there is no significant difference in cell viability after co-culture of commercially available contact lenses (CLs), the polydimethylsiloxane film (PDMS) prepared in Example 1, polyacrylonitrile nanofiber network (PANNFs), platinum-modified nanofiber network counter electrode (Pt@PANNFs), Prussian blue-modified platinum nanofiber network working electrode (PB@Pt@PANNFs), and silver / silver chloride-modified platinum nanofiber network reference electrode (Ag / AgCl@Pt@PANNFs) with the cells, indicating that the materials have good cytocompatibility and are safe and harmless to organisms.

[0098] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be obvious to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but will be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing a corneal contact lens, characterized in that: The specific steps include: (1) adding polymer material powder into dimethylformamide, stirring to obtain a precursor solution, and electrospinning to obtain a polymer material nanofiber web; (2) sputtering the nanometal onto an independent polymer material nanofiber web to obtain a nanometal-modified fiber web; (3) transferring the nanometal-modified fiber mesh onto a polydimethylsiloxane film, and then pattern-cutting the film to obtain a nanometal-modified fiber mesh counter electrode, a nanometal-modified fiber mesh working electrode, and a nanometal-modified fiber mesh reference electrode, respectively; (4) immersing the nanometal-modified fiber mesh working electrode into an electrolytic solution containing nanozymes to electro-deposit the nanozymes to obtain a nanometal fiber mesh working electrode modified with nanozymes for standby use; (5) immersing the nanometal-modified fiber mesh reference electrode in an electrolytic solution containing silver to electrodeposit silver, and then immersing the nanometal-modified fiber mesh reference electrode in an electrolytic solution containing silver chloride to electrodeposit silver chloride to obtain a silver / silver chloride-modified nanometal fiber mesh reference electrode for standby use; (6) dissolving the hydrogel material in an aqueous solution of ethanol, stirring to obtain a hydrogel solution, and repeatedly freezing-thawing to obtain a hydrogel film; (7) respectively transferring the nanometal-modified fiber mesh counter electrode, the nanozyme-modified nanometal fiber mesh working electrode and the silver / silver chloride-modified nanometal fiber mesh reference electrode onto the hydrogel film, laying them on the bottom of the contact lens mold, then adding a polydimethylsiloxane mixture on the top for polymerization, and finally placing the electrode assembly transferred to the contact lens in a water bath for heating to remove the hydrogel film, thereby completing the preparation of the electrode assembly on the contact lens; (8) The copper inductor coil, the NFC communication chip and the electrode assembly are connected and integrated onto a contact lens to obtain the corneal contact lens.

2. The method for preparing a corneal contact lens according to claim 1, characterized in that: In step (1), the polymer material is at least one of polyacrylonitrile, polyvinyl pyrrolidone, polyurethane and polylactic acid; the concentration of the polymer material powder in the precursor solution is 1wt%-50wt%; the stirring temperature is 20-200°C and the time is 1-24h.

3. The method for preparing a corneal contact lens according to claim 1, characterized in that: In step (1), the electrospinning is specifically as follows: pouring the precursor solution into a 1-10 mL plastic syringe with a #10-#30 needle, using a metal shaft or a metal collecting plate coated with a collecting membrane as a collector of the independent polymer nanofiber network, placing the shaft coaxially with the needle and maintaining a distance of 5-30 cm from the needle, applying a positive voltage of 5-20 kV to the needle, and applying a negative voltage of 5-(-10) kV to the collector to promote the formation of nanofibers, and delivering the precursor solution from the needle at a constant speed of 0.05-0.5 mm / min for 1-60 s.

4. The method for preparing a corneal contact lens according to claim 1, characterized in that: In step (2), the nano metal is at least one of gold, silver and platinum; the sputtering equipment is a vacuum ion sputtering instrument, the time is 1-30 minutes, and the thickness of the nano metal coating is 1-200nm.

5. The method for preparing a corneal contact lens according to claim 1, characterized in that: In step (3), the patterned cutting equipment is a laser cutting machine.

6. The method for preparing a corneal contact lens according to claim 1, characterized in that: In step (4), the nanozyme is at least one of cerium oxide, manganese tetraoxide and Prussian blue; the electrolytic solution containing Prussian blue includes 0.25-25mM ferric chloride, 0.25-25mM potassium cyanide, 00.1-1M hydrochloric acid and 0.01-0.5M potassium chloride; the electrodeposited nanozyme is specifically: in the potential range of -0.1 to 5.0V, 5-200 cycles are performed at a scanning rate of 10-500mV / s.

7. The method for preparing a corneal contact lens according to claim 1, characterized in that: In step (5), the silver-containing electrolytic solution includes 1-50 mM silver nitrate and 1-50 M potassium nitrate; the silver electrodeposition is specifically performed in a potential range of -2.0 to 2.0 V at a scan rate of 20-500 mV / s for 5-50 cycles.

8. The method for preparing a corneal contact lens according to claim 1, characterized in that: In step (5), the electrolytic solution containing silver chloride includes 10-500 mM potassium chloride and 1-100 mM hydrochloric acid; the electrodeposition of silver chloride is specifically: 1-50 cycles are performed at a scanning rate of 5-500 mV / s in a potential range of -1.0 to 2.0 V.

9. The method for preparing a corneal contact lens according to claim 1, characterized in that: In step (6), the hydrogel material is at least one of polyvinyl alcohol, polyethylene oxide, gelatin, agar and chitosan; the temperature of the heating and stirring is 20-200°C, the rotation speed is 20-1000rpm, and the time is 1-24h; the concentration of the hydrogel material in the hydrogel solution is 1wt%-50wt%; and the number of repeated freezing-thawing treatments is 1-10 times.

10. Use of a corneal contact lens prepared by the preparation method according to any one of claims 1 to 9 in detecting and removing active oxygen in the eye.

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