Fluorescence sensing nanofiber protective film, preparation method and toxin protective clothing

Abstract

The invention discloses a nanofiber protective film integrated with a fluorescence sensing function as well as a preparation method and application thereof, and belongs to the technical field of functional materials and biosensing. According to the protective film, thermoplastic polyurethane (TPU) serves as a base material, hydrophobic fluorescent dye is embedded in fibers through an electrostatic spinning technology, hydrophilic fluorescent dye is immobilized on the surfaces of the fibers through covalent cross-linking, and an inner and outer double-layer dye loading structure is formed. The structure can generate specific fluorescence response when the snake venom protein is contacted, and multi-dimensional fluorescent fingerprints are formed. The invention also provides a toxin protective garment comprising the protective film, and the toxin protective garment integrates a signal acquisition module, a signal processing module and an early warning module, so that rapid identification and real-time alarm of toxin types can be realized. The invention has the advantages of excellent protection performance, high environmental adaptability and active sensing capability, and is suitable for special operation and outdoor safety protection.

Description

Technical Field

[0001] This invention belongs to the technical field of functional materials, biosensors and personal protective equipment, and relates to an intelligent protective material with real-time toxin detection function and its preparation method, as well as a protective suit integrating the material. Background Technology

[0002] In wilderness environments such as special operations and outdoor adventures, accidental exposure to biological toxins such as snake venom poses a significant threat to human life. Current protective clothing designs rely on the principle of physical barriers, using high-density fabrics and coatings to prevent toxin penetration—a typical passive protection mode. However, this passive protection has insurmountable technical flaws: when toxins breach the physical barrier or penetrate the protective materials, the clothing provides no real-time detection or warning signals. Wearers often only realize the danger after experiencing poisoning symptoms, missing the optimal window for first aid and easily leading to injury or even death.

[0003] Current research on detection technologies for snake venom and other toxins mainly focuses on laboratory-grade antibody sensors or chemical detection kits. These methods have several limitations: First, they are highly demanding in terms of environment, requiring stable temperature and humidity. In hot and humid environments such as outdoors or rainforests, or in situations involving frequent mechanical deformation, detection performance drops sharply, making it difficult to meet practical protective needs. Second, most rely on the specific response of a single recognition unit. However, snake venom is complex, containing multiple protein components such as phospholipase A2, neurotoxins, hemotoxins, and myotoxins. A single sensing unit cannot comprehensively cover the detection needs of various toxins, resulting in low detection sensitivity and a narrow range of applications. Third, laboratory equipment is bulky and complex to operate, and detection kits require professional personnel and are time-consuming to use, making them unsuitable for integration into flexible protective clothing and hindering portable, real-time detection.

[0004] Furthermore, existing protective materials present a significant contradiction in balancing protective performance and wearing comfort: high-density materials used to enhance toxin barrier properties often have poor breathability, leading to stuffiness, sweating, and skin discomfort with prolonged wear, thus affecting operational efficiency; while lightweight materials with better breathability struggle to guarantee sufficient toxin barrier effectiveness, resulting in inadequate protective reliability. Simultaneously, in complex outdoor environments, protective materials must withstand various external forces such as humidity, heat, tension, friction, and bending. Existing sensing materials suffer from insufficient structural stability and performance durability, leading to dye shedding and sensor signal drift, making it difficult to maintain reliable sensing functionality over long periods.

[0005] Therefore, developing an intelligent protective material and protective clothing that combines active sensing and early warning functions, high protective performance, good environmental adaptability, and wearing comfort has become a key requirement for overcoming existing technological bottlenecks. This invention aims to achieve integrated "protection-sensing-early warning" through innovative material structure design, optimized manufacturing processes, and system integration solutions, thereby overcoming the passive protection deficiencies of traditional protective clothing and providing a novel technical solution for toxin protection. Summary of the Invention

[0006] The purpose of this invention is to address the shortcomings of existing technologies by proposing a novel intelligent protective nanofiber membrane and protective clothing. This invention overcomes the limitations of current technologies and achieves the following core objectives: First, it develops protective clothing with real-time monitoring and early warning functions, upgrading the passive barrier function of protective materials to an active sensing function by integrating multi-dye fluorescent sensing technology. Second, it employs an electrospinning process to load four fluorescent dyes (EY, FITC, SRB, and TY) onto a TPU nanofiber membrane, significantly improving the material's stability and sensing reliability under humid, hot, and mechanically deformable environments. Third, by loading different dyes, it achieves specific responses to various snake venom proteins, ensuring high sensitivity and accuracy in monitoring, and constructing an "integrated protection-sensing" material structure that combines toxin barrier properties with high breathability, ensuring wide applicability in complex environments and long-term stability of sensing performance. To achieve the above objectives, this invention adopts the following technical solution.

[0007] In a first aspect, this invention provides a fluorescent sensing nanofiber protective film, comprising a thermoplastic polyurethane (TPU) nanofiber substrate, wherein at least one hydrophobic fluorescent dye is embedded in the substrate, and at least one hydrophilic fluorescent dye is covalently fixed on the fiber surface. This invention constructs a "synergistic internal and external" dye loading structure: using a flexible and environmentally resistant thermoplastic polyurethane (TPU) nanofiber network as the matrix, the hydrophobic fluorescent dye is directly embedded inside the fiber during spinning; simultaneously, through a covalent cross-linking reaction, the hydrophilic fluorescent dye is firmly fixed to the fiber surface. This structure not only ensures the stability of the dye under complex operating environments, preventing leaching or migration, but more importantly, by utilizing the specific interactions between the hydrophobic / hydrophilic dye and different structural domains (hydrophobic pockets, hydrophilic surfaces, specific amino acid residues) in snake venom proteins, it can induce multidimensional changes in fluorescence signals (such as quenching, enhancement, and wavelength shift) upon contact with the toxin, forming a unique "fluorescent fingerprint," laying the foundation for subsequent high-precision identification.

[0008] Furthermore, the hydrophobic fluorescent dye is at least one of sulfonyl rhodamine B (SRB) and titanium yellow (TY).

[0009] Furthermore, the hydrophilic fluorescent dye is at least one of eosin Y (EY) and fluorescein isothiocyanate (FITC).

[0010] Secondly, the present invention provides a method for preparing the above-mentioned fluorescent sensing nanofiber protective film, comprising the following steps: S1 spinning solution preparation: Dissolve TPU in N,N-dimethylformamide (DMF), add hydrophobic fluorescent dye, stir and disperse evenly to obtain the spinning solution; S2 Electrospinning: The spinning solution is electrospinned to obtain a TPU nanofiber membrane loaded with the hydrophobic fluorescent dye. S3 Hydrophilic dye immobilization: The nanofiber membrane obtained in step S2 is immersed in phosphate buffer (PBS) containing hydrophilic fluorescent dye, and crosslinking agents 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) and N-hydroxysuccinimide (NHS) are added to react and covalently immobilize the hydrophilic fluorescent dye on the fiber surface to obtain the fluorescent sensing nanofiber protective membrane.

[0011] The preparation method provided by this invention achieves in-situ embedding of hydrophobic dyes through electrospinning and surface fixation of hydrophilic dyes through EDC / NHS chemical crosslinking. The process is simple and controllable, and is suitable for large-scale preparation.

[0012] Furthermore, in step S1, the mass concentration of TPU in the spinning solution is 10%-18%.

[0013] Furthermore, in step S2, the electrospinning process parameters are: voltage 10-25kV, feed rate 0.5-5.0mL / h, receiving distance 10-30cm, ambient temperature 20-40℃, and relative humidity 30%-60%.

[0014] Furthermore, in step S1, the concentration of the hydrophobic fluorescent dye is 10-25 μmol / L; and / or, in step S3, the concentration of the hydrophilic fluorescent dye is 1-10 μmol / L.

[0015] Thirdly, the present invention provides a toxin protective suit, comprising: (1) A fluorescence sensing module, which includes the above-mentioned fluorescence sensing nanofiber protective film; (2) Signal acquisition module, used to acquire the fluorescence signal generated by the fluorescence sensing module in the wavelength range of 450-605nm under excitation light of 302nm and 365nm; (3) Signal processing module, used to process the acquired signals and use machine learning algorithms to identify and classify snake venom components; (4) Early warning output module, used to output identification results and early warning information.

[0016] The toxin protective suit provided by this invention integrates a core sensing membrane and functional modules to achieve full automation of the "toxin contact - signal acquisition - component identification - early warning output" process, upgrading traditional passive protection to active intelligent protection and significantly improving the wearer's safety level.

[0017] Furthermore, the operations performed by the signal processing module include: preprocessing the original signal using Butterworth low-pass filtering and Min-Max normalization; extracting multidimensional feature vectors including peak intensity (Imax), full width at half maximum (FWHM), rise time (t-rise), and decay constant (τ); and performing pattern recognition using linear discriminant analysis (LDA) and / or hierarchical clustering analysis (HCA) algorithms.

[0018] Furthermore, the warning output module can send warning information to a mobile terminal and display it visually in the form of a heat map and probability distribution map.

[0019] The fluorescence sensing function of this invention is based on the specific interaction between multiple dyes and snake venom proteins and the fluorescence signal response. The specific mechanism is as follows: Dual response mode: The hydrophilic dye on the surface of the protective film preferentially binds to the hydrophilic proteins in snake venom (such as neurotoxins and hemotoxins), while the hydrophobic dye inside binds to the hydrophobic proteins (such as phospholipase A2 and myotoxins) that have penetrated into the fiber, forming a "surface-inside" dual sensing, which can detect toxin contact and determine the degree of toxin penetration.

[0020] Signal change principle: Four fluorescent dyes (EY, FITC, SRB, TY) act as specific response units, producing unique fluorescence signal changes after binding to different snake venom proteins. When EY binds to neurotoxins, it causes fluorescence quenching, reducing fluorescence intensity by 30%-60% and causing a blue shift of emission wavelength by 5-10 nm. After FITC binds to blood toxins, the fluorescence intensity increases by 2-5 times, and the emission wavelength redshifts by 3-8 nm. After SRB binds to phospholipase A2, the fluorescence decay constant increases by 1.5-3 times, and the full width at half maximum (FWHM) widens by 20%-40%. After TY binds to myotoxin, the fluorescence intensity first increases and then quenches, forming a characteristic "peak-shaped change".

[0021] "Fluorescent fingerprint" identification: Through the design of dual excitation wavelengths of 302nm and 365nm, multi-channel fluorescence signals in the wavelength range of 450-605nm are collected simultaneously. The interaction between different snake venom components and dyes forms a unique "fluorescent fingerprint", which provides a core basis for subsequent identification of snake venom types and components.

[0022] Compared with the prior art, the present invention has the following beneficial technical effects.

[0023] (1) Integrated: By combining the sensing function with the protective substrate through electrospinning technology, the leap from "passive protection" to "active intelligent protection" has been realized.

[0024] (2) Multi-target recognition capability: By utilizing the unique "fluorescent fingerprint" signal generated by the interaction of four dyes with different snake venom proteins, combined with machine learning algorithms (LDA / HCA), it can distinguish different types of snake venom and their mixed components, with high sensitivity and strong specificity.

[0025] (3) Excellent environmental adaptability: TPU material itself and the entire sensing structure have good flexibility, mechanical strength and resistance to damp heat, making it suitable for complex and harsh environments such as outdoor and rainforest environments.

[0026] (4) Rapid real-time early warning: The entire detection response time is short (<3 minutes), and it can issue visual early warnings in real time through mobile terminals, giving users valuable time to take countermeasures. Detailed Implementation

[0027] The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the protection scope of the present invention. Example 1

[0028] 1. Preparation of fluorescent sensing nanofiber protective film Preparation of S1 spinning solution: Weigh 1.0 g of TPU granules and dissolve them in 10 mL of DMF solvent. Stir magnetically at 30℃ and 400 r / min for 2 hours until completely dissolved to obtain a 10% (w / w) TPU solution. Add SRB and TY to this solution to make the SRB concentration 10 μmol / L and the TY concentration 10 μmol / L (concentration ratio 1:1). Continue stirring for 1 hour to obtain a uniformly dispersed spinning solution.

[0029] S2 Electrospinning: Inject the spinning solution into the injection pump and set the electrospinning parameters as follows: voltage 12 kV, feed rate 1.2 mL / h, receiving distance 24 cm, ambient temperature 30℃, and relative humidity 30%. Start the equipment to perform electrospinning and continue spinning for 4 hours to obtain an orange semi-transparent TPU nanofiber membrane with a fiber diameter of 100-200 nm and a membrane thickness of 80 μm.

[0030] S3. Hydrophilic dye immobilization: Prepare a PBS solution with pH=7.4, and add EY and FITC to it to achieve an EY concentration of 8.75 μmol / L and a FITC concentration of 1 μmol / L (concentration ratio 8.75:1). Immerse the fiber membrane prepared in step S2 into this solution, and add EDC and NHS to achieve a concentration of 5 mmol / L for both. The reaction is carried out with shaking at 25℃ and 80 r / min for 2 hours. After the reaction, rinse the membrane surface three times with deionized water and vacuum dry at 35℃ for 1.5 hours to obtain the fluorescent sensing nanofiber protective membrane.

[0031] 2. Protective film performance test Structural properties: Uniform fiber diameter with no obvious agglomeration; membrane thickness 80 μm, air permeability 550 mL / (cm²) 2 •h); Protective performance: 98.5% barrier efficiency against cobra venom; Sensing performance: Upon contact with cobra venom, the fluorescence intensity of EY decreases by 45%, the fluorescence intensity of FITC increases by 3 times, and the attenuation constant of SRB increases by 2 times, forming a characteristic "fluorescent fingerprint"; the detection response time is 2 minutes, and the minimum detection concentration is 0.8 μg / mL; Environmental stability: Under conditions of temperature 20℃-40℃ and relative humidity 30%-60%, the sensing performance showed no significant attenuation after 72 hours of continuous operation; after 100 tensile deformations (elongation of 200%), the membrane structure remained intact and the fluorescence signal intensity change rate was <5%.

[0032] 3. Assembly of toxin protective suits The toxin protective suit includes: (1) a fluorescent sensing module: the protective film prepared above is cut to a size of 20 cm × 30 cm and integrated into the torso and limbs of the protective suit; (2) a signal acquisition module: 302 nm and 365 nm LED ultraviolet lamps are selected, the array photodetector has a resolution of 0.5 nm and a sampling frequency of 10 Hz; (3) a signal processing module: an ARM Cortex-M4 microprocessor is used, the preprocessing uses Butterworth low-pass filtering (cutoff frequency 5 Hz) and Min-Max normalization, 12-dimensional feature vectors are extracted, and the LDA algorithm is used for pattern recognition; (4) a warning output module: a Bluetooth 5.0 module is integrated, which connects to a mobile terminal APP and outputs warning information in the form of heat map, probability distribution map and text; (5) a power module: a 1000 mAh flexible lithium polymer battery with a battery life of 8 hours; (6) a light-transmitting encapsulation layer: a PET film with a light transmittance of 90% is used to cover the sensing module with a flexible adhesive.

[0033] 4. Performance testing of protective clothing Identification accuracy: 96% accuracy in identifying cobra venom, and can distinguish between mixtures of cobra venom and banded krait venom; Warning Response: An alert will be issued within 2 minutes of contact with snake venom. The mobile app will display a real-time heat map of the venom contact area and the text message "Cobra venom, it is recommended to use anticobra venom serum and apply a bandage to the proximal end of the wound." Wearing experience: It has good breathability and there is no obvious stuffiness or discomfort after wearing it continuously for 6 hours; the flexible design does not affect limb movement. Example 2

[0034] 1. Preparation of fluorescent sensing nanofiber protective film Preparation of S1 spinning solution: Weigh 1.8 g of TPU granules and dissolve them in 10 mL of DMF solvent. Stir magnetically at 35℃ and 500 r / min for 2.5 hours until completely dissolved to obtain a TPU solution with a mass concentration of 18%. Add SRB and TY to this solution to make the concentrations of SRB and TY 25 μmol / L (concentration ratio 1:1). Continue stirring for 1.5 hours to obtain a uniformly dispersed spinning solution.

[0035] S2 Electrospinning: The spinning solution was injected into the injection pump, and the electrospinning parameters were set as follows: voltage 18 kV, feed rate 1.8 mL / h, receiving distance 24 cm, ambient temperature 35℃, and relative humidity 35%. The equipment was started for electrospinning, which was carried out continuously for 5 hours, resulting in an orange semi-transparent TPU nanofiber membrane with a fiber diameter of 200-300 nm and a membrane thickness of 120 μm.

[0036] S3. Hydrophilic dye immobilization: Prepare a PBS solution with pH=7.4, and add EY and FITC to it to make the EY concentration 10 μmol / L and the FITC concentration 1 μmol / L (concentration ratio 10:1). Immerse the fiber membrane prepared in step S2 into this solution, add EDC and NHS to make both concentrations 5 mmol / L, and shake the reaction at 25℃ and 90 r / min for 2 hours. After the reaction, rinse the membrane surface 4 times with deionized water and vacuum dry at 38℃ for 1 hour to obtain the fluorescent sensing nanofiber protective membrane.

[0037] 2. Protective film performance test Structural properties: uniform fiber diameter, membrane thickness 120 μm, air permeability 520 mL / (cm²) 2 •h); Protective performance: 99.2% blocking efficiency against krait venom; Sensing performance: After contact with krait venom, the FITC fluorescence intensity increased by 4 times, the emission wavelength redshifted by 6 nm, and TY showed a characteristic "peak shape change"; the detection response time was 1.8 minutes, and the minimum detection concentration was 0.6 μg / mL; Environmental stability: The sensing performance remains stable after 80 hours of continuous operation under temperature conditions of 15℃-45℃ and relative humidity of 30%-80%; after 150 tensile deformations (elongation of 250%), the membrane structure remains intact and the fluorescence signal intensity change rate is <4%.

[0038] 3. Assembly of toxin protective suits The module composition of the toxin protective suit is the same as that in Example 1. The difference is that the signal processing module uses the HCA algorithm for pattern recognition, and the power module has a capacity of 1200 mAh and a battery life of 10 hours.

[0039] 4. Performance testing of protective clothing Identification accuracy: 97% accuracy in identifying the venom of the banded krait, and can distinguish the ratio of neurotoxins to hemotoxins in the venom of the banded krait; Warning Response: An alert will be issued within 1.8 minutes of contact with snake venom. The mobile app will display a venom probability distribution map (98% confidence level for krait venom) and the text message "King krait venom is mainly neurotoxin. It is recommended to immediately inject anti-krait venom serum and keep the airway open." Wearing experience: It has good breathability and high mechanical strength. After repeated friction and bending, the sensor module was undamaged and its performance was stable. Example 3

[0040] 1. Preparation of fluorescent sensing nanofiber protective film Preparation of S1 spinning solution: Weigh 1.5 g of TPU granules and dissolve them in 10 mL of DMF solvent. Stir magnetically at 32℃ and 450 r / min for 2 hours until completely dissolved to obtain a TPU solution with a mass concentration of 15%. Add SRB and TY to this solution to make the SRB concentration 20 μmol / L and the TY concentration 25 μmol / L (concentration ratio 1:1.25). Continue stirring for 1.2 hours to obtain a uniformly dispersed spinning solution.

[0041] S2 Electrospinning: The spinning solution was injected into the injection pump, and the electrospinning parameters were set as follows: voltage 22 kV, feed rate 0.8 mL / h, receiving distance 28 cm, ambient temperature 20℃, and relative humidity 60%. The equipment was started for electrospinning, which was carried out continuously for 4.5 hours, resulting in an orange semi-transparent TPU nanofiber membrane with a fiber diameter of 150-250 nm and a membrane thickness of 100 μm.

[0042] S3. Hydrophilic dye immobilization: Prepare a PBS solution with pH=7.4, and add EY and FITC to it to achieve an EY concentration of 5 μmol / L and a FITC concentration of 5 μmol / L (concentration ratio 1:1). Immerse the fiber membrane prepared in step S2 into this solution, and add EDC and NHS to achieve a concentration of 6 mmol / L for both. The reaction is carried out with shaking at 28℃ and 70 r / min for 2.5 hours. After the reaction, rinse the membrane surface 5 times with deionized water and vacuum dry at 36℃ for 1.2 hours to obtain the fluorescent sensing nanofiber protective membrane.

[0043] 2. Protective film performance test Structural properties: uniform fiber diameter, membrane thickness 100 μm, air permeability 530 mL / (cm²) 2 •h); Protective performance: 98.8% blocking efficiency against the venom of the five-step snake; Sensing performance: Upon contact with the venom of the five-step snake, the SRB fluorescence half-width broadened by 35%, and the EY fluorescence intensity decreased by 50%, forming a characteristic "fluorescent fingerprint"; the detection response time was 1.5 minutes, and the minimum detection concentration was 0.5 μg / mL; Environmental stability: Under conditions of temperature 10℃-50℃ and relative humidity 30%-90%, the sensing performance does not degrade after 96 hours of continuous operation; after 200 tensile deformations (elongation of 300%), the membrane structure remains intact and the fluorescence signal intensity change rate is <3%.

[0044] 3. Assembly of toxin protective suits The module composition of the toxin protective suit is the same as that in Example 1. The difference is that the signal processing module uses a combination of LDA and HCA algorithms for pattern recognition, and the wireless communication unit supports Bluetooth and WiFi dual-mode connection.

[0045] 4. Performance testing of protective clothing Identification accuracy: 98% accuracy in identifying the venom of the five-step snake; it can simultaneously identify mixed systems of five-step snake venom and viper venom. Warning Response: An alert will be issued within 1.5 minutes of contact with snake venom. The mobile terminal APP will display a heat map (toxin penetration depth 10 μm), a probability distribution map, and a text prompt: "Five-step snake venom, mainly hemotoxic, it is recommended to inject anti-five-step snake venom serum, stop bleeding and rehydrate in time." Environmental adaptability: It can work continuously for 48 hours in a hot and humid rainforest environment (temperature 30℃, relative humidity 85%) with stable performance; after being washed by rain and rubbed by mud and sand, the sensor module is not damaged and the detection accuracy does not decrease significantly. Example 4

[0046] 1. Preparation of fluorescent sensing nanofiber protective film Preparation of S1 spinning solution: Weigh 1.2 g of TPU granules and dissolve them in 10 mL of DMF solvent. Stir magnetically at 31℃ and 420 r / min for 2 hours until completely dissolved to obtain a TPU solution with a mass concentration of 12%. Add SRB to this solution at a concentration of 15 μmol / L and continue stirring for 1 hour to obtain a uniformly dispersed spinning solution.

[0047] S2 Electrospinning: The spinning solution was injected into the injection pump, and the electrospinning parameters were set as follows: voltage 15 kV, feed rate 2.0 mL / h, receiving distance 18 cm, ambient temperature 25℃, and relative humidity 45%. The equipment was started for electrospinning, which was carried out continuously for 3.5 hours, resulting in an orange semi-transparent TPU nanofiber membrane with a fiber diameter of 120-180 nm and a membrane thickness of 70 μm.

[0048] S3 Hydrophilic Dye Immobilization: Prepare a PBS solution with pH=7.4, and add FITC to it at a concentration of 3 μmol / L. Immerse the fiber membrane prepared in step S2 into this solution, and add EDC and NHS to make their concentrations both 4 mmol / L. The reaction is carried out with shaking at 24℃ and 60 r / min for 1.5 hours. After the reaction, rinse the membrane surface three times with deionized water and vacuum dry at 34℃ for 1 hour to obtain the fluorescent sensing nanofiber protective membrane.

[0049] 2. Protective film performance test Structural properties: uniform fiber diameter, membrane thickness 70 μm, air permeability 560 mL / (cm²) 2 •h); Protective performance: 98.3% barrier efficiency against viper venom; Sensing performance: After contact with viper venom, the SRB fluorescence decay constant increased by 1.8 times, and the FITC fluorescence intensity increased by 2.5 times; the detection response time was 2.2 minutes, and the minimum detection concentration was 1.0 μg / mL; Environmental stability: The sensing performance remains stable after 60 hours of continuous operation under temperature conditions of 18℃-42℃ and relative humidity of 40%-70%; after 80 tensile deformations (elongation of 180%), the membrane structure remains intact and the fluorescence signal intensity change rate is <6%.

[0050] 3. Assembly of toxin protective suits The module composition of the toxin protective suit is the same as that of Example 1. The difference is that the early warning output module integrates a small flexible display screen, which can directly display early warning information without relying on a mobile terminal.

[0051] 4. Performance testing of protective clothing Identification accuracy: 95% accuracy in identifying viper venom, effectively distinguishing viper venom from other snake venoms; Warning Response: Within 2.2 minutes of contact with snake venom, the flexible display screen and mobile terminal will simultaneously issue a warning, displaying the text prompt "Viper venom, it is recommended to use anti-viper venom serum and apply cold compress to the wound" and a simplified heat map; Portability: After integrating the flexible display screen, the overall weight of the protective suit increases by ≤100 g, which does not affect the portability of wearing it; the flexible display screen is resistant to bending and wear, and will not be damaged during use.

[0052] Although embodiments of the present invention have been shown and described above, it is understood that these embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions, and alterations to the above embodiments within the scope of the present invention without departing from its principles and spirit. The scope of protection of the present invention is defined by the claims and their equivalents.

Claims

1. A fluorescent sensing nanofiber protective film, characterized in that, The invention includes a thermoplastic polyurethane nanofiber substrate, wherein at least one hydrophobic fluorescent dye is embedded in the substrate, and at least one hydrophilic fluorescent dye is covalently fixed on the surface of the fibers.

2. The fluorescent sensing nanofiber protective film according to claim 1, characterized in that, The hydrophobic fluorescent dye is at least one of sulfonyl rhodamine B and titanium yellow.

3. The fluorescent sensing nanofiber protective film according to claim 1, characterized in that, The hydrophilic fluorescent dye is at least one of eosin Y and fluorescein isothiocyanate.

4. The method for preparing the fluorescent sensing nanofiber protective film according to any one of claims 1-3, characterized in that, Includes the following steps: S1 spinning solution preparation: Thermoplastic polyurethane is dissolved in N,N-dimethylformamide, hydrophobic fluorescent dye is added, and the mixture is stirred and dispersed evenly to obtain the spinning solution; S2 Electrospinning: Electrospinning is performed on the spinning solution to obtain a thermoplastic polyurethane nanofiber membrane loaded with the hydrophobic fluorescent dye. S3 Hydrophilic dye immobilization: The nanofiber membrane obtained in step S2 is immersed in a phosphate buffer containing a hydrophilic fluorescent dye, and crosslinking agents 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide are added to react and covalently fix the hydrophilic fluorescent dye on the fiber surface to obtain the fluorescent sensing nanofiber protective membrane.

5. The method according to claim 4, characterized in that, In step S1, the mass concentration of thermoplastic polyurethane in the spinning solution is 10%-18%.

6. The method according to claim 4, characterized in that, In step S2, the electrospinning process parameters are: voltage 10-25kV, feed rate 0.5-5.0mL / h, receiving distance 10-30cm, ambient temperature 20-40℃, and relative humidity 30%-60%.

7. The method according to claim 4, characterized in that, In step S1, the concentration of the hydrophobic fluorescent dye is 10-25 μmol / L; and / or, in step S3, the concentration of the hydrophilic fluorescent dye is 1-10 μmol / L.

8. A toxin protective suit, characterized in that, include: (1) A fluorescence sensing module comprising the fluorescence sensing nanofiber protective film as described in any one of claims 1-3; (2) Signal acquisition module, used to acquire the fluorescence signal generated by the fluorescence sensing module in the wavelength range of 450-605nm under excitation light of 302nm and 365nm; (3) Signal processing module, used to process the acquired signals and use machine learning algorithms to identify and classify snake venom components; (4) Early warning output module, used to output identification results and early warning information.

9. The toxin protective suit according to claim 8, characterized in that, The operations performed by the signal processing module include: preprocessing the original signal using Butterworth low-pass filtering and Min-Max normalization; extracting multi-dimensional feature vectors including peak intensity, full width at half maximum (FWHM), rise time, and decay constant; and performing pattern recognition using linear discriminant analysis and / or hierarchical clustering analysis algorithms.

10. The toxin protective suit according to claim 8, characterized in that, The warning output module can send warning information to mobile terminals and display it visually in the form of heat maps and probability distribution maps.