An intelligent yarn and its preparation method and application

Abstract

The present invention relates to an intelligent yarn, a preparation method thereof and an application. The intelligent yarn is divided into two or more sections along the length direction. Among any two adjacent sections, the cortical fibers on one section are fibers with a visual detection effect on biochemical A, and the cortical fibers on the other section are fibers with a visual detection effect on biochemical B. Preparation method: The cortical fibers are wrapped around the surface of the core yarn through a coaxial electrospinning process, and different cortical fibers are wrapped around different length sections of the core yarn to obtain the intelligent yarn. Application: A biochemical visual sensing - physiological signal real-time monitoring sensing network includes an intelligent yarn, a fabric, an NFC sensing chip, a physiological signal sensor and an excitation terminal as described above. The intelligent yarn of the present invention can simultaneously detect a variety of harmful substances; the method of the present invention has a simple process and can continuously prepare kilometer-level intelligent yarns; the application of the present invention can simultaneously monitor the physiological health signals of the wearer while detecting hazardous chemicals.

Description

Technical Field

[0001] The present invention belongs to the technical field of hazardous chemical sensing, and relates to an intelligent yarn and its preparation method and application. Background Art

[0002] In contemporary warfare, biochemical warfare, virus warfare, and chemical warfare are rampant. In the scenario of individual combat on the battlefield, the detection of multiple harmful substances needs to be considered.

[0003] The surface-functionalized nanofiber bacterial detection membrane described in Patent CN111487239A is a functionalized nanofiber bacterial detection membrane with a chromogenic substrate grafted on the surface, and the TNT detection fluorescent nanofiber membrane prepared by electrospinning after the compounding of TNT fluorescent small molecules and a polymer matrix in Patent CN109023722A can only achieve the separate detection of a single biochemical in the same area, and cannot achieve the effect of simultaneously detecting multiple biochemicals in the same area at the same time, and cannot meet the complex detection requirements.

[0004] Current detections of biochemicals include handheld instruments, fixed imaging devices, trace analysis equipment, etc. However, these detection methods are either expensive and cumbersome to operate, such as X-ray imaging technology, or have high detection difficulty and long detection cycles, such as mass spectrometry analysis, or have high costs and low resolutions, and the detection lag is obvious. For example, for the detection of viruses, RT-PCR is the recognized standard for virus detection; however, this is a multi-step technology involving purification, nucleic acid amplification, and fluorescence detection. This process is laborious, requires trained operators, can report many false negatives, and has limited availability in resource-limited environments. Another example is the detection of nerve agents. Some analytical techniques, such as chromatography, flame photometry, and mass spectrometry, are not suitable for on-site applications due to reasons such as lack of portability, high power requirements, and the need for re-supply of consumables. Many detectors use infrared remote sensing to detect the presence of chemical warfare agents within a range of 1 to 5 kilometers from the threat. However, due to changes in relative humidity, temperature, and air composition, false readings are likely to occur, and there are problems such as uneven urban environmental backgrounds and low sensitivity. So far, there has been little research on reliable and sensitive naked-eye visual real-time detection technologies for dangerous biochemicals.

[0005] While detecting hazardous chemicals, considering their great harmfulness, which causes great harm to the health of people in the surrounding environment, for the sake of the life and health of people in the surrounding environment, it is an urgent problem to monitor the physiological characteristics of the human body in the environment in real time and transmit them to the terminal platform for analysis and then make corresponding protection and response measures.

[0006] Therefore, it is of great significance to develop an intelligent yarn and its preparation method and application to solve the above problems. Summary of the Invention

[0007] To solve the problems existing in the prior art, the present invention provides an intelligent yarn, a preparation method thereof, and an application thereof.

[0008] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0009] An intelligent yarn having a core-sheath structure includes a core yarn and cortical fibers. The intelligent yarn is divided into two or more sections along the length direction. Among any two adjacent sections, the cortical fibers on one section are fibers with a visual detection effect on biochemical A, and the cortical fibers on the other section are fibers with a visual detection effect on biochemical B. Biochemical A is different from biochemical B. It should be noted that A and B in the present invention are only used to distinguish two kinds of biochemicals and have no substantial meaning.

[0010] The intelligent yarn of the present invention can be applied to complex scenarios where multiple hazardous biochemicals coexist. The complex scenarios refer to scenarios where two or more of TNT, virus, nerve gas, and heavy metal ions coexist, such as a complex modern war scenario where nerve gas and TNT vapor coexist; explosive detection at airports and stations where the virus rages and the population is dense; individual special operations scenarios in heavy metal-polluted environments, etc.

[0011] As a preferred technical solution:

[0012] For the intelligent yarn as described above, biochemical A and biochemical B are selected from one of TNT, virus, nerve gas, and heavy metal ions (Hg ﹢ , Cu 2﹢ , Co 2﹢ ).

[0013] For the intelligent yarn as described above, the cortical fibers include a hydrophobic polymer substrate and a fluorescent detection material dispersed therein; the fluorescent detection material in the fibers with a visual detection effect on biochemical A is a detection material with a fluorescent detection ability for biochemical A, and the fluorescent detection material in the fibers with a visual detection effect on biochemical B is a detection material with a fluorescent detection ability for biochemical B;

[0014] The substrate of the cortical fibers being a hydrophobic polymer plays two crucial roles: one is that the substrate serves as a structural support for the detection material to ensure the stable and firm distribution of the detection material on the surface of the intelligent yarn, and the other is that the hydrophobic property of the substrate ensures that the intelligent yarn for integrated visualization detection of biochemicals + physiological signal wireless signal transmission is not interfered by external liquids such as sweat and water during the transmission of physiological signals and wireless signals, preventing possible failure situations during the operation of the intelligent yarn;

[0015] The fluorescence detection material needs to have good stability and solubility, and have good fluorescence detection effect on biochemicals. When the biochemical is TNT, the fluorescence detection material is preferably TPA-PPV; when the biochemical is heavy metal ions, the fluorescence detection material is preferably 4,4'-bis(diethylamino)-benzene diazole; when the biochemical is nerve gas, the fluorescence detection material is preferably 4,4'-bis(dimethylamino)-benzene diazole; when the biochemical is virus, the fluorescence detection material is preferably pyrene-naphthalimide binary group.

[0016] For the intelligent yarn as described above, the hydrophobic polymer is a high molecular polymer material with good hydrophobic properties such as polyvinylidene fluoride PVDF, polystyrene PS or polycaprolactone PCL, etc.; the content of the fluorescence detection material in the cortical fiber is 5-10 wt%.

[0017] For the intelligent yarn as described above, the diameter of the intelligent yarn is 0.1-0.4 mm, the diameter of the core yarn is 0.05-0.10 mm, and the diameter of the cortical fiber is 0.05-0.2 mm.

[0018] For the intelligent yarn as described above, the core yarn is a conductive yarn that can conduct physiological signals and wireless signals.

[0019] For the intelligent yarn as described above, the core yarn is a commercial conductive yarn such as silver-plated nylon, pure silver yarn, metal conductive wire or carbon fiber, etc., which has good conductivity, and its resistance is about 1-5 Ω / cm, and can stably transmit wireless signals.

[0020] The present invention also provides a preparation method of an intelligent yarn. The cortical fiber is wrapped around the surface of the core yarn by a conjugate electrospinning process, and different cortical fibers are wrapped around different length segments of the core yarn to obtain the intelligent yarn.

[0021] The core yarn is divided into two or more segments along the length direction. Wrapping different cortical fibers around different length segments of the core yarn means that on one of any two adjacent length segments of the core yarn, fibers with a visual detection effect on biochemical A are wrapped, and on the other segment, fibers with a visual detection effect on biochemical B are wrapped, and biochemical A and biochemical B are different.

[0022] As a preferred technical solution:

[0023] For the preparation method of the intelligent yarn as described above, biochemical A and biochemical B are selected from one of TNT, virus, nerve gas, heavy metal ions (Hg ﹢ 、Cu 2﹢ 、Co 2﹢ ).

[0024] A method for preparing an intelligent yarn as described above, wrapping different cortical fibers on different length segments of the core yarn is achieved by replacing different spinning dope during the coaxial electrospinning process;

[0025] The spinning dope includes a hydrophobic polymer, a fluorescence detection material, and a solvent;

[0026] When wrapping fibers with a visual detection effect on biochemical A, the fluorescence detection material in the spinning dope used is a detection material with fluorescence detection ability for biochemical A; when wrapping fibers with a visual detection effect on biochemical B, the fluorescence detection material in the spinning dope used is a detection material with fluorescence detection ability for biochemical B.

[0027] A method for preparing an intelligent yarn as described above, the hydrophobic polymer is a high molecular polymer material with good hydrophobic properties such as polyvinylidene fluoride (PVDF), polystyrene (PS), or polycaprolactone (PCL);

[0028] In the spinning dope, the mass ratio of the fluorescence detection material to the hydrophobic polymer is 5 - 10:95 - 90, and the mass ratio of the hydrophobic polymer to the solvent is 10 - 20:90 - 80; the mass ratio of the fluorescence detection material to the hydrophobic polymer should not be too low, otherwise the fluorescence color change effect on the biochemical will not be obvious, nor should it be too high, otherwise it will reduce the viscosity of the spinning dope, resulting in the phenomenon of floating filaments during the electrospinning process; the mass proportion of the solute hydrophobic polymer should not be too high, otherwise it will lead to too high a viscosity of the spinning dope, and too high a viscosity of the spinning dope during electrospinning will cause difficulties in extruding the spinning dope or even blockage of the needle, so that continuous and uniform wrapped fibers cannot be formed, nor should it be too low, otherwise it will lead to too low a viscosity of the spinning dope, resulting in the easy occurrence of floating filaments during the spinning process and being not conducive to the formation of uniform wrapped fibers;

[0029] The solvent is a homogeneous solution prepared by mixing N,N-dimethylformamide (DMF) and acetone in a weight ratio of 6 - 7:3 - 4; DMF is a colorless and transparent organic solvent with stable properties, which can successfully dissolve the fluorescence detection material and the hydrophobic polymer, and acetone is a common organic solvent with strong volatility. Adding acetone is to accelerate the volatilization of the organic solvent during the electrospinning process;

[0030] When preparing the spinning dope, each component is mixed and then made into a stable and uniform spinning dope through oil bath heating and stirring and ultrasonic oscillation. The temperature of the oil bath heating and stirring is 50-70 °C, the power of the ultrasonic oscillation is 30-60 W, and the time is 30-70 min. The temperature of the oil bath heating and stirring should not be too low, otherwise it will cause: 1) The hydrophobic polymer is difficult to completely dissolve in the solvent, resulting in the clogging of the needle during the electrospinning process; 2) The fluorescence detection material is difficult to be evenly distributed and dissolved in the hydrophobic polymer, resulting in the insensitive fluorescence detection effect of the intelligent yarn on biochemicals. If the time of ultrasonic oscillation is too short, the ultrasonic effect will be poor, and there will still be bubbles in the spinning dope, affecting the continuity of electrospinning. If the time of ultrasonic oscillation is too long, the preparation efficiency of the intelligent yarn will be reduced.

[0031] The specific process of preparing the spinning dope is as follows: Add the hydrophobic polymer to the solvent to form a solution. The hydrophobic polymer will not dissolve immediately in the solution. After stirring the above solution in an oil bath for a period of time, the hydrophobic polymer is completely dissolved, and the solution becomes colorless and transparent. After the hydrophobic polymer is completely dissolved, add the fluorescence detection material to the solution. After adding the fluorescence detection material, stir in the oil bath for a period of time to make the fluorescence detection material completely dissolved. After stirring for a period of time, the solution becomes a stable system. Put the solution into an ultrasonic instrument to remove the bubbles in the solution. After ultrasonic treatment, a stable and usable spinning dope is obtained. Repeat the above operations, and different spinning dopes can be prepared by changing the type of the added fluorescence detection material.

[0032] For a method for preparing an intelligent yarn as described above, the needle diameters of the two spinnerets during the conjugate electrospinning process are 18-21 G (the international standard for the needle diameter is G), the needle tube capacity is 5-20 ml, the two high-voltage power supplies with opposite polarities are ±8-10 kV, the feeding speeds of the left and right feeding pumps are 2-5 ml / h, the distance between the left and right motors is 10-16 cm, the collecting speed of the core yarn is 1-2 r / min, the spinning temperature is 40-50 °C, the relative humidity is 30-40%, the rotation speed of the bell mouth of the collecting device is 150-300 r / min, and the outlet of the left and right feeding pumps is adjusted to be parallel to the center position of the bell mouth.

[0033] For a method for preparing an intelligent yarn as described above, the core yarn is a conductive yarn that can conduct physiological signals and wireless signals.

[0034] For a method for preparing an intelligent yarn as described above, the core yarn is a commercial conductive yarn such as silver-plated nylon, silver wire, copper wire or carbon fiber, which has good conductivity and a resistance of about 0-5 Ω / cm, and can stably transmit wireless signals.

[0035] The present invention also provides a biochemical visualization sensing - physiological signal real - time monitoring sensing network, which includes an intelligent yarn, a fabric, an NFC sensing chip, a physiological signal sensor, and an excitation terminal as described above; the intelligent yarn is implanted into the fabric in the shape of an NFC antenna through embroidery or weaving processes and then connected to the NFC sensing chip and the physiological signal sensor. The intelligent yarn and the excitation terminal transfer energy to the NFC sensing chip through inductive coupling, and the NFC sensing chip outputs a voltage to provide energy for system sensing, so as to realize the monitoring and wireless transmission of the wearer's physiological signals such as body temperature, blood oxygen, and blood pressure. The physiological signals are detected by the physiological signal sensor and then stored in the NFC sensing chip, and finally wirelessly transmitted to the APP of the excitation terminal through the antenna to realize the near - field wireless transmission of human physiological signals; this biochemical visualization sensing - physiological signal real - time monitoring sensing network can simultaneously detect multiple different biochemicals in the same area and realize the real - time detection and wireless transmission of physiological signals.

[0036] The principle of the present invention is as follows:

[0037] The electrospinning of the present invention involves the electrohydrodynamic process, in which droplets are charged to generate jets, which are then stretched and elongated to produce fibers. The basic setup of electrospinning is rather simple, and the main components include a high - voltage power supply, an injection pump, a spinneret (usually a flat or blunt tip), and a conductive collector. The power supply can be direct current (DC) or alternating current (AC).

[0038] During the electrospinning process, due to surface tension, the liquid is extruded from the spinneret, producing a pendant droplet. After being electrified, the electrostatic repulsion between the surface charges of the same polarity deforms the droplet into a Taylor cone, from which a charged jet is ejected. The jet initially extends in a straight line and then undergoes a violent oscillatory motion due to bending instability.

[0039] When the jet is stretched into a finer diameter, it rapidly solidifies, resulting in the deposition of solid fibers on the grounded collector. Generally speaking, the electrospinning process can be divided into four consecutive steps:

[0040] (i) Charging the droplet and forming a Taylor cone;

[0041] (ii) The charged jet extends in a straight line;

[0042] (iii) In the presence of an electric field, the jet thins and the phenomenon of electrical bending instability appears. The growth of electrical bending instability (also known as whipping instability);

[0043] (iv) Solidifying and collecting the jet as solid fibers on the grounded collector.

[0044] The conjugated electrospinning used in the present invention is an improved electrospinning technique. Conventional electrospinning techniques use single-nozzle spinning. Due to the instability of the jet whipping during the spinning process, the nanofibers after stretching are randomly stacked on the receiving device.

[0045] The conjugated electrospinning technique is a new electrospinning method proposed based on the influence of the power supply polarity on the electrospinning process. This device mainly consists of two high-voltage power supplies with opposite polarities and two spinneret needles. The two high-voltage power supplies with opposite polarities are respectively connected to the two spinneret needles. During the conjugated electrospinning process, an electric field is formed between the two spinneret needles. The polymer solution jet at the end of the spinneret needle is stretched and vibrated under the action of the electric field to form charged nanofibers. During the stretching and flying process of the nanofibers, they attract and embrace each other, and the positive and negative charges cancel each other out. Finally, the solvent volatilizes to form solid micro-nanofibers, which are deposited on the receiving device. In the present invention, the receiving device is in the shape of a flared mouth. After a section of the fluorescent micro-nanofibers of the detectable biochemicals ejected from the spinneret mouth is deposited on the conductive core yarn and a section is deposited on the flared mouth, through the high-speed rotation of the flared mouth, it is tightly and firmly wrapped around the surface of the conductive core yarn. During the conjugated electrospinning process, parameters such as the spinning voltage, receiving distance, and solution properties play an important role in the structure and properties of the prepared fibers.

[0046] The detection principle of hazardous chemicals in the present invention is as follows:

[0047] The recognition mechanism of TNT is photo-induced electron transfer (PET). The PET mechanism refers to the process in which a fluorescent probe interacts with the analyte to form a stable electron donor-acceptor transfer channel. Under the excitation of the excitation light, electron transfer occurs between the electron donor and the electron acceptor, reducing the radiative recombination efficiency, resulting in the fluorescence quenching of the fluorescent probe. The fluorescence quenching method based on the PET mechanism is the most widely used in the detection of nitroaromatic explosives. Since the hydrogen atoms on the benzene ring of nitroaromatic explosives are replaced by strongly electron-withdrawing nitro groups, the energy level of the π* orbital on the benzene ring is reduced, becoming an electron acceptor. When a strongly electron-withdrawing group (nitro group) contacts the electron-rich group (electron-donating groups such as amino and hydroxyl groups) of the fluorescent molecule, electron donor-acceptor interaction occurs. Under the action of light excitation, the electrons on the highest occupied molecular orbital (HOMO) of the fluorescent molecule jump to the lowest unoccupied molecular orbital (LUMO) to form an exciton. Since the electrons on the LUMO are transferred to the LUMO of the nitroaromatic explosive, the exciton is separated, and the electrons return to the ground state through a non-radiative recombination pathway, thereby causing fluorescence quenching, so as to achieve the purpose of detecting nitroaromatic explosives.

[0048] The recognition mechanism of heavy metal ions and nerve agents is intramolecular charge transfer (ICT), which is a common photophysical phenomenon. In fluorescence sensing molecules based on the ICT mechanism, the electron donor and electron acceptor are generally connected through a π system, forming a D-π-A conjugated system. When the molecule is in the excited state, intramolecular electron transfer occurs, resulting in the separation of negative charges, thus forming an intramolecular charge transfer state.

[0049] ICT-based fluorescent probes generally form a charge-separated state through intramolecular charge transfer (the acceptor unit receives electrons and the donor unit provides electrons), that is, D + -π-A － . The excited-state intramolecular charge transfer state is unstable and can return to the ground state through the recombination of positive and negative charges. If this process is a radiative transition, it is often accompanied by charge transfer (CT) fluorescence emission. The stable state of intramolecular charge transfer is greatly affected by the external environment. Therefore, when affected by guest ions, the CT emission spectrum will change. A guest that can stabilize the separation of positive and negative charges will lower the energy of the charge transfer state, resulting in a red shift of the CT fluorescence spectrum, and vice versa will cause a blue shift of the CT fluorescence spectrum.

[0050] The recognition mechanism of viruses is fluorescence resonance energy transfer (FRET). FRET refers to a photophysical process in which when the fluorescence spectrum of one fluorescent group (donor unit) overlaps with the excitation spectrum of another fluorescent group (acceptor unit), the excitation energy of the donor fluorescent molecule induces the acceptor molecule to emit fluorescence, while the fluorescence intensity of the donor fluorescent molecule itself decays. The intensity of fluorescence resonance energy transfer depends on the degree of overlap between the donor emission spectrum and the acceptor excitation spectrum, as well as the relative orientation of the dipoles of the donor and acceptor for energy transfer.

[0051] Fluorescence resonance energy transfer means that in two different fluorescent groups, if the emission spectrum of one fluorescent group (donor unit) overlaps with the absorption spectrum of another group (acceptor unit) to a certain extent, when the distance between these two fluorescent groups is appropriate, the phenomenon of fluorescence energy transfer from the donor to the acceptor can be observed, that is, the FRET phenomenon. The degree of FRET is closely related to the spatial distance between the donor and acceptor molecules. Generally, FRET can occur when the distance is 7-10 nm. As the distance increases, FRET significantly weakens.

[0052] Beneficial effects:

[0053] (1) The present invention can achieve the simultaneous detection of multiple harmful substances to cope with various complex detection scenarios;

[0054] (2) The present invention combines visual detection with wearable technology, achieving good comfort, breathability, and wearable effects during visual detection;

[0055] (3) Through the conjugate electrospinning process, the present invention can continuously produce kilometer-level intelligent yarns;

[0056] (4) The present invention creatively combines wearable physiological monitoring sensing technology with visual detection, monitoring the physiological health signals of the wearer while detecting hazardous chemicals. Description of the Drawings

[0057] Figure 1 SEM image of an intelligent yarn in Example 1;

[0058] Figure 2 Comparison chart of fluorescence spectral intensities of an intelligent yarn in Example 3 before (dashed line) and after (solid line) being exposed to a biochemical environment at room temperature for 300 seconds;

[0059] Figure 3 Schematic diagram of an NFC coil made from an intelligent yarn of the present invention through an embroidery process. Detailed Embodiments

[0060] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

[0061] The manufacturers and grades of the raw materials involved in the following embodiments are as follows:

[0062] TPA-PPV: Refer to the reference "Min, Zheng. New light emitting materials: Alternating copolymers with hole transport and emitting chromophores [J]. Journal of Applied Polymer Science, 1999.";

[0063] 4,4'-bis(diethylamino)-benzene diazole: Refer to the reference "Fu Yanyan, Design of Organic Functional Molecules and Their Applications in Chemical Sensors [D]. Institute of Chemistry, Chinese Academy of Sciences, 2007.";

[0064] 4,4'-Bis(dimethylamino)-benzidine: Reference "Yanyan, Fu. Simple and Efficient Chromophoric-Fluorogenic Probes for Diethylchlorophosphate Vapor. [J]. ACS sensors, 2018.";

[0065] Pyrene-naphthalimide dyad: Reference "He X P. Rapid Identification of the Receptor-Binding Specificity of Influenza A Viruses by Fluorogenic Glycofoldamers [J]. Angewandte Chemie International Edition, 2016.";

[0066] Polyvinylidene fluoride PVDF: Macklin-P875314, Mw ~ 40w;

[0067] Polystyrene PS: Sigma-Aldrich-441147, Mw ~ 35w;

[0068] Polycaprolactone PCL: Sigma-Aldrich-440744, Mw ~ 8w;

[0069] Silver-plated nylon: Shandong Boyin Surface Functional Materials Co., Ltd., diameter 0.06mm, resistance 3Ω / cm;

[0070] Metal conductive wire: 316 stainless steel wire, manufactured by Dongguan Shengxin Special Rope Factory, diameter 0.1mm, resistance 0.41Ω / cm;

[0071] Carbon fiber: Taobao Youlida anti-static essence product, diameter 0.69mm, resistance 2.88Ω / cm;

[0072] Pure silver yarn: Taobao Tek silver fiber 5Ω / cm, diameter 0.7mm.

[0073] The test methods involved in the following examples are as follows:

[0074] Fluorescence quenching efficiency of the intelligent yarn for saturated TNT saturated vapor within 300 s: Place 10 g of the TNT compound to be tested at the bottom of a cuvette, cover the test substance with a filter paper of appropriate size to avoid direct contact between the sensor and the test substance, then seal the cuvette and place it at room temperature for 12 h to ensure that the TNT in the cuvette reaches saturated vapor (10 ppb). After that, place the cuvette in an FP-6500 fluorescence photometer, and quickly place the prepared yarn facing the excitation light source into the cuvette to test the degree of fluorescence quenching;

[0075] Instant response time to the virus: Calculate from the time when the intelligent yarn comes into contact with the virus droplets until the intelligent yarn begins to exhibit a significant color change (visually observing that the yarn emits a significant green fluorescence);

[0076] Detection limit for heavy metal ions: Immerse the yarn in a solution containing different concentrations of mercury ions. After taking it out, it is found that the color of the yarn changes to red, and the more obvious the color change is with the increase in mercury ion concentration. The lowest detection limit can reach 1×10 -5 M, that is, when the yarn is immersed in a mercury ion solution of 1 ×10 -5 M, there is no visible change in the yarn to the naked eye;

[0077] Test method for the detection limit of nerve gas mimetic vapor: Use an FP-6500 fluorescence photometer from JASCO Corporation of Japan to measure the fluorescence intensity of the intelligent yarn at different gas concentrations starting from the saturated DCP vapor concentration (the DCP vapor concentrations are 28.20, 6.60, 2.64, 1.32, 0.66, and 0.33 ppm respectively). The fluorescence enhancements of the intelligent yarn are 696%, 336%, 187%, 130%, 82.1%, and 67.5% respectively. Make a scatter plot of the fluorescence intensity response value versus the concentration, perform curve fitting on the obtained scatter plot, and take the concentration when the fluorescence intensity is 0.01 as the detection limit;

[0078] Test method for the fluorescence spectral intensity before exposure to biochemicals (saturated DCP vapor) for 300 s: Use an FP-6500 fluorescence photometer from JASCO Corporation of Japan. Put the yarn into the saturated DCP vapor, clamp it, and then measure the fluorescence intensity;

[0079] Test method for the fluorescence spectral intensity after exposure to biochemicals (saturated DCP vapor) for 300 s: Use an FP-6500 fluorescence photometer from JASCO Corporation of Japan. Take out the yarn that has been exposed to saturated DCP vapor for 300 s and immediately put it into the instrument to measure its fluorescence intensity;

[0080] The virus in the example is specifically the influenza virus (H1N1);

[0081] The nerve gas in the examples is specifically sarin gas (due to the extremely high harmfulness and strong restrictiveness of obtaining sarin agents, diethyl chlorophosphate, a commonly used sarin agent mimic in the academic community, is used as the detection object for nerve agents in the present invention).

[0082] Example 1

[0083] A preparation method of intelligent yarn is as follows:

[0084] (1) Preparation of raw materials;

[0085] TNT fluorescence detection material: TPA-PPV;

[0086] Heavy metal ion fluorescence detection material: 4,4'-bis(diethylamino)-benzene diazine;

[0087] Nerve gas fluorescence detection material: 4,4'-bis(dimethylamino)-benzene diazine;

[0088] Virus fluorescence detection material: pyrene-naphthalimide binary group;

[0089] Hydrophobic polymer: polyvinylidene fluoride PVDF;

[0090] Solvent: a homogeneous solution prepared from N,N-dimethylformamide (DMF) and acetone in a weight ratio of 7:3;

[0091] Core yarn: silver-plated nylon;

[0092] (2) Preparation of spinning dope;

[0093] Add the hydrophobic polymer to the solvent to form a solution. The hydrophobic polymer will not dissolve immediately in the solution. Heat and stir the above solution in an oil bath at 50 °C until the hydrophobic polymer is completely dissolved, and the solution becomes colorless and transparent. After the hydrophobic polymer is completely dissolved, add one of the 4 fluorescence detection materials in the raw materials, and then stir in the oil bath until the fluorescence detection material is completely dissolved to form a stable system. Put the solution into an ultrasonic instrument with a power of 30 W for ultrasonic oscillation for 30 min to remove the bubbles in the solution. After ultrasonic treatment, a stable and usable spinning dope is obtained. Among them, in the spinning dope, the mass ratio of the fluorescence detection material to the hydrophobic polymer is 5:95, and the mass ratio of the hydrophobic polymer to the solvent is 10:90;

[0094] (3) Repeat the above operations to prepare the remaining three kinds of spinning dope by changing the type of the added fluorescence detection material;

[0095] (4) Conjugate electrospinning;

[0096] Wind the core yarn around the collecting roller, suck an appropriate amount of spinning dope with a syringe. For each type of spinning dope, suck two syringes. Start the machine, and wrap the fiber made by coaxial electrospinning of the spinning dope onto the surface of the conductive core yarn. After wrapping a section of TNT fluorescence detection fiber on the conductive core yarn, replace the syringe filled with the spinning dope added with virus fluorescence detection material and then perform the coaxial electrospinning process again. Repeat the above operations. By changing four different types of spinning dope, wrap different fluorescence detection fibers on different line segments of the conductive core yarn to form an intelligent yarn that can simultaneously detect TNT / virus / heavy metal ions / nerve gas;

[0097] Among them, during the coaxial electrospinning process, the needle diameters of the two spinneret orifices are 18G, the syringe capacity is 10 ml, the two high-voltage power supplies with opposite polarities are ±8 kv, the propulsion speeds of the left and right propulsion pumps are 2 ml / h, the distance between the left and right motors is 10 cm, the collection speed of the core yarn is 1.1 r / min, the spinning temperature is 45 °C, the relative humidity is 32%, the rotation speed of the bell mouth of the collection device is 150 r / min, and the outlet of the left and right propulsion pumps is adjusted to be parallel to the center position of the bell mouth.

[0098] As Figure 1 shown, an intelligent yarn prepared has a core-shell structure, including a core yarn and cortical fibers. The diameter of the intelligent yarn is 0.12 mm, and the diameter of the cortical fibers is 0.06 mm; within 300 s, the fluorescence quenching efficiency of the intelligent yarn for saturated TNT saturated vapor reaches 30%, the instant response time for the virus is within 300 s, the detection limit for heavy metal ions (Hg ﹢ ) is 2×10 -5 M, and the lowest detection limit for nerve gas is 0.26 ppb; the fluorescence spectral intensity of the intelligent yarn before being exposed to the biochemical (saturated DCP vapor) environment at 25 °C for 300 s is 10, and the fluorescence spectral intensity after 300 s of exposure is 90.

[0099] Application: As Figure 3 shown, a biochemical visual sensing - physiological signal real-time monitoring sensing network includes an intelligent yarn, a fabric, an NFC sensing chip, a physiological signal sensor, and an excitation terminal as described above; the intelligent yarn is implanted into the fabric in the shape of an NFC antenna through embroidery or weaving processes and then connected to the NFC sensing chip and the physiological signal sensor. The intelligent yarn and the excitation terminal transfer energy to the NFC sensing chip through inductive coupling.

[0100] In the prepared biochemical visual sensing - physiological signal real-time monitoring sensing network, when the wearer wears it and the terminal excitation is started, the mobile phone terminal can read and display the physiological signals of the wearer such as temperature and heart rate within 1 min.

[0101] Example 2

[0102] A preparation method of intelligent yarn, the specific steps are as follows:

[0103] (1) Preparation of raw materials;

[0104] TNT fluorescence detection material: TPA-PPV;

[0105] Heavy metal ion fluorescence detection material: 4,4'-bis(diethylamino)-benzene diazole;

[0106] Nerve gas fluorescence detection material: 4,4'-bis(dimethylamino)-benzene diazole;

[0107] Virus fluorescence detection material: pyrene-naphthalimide binary group;

[0108] Hydrophobic polymer: polyvinylidene fluoride PVDF;

[0109] Solvent: a homogeneous solution prepared from N,N-dimethylformamide (DMF) and acetone in a weight ratio of 6:4;

[0110] Core yarn: silver-plated nylon;

[0111] (2) Preparation of spinning dope;

[0112] Add the hydrophobic polymer to the solvent to form a solution. The hydrophobic polymer will not dissolve immediately in the solution. Heat and stir the above solution in an oil bath at 60 °C until the hydrophobic polymer is completely dissolved, and the solution becomes colorless and transparent. After the hydrophobic polymer is completely dissolved, add one of the 4 fluorescence detection materials in the raw materials. After adding, stir in the oil bath until the fluorescence detection material is completely dissolved to form a stable system. Put the solution into an ultrasonic instrument with a power of 35 W for ultrasonic oscillation for 35 min to remove the bubbles in the solution. After ultrasonic treatment, a stable and usable spinning dope is obtained. Among them, in the spinning dope, the mass ratio of the fluorescence detection material to the hydrophobic polymer is 7:93, and the mass ratio of the hydrophobic polymer to the solvent is 11:89;

[0113] (3) Repeat the above operations to prepare the remaining three kinds of spinning dope by changing the type of the added fluorescence detection material;

[0114] (4) Conjugate electrospinning;

[0115] Wind the core yarn around the collecting roller, suck an appropriate amount of spinning dope with a syringe, suck two syringes of each kind of spinning dope respectively, start the machine, and wrap the fiber made by conjugate electrospinning of the spinning dope onto the surface of the conductive core yarn. After wrapping a section of TNT fluorescence detection fiber on the conductive core yarn, replace the syringe filled with the spinning dope added with virus fluorescence detection material and then carry out the conjugate electrospinning process again. Repeat the above operations. By changing four different kinds of spinning dope, wrap different fluorescence detection fibers on different line segments of the conductive core yarn respectively to form an intelligent yarn that can detect TNT / virus / heavy metal ions / nerve gas simultaneously;

[0116] Among them, in the conjugate electrospinning process, the needle diameters of the two spinnerets are 20G, the syringe capacity is 10 ml, the two high-voltage power supplies with opposite polarities are ±8 kv, the propulsion speeds of the left and right propulsion pumps are 3.5 ml / h, the distance between the left and right motors is 13 cm, the collection speed of the core yarn is 1.4 r / min, the spinning temperature is 47 °C, the relative humidity is 36%, the rotation speed of the bell mouth of the collection device is 170 r / min, and the outlet of the left and right propulsion pumps is adjusted to be parallel to the center position of the bell mouth.

[0117] An intelligent yarn obtained has a core-shell structure, including a core yarn and cortical fibers. The diameter of the intelligent yarn is 0.12 mm, and the diameter of the cortical fibers is 0.06 mm; within 300 s, the fluorescence quenching efficiency of the intelligent yarn for saturated TNT saturated vapor reaches 32%, the instant response time for the virus is within 240 s, the detection limit for heavy metal ions (Cu ﹢ ) is 1.7×10 -5 M, and the lowest detection limit for nerve gas is 0.22 ppb; the fluorescence spectral intensity of the intelligent yarn before being exposed to the biochemical (saturated DCP vapor) environment at 26 °C for 300 s is 10, and the fluorescence spectral intensity after 300 s of exposure is 103.

[0118] Application: A biochemical visualization sensing - physiological signal real-time monitoring sensing network, including an intelligent yarn, a fabric, an NFC sensing chip, a physiological signal sensor and an excitation terminal as described above; the intelligent yarn is implanted into the fabric in the shape of an NFC antenna through embroidery or weaving process and then connected to the NFC sensing chip and the physiological signal sensor, and the intelligent yarn and the excitation terminal transfer energy to the NFC sensing chip through inductive coupling.

[0119] In the obtained biochemical visualization sensing - physiological signal real-time monitoring sensing network, when the wearer wears it and the terminal excitation is started, the mobile phone terminal can read and display the physiological signals of the wearer such as temperature and heart rate within 1 min.

[0120] Example 3

[0121] A preparation method of an intelligent yarn, the specific steps are as follows:

[0122] (1) Preparation of raw materials;

[0123] TNT fluorescence detection material: TPA-PPV;

[0124] Heavy metal ion fluorescence detection material: 4,4'-bis(diethylamino)-benzene diazine;

[0125] Nerve gas fluorescence detection material: 4,4'-bis(dimethylamino)-benzene diazine;

[0126] Virus fluorescence detection material: pyrene-naphthalimide binary group;

[0127] Hydrophobic polymer: polyvinylidene fluoride;

[0128] Solvent: a homogeneous solution prepared from N,N-dimethylformamide (DMF) and acetone in a weight ratio of 7:3;

[0129] Core yarn: pure silver yarn;

[0130] (2) Preparation of spinning dope;

[0131] Add the hydrophobic polymer to the solvent to form a solution. The hydrophobic polymer will not dissolve immediately in the solution. Heat and stir the above solution in an oil bath at 70 °C until the hydrophobic polymer is completely dissolved, and the solution becomes colorless and transparent. After the hydrophobic polymer is completely dissolved, add one of the 4 fluorescence detection materials in the raw materials. After adding, stir in the oil bath until the fluorescence detection material is completely dissolved to form a stable system. Put the solution into an ultrasonic instrument with a power of 38 W for ultrasonic oscillation for 40 min to remove the bubbles in the solution. After ultrasonic treatment, a stable and usable spinning dope is obtained. Among them, in the spinning dope, the mass ratio of the fluorescence detection material to the hydrophobic polymer is 10:90, and the mass ratio of the hydrophobic polymer to the solvent is 12:88;

[0132] (3) Repeat the above operations to prepare the remaining three spinning dopes by changing the type of the added fluorescence detection material;

[0133] (4) Conjugated electrospinning;

[0134] Wind the core yarn around the collecting roller, suck an appropriate amount of spinning dope with a syringe. For each spinning dope, suck two syringes respectively. Start the machine and wrap the fiber formed by conjugated electrospinning of the spinning dope onto the surface of the conductive core yarn. After wrapping a section of TNT fluorescence detection fiber on the conductive core yarn, replace the syringe filled with the spinning dope added with virus fluorescence detection material and then carry out the conjugated electrospinning process again. Repeat the above operations. By changing four different spinning dopes, wrap different fluorescence detection fibers on different line segments of the conductive core yarn to form an intelligent yarn that can simultaneously detect TNT / virus / heavy metal ions / nerve gas;

[0135] Among them, in the conjugate electrospinning process, the needle diameters of the two spinnerets are 21G, the syringe capacities are 10 ml, the two high-voltage power supplies with opposite polarities are ±10 kv, the feeding speeds of the left and right feeding pumps are 5 ml / h, the distance between the left and right motors is 10 cm, the collecting speed of the core yarn is 2 r / min, the spinning temperature is 50 °C, the relative humidity is 30%, the rotation speed of the bell mouth of the collecting device is 200 r / min, and the spinning outlets of the left and right feeding pumps are adjusted to be parallel to the center position of the bell mouth.

[0136] A kind of intelligent yarn is prepared, which has a core-shell structure and includes a core yarn and cortical fibers. The diameter of the intelligent yarn is 0.8 mm, and the diameter of the cortical fibers is 0.1 mm; within 300 s, the fluorescence quenching efficiency of the intelligent yarn for saturated TNT saturated vapor reaches 35%, the instant response time to viruses is within 180 s, the detection limit for heavy metal ions (Co ﹢ ) is 1.2×10 -5 M, and the lowest detection limit for nerve gas is 0.15 ppb; as Figure 2 shown, the fluorescence spectrum intensity of the intelligent yarn before being exposed to the biochemical (saturated DCP vapor) environment at 27 °C for 300 s is 10, and the fluorescence spectrum intensity after 300 s of exposure is 115.

[0137] Application: A biochemical visualization sensing - physiological signal real-time monitoring sensing network, which includes an intelligent yarn, a fabric, an NFC sensing chip, a physiological signal sensor and an excitation terminal as described above; the intelligent yarn is implanted into the fabric in the shape of an NFC antenna through embroidery or weaving processes and then connected to the NFC sensing chip and the physiological signal sensor, and the intelligent yarn and the excitation terminal transfer energy to the NFC sensing chip through inductive coupling.

[0138] In the prepared biochemical visualization sensing - physiological signal real-time monitoring sensing network, when the wearer wears it and the terminal excitation is started, the mobile phone terminal can read and display the physiological signals of the wearer such as temperature and heart rate within 1 min.

[0139] Example 4

[0140] A preparation method of an intelligent yarn, the specific steps are as follows:

[0141] (1) Preparation of raw materials;

[0142] TNT fluorescence detection material: TPA-PPV;

[0143] Heavy metal ion fluorescence detection material: 4,4'-bis(diethylamino)-benzene diazole;

[0144] Nerve gas fluorescence detection material: 4,4'-bis(dimethylamino)-benzene diazole;

[0145] Virus fluorescence detection material: pyrene-naphthalimide binary group;

[0146] Hydrophobic polymer: polystyrene PS;

[0147] Solvent: a homogeneous solution prepared by mixing N,N-dimethylformamide (DMF) and acetone in a weight ratio of 7:3;

[0148] Core yarn: pure silver yarn;

[0149] (2) Preparation of spinning dope;

[0150] Add the hydrophobic polymer to the solvent to form a solution. The hydrophobic polymer will not dissolve immediately in the solution. Heat and stir the above solution in an oil bath at 50 °C until the hydrophobic polymer is completely dissolved and the solution becomes colorless and transparent. After the hydrophobic polymer is completely dissolved, add one of the 4 fluorescence detection materials in the raw materials. After adding, stir in the oil bath until the fluorescence detection material is completely dissolved to form a stable system. Place the solution in an ultrasonic instrument with a power of 42 W for ultrasonic treatment for 45 min to remove the bubbles in the solution. After ultrasonic treatment, a stable and usable spinning dope is obtained. Among them, in the spinning dope, the mass ratio of the fluorescence detection material to the hydrophobic polymer is 5:95, and the mass ratio of the hydrophobic polymer to the solvent is 18:82;

[0151] (3) Repeat the above operations to prepare the remaining three spinning dopes by changing the type of the added fluorescence detection material;

[0152] (4) Conjugate electrospinning;

[0153] Wind the core yarn on the collecting roller, suck an appropriate amount of spinning dope with a syringe. For each spinning dope, suck two syringes respectively. Start the machine and wrap the fiber formed by conjugate electrospinning of the spinning dope onto the surface of the conductive core yarn. After wrapping a section of TNT fluorescence detection fiber on the conductive core yarn, replace the syringe filled with the spinning dope added with virus fluorescence detection material and then perform the conjugate electrospinning process again. Repeat the above operations. By changing four different spinning dopes, wrap different fluorescence detection fibers on different line segments of the conductive core yarn to form an intelligent yarn that can simultaneously detect TNT / virus / heavy metal ions / nerve gas;

[0154] Among them, in the conjugate electrospinning process, the needle diameters of the two spinnerets are 18G, the syringe capacity is 10 ml, the two high-voltage power supplies with opposite polarities are ±8 kv, the propulsion speeds of the left and right propulsion pumps are 2 ml / h, the distance between the left and right motors is 10 cm, the collecting speed of the core yarn is 1.1 r / min, the spinning temperature is 45 °C, the relative humidity is 32%, the rotation speed of the bell mouth of the collecting device is 150 r / min, and the spinning outlets of the left and right propulsion pumps are adjusted to be parallel to the center position of the bell mouth.

[0155] An intelligent yarn is prepared, which has a core - sheath structure, including a core yarn and cortical fibers. The diameter of the intelligent yarn is 0.8 mm, and the diameter of the cortical fibers is 0.1 mm; within 300 s, the fluorescence quenching efficiency of the intelligent yarn for saturated TNT saturated vapor reaches 30%, the instant response time to viruses is within 300 s, the detection limit for heavy metal ions (Hg ﹢ ) is 2×10 -5 M, and the lowest detection limit for nerve gas is 0.26 ppb; the fluorescence spectral intensity of the intelligent yarn before being exposed to a biochemical (saturated DCP vapor) environment at 25°C for 300 s is 10, and the fluorescence spectral intensity after 300 s of exposure is 90.

[0156] Application: A biochemical visualization sensing - physiological signal real - time monitoring sensing network, including an intelligent yarn, a fabric, an NFC sensing chip, a physiological signal sensor, and an excitation terminal as described above; the intelligent yarn is implanted into the fabric in the shape of an NFC antenna through embroidery or weaving processes and then connected to the NFC sensing chip and the physiological signal sensor. The intelligent yarn and the excitation terminal transfer energy to the NFC sensing chip through inductive coupling.

[0157] In the prepared biochemical visualization sensing - physiological signal real - time monitoring sensing network, when the wearer wears it and the terminal excitation is started, the mobile phone terminal can read and display the physiological signals of the wearer, such as temperature and heart rate, within 1 min.

[0158] Example 5

[0159] A preparation method of an intelligent yarn, the specific steps are as follows:

[0160] (1) Preparation of raw materials;

[0161] Fluorescence detection material for TNT: TPA - PPV;

[0162] Fluorescence detection material for heavy metal ions: 4,4'-bis(diethylamino)-benzidine diazide;

[0163] Fluorescence detection material for nerve gas: 4,4'-bis(dimethylamino)-benzidine diazide;

[0164] Fluorescence detection material for viruses: Pyrene - naphthalimide binary group;

[0165] Hydrophobic polymer: Polystyrene PS;

[0166] Solvent: A homogeneous solution prepared by mixing N,N - dimethylformamide (DMF) and acetone in a weight ratio of 6:4;

[0167] Core yarn: Silver - plated nylon;

[0168] (2) Preparation of spinning dope;

[0169] Add a hydrophobic polymer to a solvent to form a solution. The hydrophobic polymer does not immediately dissolve in the solution. Heat and stir the above solution in an oil bath at 60 °C until the hydrophobic polymer is completely dissolved, and the solution becomes colorless and transparent. After the hydrophobic polymer is completely dissolved, add one of the 4 fluorescence detection materials in the raw materials to the solution, and then stir in the oil bath until the fluorescence detection material is completely dissolved to form a stable system. Place the solution in an ultrasonic instrument with a power of 46 W for ultrasonic oscillation for 50 min to remove the bubbles in the solution. After ultrasonic treatment, a stable and usable spinning dope is obtained. Among them, in the spinning dope, the mass ratio of the fluorescence detection material to the hydrophobic polymer is 7:93, and the mass ratio of the hydrophobic polymer to the solvent is 19:81;

[0170] (3) Repeat the above operations to prepare the remaining three spinning dopes by changing the type of the added fluorescence detection material;

[0171] (4) Coaxial electrospinning;

[0172] Wind the core yarn on the collecting roller, suck an appropriate amount of spinning dope with a syringe. For each spinning dope, suck two syringes respectively. Start the machine, and wrap the fiber formed by coaxial electrospinning of the spinning dope onto the surface of the conductive core yarn. After wrapping a section of TNT fluorescence detection fiber on the conductive core yarn, replace the syringe filled with the spinning dope containing the virus fluorescence detection material and then perform the coaxial electrospinning process again. Repeat the above operations. By changing four different spinning dopes, wrap different fluorescence detection fibers on different line segments of the conductive core yarn to form an intelligent yarn that can simultaneously detect TNT / virus / heavy metal ions / nerve gas;

[0173] Among them, during the coaxial electrospinning process, the needle diameters of the two spinnerets are 20G, the syringe capacity is 10 ml, the two high-voltage power supplies with opposite polarities are ±8 kV, the feeding speeds of the left and right feeding pumps are 3.5 ml / h, the distance between the left and right motors is 13 cm, the collecting speed of the core yarn is 1.4 r / min, the spinning temperature is 47 °C, the relative humidity is 36%, the rotation speed of the bell mouth of the collecting device is 170 r / min, and the outlets of the left and right feeding pumps are adjusted to be parallel to the center position of the bell mouth.

[0174] An intelligent yarn prepared has a core-shell structure, including a core yarn and cortical fibers. The diameter of the intelligent yarn is 0.12 mm, and the diameter of the cortical fibers is 0.06 mm; within 300 s, the fluorescence quenching efficiency of the intelligent yarn for saturated TNT saturated vapor reaches 32%, the instant response time for the virus is within 240 s, and the detection limit for heavy metal ions (Cu ﹢ ) is 1.7×10 -5For M, the lowest detection limit for nerve gas is 0.22 ppb; the fluorescence spectral intensity of the intelligent yarn before exposure to a biochemical (saturated DCP vapor) environment at 26 °C for 300 seconds is 10, and the fluorescence spectral intensity after 300 seconds of exposure is 103.

[0175] Application: A biochemical visualization sensing - real - time physiological signal monitoring sensing network, including an intelligent yarn, a fabric, an NFC sensing chip, a physiological signal sensor, and an excitation terminal as described above; the intelligent yarn is implanted into the fabric in the shape of an NFC antenna through embroidery or weaving processes and then connected to the NFC sensing chip and the physiological signal sensor, and the intelligent yarn and the excitation terminal transfer energy to the NFC sensing chip through inductive coupling.

[0176] In the prepared biochemical visualization sensing - real - time physiological signal monitoring sensing network, when the wearer wears it and the terminal excitation is started, the mobile phone terminal can read and display the wearer's physiological signals such as temperature and heart rate within 1 minute.

[0177] Example 6

[0178] A preparation method of an intelligent yarn, the specific steps are as follows:

[0179] (1) Preparation of raw materials;

[0180] TNT fluorescence detection material: TPA - PPV;

[0181] Heavy metal ion fluorescence detection material: 4,4'-bis(diethylamino)-benzidine diazide;

[0182] Nerve gas fluorescence detection material: 4,4'-bis(dimethylamino)-benzidine diazide;

[0183] Virus fluorescence detection material: Pyrene - naphthalimide binary group;

[0184] Hydrophobic polymer: Polystyrene PS;

[0185] Solvent: A homogeneous solution prepared by mixing N,N - dimethylformamide (DMF) and acetone in a weight ratio of 7:3;

[0186] Core yarn: Metal conductive wire;

[0187] (2) Preparation of the spinning dope;

[0188] A hydrophobic polymer is added to a solvent to prepare a solution. The hydrophobic polymer does not immediately dissolve in the solution. The above solution is heated and stirred in an oil bath at 70 °C until the hydrophobic polymer is completely dissolved, and the solution becomes colorless and transparent. After the hydrophobic polymer is completely dissolved, one of the 4 fluorescence detection materials in the raw materials is added to the solution. After addition, it is stirred in the oil bath until the fluorescence detection material is completely dissolved to form a stable system. The solution is placed in an ultrasonic instrument with a power of 48 W for ultrasonic oscillation for 55 min to remove the bubbles in the solution. After ultrasonic treatment, a stable and usable spinning dope is obtained. Among them, in the spinning dope, the mass ratio of the fluorescence detection material to the hydrophobic polymer is 10:90, and the mass ratio of the hydrophobic polymer to the solvent is 20:80.

[0189] (3) Repeat the above operation to prepare the remaining three spinning dopes by changing the type of the added fluorescence detection material.

[0190] (4) Coaxial electrospinning;

[0191] Wind the core yarn on the collecting roller, suck an appropriate amount of spinning dope with a syringe. For each spinning dope, suck two syringes respectively. Start the machine, and use coaxial electrospinning to wrap the fiber made from the spinning dope onto the surface of the conductive core yarn. After wrapping a section of TNT fluorescence detection fiber on the conductive core yarn, replace the syringe filled with the spinning dope added with the virus fluorescence detection material and then carry out the coaxial electrospinning process again. Repeat the above operation. By changing four different spinning dopes, different fluorescence detection fibers are wrapped on different line segments of the conductive core yarn to form an intelligent yarn that can simultaneously detect TNT / virus / heavy metal ions / nerve gas.

[0192] Among them, in the coaxial electrospinning process, the needle diameters of the two spinnerets are 21G, the syringe capacity is 10 ml, the two high-voltage power supplies with opposite polarities are ±10 kv, the propulsion speeds of the left and right propulsion pumps are 5 ml / h, the distance between the left and right motors is 10 cm, the collecting speed of the core yarn is 2 r / min, the spinning temperature is 50 °C, the relative humidity is 30%, the rotation speed of the bell mouth of the collecting device is 200 r / min, and the spinning outlets of the left and right propulsion pumps are adjusted to be parallel to the center position of the bell mouth.

[0193] An intelligent yarn is prepared, which has a core-shell structure and includes a core yarn and cortical fibers. The diameter of the intelligent yarn is 0.15 mm, and the diameter of the cortical fibers is 0.05 mm. The fluorescence quenching efficiency of the intelligent yarn for saturated TNT saturated vapor reaches 35% within 300 s, the instant response time to the virus is within 180 s, and the detection limit for heavy metal ions (Co ﹢ ) is 1.2×10 -5For M, the lowest detection limit for nerve gas is 0.15 ppb; the fluorescence spectral intensity of the intelligent yarn before exposure to a biochemical (saturated DCP vapor) environment at 27 °C for 300 seconds is 10, and the fluorescence spectral intensity after 300 seconds of exposure is 115.

[0194] Application: A biochemical visualization sensing - real - time physiological signal monitoring sensing network, including an intelligent yarn, a fabric, an NFC sensing chip, a physiological signal sensor, and an excitation terminal as described above; the intelligent yarn is implanted into the fabric in the shape of an NFC antenna through embroidery or weaving processes and then connected to the NFC sensing chip and the physiological signal sensor, and the intelligent yarn and the excitation terminal transfer energy to the NFC sensing chip through inductive coupling.

[0195] In the prepared biochemical visualization sensing - real - time physiological signal monitoring sensing network, when the wearer wears it and the terminal excitation is started, the mobile phone terminal can read and display the physiological signals of the wearer, such as temperature and heart rate, within 1 minute.

[0196] Example 7

[0197] A preparation method of an intelligent yarn is as follows:

[0198] (1) Preparation of raw materials;

[0199] TNT fluorescence detection material: TPA - PPV;

[0200] Heavy metal ion fluorescence detection material: 4,4'-bis(diethylamino)-benzidine diazide;

[0201] Nerve gas fluorescence detection material: 4,4'-bis(dimethylamino)-benzidine diazide;

[0202] Virus fluorescence detection material: pyrene - naphthalimide binary group;

[0203] Hydrophobic polymer: polycaprolactone PCL;

[0204] Solvent: A homogeneous solution prepared by mixing N,N - dimethylformamide (DMF) and acetone in a weight ratio of 7:3;

[0205] Core yarn: metal conductive wire;

[0206] (2) Preparation of the spinning dope;

[0207] A hydrophobic polymer is added to a solvent to prepare a solution. The hydrophobic polymer does not immediately dissolve in the solution. The above solution is heated and stirred in an oil bath at 50 °C until the hydrophobic polymer is completely dissolved, and the solution becomes colorless and transparent. After the hydrophobic polymer is completely dissolved, one of the 4 fluorescence detection materials in the raw materials is added to the solution. After adding, it is stirred in an oil bath until the fluorescence detection material is completely dissolved to form a stable system. The solution is placed in an ultrasonic instrument with a power of 50 W for ultrasonic oscillation for 60 min to remove the bubbles in the solution. After ultrasonic treatment, a stable and usable spinning dope is obtained. Among them, in the spinning dope, the mass ratio of the fluorescence detection material to the hydrophobic polymer is 5:95, and the mass ratio of the hydrophobic polymer to the solvent is 10:90;

[0208] (3) Repeat the above operations to prepare the remaining three spinning dopes by changing the type of the added fluorescence detection material;

[0209] (4) Coaxial electrospinning;

[0210] Wind the core yarn on the collecting roller, suck an appropriate amount of spinning dope with a syringe. Two syringes are sucked for each type of spinning dope. Start the machine, and use coaxial electrospinning to wrap the spinning dope into fibers on the surface of the conductive core yarn. After wrapping a section of TNT fluorescence detection fiber on the conductive core yarn, replace the syringe filled with the spinning dope added with the virus fluorescence detection material and then perform the coaxial electrospinning process again. Repeat the above operations. By changing four different spinning dopes, different fluorescence detection fibers are wrapped on different line segments of the conductive core yarn to form an intelligent yarn that can simultaneously detect TNT / virus / heavy metal ions / nerve gas;

[0211] Among them, in the coaxial electrospinning process, the needle diameters of the two spinnerets are 18G, the syringe capacity is 10 ml, the two high-voltage power supplies with opposite polarities are ±8 kv, the propulsion speeds of the left and right propulsion pumps are 2 ml / h, the distance between the left and right motors is 10 cm, the collection speed of the core yarn is 1.1 r / min, the spinning temperature is 45 °C, the relative humidity is 32%, the rotation speed of the bell mouth of the collection device is 150 r / min, and the spinning outlets of the left and right propulsion pumps are adjusted to be parallel to the center position of the bell mouth.

[0212] An intelligent yarn prepared has a core-shell structure, including a core yarn and cortical fibers. The diameter of the intelligent yarn is 0.15 mm, and the diameter of the cortical fibers is 0.05 mm; within 300 s, the fluorescence quenching efficiency of the intelligent yarn for saturated TNT saturated vapor reaches 30%, the instant response time to the virus is within 300 s, and the detection limit for heavy metal ions (Hg ﹢ ) is 2×10 -5For M, the lowest detection limit for nerve gas is 0.26 ppb; the fluorescence spectral intensity of the intelligent yarn before exposure to a biochemical (saturated DCP vapor) environment at 25°C for 300 seconds is 10, and the fluorescence spectral intensity after 300 seconds of exposure is 90.

[0213] Application: A biochemical visualization sensing - real - time monitoring sensing network for physiological signals, including an intelligent yarn, a fabric, an NFC sensing chip, a physiological signal sensor, and an excitation terminal as described above; the intelligent yarn is implanted into the fabric in the shape of an NFC antenna through embroidery or weaving processes and then connected to the NFC sensing chip and the physiological signal sensor, and the intelligent yarn and the excitation terminal transfer energy to the NFC sensing chip through inductive coupling.

[0214] In the prepared biochemical visualization sensing - real - time monitoring sensing network for physiological signals, when the wearer wears it and the terminal excitation is started, the mobile phone terminal can read and display the physiological signals of the wearer, such as temperature and heart rate, within 1 minute.

[0215] Example 8

[0216] A preparation method of an intelligent yarn, the specific steps are as follows:

[0217] (1) Preparation of raw materials;

[0218] TNT fluorescence detection material: TPA - PPV;

[0219] Heavy metal ion fluorescence detection material: 4,4'-bis(diethylamino)-benzidine diazide;

[0220] Nerve gas fluorescence detection material: 4,4'-bis(dimethylamino)-benzidine diazide;

[0221] Virus fluorescence detection material: pyrene - naphthalimide binary group;

[0222] Hydrophobic polymer: polycaprolactone PCL;

[0223] Solvent: a homogeneous solution prepared by mixing N,N - dimethylformamide (DMF) and acetone in a weight ratio of 6:4;

[0224] Core yarn: carbon fiber;

[0225] (2) Preparation of the spinning dope;

[0226] A hydrophobic polymer is added to a solvent to prepare a solution. The hydrophobic polymer does not immediately dissolve in the solution. The above solution is heated and stirred in an oil bath at 60 °C until the hydrophobic polymer is completely dissolved, and the solution becomes colorless and transparent. After the hydrophobic polymer is completely dissolved, one of the 4 fluorescence detection materials in the raw materials is added to the solution. After adding, it is stirred in an oil bath until the fluorescence detection material is completely dissolved to form a stable system. The solution is placed in an ultrasonic instrument with a power of 55 W for ultrasonic oscillation for 65 min to remove the bubbles in the solution. After ultrasonic treatment, a stable and usable spinning dope is obtained. Among them, in the spinning dope, the mass ratio of the fluorescence detection material to the hydrophobic polymer is 7:93, and the mass ratio of the hydrophobic polymer to the solvent is 11:89;

[0227] (3) Repeat the above operation to prepare the remaining three spinning dopes by changing the type of the added fluorescence detection material;

[0228] (4) Coaxial electrospinning;

[0229] Wind the core yarn on the collecting roller, suck an appropriate amount of spinning dope with a syringe. For each spinning dope, suck two syringes respectively. Start the machine, and wrap the fiber prepared by coaxial electrospinning of the spinning dope onto the surface of the conductive core yarn. After wrapping a section of TNT fluorescence detection fiber on the conductive core yarn, replace the syringe filled with the spinning dope added with the virus fluorescence detection material and then perform the coaxial electrospinning process again. Repeat the above operation. By changing four different spinning dopes, different fluorescence detection fibers are wrapped on different line segments of the conductive core yarn to form an intelligent yarn that can simultaneously detect TNT / virus / heavy metal ions / nerve gas;

[0230] Among them, in the coaxial electrospinning process, the needle diameters of the two spinnerets are 20G, the syringe capacity is 10 ml, the two high-voltage power supplies with opposite polarities are ±8 kv, the propulsion speeds of the left and right propulsion pumps are 3.5 ml / h, the distance between the left and right motors is 13 cm, the collection speed of the core yarn is 1.4 r / min, the spinning temperature is 47 °C, the relative humidity is 36%, the rotation speed of the bell mouth of the collection device is 170 r / min, and the spinning outlets of the left and right propulsion pumps are adjusted to be parallel to the center position of the bell mouth.

[0231] An intelligent yarn is prepared, which has a core-shell structure and includes a core yarn and cortical fibers. The diameter of the intelligent yarn is 0.79 mm, and the diameter of the cortical fibers is 0.1 mm; within 300 s, the fluorescence quenching efficiency of the intelligent yarn for saturated TNT saturated vapor reaches 32%, the instant response time for the virus is within 240 s, and the detection limit for heavy metal ions (Cu ﹢ ) is 1.7×10 -5For M, the lowest detection limit for nerve gas is 0.22 ppb; the fluorescence spectral intensity of the intelligent yarn before exposure to a biochemical (saturated DCP vapor) environment at 26°C for 300 seconds is 10, and the fluorescence spectral intensity after 300 seconds of exposure is 103.

[0232] Application: A biochemical visualization sensing - real - time physiological signal monitoring sensing network, including an intelligent yarn, fabric, NFC sensing chip, physiological signal sensor, and excitation terminal as described above; the intelligent yarn is implanted into the fabric in the shape of an NFC antenna through embroidery or weaving processes and then connected to the NFC sensing chip and the physiological signal sensor, and the intelligent yarn and the excitation terminal transfer energy to the NFC sensing chip through inductive coupling.

[0233] In the prepared biochemical visualization sensing - real - time physiological signal monitoring sensing network, when the wearer wears it and the terminal excitation is started, the mobile phone terminal can read and display the wearer's physiological signals such as temperature and heart rate within 1 minute.

[0234] Example 9

[0235] A preparation method of an intelligent yarn, the specific steps are as follows:

[0236] (1) Preparation of raw materials;

[0237] TNT fluorescence detection material: TPA - PPV;

[0238] Heavy metal ion fluorescence detection material: 4,4'-bis(diethylamino)-benzidine diazide;

[0239] Nerve gas fluorescence detection material: 4,4'-bis(dimethylamino)-benzidine diazide;

[0240] Virus fluorescence detection material: Pyrene - naphthalimide binary group;

[0241] Hydrophobic polymer: Polycaprolactone PCL;

[0242] Solvent: A homogeneous solution prepared by mixing N,N - dimethylformamide (DMF) and acetone in a weight ratio of 7:3;

[0243] Core yarn: Carbon fiber;

[0244] (2) Preparation of the spinning dope;

[0245] A hydrophobic polymer is added to a solvent to prepare a solution. The hydrophobic polymer does not immediately dissolve in the solution. The above solution is heated and stirred in an oil bath at 70 °C until the hydrophobic polymer is completely dissolved, and the solution becomes colorless and transparent. After the hydrophobic polymer is completely dissolved, one of the 4 fluorescence detection materials in the raw materials is added to the solution. After adding, it is stirred in the oil bath until the fluorescence detection material is completely dissolved to form a stable system. The solution is placed in an ultrasonic instrument with a power of 60 W for ultrasonic oscillation for 70 min to remove the bubbles in the solution. After ultrasonic treatment, a stable and usable spinning dope is obtained. Among them, in the spinning dope, the mass ratio of the fluorescence detection material to the hydrophobic polymer is 10:90, and the mass ratio of the hydrophobic polymer to the solvent is 12:88;

[0246] (3) Repeat the above operation to prepare the remaining three spinning dopes by changing the type of the added fluorescence detection material;

[0247] (4) Coaxial electrospinning;

[0248] Wind the core yarn on the collecting roller, suck an appropriate amount of spinning dope with a syringe. Two syringes are sucked for each kind of spinning dope. Start the machine, and wrap the fibers made from the spinning dope onto the surface of the conductive core yarn through coaxial electrospinning. After wrapping a section of TNT fluorescence detection fiber on the conductive core yarn, replace the syringe filled with the spinning dope added with the virus fluorescence detection material and then carry out the coaxial electrospinning process again. Repeat the above operation. By changing four different spinning dopes, different fluorescence detection fibers are wrapped on different line segments of the conductive core yarn to form an intelligent yarn that can simultaneously detect TNT / virus / heavy metal ions / nerve gas;

[0249] Among them, in the coaxial electrospinning process, the needle diameters of the two spinnerets are 21G, the syringe capacity is 10 ml, the two high-voltage power supplies with opposite polarities are ±10 kv, the feeding speeds of the left and right feeding pumps are 5 ml / h, the distance between the left and right motors is 10 cm, the collecting speed of the core yarn is 2 r / min, the spinning temperature is 50 °C, the relative humidity is 30%, the rotation speed of the bell mouth of the collecting device is 200 r / min, and the spinning outlets of the left and right feeding pumps are adjusted to be parallel to the center position of the bell mouth.

[0250] An intelligent yarn is prepared, which has a core-shell structure and includes a core yarn and cortical fibers. The diameter of the intelligent yarn is 0.79 mm, and the diameter of the cortical fibers is 0.1 mm; within 300 s, the fluorescence quenching efficiency of the intelligent yarn for saturated TNT saturated vapor reaches 35%, the instant response time for the virus is within 180 s, and the detection limit for heavy metal ions (Co ﹢ ) is 1.2×10 -5M has a minimum detection limit for nerve gas of 0.15 ppb; the fluorescence spectral intensity of the intelligent yarn before exposure to a biochemical (saturated DCP vapor) environment at 27 °C for 300 seconds is 10, and the fluorescence spectral intensity after 300 seconds of exposure is 115.

[0251] Application: A biochemical visualization sensing - physiological signal real - time monitoring sensing network, comprising an intelligent yarn, a fabric, an NFC sensing chip, a physiological signal sensor, and an excitation terminal as described above; the intelligent yarn is implanted into the fabric in the shape of an NFC antenna through embroidery or weaving processes and then connected to the NFC sensing chip and the physiological signal sensor, and the intelligent yarn and the excitation terminal transfer energy to the NFC sensing chip through inductive coupling.

[0252] In the prepared biochemical visualization sensing - physiological signal real - time monitoring sensing network, when the wearer wears it and the terminal excitation is started, the mobile phone terminal can read and display the physiological signals of the wearer, such as temperature and heart rate, within 1 minute.

Claims

1. An intelligent yarn applied to biochemical visualization sensing - real - time monitoring of physiological signals, having a core - sheath structure, including a core yarn and cortical fibers, characterized in that, The intelligent yarn is divided into two or more segments along the length direction. Among any two adjacent segments, the cortical fibers on one segment are fibers with a visual detection effect on biochemical A, and the cortical fibers on the other segment are fibers with a visual detection effect on biochemical B. Biochemical A is different from biochemical B, and biochemical A and biochemical B are selected from one of TNT, virus, nerve gas, and heavy metal ions Hg ﹢ , Cu 2﹢ , Co 2﹢ ; The core yarn is a conductive yarn capable of conducting physiological signals and wireless signals; The cortical fiber comprises a hydrophobic polymer substrate and a fluorescent detection material dispersed therein; The fluorescent detection material in the fiber with a visual detection effect on biochemical A is a detection material with a fluorescent detection ability for biochemical A, and the fluorescent detection material in the fiber with a visual detection effect on biochemical B is a detection material with a fluorescent detection ability for biochemical B.

2. The intelligent yarn according to claim 1, applied to biochemical visualization sensing - real - time monitoring of physiological signals, characterized in that, The hydrophobic polymer is polyvinylidene fluoride (PVDF), polystyrene (PS) or polycaprolactone (PCL); the content of the fluorescent detection material in the cortical fiber is 5-10 wt%.

3. The intelligent yarn according to claim 1, applied to biochemical visualization sensing - real - time monitoring of physiological signals, characterized in that, The diameter of the intelligent yarn is 0.1-0.4 mm, the diameter of the core yarn is 0.05-0.10 mm, and the diameter of the cortical fiber is 0.05-0.2 mm.

4. A preparation method of the intelligent yarn according to any one of claims 1 to 3, applied to biochemical visualization sensing - real - time monitoring of physiological signals, characterized in that, The cortical fiber is wrapped around the surface of the core yarn by a coaxial electrospinning process, and different cortical fibers are wrapped around different length segments of the core yarn, thus obtaining an intelligent yarn applied to visual sensing of biochemicals - real-time monitoring of physiological signals; The core yarn is divided into two or more segments along the length direction. Wrapping different cortical fibers around different length segments of the core yarn means that on one of any two adjacent length segments of the core yarn, fibers with a visual detection effect on biochemical A are wrapped, and on the other segment, fibers with a visual detection effect on biochemical B are wrapped.

5. The preparation method of the intelligent yarn according to claim 4, applied to biochemical visualization sensing - real - time monitoring of physiological signals, characterized in that, Wrapping different cortical fibers around different length segments of the core yarn is achieved by changing different spinning dope during the coaxial electrospinning process; The spinning dope comprises a hydrophobic polymer, a fluorescent detection material and a solvent; When wrapping fibers with a visual detection effect on biochemical A, the fluorescent detection material in the adopted spinning dope is a detection material with a fluorescent detection ability for biochemical A; when wrapping fibers with a visual detection effect on biochemical B, the fluorescent detection material in the adopted spinning dope is a detection material with a fluorescent detection ability for biochemical B.

6. The preparation method of the intelligent yarn according to claim 5, applied to biochemical visualization sensing - real - time monitoring of physiological signals, characterized in that, In the spinning dope, the mass ratio of the fluorescent detection material to the hydrophobic polymer is 5-10:95-90, and the mass ratio of the hydrophobic polymer to the solvent is 10-15:90-85.

7. A biochemical visualization sensing - real - time monitoring sensor network, characterized in that, Comprising an intelligent yarn, a fabric, an NFC sensing chip, a physiological signal sensor and an excitation terminal as described in any one of claims 1-3 for visual sensing of biochemicals - real-time monitoring of physiological signals; The intelligent yarn is implanted into the fabric in the shape of an NFC antenna through an embroidery or weaving process and then connected to the NFC sensing chip and the physiological signal sensor. The intelligent yarn and the excitation terminal transfer energy to the NFC sensing chip through inductive coupling.

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