A jellyfish repellent and its application

Abstract

This invention discloses a jellyfish repellent and its applications. The active ingredient of the jellyfish repellent contains micro / nano particles formed from elemental sulfur or micro / nano particles formed from a mixture of elemental sulfur and lanthanum chloride. Experimental results show that the jellyfish repellent of this invention not only significantly inhibits the emission of nematocysts from jellyfish, but also possesses good sustained-release and hydrophobic properties. It is expected to be used as an active ingredient in the preparation of skin care products for direct application to prevent jellyfish stings and as a protective coating for wearables to prevent jellyfish stings. Furthermore, the jellyfish repellent of this invention has advantages such as readily available raw materials, ease of preparation, and environmental friendliness; therefore, the jellyfish repellent of this invention has broad application prospects.

Description

Technical Field

[0001] This invention relates to a jellyfish repellent and its application, belonging to the field of marine biological protection technology. Background Technology

[0002] Jellyfish are planktonic organisms that live in the ocean and belong to the phylum Cnidaria. The nematocyst of a jellyfish consists of three parts: the cyst wall, hollow nematocysts, and receptors. When at rest, the nematocysts are upside down inside the cyst, but once stimulated, they will launch barbed nematocysts at high speed into the body of people or animals in the ocean. The process of the nematocyst launching nematocysts is the release of jellyfish venom, which is the essence of jellyfish stings. Once stung by a jellyfish, a person will feel itching, numbness, or burning sensations, followed by local erythema, papules, or urticaria-like rashes. The intense itching can affect daily life, especially sleep. Large jellyfish, in particular, have very long tentacles, and the resulting rashes are often linear, band-like, whip-like, coiled, or serrated, ranging from several to dozens of lines. If a person is stung in multiple places on their body, they may experience fatigue, muscle pain, palpitations, shortness of breath, chest tightness, thirst, cold sweats, and insomnia. Those who are particularly sensitive to the toxins may experience difficulty breathing, pulmonary edema, and a drop in blood pressure, and even death, thus posing a safety threat to personnel engaged in marine operations and combat.

[0003] Existing research indicates that the nematocyst firing process of jellyfish is not controlled by nerves, but is influenced by a variety of external physical and chemical factors, with each jellyfish independently firing its nematocysts. If the firing of nematocysts can be suppressed by external means, it can effectively protect against jellyfish attacks. Therefore, if a method can be developed to suppress the firing of jellyfish nematocysts, it would be the safest and most effective fundamental protective measure to prevent jellyfish stings. However, no related technologies or products have been reported to date. Summary of the Invention

[0004] In view of the above-mentioned problems and needs of the existing technology, the purpose of this invention is to provide a jellyfish repellent that can suppress the emission of jellyfish nematocysts and its application.

[0005] To achieve the above-mentioned objectives, the present invention adopts the following specific technical solution:

[0006] First, the jellyfish repellent of the present invention contains micro-nano particles formed from elemental sulfur or micro-nano particles formed from a mixture of elemental sulfur and lanthanum chloride as its active ingredient.

[0007] In a preferred embodiment, the mass ratio of elemental sulfur to lanthanum chloride in the mixture is 5:1.

[0008] In a preferred embodiment, the particle size of the micro / nano particles is between 500 nanometers and 2 micrometers.

[0009] In one embodiment, the micro / nanoparticles are prepared using a high-voltage electrostatic spraying method.

[0010] In a preferred embodiment, the parameters of the high-voltage electrostatic spraying process are controlled as follows: voltage 7-11kV, flow rate 1-2mL / h, distance between the receiving substrate and the spray nozzle 9-11cm, ambient temperature 20-25℃, and ambient relative humidity 40-60%.

[0011] In one embodiment, the solution for electro-spraying is formed by dissolving sublimed sulfur (S) in carbon disulfide (CS2) solvent, wherein the concentration of sulfur is 5% to 10%, and the concentration is expressed in g / mL.

[0012] In another embodiment, the solution for electro-spraying is formed by dissolving a mixture of sublimed sulfur (S) and lanthanum chloride (LaCl3) in a carbon disulfide (CS2) solvent, wherein the concentration of sulfur is 5% to 10% and the concentration of lanthanum chloride is 0.01% to 1.0%, and the concentration is expressed in g / mL.

[0013] In a preferred embodiment, the solution used for electro-spraying has a sulfur concentration of 5% and a lanthanum chloride concentration of 1%, wherein the concentrations are expressed in g / mL.

[0014] One application of the jellyfish repellent described in this invention is to use the jellyfish repellent as an active ingredient in the preparation of a skin care product that can be directly applied to the skin to prevent jellyfish stings.

[0015] Another application of the jellyfish repellent described in this invention is to use the jellyfish repellent as an active ingredient in the preparation of a protective coating for wearables to prevent jellyfish stings.

[0016] Compared with the prior art, the present invention has the following significant advantages:

[0017] The experimental results of this invention show that the jellyfish repellent described in this invention can not only significantly inhibit the emission of nematocysts from jellyfish, but also has good sustained-release and hydrophobic properties. It is expected to be used as an effective ingredient in the preparation of skin care products that can be directly applied to the skin to prevent jellyfish stings and protective coatings for wearables to prevent jellyfish stings. In addition, the jellyfish repellent described in this invention has the advantages of readily available raw materials, easy preparation, and environmental friendliness. Therefore, the jellyfish repellent described in this invention has broad application prospects. Attached Figure Description

[0018] Figure 1 These are scanning electron microscope images of the micro-nanoparticles prepared in Example 1, wherein: (a) are micro-nanoparticles prepared by high-voltage electrostatic spraying of a carbon disulfide solution with a sulfur concentration (in g / mL) of 5%, and (b) are micro-nanoparticles prepared by high-voltage electrostatic spraying of a carbon disulfide solution with a sulfur concentration (in g / mL) of 10%.

[0019] Figure 2 This is a particle size distribution diagram of the micro-nanoparticles prepared in Example 1, wherein: A is micro-nanoparticles prepared by high-pressure electrostatic spraying of a sulfur carbon disulfide solution with a concentration (in g / mL) of 5%, and B is micro-nanoparticles prepared by high-pressure electrostatic spraying of a sulfur carbon disulfide solution with a concentration (in g / mL) of 10%.

[0020] Figure 3 This is a scanning electron microscope image of the micro / nanoparticles prepared in Example 2;

[0021] Figure 4 This is a particle size distribution diagram of the micro / nano particles obtained in Example 2;

[0022] Figure 5 These are photomicrographs of nematocysts in each experimental group before and after stimulation. Among them: A is a photomicrograph of artificial seawater (blank control group) before stimulation; B is a photomicrograph of artificial seawater (blank control group) after stimulation; C is a photomicrograph of the experimental solution containing the jellyfish repellent of Example 1 before stimulation; D is a photomicrograph of the experimental solution containing the jellyfish repellent of Example 1 after stimulation; E is a photomicrograph of the experimental solution containing the jellyfish repellent of Example 2 before stimulation; and F is a photomicrograph of the experimental solution containing the jellyfish repellent of Example 2 after stimulation.

[0023] Figure 6 The release curves of the jellyfish repellent described in Example 2 in artificial seawater are shown, where: A is the release curve of sulfur and B is the release curve of lanthanum chloride.

[0024] Figure 7 The hydrophobic properties of the fabric (spandex fabric) loaded with the jellyfish repellent described in Examples 1 and 2 are shown, wherein: the blank sample is the spandex fabric as the loading substrate, sample A is the spandex fabric with the jellyfish repellent described in Example 1 loaded on its surface, and sample B is the spandex fabric with the jellyfish repellent described in Example 2 loaded on its surface. Detailed Implementation

[0025] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Experimental methods in the following embodiments, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer.

[0026] Example 1

[0027] The jellyfish repellent described in this embodiment has an effective component consisting of micro-nano particles formed from a single element, sulfur. The specific preparation method of the micro-nano particles is as follows:

[0028] 1) Weigh 0.5g and 1g of sublimed sulfur (commercially available), respectively, and dissolve them in 10mL of carbon disulfide (CS2) solvent (commercially available) to prepare carbon disulfide solutions with sulfur concentrations (in g / mL) of 5% and 10%, respectively.

[0029] 2) The sulfur-carbon disulfide solution prepared in step 1) was injected into the electrospray nozzle through a micro-injection pump for high-voltage electrostatic spraying. (It should be noted that the principle and specific operation of preparing micro- and nano-particles by high-voltage electrostatic spraying can be found in the Chinese patent application number 201110163297.X, entitled "Method for preparing hydrophobic drug nanoparticle solid dispersion by high-voltage electrostatic spraying".) During the preparation process, the parameters of high-voltage electrostatic spraying were controlled as follows: voltage 10kV, flow rate 1mL / h, distance between the receiving substrate (the receiving substrate is laid on the receiving plate, which is a cardboard wrapped with aluminum foil; in this embodiment, the receiving substrate is spandex cloth) and the spray nozzle was 10cm, ambient temperature was 23℃, and ambient relative humidity was 50%.

[0030] 3) Place the prepared micro and nano particles in a 40°C oven for vacuum drying for 72 hours to remove the solvent.

[0031] Figure 1 The images show scanning electron microscope (SEM) images of the micro / nanoparticles obtained, where the substrate to which the micro / nanoparticles are attached is spandex fiber. Specifically: (a) micro / nanoparticles were obtained by high-voltage electrostatic spraying of a 5% sulfur-carbon disulfide solution; (b) micro / nanoparticles were obtained by high-voltage electrostatic spraying of a 10% sulfur-carbon disulfide solution. Figure 1 As shown, when the sulfur concentration is 5%, the particle packing density is very small (almost negligible), and the particle size is uneven. This phenomenon may be attributed to the fact that during the cracking process of the hybrid droplets, a small amount of sulfur separates from the hybrid droplets because sulfur is a non-solidifying liquid, and the particles are eventually dispersed in a "planetary" shape. As the sulfur concentration increases, the particle packing density gradually increases, and the number of small particles gradually decreases. When the sulfur concentration reaches 10%, the electrospray particles are more evenly distributed, and the particle packing density is relatively large, which meets the experimental requirements.

[0032] Figure 2 This is a particle size distribution diagram of the prepared micro / nanoparticles, where: A represents micro / nanoparticles prepared by high-pressure electrostatic spraying of a 5% sulfur-carbon disulfide solution; B represents micro / nanoparticles prepared by high-pressure electrostatic spraying of a 10% sulfur-carbon disulfide solution. Figure 2As shown, the change in sulfur concentration has little effect on the particle size of micro and nanoparticles. Under the condition that the electrostatic force remains unchanged, the particle sizes of the prepared micro and nanoparticles reach 1.267±0.498μm and 1.061±0.465μm, respectively, and the particle sizes of the micro and nanoparticles are between 500 nanometers and 2 micrometers.

[0033] Example 2

[0034] The jellyfish repellent described in this embodiment has an effective component consisting of micro / nano particles formed from a mixture of elemental sulfur and lanthanum chloride. The specific preparation method of the micro / nano particles is as follows:

[0035] 1) Weigh 0.5g of sublimed sulfur (commercially available) and 0.1g of lanthanum chloride (LaCl3, commercially available) separately, dissolve them in 10mL of carbon disulfide (CS2) solvent (commercially available), and prepare a carbon disulfide solution with a sulfur concentration of 5% and a lanthanum chloride concentration of 1%.

[0036] 2) The carbon disulfide solution prepared in step 1) is injected into the electrospray nozzle through a micro-injection pump for high-voltage electrostatic spraying. During the preparation process, the parameters of the high-voltage electrostatic spraying are controlled as follows: voltage 10kV, flow rate 1mL / h, distance between the receiving substrate (the receiving substrate is laid on the receiving plate, which is a cardboard wrapped with aluminum foil; in this embodiment, the receiving substrate is spandex cloth) and the spray nozzle is 10cm, ambient temperature is 23℃, and ambient relative humidity is 50%.

[0037] 3) Place the prepared micro and nano particles in a 40°C oven for vacuum drying for 72 hours to remove the solvent.

[0038] Figure 3 This is a scanning electron microscope image of the prepared micro / nanoparticles, where the substrate to which the micro / nanoparticles are attached is spandex fabric fibers; Figure 3 As shown, the particles are relatively evenly distributed and have a high degree of dense packing, which meets the expected experimental requirements. Figure 4 This is a particle size distribution diagram of the prepared micro / nano particles, from... Figure 4 As shown, the particle size of the prepared micro-nano particles is 1.301±0.327μm, and the particle size ranges from 500 nanometers to 2 micrometers.

[0039] The experimental results regarding the inhibitory effect of the jellyfish repellent on jellyfish nematocyst emission are as follows:

[0040] I. Preparation of freeze-dried samples of unlaunched jellyfish nematocysts

[0041] ① Take out the frozen jellyfish tentacles, add an equal amount of artificial seawater, and autolyze at 4℃ for 4 days. Then, sieve the sample twice, centrifuge the filtrate at 4℃ and 2000×g for 3 minutes, and then re-dissolve the precipitate with artificial seawater.

[0042] ② Prepare Percoll cell separation solutions with concentrations of 0%, 50%, 70%, and 90% using artificial seawater, and lay the tubes in descending order of concentration. Then mix the reconstituted sample obtained in step ① with the 60% Percoll cell separation solution at a volume ratio of 1:1, and then spread it evenly on top of the medium.

[0043] ③ Using a horizontal rotor, centrifuge at 1000×g for 20 min at 4℃. Based on the color and turbidity of the separation system, remove the tissue cell fragments and emitted nematocysts from the upper part. Centrifuge the remaining nematocyst suspension at 10000×g for 20 min at 4℃. Then wash once with artificial seawater and centrifuge at 10000×g for 20 min at 4℃. Freeze-dry the resulting precipitate to obtain the freeze-dried sample of unemitted jellyfish nematocysts.

[0044] II. Inhibition Experiment

[0045] Take 1.5 mg of lyophilized jellyfish nematocysts that have not yet emitted and place them in a 1.5 mL centrifuge tube. Add artificial seawater at 4°C to make up the volume, and then place the tube in a 25°C water bath and shake for 10 min to obtain a nematocyst suspension. Then, divide the obtained nematocyst suspension equally into three centrifuge tubes. Use the nematocyst suspension in one centrifuge tube as a blank control solution. Add 2.5 mg of the jellyfish repellent prepared in Example 1 from a 10% sulfur carbon disulfide solution to the nematocyst suspension in another centrifuge tube. Add 2.5 mg of the jellyfish repellent described in Example 2 to the nematocyst suspension in the remaining centrifuge tube. Then, place all three centrifuge tubes in a 25°C water bath and shake for 10 min.

[0046] Take three slides in parallel for each solution, add 20 μL of solution to each slide, cover with a coverslip, and observe under a microscope the total number of nematocysts on each slide and the number of emitted nematocysts before the stimulation is applied.

[0047] Then, a 5-gram weight was placed on each coverslip to apply pressure to the nematocysts. After applying pressure for 5 minutes, the number of nematocysts emitted on each slide after the stimulation was observed under a microscope.

[0048] Finally, the discharged nematocytic ratio of the jellyfish nematocysts in each experimental solution was calculated:

[0049] Splinter sac firing rate = number of fired splinters / total number of splinters × 100%;

[0050] To reduce subjective errors in counting, Photoshop software was used for counting and statistics.

[0051] The experimental results are shown in Table 1:

[0052] Table 1. Emission rate of nematocysts before and after stimulation in each experimental group.

[0053]

[0054] Figure 5 These are photomicrographs of nematocysts in each experimental group before and after stimulation. Among them: A is a photomicrograph of artificial seawater (blank control group) before stimulation; B is a photomicrograph of artificial seawater (blank control group) after stimulation; C is a photomicrograph of the experimental solution containing the jellyfish repellent of Example 1 before stimulation; D is a photomicrograph of the experimental solution containing the jellyfish repellent of Example 1 after stimulation; E is a photomicrograph of the experimental solution containing the jellyfish repellent of Example 2 before stimulation; and F is a photomicrograph of the experimental solution containing the jellyfish repellent of Example 2 after stimulation.

[0055] Combining Table 1 and Figure 5 It is evident that the jellyfish repellent described in this invention can significantly inhibit the emission of jellyfish nematocysts and has a repellent and protective effect against jellyfish stings in seawater.

[0056] Figure 6 These are the release curves of the jellyfish repellent described in Example 2 in artificial seawater, where: A is the release curve of sulfur, and B is the release curve of lanthanum chloride; from Figure 6 As shown, the jellyfish repellent described in this invention has good slow-release properties in artificial seawater.

[0057] Figure 7 The hydrophobic properties of fabrics (spandex fabrics) loaded with the jellyfish repellents described in Examples 1 and 2 are shown, wherein: the blank sample is a spandex fabric as the loading substrate, sample A is a spandex fabric with the jellyfish repellent described in Example 1 loaded on its surface, and sample B is a spandex fabric with the jellyfish repellent described in Example 2 loaded on its surface; Figure 7 As can be seen from the figure, the jellyfish repellent of the present invention has good hydrophobic properties and can reach a contact angle of 120 degrees or more with artificial seawater.

[0058] As can be seen from the above experimental results, the jellyfish repellent described in this invention can not only significantly inhibit the emission of jellyfish nematocysts, but also has good slow-release and hydrophobic properties. Therefore, it is expected to be used to prepare skin care products that can be directly applied to the skin to prevent jellyfish stings and protective coatings for wearables to prevent jellyfish stings, and has broad application prospects.

[0059] Finally, it is necessary to state that the above embodiments are only used to further illustrate the technical solution of the present invention in detail, and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention shall fall within the scope of protection of the present invention.

Claims

1. A jellyfish repellent, characterized by: The effective component contains micro-nanoparticles formed by a mixture of elemental sulfur and lanthanum chloride, wherein the mass ratio of elemental sulfur to lanthanum chloride in the mixture is 5:

1.

2. The jellyfish repellent of claim 1, wherein: The particle size of the micro-nanoparticles is between 500 nanometers and 2 micrometers.

3. The jellyfish repellent of claim 1, wherein: The micro-nanoparticles are prepared by using a high-voltage electrostatic spraying method.

4. The jellyfish repellent of claim 3, wherein: In the preparation process, the parameters of the high-voltage electrostatic spraying are controlled as follows: voltage 7-11 kV, flow rate 1-2 mL / h, distance between the receiving substrate and the spraying port 9-11 cm, ambient temperature 20-25℃, and ambient relative humidity 40-60%.

5. The jellyfish repellent of claim 3, wherein: The solution for electrostatic spraying is formed by dissolving a mixture of sublimed sulfur and lanthanum chloride in carbon disulfide solvent, wherein the concentration of sulfur is 5%-10% and the concentration of lanthanum chloride is 0.01%-1.0%, and the concentration units are g / mL.

6. The jellyfish repellent of claim 5, wherein: In the solution for electrostatic spraying, the concentration of sulfur is 5% and the concentration of lanthanum chloride is 1%, and the concentration units are g / mL.

7. Use of a jellyfish repellent according to any one of claims 1 to 6, characterized in that: The jellyfish repellent is used as an effective component for preparing a skin care product for directly smearing the skin to prevent jellyfish stings.

8. Use of a jellyfish repellent according to any one of claims 1 to 6, characterized in that: The jellyfish repellent is used as an effective component for preparing a protective coating of a wear to prevent jellyfish stings.

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