Use of nicotine and its salts, nicotine derivatives and their salts for the preparation of marine biofouling antifouling agents

Abstract

The application discloses a use of nicotine and its salt, a nicotine derivative and its salt in preparation of a marine biofouling antifouling agent. The application first discovers that nicotine can inhibit the adhesion of marine fouling organisms at a lower concentration. Nicotine has the characteristics of easy decomposition under light, does not pollute the marine environment, and can avoid the long-term influence on the marine ecological environment caused by the release in the marine environment. Meanwhile, nicotine can be dissolved in water and oil, is hydrophilic and lipophilic, is suitable for preparation of an antifouling coating, and can easily control the release speed, effectively avoid the burst release phenomenon of the antifouling agent, improve the utilization rate, and prolong the antifouling time. Nicotine is mainly extracted from tobacco and can also be prepared by chemical synthesis. Nicotine has a high content in tobacco and a mature extraction process, which provides a guarantee for the development of nicotine into an antifouling agent, and solves the problems of difficult extraction, difficult synthesis, low yield and difficult practical application and popularization of natural products in the development of natural antifouling agents.

Description

Technical Field

[0001] This invention relates to the field of marine antifouling technology, specifically to the use of nicotine and its salts, nicotine derivatives and their salts in the preparation of marine biofouling antifouling agents. Background Technology

[0002] Marine biofouling refers to the phenomenon where fouling organisms such as algae, barnacles, and mussels attach to and aggregate on the surfaces of marine artificial facilities, causing serious harm to human economic activities. It leads to increased drag on ships, reduced speed, increased fuel consumption, and accelerated corrosion of metal surfaces such as ships and platforms, shortening their service life. Furthermore, it affects the optical and acoustic signal transmission of marine monitoring instruments, increasing equipment maintenance frequency and costs. Marine fouling organisms can also attach to and clog marine aquaculture nets, competing with farmed organisms for nutrients, affecting their growth, and even causing their death, resulting in significant damage to the marine aquaculture industry. In conclusion, marine biofouling has become an obstacle that humanity must overcome to utilize the ocean.

[0003] In the fight against marine biofouling, marine antifouling coatings have been found to be the most effective and economical method for preventing biofouling of ship hulls and marine facilities. Antifouling coatings contain antifouling agents that, once released onto the surface, effectively prevent the attachment of marine fouling organisms. In the past, organotin compounds such as tributyltin were commonly added to coatings as antifouling agents. However, organotin antifouling agents are highly toxic to all organisms, affecting the growth and development of marine life such as fish, snails, and oysters, damaging their immune systems, and harming the marine environment. The International Maritime Organization (IMO) completely banned the use of organotin antifouling agents on January 1, 2008. Currently, cuprous oxide antifouling agents have replaced organotin compounds; however, copper, as a heavy metal, accumulates in the marine environment, also causing adverse effects. Therefore, there is an urgent need to develop environmentally friendly, non-toxic, or low-toxicity antifouling compounds.

[0004] Natural products isolated from marine microorganisms, algae and aquatic plants, marine invertebrates, and terrestrial and other sources have become a new direction for the development of antifouling agents. These products possess good biocompatibility and biodegradability, and are harmless to the marine environment. Examples include indole and its derivatives extracted from marine organisms, and capsaicin and its derivatives extracted from terrestrial plants. However, natural antifouling agents suffer from drawbacks such as low extract content, high extraction difficulty, low yield, and high synthesis difficulty. Therefore, finding a highly efficient, low-toxicity, easily extracted or synthesized, and environmentally friendly antifouling agent has become a current research hotspot. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the aforementioned technologies. Addressing the drawbacks of existing antifouling agents, such as environmental pollution, poor biocompatibility, and the difficulty in extracting and synthesizing natural antifouling agents, this invention proposes for the first time the use of nicotine and its salts, nicotine derivatives and their salts, in the preparation of marine biofouling antifouling agents. This invention also discovers for the first time that nicotine can inhibit the attachment of marine fouling organisms at low concentrations. Nicotine is easily decomposed in light, causing no pollution to the marine environment and avoiding long-term impacts on the marine ecosystem from release. Furthermore, nicotine is soluble in both water and oil, making it suitable for preparing antifouling coatings due to its hydrophilic and lipophilic properties. Its release rate can be easily controlled, effectively preventing explosive release of antifouling agents, improving utilization, and extending antifouling time. Nicotine is mainly extracted from tobacco and can also be prepared through chemical synthesis. The high content of nicotine in tobacco and the mature extraction process provide a guarantee for developing nicotine into an antifouling agent, and solve the problems often encountered in the development of natural antifouling agents, such as the difficulty in extracting and synthesizing natural products, low yield, and difficulty in practical application and promotion.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] This invention proposes for the first time the use of nicotine and its salts, nicotine derivatives and their salts in the preparation of marine biofouling antifouling agents, wherein the active component of the marine biofouling antifouling agent is one or more of nicotine, nicotine salts, nicotine derivatives or nicotine derivative salts.

[0008] Furthermore, the nicotine mentioned above is also known as nicotine, and its molecular formula is C60000. 10 H 14 N2, with a molecular weight of 162.2, has the structural formula shown in the figure below.

[0009]

[0010] Nicotine is abundant in tobacco plants and is one of the main alkaloids in tobacco. It can be extracted from the leaves and stems of tobacco. The extraction process of nicotine is relatively mature and has been publicly reported. Nicotine can also be obtained through chemical synthesis.

[0011] Furthermore, the nicotine salts mentioned refer to nicotine salt compounds prepared by reacting nicotine with acids, including but not limited to: benzoic acid nicotine salt, malic acid nicotine salt, citric acid nicotine salt, tartrate nicotine salt, salicylic acid nicotine salt, and orotic acid nicotine salt.

[0012] Furthermore, the nicotine derivatives refer to products derived from nicotine by replacing hydrogen atoms or groups of atoms with other atoms or groups, including but not limited to: cotinine, mesmin, demethylnicotine, and diene nicotine. Nicotine derivative salts; the nicotine derivative salts refer to nicotine derivative salt compounds prepared by reacting nicotine derivatives with acids, including but not limited to: benzoic acid nicotine derivative salts, malic acid nicotine derivative salts, citric acid nicotine derivative salts, tartaric acid nicotine derivative salts, salicylic acid nicotine derivative salts, or orotic acid nicotine derivative salts.

[0013] Furthermore, the active ingredient of the marine biofouling antifouling agent contains one or more of nicotine, nicotine derivatives, and nicotine salts; preferably, the active component in the marine biofouling antifouling agent is a combination of nicotine and its salts, nicotine derivatives and their salts, nicotine derivatives and nicotine salts, or nicotine and nicotine derivative salts. Further, the mass ratio of nicotine or nicotine derivatives to nicotine salts or nicotine derivative salts is 1-4:1-4.

[0014] Furthermore, the aforementioned marine fouling organisms refer to the various major phyla of marine bacteria, algae, and marine animals that can attach to and grow on marine artificial facilities, causing damage to the facilities.

[0015] Furthermore, the aforementioned marine artificial facilities refer to man-made facilities that come into contact with seawater, including but not limited to marine aquaculture equipment, marine aquaculture platforms, marine monitoring instruments, buoys, pipelines, oil extraction platforms, docks, and ships. The marine artificial facilities of this invention are not limited to the above-mentioned limitations; any artificial facility that comes into contact with seawater should be included within the scope of the above definition.

[0016] The present invention further provides a method for preparing the above-mentioned nicotine salt, comprising:

[0017] Step 1. Mix nicotine or nicotine derivatives, acid, and solvent, and react at 10-80℃ for 1-7 hours to obtain solution A;

[0018] Step 2. Add a poor solvent to solution A, and after filtration, washing, and distillation, obtain nicotine salt or nicotine derivative salt;

[0019] The acid mentioned is one or more of the following: benzoic acid, malic acid, citric acid, orotic acid, tartaric acid, salicylic acid, alginic acid, gentian acid, citric acid, ascorbic acid, oxalic acid, caffeic acid, acetic acid, and lactic acid.

[0020] Furthermore, the molar ratio of the aforementioned nicotine or nicotine derivatives to organic acids is 0.1-10.0.

[0021] Furthermore, the solvent mentioned above is one or more of ethanol, methanol, acetonitrile, or carbon tetrachloride.

[0022] Furthermore, the aforementioned unsuitable solvents are one or more of ethyl acetate, n-heptane, and toluene.

[0023] Furthermore, the marine biofouling antifouling agent is used to prevent marine fouling organisms from attaching to and aggregating on marine artificial facilities.

[0024] Furthermore, the marine biofouling antifouling agent is in the form of a coating that can be impregnated, sprayed, brushed, or rolled.

[0025] Furthermore, the aforementioned coating also includes a base material, pigments, additives, and solvents. The base material includes (but is not limited to): acrylic resin, chloroprene resin, chlorinated rubber, epoxy resin, polyvinyl alcohol, polyvinyl acetate, and amino resin. The pigments include (but are not limited to): titanium dioxide, zinc oxide, iron oxide red, and talc. Additives mainly include thixotropic agents, stabilizers, and anti-settling agents. Solvents include (but are not limited to): toluene, xylene, cyclohexanone, and n-butanol.

[0026] The beneficial effects of this invention are:

[0027] (1) Nicotine, nicotine salt, nicotine derivative or derivative salt in this invention can significantly inhibit the attachment of marine fouling organisms at low concentrations.

[0028] (2) The nicotine in this invention is derived from tobacco, does not contain heavy metal compounds, has good biocompatibility, and does not pollute the marine environment; secondly, nicotine is easily decomposed by light, avoiding release into the environment and causing long-term impact on the marine ecological environment; the nicotine and its derivatives in this invention can also be obtained by existing synthesis methods.

[0029] (3) The nicotine in this invention is soluble in both water and oil, and has the characteristics of being both hydrophilic and oleophilic. It is suitable for preparing antifouling coatings, and its release rate is easy to control. It can effectively avoid the phenomenon of explosive release of antifouling agents, extend the antifouling time, and improve the utilization rate.

[0030] (4) In this invention, nicotine can be extracted from the roots, stems, and leaves of tobacco. Tobacco has a high nicotine content, is easy to extract, and is suitable for large-scale preparation. Furthermore, the extraction process for nicotine is relatively mature, providing support for its development into a marine antifouling agent. This also solves the problems frequently encountered in the development of natural antifouling agents, such as the difficulty in extracting and synthesizing natural products, low yields, and difficulties in practical application and promotion. Of course, synthetic nicotine products are also within the scope of protection of this invention. Attached Figure Description

[0031] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings of the embodiments will be briefly described below.

[0032] Figure 1The graph shows the antibacterial effect of nicotine on Staphylococcus aureus. The left graph is the blank control, and the right graph shows the antibacterial effect of adding 1.25 mg / mL nicotine solution. Detailed Implementation

[0033] Those skilled in the art can refer to the content of this document and appropriately improve the process parameters to achieve the desired result. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art and are considered to be included in this invention. The product of this invention has been described through preferred embodiments, and those skilled in the art can obviously make modifications or appropriate alterations and combinations to the product described herein without departing from the content, spirit, and scope of this invention to realize and apply the technology of this invention. The invention is further illustrated below through specific embodiments; it should be noted that the following embodiments should not be construed as limiting the invention.

[0034] The terms “comprising,” “including,” “having,” “containing,” or any other variations thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such composition, step, method, article, or apparatus.

[0035] The phrase "composed of..." excludes any unspecified elements, steps, or components. If used in a claim, this phrase makes the claim closed, excluding materials other than those described, except for conventional impurities associated with them. When the phrase "composed of..." appears in a clause of the body of a claim rather than immediately following it, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0036] When a quantity, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1 to 5” is disclosed, the described range should be interpreted as including the ranges “1 to 4”, “1 to 3”, “1 to 2”, “1 to 2 and 4 to 5”, “1 to 3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range.

[0037] In some instances, approximate terms may correspond to the precision of the instrument used to measure the value. In this specification and claims, scope definitions may be combined and / or interchanged, unless otherwise stated, these scopes include all sub-scopes contained therein.

[0038] The indefinite articles “a” and “an” preceding an element or component of this invention do not impose any limitation on the quantity (i.e., number of times) of the element or component. Therefore, “an” or “a” should be interpreted as including one or at least one, and the singular form of an element or component also includes the plural form, unless the quantity clearly refers only to the singular form.

[0039] The terms "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., used in this invention refer to a specific feature, structure, material, or characteristic described in connection with that embodiment or example, which is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms are not necessarily directed at the same embodiment or example. Furthermore, the technical features involved in the various embodiments of the invention can be combined with each other as long as they do not conflict with each other.

[0040] Unless otherwise specified, the raw materials and equipment used in this invention can be purchased from the market or are commonly used in the field. Unless otherwise specified, the methods in the embodiments are conventional methods in the field.

[0041] In some embodiments, the present invention provides the use of nicotine and its salts, nicotine derivatives and their salts, in the preparation of marine biofouling antifouling agents, wherein the active component of the marine biofouling antifouling agent is one or more of nicotine, nicotine salts, nicotine derivatives, or nicotine derivative salts. Further, the mass ratio of nicotine / nicotine derivative and nicotine salt / nicotine derivative salt is 1-4:1-4.

[0042] In some embodiments, nicotine derivatives refer to products derived from nicotine by replacing hydrogen atoms or groups of atoms with other atoms or groups of atoms, including but not limited to: cotinine, mesmin, demethylnicotine, or dienicotine.

[0043] In some embodiments, nicotine salts and nicotine derivative salts refer to nicotine salt compounds prepared by reacting nicotine with acids, including but not limited to: benzoic acid nicotine salt, malic acid nicotine salt, citrate nicotine salt, tartrate nicotine salt, salicylic acid nicotine salt, or orotic acid nicotine salt, and their corresponding nicotine derivative salts.

[0044] In some embodiments, the method for preparing nicotine salts or nicotine derivative salts of the present invention includes the following steps:

[0045] Step 1. Mix nicotine or nicotine derivative salt, acid, and solvent, and react at 10-80℃ for 1-7 hours to obtain solution A;

[0046] Step 2. Add a poor solvent to solution A, and after filtration, washing, and distillation, obtain nicotine salt or nicotine derivative salt;

[0047] The acid mentioned is one or more of the following: benzoic acid, malic acid, citric acid, orotic acid, tartaric acid, salicylic acid, alginic acid, gentian acid, citric acid, ascorbic acid, oxalic acid, caffeic acid, acetic acid, and lactic acid.

[0048] The molar ratio of nicotine or nicotine derivative to organic acid is 0.1-10.0. Preferably, the molar ratio of nicotine or nicotine derivative to organic acid can be 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, or 10. Further, the reaction temperature is 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, or 80°C.

[0049] In some embodiments, the solvent is one or more of ethanol, methanol, acetonitrile, or carbon tetrachloride; the undesirable solvent is one or more of ethyl acetate, n-heptane, and toluene.

[0050] In some embodiments, the marine biofouling antifouling agent is used for antifouling of marine artificial facilities, which include one of the following: marine aquaculture equipment, marine aquaculture platforms, marine monitoring instruments, buoys, pipelines, oil extraction platforms, docks, or ships. Furthermore, the marine artificial facilities include not only the devices listed above, but also any artificial facilities that require antifouling and come into contact with seawater.

[0051] In some embodiments, the aforementioned marine biofouling antifouling agent is in the form of a coating that can be impregnated, sprayed, brushed, or rolled. The antifouling agent is added as an active ingredient in the coating, and the amount of antifouling agent can be added as needed based on actual circumstances.

[0052] In some embodiments, the coating comprises a base material, pigments, additives, solvents, and antifouling active components.

[0053] In some embodiments, the base material includes one or more of acrylic resin, chlorinated ether resin, chlorinated rubber, epoxy resin, polyvinyl alcohol, polyvinyl acetate, or amino resin; the pigment includes one or more of titanium dioxide, zinc oxide, iron oxide red, or talc.

[0054] The following will describe the specific solutions and implementation methods in detail:

[0055] The present invention will be further described below through specific embodiments.

[0056] Example 1

[0057] Nicotine antibacterial performance test

[0058] The implementation steps of this embodiment are as follows:

[0059] The antibacterial performance test conditions are as follows: Representative strains of Staphylococcus aureus and Escherichia coli, both Gram-negative and Gram-positive, were purchased from Beijing Sanyao Technology Co., Ltd.; the strain activation culture conditions were: constant temperature and shaking; 2216E liquid culture medium was sold by Qingdao Haibo Biotechnology Co., Ltd. under the trade name 2216E liquid culture medium; the constant temperature shaking incubator was sold by Shanghai Yiheng Scientific Instruments Co., Ltd. under the trade name Shanghai Yiheng Constant Temperature Shaking Incubator THZ-98AB.

[0060] The antibacterial performance testing steps are as follows:

[0061] One bacterial strain was activated at 37°C for 24 hours using one milliliter of activation medium. The bacteria were then cultured in 2216E liquid medium for 24 hours. Next, the strain was inoculated into the 2216E liquid medium using an inoculation loop as described previously, and incubated in a constant temperature shaking incubator at 37°C for 24 hours to obtain a bacterial suspension for antibacterial detection. Nicotine solution (1 mL, deionized water as solvent) and bacterial solution (0.2 mL) were added to 13.8 mL of 2216E liquid medium; the suspension was then incubated in a constant temperature shaking incubator at 37°C for 24 hours. The resulting culture was then serially diluted 10-fold with 9 g / L physiological saline to a final concentration of 10. 8 cells / mL; then, 0.2 mL of the diluted bacterial solution was placed on 2216E solid medium. After complete absorption, the solid medium was incubated at 37°C for 18 h. The antibacterial rate was determined according to the following formula:

[0062]

[0063] Where S represents the antibacterial rate, S0 represents the average colony count of the control group, and Si represents the average colony count of the experimental group. The results of the antibacterial performance tests of different concentrations of nicotine solution are shown in Appendix Table 1. As shown in the table, the nicotine solution at a concentration of 1.25 mg / mL achieved a 100% inhibition rate against *Escherichia coli* and *Staphylococcus aureus*, indicating that nicotine has an excellent inhibitory effect on bacterial growth and reproduction. This is because nicotine hinders DNA replication and protein synthesis, restricting cell circulation and inhibiting bacterial growth.

[0064] Table 1. Antibacterial rate of nicotine solutions at different concentrations

[0065]

[0066]

[0067] Example 2

[0068] Nicotine salt antibacterial performance test

[0069] The antibacterial performance test conditions and test steps are the same as in Example 1. The difference is that the antibacterial performance of malic acid nicotine salt, citrate nicotine salt, benzoic acid nicotine salt, tartrate nicotine salt, salicylic acid nicotine salt, and whey acid nicotine salt are tested, and the nicotine salt concentration is fixed at 1.25 mg / mL.

[0070] The antibacterial properties of different types of nicotine salts are shown in Appendix Table 2. Different nicotine salts at a concentration of 1.25 mg / mL all exhibited good growth inhibition effects against *Escherichia coli* and *Staphylococcus aureus*.

[0071] Table 2 Antibacterial rates of different nicotine salt solutions

[0072]

[0073] Example 3

[0074] Antibacterial performance test of nicotine and nicotine salt mixture

[0075] The antibacterial performance test conditions and test steps are the same as in Example 1. The difference is that the antibacterial performance of benzoic acid nicotine salt, citrate nicotine salt, whey acid nicotine salt and nicotine mixtures are tested separately. The total concentration of nicotine and nicotine salt mixtures is controlled at 3 mg / mL. Different mass ratios of nicotine and nicotine salt mixtures are tested.

[0076] Experiments have shown that when the total concentration of the mixture of nicotine and nicotine salt is fixed at 3 mg / mL, mixtures of different mass ratios have a good growth inhibitory effect on Escherichia coli and Staphylococcus aureus.

[0077] Table 3 Antibacterial rates of nicotine and nicotine benzoate salts at different mass ratios

[0078]

[0079] Table 4. Antibacterial rates of nicotine and citrate nicotine salt at different mass ratios

[0080]

[0081] Table 5 Antibacterial rates of nicotine and orotic nicotine salt at different mass ratios

[0082]

[0083]

[0084] Example 4

[0085] Nicotine algae-inhibiting performance test

[0086] The implementation method of this embodiment is the same as that of Example 1, except that this embodiment tests the algicidal performance of the compound. The algae used in this embodiment are *Chlorella* (a green algae) and *Phaeodactylum tricornutum* (a diatom), both of which are widely distributed planktonic microalgae in the ocean and are typical fouling organisms. The maximum ultraviolet absorption wavelength of *Chlorella* and *Phaeodactylum tricornutum* was determined to be 680 nm using an ultraviolet spectrophotometer. The absorbance of the diluted algal solution was diluted to 0.06–0.10 using culture medium. 100 mL of the diluted algal solution was placed in a container, and 0.5 mL of nicotine solution was added and mixed thoroughly. The absorbance of the algal solution at 680 nm was measured daily at the same time. A growth inhibition curve of the compound on the algae was plotted based on the algal solution standard working curve to determine the growth inhibition effect of the compound on the algae. The algicidal inhibition rate was calculated according to the following formula (II).

[0087]

[0088] Where T represents the anti-algae rate, T0 is the average algae concentration of the control group, and Ti is the average algae concentration of the experimental group. The antibacterial performance test results of nicotine solutions at different concentrations are shown in Appendix 3. As shown in Appendix 3, the nicotine solution at a concentration of 2 mg / mL achieved an average algae inhibition rate of over 80% against *Chlorella vulgaris* and *Nyctaginus spp.*, similar to the algae inhibition rate of chlorothalonil sold by Shanghai Aladdin Biochemical Technology Co., Ltd. under the trade name chlorothalonil. When the concentration was further increased to 4 mg / mL, the algae inhibition rate reached 100%. Based on the chemical structural characteristics of nicotine, nicotine limits cellular calcium... 2+ The influx of calcium into the cells leads to the increase of calcium in the cells. 2+ The reduced content helps to inhibit bioattachment.

[0089] Table 6 Algae Inhibition Rate of Nicotine Solutions at Different Concentrations

[0090]

[0091] Example 5

[0092] Nicotine salt algae-inhibiting performance test

[0093] The algae-inhibiting performance testing conditions were the same as in Example 4, except that the algae-inhibiting performance of malic acid nicotinic acid, citrate nicotinic acid, benzoic acid nicotinic acid, tartrate nicotinic acid, salicylic acid nicotinic acid, and orotic acid nicotinic acid was tested, and the nicotinic acid solution concentration was fixed at 3 mg / mL. The algae-inhibiting performance test results for different nicotinic acid salts are shown in Appendix Table 7.

[0094] Table 7 Algae Inhibition Rate of Different Nicotinic Acid Solutions

[0095]

[0096] Example 6

[0097] Algae-inhibiting performance test of nicotine and nicotine salt mixture

[0098] The algae-inhibiting performance test conditions and test steps are the same as in Example 4. The difference is that the algae-inhibiting performance of benzoic acid nicotine salt, citrate nicotine salt, whey acid nicotine salt and nicotine mixtures are tested separately. The total concentration of nicotine and nicotine salt mixtures is controlled at 3 mg / mL. Mixtures with different mass ratios are tested.

[0099] Experiments have shown that when the total concentration of the mixture of nicotine and nicotine salt is fixed at 3 mg / mL, mixtures of different mass ratios have a good growth inhibitory effect on Chlorella and Rhizoctonia solani.

[0100] Table 8 Algae inhibition rates of nicotine and nicotine benzoate salt at different mass ratios

[0101]

[0102] Table 9 Algae inhibition rates of nicotine and citrate nicotine salt at different mass ratios

[0103]

[0104] Table 10 Algae inhibition rates of nicotine and orotic nicotine salt at different mass ratios

[0105]

[0106]

[0107] Comparative Example 1

[0108] Capsaicin antibacterial performance test

[0109] The antibacterial performance testing conditions and procedures were the same as in Example 1, except that a capsaicin solution with a concentration of 1.25 mg / mL was used for the antibacterial performance test. Experiments showed that the 1.25 mg / mL capsaicin solution exhibited antibacterial rates of 86.6% against Escherichia coli and 90.4% against Staphylococcus aureus.

[0110] Comparative Example 2

[0111] Antibacterial performance test of capsaicin derivative N-(3,4-dimethoxybenzyl)phthalimide

[0112] The antibacterial performance testing conditions and procedures were the same as in Example 1, except that an antibacterial performance test was conducted on a 1.25 mg / mL N-(3,4-dimethoxybenzyl)phthalimide solution. Experiments showed that the 1.25 mg / mL N-(3,4-dimethoxybenzyl)phthalimide solution exhibited antibacterial rates of 91.2% and 88.1% against *Escherichia coli* and *Staphylococcus aureus*, respectively.

[0113] Comparative Example 3

[0114] Antibacterial performance test of capsaicin derivative N-(2,4,6-trimethylbenzyl)phthalimide

[0115] The antibacterial performance testing conditions and procedures were the same as in Example 1, except that an antibacterial performance test was conducted on a 1.25 mg / mL N-(2,4,6-trimethylbenzyl)phthalimide solution. Experiments showed that the 1.25 mg / mL N-(2,4,6-trimethylbenzyl)phthalimide solution exhibited antibacterial rates of 95.3% and 97.2% against *Escherichia coli* and *Staphylococcus aureus*, respectively.

[0116] Comparative Example 4

[0117] Indole antibacterial performance test

[0118] The antibacterial performance testing conditions and procedures were the same as in Example 1, except that an indole solution with a concentration of 1.25 mg / mL was used for the antibacterial performance test. Experiments showed that the 1.25 mg / mL indole solution exhibited antibacterial rates of 86.2% and 88.5% against *Escherichia coli* and *Staphylococcus aureus*, respectively.

[0119] Comparative Example 5

[0120] Antibacterial performance test of indole derivative 5,6-dichloroarbufonin

[0121] The antibacterial performance testing conditions and procedures were the same as in Example 1, except that an antibacterial performance test was performed on a 1.25 mg / mL solution of 5,6-dichloroarbutin. Experiments showed that the 1.25 mg / mL solution of 5,6-dichloroarbutin exhibited antibacterial rates of 87.4% against Escherichia coli and 91.6% against Staphylococcus aureus.

[0122] Comparative Example 6

[0123] Antibacterial performance test of indole derivative N,N-dimethyl-3,4-dichlorobenzylamine

[0124] The antibacterial performance testing conditions and procedures were the same as in Example 1, except that an antibacterial performance test was performed on a 1.25 mg / mL solution of N,N-dimethyl-3,4-dichlorobenzylamine. Experiments showed that 1.25 mg / mL N,N-dimethyl-3,4-dichlorobenzylamine exhibited antibacterial rates of 96.9% and 93.5% against *Escherichia coli* and *Staphylococcus aureus*, respectively.

[0125] Comparative Example 7

[0126] Capsaicin algae-inhibiting performance test

[0127] The algae-inhibiting performance test conditions and procedures were the same as in Example 3, except that a capsaicin solution with a concentration of 1.25 mg / mL was used for the algae-inhibiting performance test. Experiments showed that the 1.25 mg / mL capsaicin solution exhibited antibacterial rates of 90.8% and 87.9% against Chlorella and Rhizoctonia solani, respectively.

[0128] Comparative Example 8

[0129] Algal Inhibition Performance Test of Capsaicin Derivative N-(3,4-Dimethoxybenzyl)phthalimide

[0130] The algae-inhibiting performance test conditions and procedures were the same as in Example 3, except that an N-(3,4-dimethoxybenzyl)phthalimide solution with a concentration of 1.25 mg / mL was used for the algae-inhibiting performance test. Experiments showed that the 1.25 mg / mL N-(3,4-dimethoxybenzyl)phthalimide solution exhibited algae-inhibiting rates of 81.6% and 84.5% against Chlorella vulgaris and Rhizophora spp., respectively.

[0131] Comparative Example 9

[0132] Algal Inhibition Performance Test of Capsaicin Derivative N-(2,4,6-Trimethylbenzyl)phthalimide

[0133] The algae-inhibiting performance test conditions and procedures were the same as in Example 1, except that an N-(2,4,6-trimethylbenzyl)phthalimide solution with a concentration of 1.25 mg / mL was used for the algae-inhibiting performance test. Experiments showed that the 1.25 mg / mL N-(2,4,6-trimethylbenzyl)phthalimide solution exhibited algae-inhibiting rates of 88.7% and 92.1% against Chlorella vulgaris and Rhizophora spp., respectively.

[0134] Comparative Example 10

[0135] Indole Algal Inhibition Performance Test

[0136] The algae-inhibiting performance test conditions and procedures were the same as in Example 1, except that an indole solution with a concentration of 1.25 mg / mL was used for the algae-inhibiting performance test. Experiments showed that the 1.25 mg / mL indole solution exhibited algae-inhibiting rates of 96.1% and 93.5% against Chlorella vulgaris and Rhizophora spp., respectively.

[0137] Comparative Example 11

[0138] Algal Inhibition Performance Test of Indole Derivative 5,6-Dichloroarbufonin

[0139] The algicidal performance testing conditions and procedures were the same as in Example 1, except that an algicidal performance test was conducted using a 1.25 mg / mL solution of 5,6-dichloroarbutin. Experiments showed that the 1.25 mg / mL 5,6-dichloroarbutin solution exhibited algicidal inhibition rates of 92.0% and 91.8% against Chlorella vulgaris and Rhizophora spp., respectively.

[0140] Comparative Example 12

[0141] Algal Inhibition Performance Test of Indole Derivative N,N-Dimethyl-3,4-Dichlorobenzylamine

[0142] The algae-inhibiting performance test conditions and procedures were the same as in Example 1, except that an N,N-dimethyl-3,4-dichlorobenzylamine solution with a concentration of 1.25 mg / mL was used for the algae-inhibiting performance test. Experiments showed that 1.25 mg / mL N,N-dimethyl-3,4-dichlorobenzylamine exhibited algae-inhibiting rates of 94.3% and 97.1% against Chlorella vulgaris and Rhizophora spp., respectively.

[0143] As can be seen from the various embodiments, nicotine and its salts, as well as nicotine derivatives and their salts, all have excellent antibacterial and antialgal properties, and are suitable for use as antifouling agents to prevent the attachment of marine fouling organisms.

[0144] According to Comparative Examples 1-6, nicotine and its salts have better antibacterial properties than existing natural antifouling agents such as indole and its derivatives and capsaicin and its derivatives.

[0145] According to Comparative Examples 7-12, nicotine and its salts exhibit superior anti-algae properties compared to existing natural antifouling agents such as indole and its derivatives, and capsaicin and its derivatives.

[0146] Finally, it should be noted that all the above embodiments belong to the same inventive concept, and the descriptions of each embodiment have different focuses. Where the description in a particular embodiment is not detailed, please refer to the description in other embodiments.

[0147] The embodiments described above are merely illustrative of implementation methods of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. The use of nicotine and its salts, nicotine derivatives and their salts in the preparation of marine biofouling antifouling agents, characterized in that, The active component of the marine biofouling antifouling agent is one or more of nicotine, nicotine salts, nicotine derivatives, or nicotine derivative salts.

2. The use of nicotine and its salts, nicotine derivatives and their salts according to claim 1 in the preparation of marine biofouling antifouling agents, characterized in that, The nicotine derivatives refer to products derived from nicotine by replacing hydrogen atoms or groups of atoms with other atoms or groups of atoms, including but not limited to: cotinine, mesmin, demethylnicotine, or diene nicotine; the nicotine derivative salts refer to nicotine derivative salt compounds prepared by reacting nicotine derivatives with acids, including but not limited to: benzoic acid nicotine derivative salts, malic acid nicotine derivative salts, citric acid nicotine derivative salts, tartrate nicotine derivative salts, salicylic acid nicotine derivative salts, or orotic acid nicotine derivative salts.

3. The use of nicotine and its salts, nicotine derivatives and their salts according to claim 1 in the preparation of marine biofouling antifouling agents, characterized in that, The nicotine salts mentioned refer to nicotine salt compounds prepared by reacting nicotine with acids, including but not limited to: benzoic acid nicotine salt, malic acid nicotine salt, citrate nicotine salt, tartrate nicotine salt, salicylic acid nicotine salt, or orotic acid nicotine salt; preferably, the active components contained in the marine biofouling antifouling agent are nicotine and its salts, nicotine derivatives and their salts, nicotine derivatives and nicotine salts, or a combination of nicotine and nicotine derivative salts.

4. The use of nicotine and its salts, nicotine derivatives and their salts according to claims 1-3 in the preparation of marine biofouling antifouling agents, characterized in that, The preparation method of the nicotine salt or nicotine derivative salt includes the following steps: Step 1. Mix nicotine or nicotine derivatives, acid, and solvent, and react at 10-80℃ for 1-7 hours to obtain solution A; Step 2. Add a poor solvent to solution A, and after filtration, washing, and distillation, obtain nicotine salt or nicotine derivative salt; The acid mentioned is one or more of the following: benzoic acid, malic acid, citric acid, orotic acid, tartaric acid, salicylic acid, alginic acid, gentian acid, citric acid, ascorbic acid, oxalic acid, caffeic acid, acetic acid, and lactic acid.

5. The use of nicotine and its salts, nicotine derivatives and their salts according to claim 4 in the preparation of marine biofouling antifouling agents, characterized in that, The molar ratio of nicotine or nicotine derivatives to organic acid is 0.1-10.

0.

6. The use of nicotine and its salts, nicotine derivatives and their salts according to claim 4 in the preparation of marine biofouling antifouling agents, characterized in that, The solvent is one or more of ethanol, methanol, acetonitrile, or carbon tetrachloride; the undesirable solvent is one or more of ethyl acetate, n-heptane, and toluene.

7. The use of nicotine and its salts, nicotine derivatives and their salts according to any one of claims 1-6 in the preparation of marine biofouling antifouling agents, characterized in that: The marine biofouling antifouling agent is used for antifouling of marine artificial facilities.

8. The use of nicotine and its salts, nicotine derivatives and their salts according to any one of claims 1-7 in the preparation of marine biofouling antifouling agents, characterized in that, The marine biofouling antifouling agent is in the form of a coating that can be impregnated, sprayed, brushed, or rolled.

9. The use of nicotine and its salts, nicotine derivatives and their salts according to claim 8 in the preparation of marine biofouling antifouling agents, characterized in that, The coating comprises a base material, pigments, additives, solvents, and antifouling active components.

10. The use of nicotine and its salts, nicotine derivatives and their salts according to claim 9 in the preparation of marine biofouling antifouling agents, characterized in that, The base material includes one or more of acrylic resin, chlorinated ether resin, chlorinated rubber, epoxy resin, polyvinyl alcohol, polyvinyl acetate, or amino resin; the pigment includes one or more of titanium dioxide, zinc oxide, iron oxide red, or talc.

Images