CN110724403A - Application of quinazolinone alkaloid compound derived from marine fungi in preventing and removing marine fouling organisms - Google Patents
Application of quinazolinone alkaloid compound derived from marine fungi in preventing and removing marine fouling organisms Download PDFInfo
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- CN110724403A CN110724403A CN201910992812.1A CN201910992812A CN110724403A CN 110724403 A CN110724403 A CN 110724403A CN 201910992812 A CN201910992812 A CN 201910992812A CN 110724403 A CN110724403 A CN 110724403A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P17/00—Preparation of heterocyclic carbon compounds with only O, N, S, Se or Te as ring hetero atoms
- C12P17/18—Preparation of heterocyclic carbon compounds with only O, N, S, Se or Te as ring hetero atoms containing at least two hetero rings condensed among themselves or condensed with a common carbocyclic ring system, e.g. rifamycin
- C12P17/182—Heterocyclic compounds containing nitrogen atoms as the only ring heteroatoms in the condensed system
Abstract
The invention discloses application of a quinazolinone alkaloid compound derived from marine fungi in preventing and removing marine fouling organisms. The quinazolinone alkaloid compound is disclosed to be used for preventing and removing marine fouling organisms for the first time, has a remarkable inhibiting effect on the adhesion of the marine fouling organisms on solids, and has a remarkable effect under the condition of low-content coating. Meanwhile, marine organisms are not killed when the marine organisms are inhibited from attaching, and the repellent effect is achieved. The compound can be extracted from fermentation products of marine fungi, can also be obtained by an artificially mature synthesis process, has a reliable and stable source, and has good application prospect in preventing and removing fouling organisms of various marine artificial facilities.
Description
Technical Field
The invention belongs to the field of marine antifouling paint, and particularly relates to application of a quinazolinone alkaloid compound derived from marine fungi in marine fouling organism prevention and removal.
Background
Marine biofouling refers to the phenomenon that various artificial facilities or ships immersed in seawater are attached by marine microorganisms, plants or animals to have adverse effects on human economic activities, and the main harm is to increase the roughness and weight of the ships, thereby increasing the resistance, reducing the navigational speed, increasing the fuel consumption and the maintenance cost of the ship body; the normal work of various ocean facilities is hindered, and drifting, unbalance and even overturning are caused; in the aspect of marine aquaculture, the aquatic culture device can compete for attachment bases and baits with cultured shellfish or block net cages to cause unsmooth water flow and insufficient oxygen supply, thereby influencing the yield and quality of cultured aquatic products. In the historical process of developing and utilizing the ocean by human beings, biofouling is one of the major problems to be solved urgently in the industries of ocean transportation, ocean engineering, ocean fishery and the like.
Currently, among the technologies and methods for preventing and removing marine fouling organisms, the antifouling paint is most widely used, and the most commonly used antifouling paints are roughly classified into three categories: cuprous oxide, organotin, and other compounds. The traditional antifouling paint forms a poison concentration layer with toxic and killing effects on marine plant spores or marine animal larvae by releasing antifouling agents such as copper, mercury, tin, arsenic and the like in the paint, so that the antifouling purpose is achieved. However, due to teratogenic toxicity to marine organisms, organotin antifouling paints have been banned globally by the International Maritime Organization (IMO) from 2008/9/17. The copper oxide coating is listed in the product list of 'high pollution and high environmental risk' by the national environmental protection department of China, and is prohibited to be used in 2012. Therefore, the need for a nontoxic, environment-friendly and efficient alternative coating is urgently needed.
The marine fungus-derived natural product has the characteristics of sustainability, environmental friendliness, abundant and various metabolites and the like. The competition of various species in the marine environment to the space is very violent, in order to avoid the possible harm caused by the attachment of other organisms, some organisms in the sea form a unique self-defense mechanism in the long-term evolution process, and the fouling and the attachment of other organisms can be prevented by generating secondary metabolites which are harmless to the environment and have antifouling activity, so that the marine environment is favorable for self survival. These natural antifouling compounds are a very desirable class of antifouling agents which achieve an antifouling effect by a repellent effect rather than a poisoning effect, which not only have excellent antifouling properties, but also do not cause environmental damage. Therefore, the method has important significance and value for searching novel, nontoxic, environment-friendly and efficient natural antifouling compounds from natural resources.
The quinazolinone alkaloid compounds are alkaloid compounds with quinazolinone fragments. The literature (J.Comm.chem.2000, 2,186-194) discloses the synthesis of such compounds using combinatorial chemical synthesis methods. However, at present, in the field of marine antifouling, no relevant report discloses the effect of the compounds in preventing and removing fouling organisms.
Disclosure of Invention
The invention aims to provide the application of a quinazolinone alkaloid compound which is safe, nontoxic and easy to artificially synthesize and is derived from marine fungi in preventing and removing marine fouling organisms aiming at the defects of the prior art.
The invention realizes the aim through the following technical scheme:
the invention relates to application of quinazolinone alkaloid compound in preventing and removing marine fouling organisms, which has the chemical name of (S) -4-benzyl-1, 2-dihydro-6H-pyrazine [2,1-B ]]Quinazoline-3, 6(4H) -dione [ (S) -4-benzyl-1,2-dihydro-6H-pyrazino [2,1-b ]]quinazoline-3,6(4H)-dione]The molecular formula is C18H15N3O2Molecular weight is 305, and structural formula is as follows:
the quinazolinone alkaloid compound provided by the invention can be coated on a solid surface, so that the attachment of marine fouling organisms on the solid surface can be inhibited. However, the application to the solid surface is only one mode of applying the invention, and any application of the compound to preventing the attachment of marine fouling organisms belongs to the protection scope of the invention.
The coating amount of the quinazolinone alkaloid compound is 10 mu g/cm2Sometimes, attachment to fouling organisms occursObvious inhibiting effect, no killing of marine organism and very low toxicity.
Through a large number of experiments, the quinazolinone alkaloid compound is found to have a good inhibition effect on the attachment of the tendrils. The marine fouling organisms comprise three major types of animals, plants and microorganisms, wherein the types which are harmful and difficult to remove after attachment are mainly organisms with calcareous shells, sessile stemmed leg (barnacles) living in campuses and bivalve mollusks (mussels and oysters) and the like. Among them, the stemless vine is represented by the reticulate barnacle. The balanus reticulatus is one of the main fouling organisms, is widely distributed in south China sea, and has absolute advantages in fouling organism communities. Therefore, the method has important representative significance in the verification test of the invention by selecting the balanus reticulatus as an experimental object.
Based on fouling organisms, the method can be generally divided into two life stages, namely a planktonic life stage from the development of larva out of an egg membrane to the intermittent exploration of the surface of an object to prepare for attachment and metamorphosis; the self-larvae are selected to settle at the positions, and after adhering to the surfaces of the self-larvae and being metamorphosed to form larvae, the larvae are in a fixed or adhering life stage. From a fouling point of view, the danger that fouling organisms pose to humans begins after their nutritional fixation or attachment life. If the settlement and metamorphosis of the larvae can be effectively inhibited, the purpose of preventing and removing fouling organisms can be achieved. Therefore, the method adopts the larvae of the balanus reticulatus as an experimental object to test the antifouling effect of the compound, and has scientific reasonability and representative significance.
The quinazolinone alkaloid compound can be obtained by extracting from fermentation products of marine fungi. The extraction method comprises the following steps:
(1) inoculating a strain Aspergillus sp.SK-28 of a marine fungus into a seed culture medium from a slant culture medium, and performing shake culture to obtain a seed culture solution (the marine fungus Aspergillus sp.SK-28 is preserved in Guangdong province microbial culture collection center (GDMCC) in 2019, 9, 26, with the preservation number of GDMCC No. 60790, and the classified name of the preservation unit is Aspergillus sp.100, 59, 5, th of Dazhou yard, Miao, Guangzhou city);
(2) inoculating the seed culture solution into a fermentation culture medium, and standing for culture;
(3) soaking the fermentation product in ethyl acetate, concentrating under reduced pressure to obtain ethyl acetate crude extract, and separating the ethyl acetate crude extract by column chromatography to obtain the quinazolinone alkaloid compound.
Preferably, in the above preparation method, the seed culture medium comprises: each 0.5-1.5L of water contains 100-300 g of potato and 10-30 g of glucose.
Preferably, in the above preparation method, the shake culture conditions are: the rotating speed is 100-300 rpm, the temperature is 20-28 ℃, and the culture time is 48-168 hours.
Preferably, in the above preparation method, the fermentation medium comprises: each 1.5-10L of water contains 1500-10000 g of rice and 45-300 g of sea salt.
Preferably, in the above preparation method, the temperature of the static culture is 20 to 28 ℃ and the culture time is 20 to 60 days.
Compared with the prior art, the invention has the following beneficial effects:
1. the quinazolinone alkaloid compound disclosed by the invention has a remarkable inhibiting effect on the attachment of marine fouling organisms on a solid, and has an obvious effect of preventing the attachment of the marine fouling organisms when the surface of the solid is coated with a low content of the substance.
2. The quinazolinone alkaloid compound disclosed by the invention does not contain heavy metal elements such as tin and copper while effectively inhibiting the attachment of marine fouling organisms, is safe and non-toxic, does not kill marine organisms, plays a role in repelling, and has good social benefits from the aspect of environmental protection.
3. The quinazolinone alkaloid compound disclosed by the invention is a natural product, can be obtained by large-scale fermentation and extraction of fungi, can also be obtained by an artificially mature synthesis process, has reliable and stable sources, has large popularization and application potentials, and has good application prospects in prevention and removal of fouling organisms of various marine artificial facilities.
Detailed Description
The present invention is further explained with reference to the following examples, which are not intended to limit the scope of the present invention in any way.
Example 1
The quinazolinone alkaloid compound can be separated from thallus of Aspergillus sp.SK-28. The marine fungus is obtained from the leaf part of the Kandelia candel of the mangrove plant in the Shankou mangrove forest protection area of the Guangxi Zhuang nationality; the method comprises the following specific steps:
1. seed culture:
1.1 preparing a seed culture medium: 200g of potatoes, 20g of glucose and 1L of tap water are evenly distributed in 5 500mL conical bottles and are killed for 30 minutes at 121 ℃.
1.2 seed culture: inoculating strain of marine fungus into seed culture medium, and culturing at 28 deg.C on shaker at 200rpm for 72 hr to obtain seed culture solution.
2. Fermentation culture:
2.1 preparing a fermentation medium: 6000g of rice, 180g of sea salt and 6L of tap water, and then the mixture is sterilized for 30 minutes at 121 ℃.
2.2 fermentation culture: aseptically inoculating 5mL of the seed solution into a conical flask containing a fermentation medium, and performing static culture at 25 ℃ for 28 days.
3. Extraction and separation:
soaking the fermented product in ethyl acetate, decompression concentrating the soaked liquid at 50 deg.c to obtain ethyl acetate crude extract, silica gel column chromatography to separate, collecting 10-50% ethyl acetate/petroleum ether eluent and separating into 10 components. Wherein the 5 th component is purified by silica gel column chromatography, and is eluted by using methanol-dichloromethane with the volume ratio of 2:100 as an eluent to obtain the quinazolinone alkaloid compound.
Example 2
The quinazolinone alkaloid compound of example 1 was tested for anti-biofouling activity:
experimental group quinazolinone alkaloid compound was dissolved in methanol to prepare 282.6 μ g/mL solution. 1mL of this solution was added to a 6 cm-diameter petri dish and allowed to cover the culture evenlyThe bottom of the dish. After the solvent is completely volatilized, the content of the quinazolinone alkaloid compound coated on the bottom of the culture dish is 10 mu g/cm2。
Adding 1mL of methanol into the control group to uniformly distribute the solution at the bottom of the culture dish, and adding 10mL of seawater after the solvent is completely volatilized.
Only 10mL of seawater was added to the blank.
Each of the experimental, control and blank groups was provided with 3 replicates. 30 cyprids of balanus reticulates were added to each sample. Culturing in a constant temperature incubator at about 30 deg.C. The observation was performed every 24 hours. Statistical analysis of the final attachment and death status of each group of larvae was performed after 120 hours of culture.
Table 1 shows the attachment rate and mortality rate of cyprids of balanus reticulates in the experimental, control and blank groups. It can be seen that the attachment rate of larvae in the control group was 78.1% and the attachment rate in the blank group was 77.2% after 120 hours of incubation in the incubator, and there was no significant difference in the attachment rate between the cyprids of the control group and the blank group (p)>0.05), indicating that methanol as a solvent does not leave harmful substances affecting the activity of the cyprids after volatilization, and is suitable for dissolving the compound. The attachment rate of the cyprids of the experimental group treated by the quinazolinone alkaloid compound is obviously lower than that of the control group, and the difference is obvious (p)<0.05), indicating that the quinazolinone alkaloid compound can effectively inhibit the attachment of cyprids of balanus reticulatus. In addition, the death rate of the cyprids in the experimental group, the control group and the blank group is 0, and the results of the three groups have no significant difference (p)>0.05), indicating that the quinazolinone alkaloid compound is present at a dose of 10 μ g/cm2The quinazolinone alkaloid compound has no toxic effect on cyprids of balanus reticulatus, can not kill marine organisms, has marine organism fouling resistance activity as a repellent effect, and has good application prospect in marine fouling organism prevention and removal from the aspect of environmental protection.
TABLE 1 results of anti-biofouling activity of quinazoline alkaloid compounds
| Compound (I) | Percentage of adhesion% | The mortality rate is% |
| Quinazoline alkaloids | 27.1 | 0 |
| Control group | 78.1 | 0 |
| Blank group | 77.2 | 0 |
Claims (8)
1. An application of quinazolinone alkaloid compound from marine fungi in preventing and removing marine fouling organisms; the quinazolinone alkaloid compound has the following structural formula:
2. the use of claim 1, wherein: the quinazolinone alkaloid compound is coated on a solid surface.
3. Use according to claim 1 or 2, characterized in that: the coating amount of the quinazolinone alkaloid compound is 10 mu g/cm2(ii) a The marine fouling organism is reticulate barnacle.
4. A process for preparing a quinazolinone alkaloid compound according to claim 1, characterized in that it comprises the following steps:
(1) inoculating Aspergillus sp.SK-28 strain of marine fungus into a seed culture medium from a slant culture medium, and performing shake culture to obtain a seed culture solution; SK-28 of marine fungus is preserved in Guangdong province microorganism culture collection center in 2019, 9, 26 months, with the preservation number GDMCC No. 60790;
(2) inoculating the seed culture solution into a fermentation culture medium, and standing for culture;
(3) soaking the fermentation product in ethyl acetate, concentrating under reduced pressure to obtain ethyl acetate crude extract, and separating the ethyl acetate crude extract by column chromatography to obtain the quinazolinone alkaloid compound.
5. The method of claim 4, wherein the seed medium comprises: each 0.5-1.5L of water contains 100-300 g of potato and 10-30 g of glucose.
6. The method of claim 4, wherein the shake culture conditions are: the rotating speed is 100-300 rpm, the temperature is 20-28 ℃, and the culture time is 48-168 hours.
7. The method of claim 4, wherein the fermentation medium comprises: each 1.5-10L of water contains 1500-10000 g of rice and 45-300 g of sea salt.
8. The method according to claim 4, wherein the temperature of the static culture is 20 to 28 ℃ and the culture time is 20 to 60 days.
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Cited By (3)
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| CN111234586A (en) * | 2020-02-24 | 2020-06-05 | 中国科学院南海海洋研究所 | Application of pyrazinoquinazolinetrione alkaloid compound in preparation of marine fouling organism control agent |
| CN111269603A (en) * | 2020-02-24 | 2020-06-12 | 中国科学院南海海洋研究所 | Application of pyrazine quinazolinedione alkaloid compound in preparation of marine fouling organism control agent |
| CN112209935A (en) * | 2020-10-31 | 2021-01-12 | 温州大学 | Preparation method of pyrazino-fused quinazolinone substance |
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Cited By (4)
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| CN111234586A (en) * | 2020-02-24 | 2020-06-05 | 中国科学院南海海洋研究所 | Application of pyrazinoquinazolinetrione alkaloid compound in preparation of marine fouling organism control agent |
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| CN112209935A (en) * | 2020-10-31 | 2021-01-12 | 温州大学 | Preparation method of pyrazino-fused quinazolinone substance |
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