CN101724305A - Application of cycle (proline-alanine) in preventing and removing marine fouling organism - Google Patents
Application of cycle (proline-alanine) in preventing and removing marine fouling organism Download PDFInfo
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- CN101724305A CN101724305A CN200910213679A CN200910213679A CN101724305A CN 101724305 A CN101724305 A CN 101724305A CN 200910213679 A CN200910213679 A CN 200910213679A CN 200910213679 A CN200910213679 A CN 200910213679A CN 101724305 A CN101724305 A CN 101724305A
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Abstract
The invention discloses an application of cycle (proline-alanine) in preventing and removing marine fouling organism; the molecular formula of the cycle (proline-alanine) is C8H12N202, the molecular weight thereof is 168, the structural formula thereof can be seen in the chart. The cycle (proline-alanine) enjoys remarkable inhibitory action on attachment of marine organism to solids and demonstrates remarkable effect in case of low-content coating on the marine organism; meanwhile, the cycle (proline-alanine) is organic compound featuring natural existence, thus not polluting water environment; being safe and non-toxic, the cycle (proline-alanine) does not kill marine organism while inhibiting attachment thereof; moreover, being different existing antifouling materials extracted from marine organism, the cycle (proline-alanine) features mature artificial synthesis process, simple and convenient access, adaptability to mass production, reliable and stable source, thus enjoying very good application prospect in preventing and removing fouling organisms in various ocean artificial facilities.
Description
Technical field
The invention belongs to the marine antifouling coating field, be specifically related to a kind of application of dipeptides in preventing and removing marine fouling organisms that encircle.
Background technology
Marine fouling organism is meant set or perches at boats and ships and various artificial facility under water on the solid surface that to the marine organisms that economical activities of mankind has a negative impact, its harm is mainly increases the boats and ships running resistance, reduces the speed of a ship or plane, increases fuel consumption; Stop up the water pipeline; Change the metallic corrosion process, cause local corrosion or perforation; Hinder the works better of all kinds of maritime facilitieies, cause drift, unbalance even cause toppling; Aspect marine aquaculture, also can fight for adherance and bait with cultivated shellfish, hinder and culture growing of object, and reduce fishery products quality etc.
In preventing and removing marine fouling organisms technology and method, with being most widely used of antifouling paint.Traditional antifouling paint with poison expect release type antifouling be main path, by stain control agents such as the copper in the release coatings, mercury, tin, arsenic, forming around material has the concentration of poisons layer of toxic action to marine plant spore and marine animal larva, thereby reaches antifouling purpose.Yet, be that the antifouling paint of stain control agent is too big because of toxicity with the compound of arsenic, mercury etc., be eliminated 50 years last century, from the sixties in 20th century, stanniferous and copper bearing antifouling paint begin to be used in a large number.
Organo-tin compound coating once was the marine anti-pollution product that is most widely used in the world, with tributyl tin (TBT, Tribultytin) be representative, its mechanism of action is to destroy the normal function of biological cell membrane, hinder oxidative phosphorylation process, destroy the plastosome of animal, influence the normal vital movement of organism, cause the death of fouling organism body and come off.Since putting goods on the market its sixties in 20th century, because of the extremely favor in market of good anti-fouling effect.Yet the organic tin compound can disturb the calcium metabolism of oyster, brings out marine products snails sex distortion, is accumulated in the organisms such as fish, shellfish, by food chain human health is produced detrimentally affect, and Marine ecosystems are caused serious destruction.Since last century the mid-80, all found the existence of organo-tin compound in the seawater all over the world, bed mud and the biology in succession.Therefore, International Maritime Organizaton (IMO) regulation is used organo-tin compound from complete prohibition in 2008 in antifouling paint.
A large amount of uses of copper bearing antifouling paint then can cause the copper also can be in the ocean, particularly a large amount of gathering in the harbour, thus the marine eco-environment is produced detrimentally affect, so its application certainly will also can be subjected to certain limitation.
The marine anti-pollution field still lacks effectively and the antifouling paint of safety at present, and the environmental problem that causes thus is very severe, and therefore, the research object of antifouling paint is more and more tended to by obtaining natural antifouling material in the marine animal.As having a series of halogenated furan ketone mixtures that separation and purification obtains from red algae (Delisea pulchra) of reporting for work at present, can effectively suppress adhering to of line barnacle, sea lettuce and some marine bacteria; From moss animal (Zoobotryon pellucidum), extract 2,5,6-three bromo-1-methyl gramines (TBG) are to the restraining effect significantly that is attached with of line kentrogon; Also can suppress adhering to of line barnacle and multicell grass tongue worm Bugula neritina from the body wall extract of echinoderms starfish; From the sponge extract, isolate multiple secondary metabolites such as sulfation sterol, terpene, brominated product and lipid acid, wherein 9 kinds of pyrans class secondary metabolites that extract from sponge Acanthellacavernosa are to the restraining effect that is attached with of line barnacle, and 3 kinds of steroidal vitriol that extract from sponge Toxadocia zumi then can stop the dwell growth of polychetes Salmacinatribranchiata of pipe; And isolated two kinds of mixtures are also relevant with the good antifouling properties of this sponge from sponge Aplysina fistularis wounded tissue.In addition, purine bases, acid amides and furans terpene secondary metabolites that people extract from different sponges all are proved and have certain antifouling effect.Having the so abundant material with anti-fouling effect in the marine organisms, is closely-related with their physiological habit and secular purification result.Because it is very fierce between each species in the ocean environment to the spatial competition; various macrofaunas and plant all are that the other biological potential adheres to stained object; for avoiding the issuable harm of other biological attachment; some biologies are in the evolution of long period of time process in the ocean, and each has become the self-protective mechanism of many uniquenesses to keep the cleaning of self body surface voluntarily.
Therefore, containing very abundant antifouling resource in the Sea World requires study and utilizes exploitation.But, to use still seldom in the correlative study in antifouling field at present, found antifouling material only accounts for few part, and these materials mostly are the low meta-bolites of content in the marine organism, and its complex process, are unfavorable for applying.Therefore, seek more to be applicable to extensive synthetic and the antifouling material of the natural marine of applying, become this field one big urgent problem.
Ring dipeptides (2, the 5-diketopiperazine) is minimum cyclic peptide, and many native annulus dipeptide compounds all have clear and definite biological activity.The singularity of ring dipeptides structure makes the synthetic of this compounds establish one's own system, and the linear peptides ester by the N end dissociative refluxes in polar solvent usually, just can obtain object at an easy rate.Therefore, this class material is studied aspect synthetic deeply, the synthesis technique maturation, and acquiring way is easy, is suitable for scale operation.In the marine anti-pollution field, not having any relevant report openly to cross has the effect of ring dipeptides in fouling organism is prevented and kill off but at present.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of safety non-toxic is provided, be easy to the application of natural product in preventing and removing marine fouling organisms of synthetic.
The present invention is achieved through the following technical solutions above-mentioned purpose:
The present invention is ring (proline(Pro)-L-Ala) application in preventing and removing marine fouling organisms, and its molecular formula is C
8H
12N
2O
2, molecular weight is 168, structural formula is as follows:
Ring of the present invention (proline(Pro)-L-Ala) can suppress marine organisms adhering at solid surface by being coated on solid surface.But be coated on solid surface and only be the wherein a kind of mode of the present invention of using, anyly this material is applied to prevent and treat marine organisms adhere to all belongs to protection scope of the present invention.
Ring of the present invention (proline(Pro)-L-Ala) is 1 μ g/cm at coated weight
2When above, promptly adhering to of fouling organism produced the obvious suppression effect.Its preferred coated weight is 3.5 μ g/m
2More than.Test shows that ring (proline(Pro)-L-Ala) can't be killed marine organisms when the inhibition marine animal adheres to, and toxicity is minimum.
The present invention finds the be attached with good restraining effect of ring (proline(Pro)-L-Ala) to cirrus class and mussels through a large amount of experiments.Because marine fouling organism is made up of animal, plant and microorganism three major types, wherein harm big and adhere to after the kind that is difficult to remove mainly be biologies such as the stockless cirrus class (barnacle) of tool calcium carbonate shell, battalion's set life and bivalve (mussel and oyster).Therefore, anti-fouling compound filler test work multiselect is an experimental subjects with cirrus class and mussels.Cirrus class wherein is representative with the reticulate pattern barnacle again, and the reticulate pattern barnacle is a kind of in the main fouling organism, marine site on the south the island, Dongtou in south, Zhejiang, and it has comparative advantage in fouling organism group; And pteria martensii is a kind of bivalve of living in the torrid zone, sea area, subtropics, extensively distribute at China South Sea, inhabit near the seabed to the depth of water 10m subtidal line, adult throughout one's life with byssus attached to living on cay, the chad, can be used as the representative of mussels fouling organism.Therefore, proof test of the present invention adopts reticulate pattern barnacle and pteria martensii as experimental subjects, has important representative meaning.
Usually can be divided into two life stages based on fouling organism, one is grown till explore body surface off and on and prepare settlement and metamorphosis for deviate from egg membrane from larva, for swimming life stage; Choose from larva and to settle down the position, its surface attachment, abnormal form the young after, be set or epiphytism stage.From stained angle, fouling organism produces after harm starts from its battalion set or epiphytism the mankind.The settlement and metamorphosis of larva if can be suppressed effectively, just the purpose that fouling organism is prevented and kill off can be reached.Therefore, it is the anti-fouling effect that experimental subjects is checked compound that the present invention adopts the halobiontic larva of this two class, has scientific rationality and representative meaning.
Ring of the present invention (proline(Pro)-L-Ala) can obtain by extracting from marine organisms.
Its extracting method may further comprise the steps: sponge is used alcoholic extraction, and extracting solution gets extract just with petroleum ether extraction again behind concentrating under reduced pressure, ethyl acetate extraction; Just extract is after silicagel column carries out the purifying first time, elutriant again through Sephadex LH-20 and silicagel column carry out the second time purifying promptly.The industrial spirit of wherein said alcohol preferred 90%; The elutriant of crossing column purification for the first time is ethyl acetate/acetone and chloroform/methanol; The elutriant of crossing column purification for the second time is a chloroform/methanol.
The preferred following scheme of extracting method of the present invention: under normal temperature condition, the beauty of gathering is belonged to the Alcoholic extraction of sponge (Callyspongia sp.) with 95% three times, each 4 days; Alcoholic extract in 50 ℃ of concentrating under reduced pressure, is used ethyl acetate extraction three times, and used petroleum ether extraction; Cross silicagel column (200-300 order) three times, use ethyl acetate/acetone (50: 50), chloroform/methanol (95: 5 and 98: 2) wash-out respectively; Use chloroform/methanol (2: 8 and 98: 2) wash-out to obtain respectively after Sephadex LH-20 and silicagel column (200-300 order).
Ring of the present invention (proline(Pro)-L-Ala) can also obtain by synthetic.Ring (proline(Pro)-L-Ala) belongs to a kind of in the dipeptides of ring, obtains by the synthetic approach easily.
Compared with prior art, the present invention has following beneficial effect:
1. ring disclosed by the invention (proline(Pro)-L-Ala) has significant inhibitory effect to marine organisms adhering on solid, when solid surface has applied this material of low levels, the effect that prevents that significantly marine organisms from adhering to is arranged promptly.
2. ring disclosed by the invention (proline(Pro)-L-Ala) is naturally occurring organic compound, can not cause the pollution of water body environment, can not cause its enrichment in organism by the food chain transmission, and is environmentally friendly, safe.
3. ring disclosed by the invention (proline(Pro)-L-Ala) is when effectively the inhibition marine organisms adhere to; safety non-toxic, heavy metal element such as cupric and tin can not killed marine organisms; only play the effect of driveing, have good social benefit from the environment protection angle.
4. ring disclosed by the invention (proline(Pro)-L-Ala) is a natural product, but its process for artificial maturation, acquiring way is easy, be suitable for scale operation, be not subject to biological intravital content, have reliable and stable source, it is big to apply potentiality, has a good application prospect in the fouling organism of all kinds of artificial ocean facilities is prevented and kill off.
Embodiment
Embodiment 1
Experimental group I: will encircle (proline(Pro)-L-Ala) and use dissolve with methanol, compound concentration is the solution of 28.26 μ g/ml.At diameter is to add this solution of 1ml in the culture dish of 6cm, and makes it evenly cover culture dish bottom.After treating that solvent volatilizees fully, ring (proline(Pro)-L-Ala) content that is coated on the culture dish bottom is 1 μ g/cm
2Add the 10ml seawater.
Experimental group II: will encircle (proline(Pro)-L-Ala) and use dissolve with methanol, compound concentration is the solution of 98.91 μ g/ml.At diameter is to add this solution of 1ml in the culture dish of 6cm, and makes it evenly cover culture dish bottom.After treating that solvent volatilizees fully, ring (proline(Pro)-L-Ala) content that is coated on the culture dish bottom is 3.5 μ g/cm
2Add the 10ml seawater.
Control group: add 1ml methyl alcohol, make solution be uniformly distributed in the culture dish bottom, treat that solvent evaporates is complete, add the 10ml seawater again.
Blank group: add the 10ml seawater.
Experimental group, blank group are respectively established 5 parallel samples with control group.In each sample, add 30 reticulate pattern barnacle cyprids respectively.Placing temperature is to cultivate in dark surrounds in the constant incubator about 29 ℃.Observed once every 24 hours.Cultivate after 72 hours statistical study is carried out in final the adhering to death state of each group larva.
Table 1 has been listed adhering to and mortality ratio of experimental group, control group and blank group cyprids.As seen, in constant incubator, cultivate after 72 hours, the larva adhesive rate of blank group is about 86%, control group about 82%, the adhesive rate of blank group and control group cyprids does not have significant difference (p＞0.05), not showing as not leaving over after the volatilization of the methyl alcohol of solvent influences the active objectionable impurities of cyprids, is suitable for dissolving this compound.And the experimental group I and the II that handle through ring (proline(Pro)-L-Ala), the adhesive rate of its cyprids is all less than 50%, well below control group, and significant difference (p＜0.01), show that this compound can suppress adhering to of reticulate pattern barnacle cyprids effectively.
Table 1.
| Group | Proof load | Adhesive rate % | Mortality ratio % |
| Blank group | ??- | ??86.1 | ??0 |
| Control group | ??- | ??81.8 | ??0 |
| Experimental group I | ??1μg/cm 2 | ??49.5 | ??0 |
| Experimental group II | ??3.5μg/cm 2 | ??32.3 | ??0 |
Embodiment 2
Experimental group: will encircle (proline(Pro)-L-Ala) and use dissolve with methanol, compound concentration is the solution of 282.6 μ g/ml.At diameter is to add this solution of 1ml in the culture dish of 6cm, and makes it evenly cover culture dish bottom.After treating that solvent volatilizees fully, ring (proline(Pro)-L-Ala) content that is coated on the culture dish bottom is 10 μ g/cm
2Add the 10ml seawater.
Control group: add 1ml methyl alcohol, make solution be uniformly distributed in the culture dish bottom, treat that solvent evaporates is complete, add the 10ml seawater again.
Blank group: add the 10ml seawater.
Determining of larva quantity: get the water body that contains the pteria martensii veliger and concentrate with bolting silk from nursery pond.Divide and respectively to get 50ml three times, splash into 1-2 and drip formalin solution and kill behind the larva in the microscopically counting, the averaging of income value is the density of larva in the water body.
Experimental group, blank group are all established 5 parallel samples with control group, add about 30 larvas in each sample.In being about 26 ℃ incubator, temperature under dark surrounds, cultivates.Observed once every 24 hours.Cultivate after 72 hours statistical study is carried out in final the adhering to death state of each group larva.
Table 2 has been listed adhering to and mortality ratio of experimental group, control group and blank group pteria martensii larva.As seen, in constant incubator, cultivate after 72 hours, the larva adhesive rate of blank group is about 33%, control group about 32%, the adhesive rate of blank group and control group veliger does not have significant difference (p＞0.05), not showing as not leaving over after the volatilization of the methyl alcohol of solvent influences the active objectionable impurities of veliger, is suitable for dissolving this compound.And through the experimental group of loop proline-L-Ala, the adhesive rate of its larva is 0, and well below control group, difference is (p＜0.01) extremely significantly, shows that this compound can suppress adhering to of pteria martensii larva effectively.
Table 2.
| Group | Proof load | Adhesive rate % | Mortality ratio % |
| Blank group | ??- | ??32.6 | ??0 |
| Control group | ??- | ??31.8 | ??0 |
| Experimental group | ??10μg/cm 2 | ??0 | ??0 |
Claims (4)
1. ring (proline(Pro)-L-Ala) application in preventing and removing marine fouling organisms, its molecular formula is C
8H
12N
2O
2, molecular weight is 168, structural formula is as follows:
2. application as claimed in claim 1 is characterized in that: described ring (proline(Pro)-L-Ala) is coated on solid surface.
3. application as claimed in claim 1 or 2 is characterized in that: the minimum coated weight of described ring (proline(Pro)-L-Ala) is 1 μ g/cm
2
4. application as claimed in claim 1 is characterized in that: described ring (proline(Pro)-L-Ala) is to obtain or obtain by synthetic by extracting from marine organisms.
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| CN200910213679A CN101724305B (en) | 2009-12-08 | 2009-12-08 | Application of cycle (proline-alanine) in preventing and removing marine fouling organism |
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| CN101724305B CN101724305B (en) | 2012-09-05 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130807A (en) * | 2013-01-30 | 2013-06-05 | 青岛农业大学 | Separating method of cyclic dipeptide C9 from phellinus igniarius |
| CN103130808A (en) * | 2013-01-30 | 2013-06-05 | 青岛农业大学 | Normal pressure reverse phase preparation and separating method of dipeptide C8 in phellinus igniarius |
| CN106189542A (en) * | 2016-08-29 | 2016-12-07 | 广州天朗涂料化工有限公司 | A kind of marine organisms prevent and kill off coating and preparation method thereof |
| CN111406759A (en) * | 2020-03-31 | 2020-07-14 | 中国科学院南海海洋研究所 | Grateloupia filicina extract and application thereof in preparation of marine fouling organism control agent |
| CN114716413A (en) * | 2022-04-24 | 2022-07-08 | 江苏海洋大学 | Separation and purification method of cyclic dipeptide algae inhibiting active compound in large-scale seaweed |
-
2009
- 2009-12-08 CN CN200910213679A patent/CN101724305B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 漆淑华等: "海洋细菌Pseudomona sp.抗菌代谢产物的研究", 《天然产物研究与开发》 * |
| 郭秀春等: "海洋微生物中二酮哌嗪类化合物的研究进展", 《微生物学通报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130807A (en) * | 2013-01-30 | 2013-06-05 | 青岛农业大学 | Separating method of cyclic dipeptide C9 from phellinus igniarius |
| CN103130808A (en) * | 2013-01-30 | 2013-06-05 | 青岛农业大学 | Normal pressure reverse phase preparation and separating method of dipeptide C8 in phellinus igniarius |
| CN106189542A (en) * | 2016-08-29 | 2016-12-07 | 广州天朗涂料化工有限公司 | A kind of marine organisms prevent and kill off coating and preparation method thereof |
| CN106189542B (en) * | 2016-08-29 | 2017-08-04 | 广东天朗化工实业有限公司 | A kind of marine organisms prevent and kill off coating and preparation method thereof |
| CN111406759A (en) * | 2020-03-31 | 2020-07-14 | 中国科学院南海海洋研究所 | Grateloupia filicina extract and application thereof in preparation of marine fouling organism control agent |
| CN114716413A (en) * | 2022-04-24 | 2022-07-08 | 江苏海洋大学 | Separation and purification method of cyclic dipeptide algae inhibiting active compound in large-scale seaweed |
| CN114716413B (en) * | 2022-04-24 | 2023-04-28 | 江苏海洋大学 | Separation and purification method of cyclic dipeptide algae inhibiting active compound in large-scale algae |
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