CN101715770A - Application of loop proline-3-hydroxy-2-aminobutyric acid in preventing and removing marine fouling organisms - Google Patents
Application of loop proline-3-hydroxy-2-aminobutyric acid in preventing and removing marine fouling organisms Download PDFInfo
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Abstract
The invention discloses application of loop proline-3-hydroxy-2-aminobutyric acid in preventing and removing marine fouling organisms. The molecular formula of the loop proline-3-hydroxy-2-aminobutyric acid is C9H14N203, and the molecular weight is 198. The loop proline-3-hydroxy-2-aminobutyric acid has an obvious inhibition function on the attachment of marine organisms on solids and has an obvious effect when coated with low content; meanwhile, the loop proline-3-hydroxy-2-aminobutyric acid as a naturally existing organic compound can not pollute the water environment, has safety and no toxicity, and can not kill the marine organisms while inhibiting the attachment of the marine organisms, and is different from most of existing anti-fouling substances extracted from the marine organisms. The invention has the advantages of mature artificial synthesizing technology, simple obtaining way, reliable and stable source and favorable application prospect in preventing and removing fouling organisms of various marine artificial facilities, and is suitable for mass production.
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 surface of solids 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 metal erosion process, cause local corrosion or perforation; Hinder the operate as normal of all kinds of marine facilities, 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 aquatic 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 antifouling compositions such as the copper in the release coatings, mercury, tin, arsenic, forming around material has the concentration of poisons layer of toxic action to sea-plant spore and marine animal larva, thereby reaches antifouling purpose.Yet, be that the antifouling paint of antifouling composition 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, the antifouling paint of cupric and stanniferous begins to be used in a large number.
With tributyl tin (TBT, Tribultytin) once be the marine anti-pollution product that is most widely used in the world for the organo-tin compound coating of representative, its mechanism of action is to destroy the normal function of biological cell membrane, hinder oxidative phosphorylation process, destroy the mitochondria 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 gastropod sex distortion, is accumulated in the organisms such as fish, shellfish, by food chain human health is produced harmful effect, 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 Organization (IMO) regulation is used organo-tin compound from complete prohibition in 2008 in antifouling paint.
A large amount of uses of the antifouling paint of cupric 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 harmful effect, 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 bryozoan (Zoobotryon pellucidum), extract 2,5,6-three bromo-1-methyl donaxines (TBG) are to the inhibitory action 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 echinoderm starfish; Multiple secondary metabolites such as sulphation sterol, terpene, brominated product and fatty acid from the sponge extract, have been isolated, wherein 9 kinds of pyrans class secondary metabolites that extract from sponge Acanthellacavernosa are to the inhibitory action that is attached with of line barnacle, and 3 kinds of steroidal sulphate that extract from sponge Toxadocia zumi then can stop the dwell growth of Polychaeta Salmacinatribranchiata of pipe; And isolated two kinds of compounds are also relevant with the good antifouling properties of this sponge from sponge Aplysina fistularis wounded tissue.In addition, purine base, 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 long-term purification result.Because it is very fierce between each species in the marine environment to the competition in space; various larger animals and plant all be other biological potential adhere 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, each self-forming the cleaning that keeps self body surface of the self-protective mechanism of many uniquenesses.
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 metabolite 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 anti-pollution 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 biologically active.The particularity 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 large-scale production.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 products in preventing and removing marine fouling organisms of synthetic.
The present invention is achieved through the following technical solutions above-mentioned purpose:
The application of loop proline-3-hydroxy-2-aminobutyric acid Cyclo (Pro-3-hydroxy-2-aminobutanoic acid) in preventing and removing marine fouling organisms, its molecular formula is C
9H
14N
2O
3, molecular weight 198, chemical structural formula is as follows:
Loop proline-3-hydroxy-2-aminobutyric acid of the present invention can suppress marine organisms adhering at the surface of solids by being coated on the surface of solids.But be coated on the surface of solids 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.
Loop proline-3-hydroxy-2-aminobutyric acid of the present invention 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 6.5 μ g/cm
2More than.Test shows that loop proline-3-hydroxy-2-aminobutyric acid 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 loop proline-3-hydroxy-2-aminobutyric acid to cirrus class and Bivalve 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 stockless cirrus class and Bivalve.Stockless 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 Bivalve fouling organism.Therefore, demonstration 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.
Loop proline-3-hydroxy-2-aminobutyric acid of the present invention can obtain by extracting from marine organisms.
Its extracting method may further comprise the steps: sponge is used alcoholic extraction, and extract 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, eluent again through Sephadex LH-20 carry out the second time purifying promptly.The industrial alcohol of wherein said alcohol preferred 95%; The eluent of crossing the post purifying for the first time is ethyl acetate/acetone and chloroform/methanol; The eluent of crossing the post purifying for the second time is a chloroform/methanol.
The preferred following scheme of extracting method of the present invention: under normal temperature condition, with the beautiful sponge of gathering with 90% Alcoholic extraction 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 (85: 15 and 9: 1) wash-out respectively; Can obtain with chloroform/methanol (2: 8) wash-out after Sephadex LH-20.
Loop proline-3-hydroxy-2-aminobutyric acid of the present invention can also obtain by synthetic.Loop proline-3-hydroxy-2-aminobutyric acid 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. loop proline-3-hydroxy-2-aminobutyric acid disclosed by the invention has significant inhibitory effect to marine organisms adhering on solid, when the surface of solids has applied this material of low content, and the effect that promptly has tangible control marine organisms to adhere to.
2. loop proline-3-hydroxy-2-aminobutyric acid disclosed by the invention 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. loop proline-3-hydroxy-2-aminobutyric acid disclosed by the invention 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 environmental protection angle.
4. loop proline-3-hydroxy-2-aminobutyric acid disclosed by the invention is a natural products, but its process for artificial maturation, acquiring way is easy, be suitable for large-scale production, be not subject to the content in the organism, 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: with the loop proline-3-hydroxy-2-aminobutyric acid 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, the loop proline-3-hydroxy-2-aminobutyric acid content that is coated on the culture dish bottom is 1 μ g/cm
2Add the 10ml seawater.
Experimental group II: with the loop proline-3-hydroxy-2-aminobutyric acid dissolve with methanol, compound concentration is the solution of 183.69 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, the loop proline-3-hydroxy-2-aminobutyric acid content that is coated on the culture dish bottom is 6.5 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 analysis is carried out in final the adhering to death state of each group larva.
Table 1 has been listed adhering to and lethality of experimental group, control group and blank networking line barnacle cyprids 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), can not leave over the harmful substance that influences the cyprids activity after showing methyl alcohol volatilization, be suitable for dissolving this compound as solvent.And the experimental group of handling through loop proline-3-hydroxy-2-aminobutyric acid, the adhesive rate of its cyprids all is lower than control group, and significant difference (p＜0.05), shows that this compound can suppress adhering to of reticulate pattern barnacle cyprids effectively.
Table 1
| Group | Proof load | Adhesive rate (%) | Lethality (%) |
| Blank group | ??- | ??86.1 | ??0 |
| Control group | ??- | ??81.8 | ??0 |
| Experimental group I | ??1μg/cm 2 | ??48.9 | ??0 |
| Experimental group II | ??6.5μg/cm 2 | ??36.1 | ??0 |
Embodiment 2
Experimental group: with the loop proline-3-hydroxy-2-aminobutyric acid 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, the loop proline-3-hydroxy-2-aminobutyric acid 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 analysis is carried out in final the adhering to death state of each group larva.
Table 2 has been listed adhering to and lethality 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), can not leave over the harmful substance that influences the veliger activity after showing methyl alcohol volatilization, be suitable for dissolving this compound as solvent.And the experimental group of handling through loop proline-3-hydroxy-2-aminobutyric acid, the adhesive rate of its larva is 0, 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 (%) | Lethality (%) |
| Blank group | ??- | ??32.6 | ??0 |
| Control group | ??- | ??31.8 | ??0 |
| Experimental group | ??10μg/cm 2 | ??0 | ??0 |
Claims (4)
1. the application of loop proline-3-hydroxy-2-aminobutyric acid in preventing and removing marine fouling organisms, its molecular formula are C
9H
14N
2O
3, molecular weight is 198, structural formula is as follows:
2. application as claimed in claim 1 is characterized in that: described loop proline-3-hydroxy-2-aminobutyric acid is coated on the surface of solids.
3. application as claimed in claim 1 or 2 is characterized in that: the minimum coated weight of described loop proline-3-hydroxy-2-aminobutyric acid is 1 μ g/cm
2
4. application as claimed in claim 1 is characterized in that: described loop proline-3-hydroxy-2-aminobutyric acid is to obtain or obtain by synthetic by extracting from marine organisms.
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| WO2015007682A1 (en) | 2013-07-15 | 2015-01-22 | Basf Se | Pesticide compounds |
| WO2018166855A1 (en) | 2017-03-16 | 2018-09-20 | Basf Se | Heterobicyclic substituted dihydroisoxazoles |
| US10149477B2 (en) | 2014-10-06 | 2018-12-11 | Basf Se | Substituted pyrimidinium compounds for combating animal pests |
| WO2020239517A1 (en) | 2019-05-29 | 2020-12-03 | Basf Se | Mesoionic imidazolium compounds and derivatives for combating animal pests |
| WO2021130143A1 (en) | 2019-12-23 | 2021-07-01 | Basf Se | Enzyme enhanced root uptake of agrochemical active compound |
| WO2021170463A1 (en) | 2020-02-28 | 2021-09-02 | BASF Agro B.V. | Methods and uses of a mixture comprising alpha-cypermethrin and dinotefuran for controlling invertebrate pests in turf |
| WO2021219513A1 (en) | 2020-04-28 | 2021-11-04 | Basf Se | Pesticidal compounds |
| WO2022167488A1 (en) | 2021-02-02 | 2022-08-11 | Basf Se | Synergistic action of dcd and alkoxypyrazoles as nitrification inhibitors |
| EP4043444A1 (en) | 2021-02-11 | 2022-08-17 | Basf Se | Substituted isoxazoline derivatives |
| WO2022243521A1 (en) | 2021-05-21 | 2022-11-24 | Basf Se | Use of ethynylpyridine compounds as nitrification inhibitors |
| WO2022243523A1 (en) | 2021-05-21 | 2022-11-24 | Basf Se | Use of an n-functionalized alkoxy pyrazole compound as nitrification inhibitor |
| WO2022268810A1 (en) | 2021-06-21 | 2022-12-29 | Basf Se | Metal-organic frameworks with pyrazole-based building blocks |
| EP4119547A1 (en) | 2021-07-12 | 2023-01-18 | Basf Se | Triazole compounds for the control of invertebrate pests |
| EP4140995A1 (en) | 2021-08-27 | 2023-03-01 | Basf Se | Pyrazine compounds for the control of invertebrate pests |
| EP4140986A1 (en) | 2021-08-23 | 2023-03-01 | Basf Se | Pyrazine compounds for the control of invertebrate pests |
| EP4151631A1 (en) | 2021-09-20 | 2023-03-22 | Basf Se | Heterocyclic compounds for the control of invertebrate pests |
| EP4194453A1 (en) | 2021-12-08 | 2023-06-14 | Basf Se | Pyrazine compounds for the control of invertebrate pests |
| EP4198033A1 (en) | 2021-12-14 | 2023-06-21 | Basf Se | Heterocyclic compounds for the control of invertebrate pests |
| EP4342885A1 (en) | 2022-09-20 | 2024-03-27 | Basf Se | N-(3-(aminomethyl)-phenyl)-5-(4-phenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-amine derivatives and similar compounds as pesticides |
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| WO2015007682A1 (en) | 2013-07-15 | 2015-01-22 | Basf Se | Pesticide compounds |
| US10149477B2 (en) | 2014-10-06 | 2018-12-11 | Basf Se | Substituted pyrimidinium compounds for combating animal pests |
| WO2018166855A1 (en) | 2017-03-16 | 2018-09-20 | Basf Se | Heterobicyclic substituted dihydroisoxazoles |
| WO2020239517A1 (en) | 2019-05-29 | 2020-12-03 | Basf Se | Mesoionic imidazolium compounds and derivatives for combating animal pests |
| WO2021130143A1 (en) | 2019-12-23 | 2021-07-01 | Basf Se | Enzyme enhanced root uptake of agrochemical active compound |
| WO2021170463A1 (en) | 2020-02-28 | 2021-09-02 | BASF Agro B.V. | Methods and uses of a mixture comprising alpha-cypermethrin and dinotefuran for controlling invertebrate pests in turf |
| WO2021219513A1 (en) | 2020-04-28 | 2021-11-04 | Basf Se | Pesticidal compounds |
| WO2022167488A1 (en) | 2021-02-02 | 2022-08-11 | Basf Se | Synergistic action of dcd and alkoxypyrazoles as nitrification inhibitors |
| EP4043444A1 (en) | 2021-02-11 | 2022-08-17 | Basf Se | Substituted isoxazoline derivatives |
| WO2022243521A1 (en) | 2021-05-21 | 2022-11-24 | Basf Se | Use of ethynylpyridine compounds as nitrification inhibitors |
| WO2022243523A1 (en) | 2021-05-21 | 2022-11-24 | Basf Se | Use of an n-functionalized alkoxy pyrazole compound as nitrification inhibitor |
| WO2022268810A1 (en) | 2021-06-21 | 2022-12-29 | Basf Se | Metal-organic frameworks with pyrazole-based building blocks |
| EP4119547A1 (en) | 2021-07-12 | 2023-01-18 | Basf Se | Triazole compounds for the control of invertebrate pests |
| EP4140986A1 (en) | 2021-08-23 | 2023-03-01 | Basf Se | Pyrazine compounds for the control of invertebrate pests |
| EP4140995A1 (en) | 2021-08-27 | 2023-03-01 | Basf Se | Pyrazine compounds for the control of invertebrate pests |
| EP4151631A1 (en) | 2021-09-20 | 2023-03-22 | Basf Se | Heterocyclic compounds for the control of invertebrate pests |
| EP4194453A1 (en) | 2021-12-08 | 2023-06-14 | Basf Se | Pyrazine compounds for the control of invertebrate pests |
| EP4198033A1 (en) | 2021-12-14 | 2023-06-21 | Basf Se | Heterocyclic compounds for the control of invertebrate pests |
| EP4342885A1 (en) | 2022-09-20 | 2024-03-27 | Basf Se | N-(3-(aminomethyl)-phenyl)-5-(4-phenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-amine derivatives and similar compounds as pesticides |
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