CN102613201A - Isoflavanone compound for protecting underwater structure surface and application thereof - Google Patents
Isoflavanone compound for protecting underwater structure surface and application thereof Download PDFInfo
- Publication number
- CN102613201A CN102613201A CN2012100451276A CN201210045127A CN102613201A CN 102613201 A CN102613201 A CN 102613201A CN 2012100451276 A CN2012100451276 A CN 2012100451276A CN 201210045127 A CN201210045127 A CN 201210045127A CN 102613201 A CN102613201 A CN 102613201A
- Authority
- CN
- China
- Prior art keywords
- isoflavanone
- formula
- structure surface
- compounds
- fouling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses an isoflavanone compound for protecting the underwater structure surface and application thereof, which belong to the field of injurious insect repellence and mainly solve the fouling problem of marine organisms. Specifically, a chemical structure general formula is a formula I, the isoflavanone compound represented by the formula I is mainly made form peanuts and includes but is not limited to 5,7-dyhydroxy-2'-methoxyl-3',4'-methylenedioxy isoflavanone, 5,7-dyhydroxy-2',4'-dimethoxy isoflavanone, 5,7,2',4'-tetrahydroxy isoflavanone and anti-fouling paint prepared by the 5,7-dyhydroxy-2'-methoxyl-3',4'-methylenedioxy isoflavanone, the 5,7-dyhydroxy-2',4'-dimethoxy isoflavanone and the 5,7,2',4'-tetrahydroxy isoflavanone which serve as anti-fouling components. The isoflavanone compound can restrain adhesion of marine fouling organisms and be used fro prevention and control of marine organism fouling and has good application prospect.
Description
Technical field
The present invention relates to marine fouling organism repellent field, be specifically related to be used to protect the isoflavanone compounds and the application thereof on submerged structure surface.
Background technology
Marine fouling organism perches or attached on boats and ships, buoy and the various artificial under water facility, to human marine economy activity deleterious impact.There is the marine fouling organism that seriously adheres to influence to have nearly hundred kinds, can be divided into three major types: mushroom, attached plant and epizoite.Its representational kind has bacterium, fungi (mushroom), silk algae, diatom, Enteromorpha, sea lettuce (plant class), barnacle, mussel, lime worm, Ascidian, oyster, bryozoan, cylindrical fireworks Xi (animal class) etc., and what boats and ships were had the greatest impact is an algae, Enteromorpha, barnacle, lime worm, bryozoan, Ascidian etc.In a single day marine fouling organism will produce serious harm in the marine facility surface attachment, as increasing the resistance of ships navigation; The condenser pipe caliber of cooled with seawater pipeline and heat exchanger is dwindled, even stop up fully; Promote corrosion and cause crevice corrosion; Make marine instrument malfunctioning with machinery; Absorb acoustic energy, acoustic instrument is subtracted imitate or inefficacy; Increase the sectional area of marine building pile, post, strengthen the impulsive force of wave and ocean current; The depthkeeping of buoyancy aid in the water such as change submarine mine; Stop up mesh; With the shellfish of culturing, algae contention adherance and bait etc.The harm that marine fouling organism brings causes enormous economic loss for industries such as sea transport, aquaculture, and according to estimates, countries in the world every year, the expense because of prevention and control marine biofouling reached more than 6,500,000,000 dollars.
At present fouling organism prevent and kill off mainly through physical measure, chemical means and biological method, or act synergistically through above-mentioned several class methods and to realize anti-fouling purpose.Chemical means specifically can be divided into drug immersion method, paint coatings Protection Code, electrolysis anti-soil method and directly poisoning method etc.Wherein the method for application antifouling paint is the method the most widely of using at present, and easy and simple to handle, and anti-fouling effect is lasting, is considered to effective method.Since having developed antifouling paint from 20 beginnings of the century, antifouling products such as organo-arsenic, organic lead, mercury oxide, organotin successively occur, solved the marine organisms attachment issue basically.After the seventies in 20th century, the forbidding along with antifouling compositions such as DDT, organo-arsenic, organic lead and mercury oxide begins to use in a large number tributyl tin (TBT) and cuprous oxide as antifouling composition both at home and abroad.Though organotin coating has broad spectrum activity aspect the anti-fouling biological attachment; Can not receive pollutant effects such as sulphide and sulphate in the water environment yet and lose antifouling activity; But since the eighties in 20th century; Find that organo-tin compound has toxicity to most of marine organisms, its high toxicity is its difficult degradation in marine environment, has enrichment.Tributyl tin is considered to introduce up to now one of maximum chemical substance of marine environment toxic and harmfulness, thereby various countries successively make laws, and forbids or limits the use of organo-tin compound in the ocean.International Maritime Organization (IMO) clearly proposes to come into effect from the bill of forbidding organo-tin compound in 2003, completely forbids organo-tin compound by 2008 and makees antifouling composition.Cuprous oxide is to use the most a kind of marine antifoulant at present; It has antifouling activity to the overwhelming majority's animal class marine growth with most plant class marine growths; But not good to soft stained marine growth anti-fouling effect, need to add auxiliary antifouling composition and reach comprehensive anti-fouling effect.Copper also has toxic action, and it can especially gather in the harbour in the ocean in a large number, causes the marine alga mortality.The natural biological preparation has environmental acceptability preferably usually, and majority can natural decomposition, can not produce nonvolatil biological accumulation, and wide material sources.From natural products, be expected to obtain the marine active antifouling composition of low toxicity, efficient, wide spectrum, thereby substitute the antifouling composition poisonous environment.At present from ocean and terrestrial life, found many materials, comprised the material of types such as terpene, alkynes class, polycyclic compound, steroid, isothiocyanate with anti-fouling activity.
Application number is that 200810087953.0 Chinese invention patent discloses flavones and isoflavone derivative as the application of anti-biofouling substances and method and the coating that prevents marine biofouling, specifically, relates to marine microorganism and produces 4 ', 5, the method for 7-trihydroxy-isoflavone; Also relate to and utilize 4 ', 5,7-trihydroxy-isoflavone, 4 ', 5-dihydroxy-3,6; 7,8-tetramethoxy flavones, 3 ', 5-dihydroxy-3,4 ', 6; 7-tetramethoxy flavones, 4 ', 5-dihydroxy-3,6,7-trimethoxy flavones, 4 ', 5; 7-trihydroxyflavone, 3 ', 4 ', 5,7-kaempferol and 5-flavonol are used to prevent the biodeterioration on submerged structure surface.
Summary of the invention
The use difficulty that the objective of the invention is to exist to the deficiency of anti-marine biofouling prior art and marine antifouling coating, efficient is low and have toxicity and problem such as pollute, provide isolation identification in the Papillionoideae leopard cat tail bean plant open country kind beans from the natural products pulse family go out 3 kinds nontoxic and have an isoflavanone compounds of remarkable anti-fouling activity.Be to solve the problems referred to above that exist in the prior art, the present invention provides the purposes of isoflavanone compounds in preventing marine biofouling, is used to prevent the antifouling paint of marine biofouling and is used to prevent that the submerged structure surface from receiving halobiontic adhering to and/or stained method.
The application of isoflavanone compounds in preventing marine biofouling, this isoflavanone compounds have the activity that inhibition large ocean fouling organism adheres to, and can not pollute water body environment again simultaneously, can be applicable to the marine biofouling control.
Its chemical structure of general formula is the formula I:
（Ⅰ）
In formula I, R
1, R
2, R
3, R
4, R
5Be respectively " H " or " OH " or " OCH
3".
Preferably, said isoflavanone compounds is 5,7-dihydroxy-2 '-methoxyl group-3 '; 4 '-methylene-dioxy isoflavanone, 5,7-dihydroxy-2 ', 4 '-dimethoxy isoflavanone and 5; 7,2 ', 4 '-in the tetrahydroxy isoflavanone one or more.
5,7-dihydroxy-2 '-methoxyl group-3 ', 4 '-chemical structural formula of methylene-dioxy isoflavanone is:
5,7-dihydroxy-2 ', 4 '-chemical structural formula of dimethoxy isoflavanone is:
5,7,2 ', 4 '-chemical structural formula of tetrahydroxy isoflavanone is:
Said a kind of isoflavanone compounds that is used to protect the submerged structure surface is preventing barnacle class biological attachment and/or the stained surperficial application of submerged structure.
A kind of antifouling paint that is used to protect the submerged structure surface, antifouling paint comprises fouling resistance composition and film forming component, described fouling resistance composition is one or more in the above-mentioned isoflavanone compounds.
A kind of antifouling paint that is used to protect the submerged structure surface is characterized in that: said film forming component is one or more in hydrolyzable, the solvable or insoluble resin.
A kind of antifouling paint that is used to protect the submerged structure surface is preventing barnacle class biological attachment and/or the stained surperficial application of submerged structure.
The present invention has following beneficial effect:
1. the isoflavanone compounds among the present invention can be naturally occurring organic compound; And be non-toxic compound, do not contain poisonous heavy metal, in marine environment, be prone to degraded; Can not cause the pollution of water body environment; Can not cause its enrichment in organism through the food chain transmission, environmentally friendly, safe.
2. to show stronger inhibition biodeterioration active for the isoflavanone compounds among the present invention, can be fouling resistance coating or other fouling resistance Products Development provides valuable lead compound, and good application prospects is arranged.
3. the Flavane compound among the present invention is a natural products, but its process for artificial is ripe, and acquiring way is easy, is suitable for large-scale production, is not subject to the content in the organism, the source with reliable and stable, and it is big to apply potentiality.
4. anti-biofouling substances provided by the invention; It is the Chemical Decomposition method that instructs through biological test; Isolation identification is come out from wild kind beans; Or utilizing the structure-activity relationship analysis result from the compound in other source, to screen, experiment proof compound involved in the present invention is the anti-biofouling compound of Nantural non-toxic.Utilizing the made anti-biofouling coating of said non-toxic compound is harmless to environment.
Description of drawings
Fig. 1 follows the trail of separation process figure for the activity of the active isoflavanone compounds of 3 kinds of anti-biofoulings described in the present invention;
Fig. 2 is 5,7-dihydroxy-2 '-methoxyl group-3 ', 4 '-the methylene-dioxy isoflavanone to the line barnacle (
Balanus amphitrite) the inhibiting figure that adheres to of larva.Repeat appearance mean value and standard variance at least 3 shown in the figure;
Fig. 3 is 5,7-dihydroxy-2 ', 4 '-the dimethoxy isoflavanone to the line barnacle (
Balanus amphitrite) the inhibiting figure that adheres to of larva.Repeat appearance mean value and standard variance at least 3 shown in the figure;
Fig. 4 is 5,7,2 ', 4 '-the tetrahydroxy isoflavanone to the line barnacle (
Balanus amphitrite) the inhibiting figure that adheres to of larva.Repeat appearance mean value and standard variance at least 3 shown in the figure.
Embodiment
Below through the description of embodiment and with reference to accompanying drawing the present invention is described further; But this is not to be limitation of the present invention; Those skilled in the art are according to basic thought of the present invention; Can make various modifications or improvement, but only otherwise break away from basic thought of the present invention, all within scope of the present invention.
Isoflavanone compounds among the present invention can be naturally occurring compound, also can be the compound of synthetic.
The kind of " antifouling paint " among the present invention can be the antifouling paint that is used to prevent marine biofouling known in the art; For example: solubility body coating, automatic polishing copolymer class coating, non-bonding type coating, low surface energy anti-fouling paint, bonding formulation coating, bionical coating and natural antifouling composition coating etc. (can be referring to scientific and technical literature: Zhang Donghui etc.; " antifouling paint summary "
Modern coating and application, the 10th the 5th phase of volume, 2007), as long as wherein contain fouling resistance composition described in film forming component and the present invention.
To film forming component among the present invention and the not special qualification of fouling resistance components in proportions, as long as the content of fouling resistance composition is effective dose.For example, the addition of fouling resistance composition can be film forming component weight 0.1% ~ 20%, preferably 1% ~ 15%.
The term that relates in this article " effective dose " promptly reaches the amount of the active component of fouling resistance effect in specific environment.
Film forming component described in the present invention can be known in the art is used for preventing the film forming component of the antifouling paint of marine biofouling, and can be in hydrolyzable, the solvable or insoluble resin one or more; For example, can be alkyd resins, acrylic resin, chlorinated rubber resin, epoxy resin, silicone resin, polyester, polyurethane and fluoropolymer etc.
The composition of fouling resistance described in the present invention comprises by in the compound shown in the formula one or more:
Formula;
In formula I, R
1, R
2, R
3, R
4, R
5Be respectively " H " or " OH " or " OCH
3".
About 20 kinds of this platymiscium whole world mainly is distributed in Tropical Africa, Asia and Australia.China has 9 species within the border, from the warp of the west and south, reaches the southeast in the south, and most of species mainly concentrate on 25 ° of areass to the south of north latitude.This platymiscium has heat-clearing, detoxifcation, and hemostasis, effects such as carbuncle disappear.Pharmacological research shows that this platymiscium has anti-inflammatory, effect such as anti-oxidant, antibacterial.
The inventor finds that solvent (like the ethanol/water of the 90 volume %) extract of leopard cat tail bean plant (like wild kind beans) has anti-biofouling activity preferably; And under biological activity test instructs, extract is carried out chemical constitution study, therefrom obtained anti-biofouling activity isoflavanone active component preferably.Structure from the isoflavanone compounds of wild kind beans is made up of the precursor structure of isoflavanone, and other difference is substituting group and substituent position difference just.
(1) precursor structure of isoflavanone class:
(2) said compound can be represented with following structural formula:
Formula
In formula I, R
1, R
2, R
3, R
4, R
5Be respectively " H " or " OH " or " OCH
3".
Said isoflavanone compounds mainly from wild kind beans, includes, but is not limited to: 5, and 7-dihydroxy-2 '-methoxyl group-3 ', 4 '-the methylene-dioxy isoflavanone; 5,7-dihydroxy-2 ', 4 '-dimethoxy isoflavanone and 5; 7,2 ', 4 '-the tetrahydroxy isoflavanone.
5,7-dihydroxy-2 '-methoxyl group-3 ', 4 '-the methylene-dioxy isoflavanone (5,7-dihydroxy-2 '-methoxy-3 ', 4 '-methylenedioxyisoflavanone) structural formula is:
5,7-dihydroxy-2 ', 4 '-the dimethoxy isoflavanone (5,7-dihydroxy-2 ', 4 '-dimethoxy isoflavanone) structural formula be:
5,7,2 ', 4 '-the tetrahydroxy isoflavanone (5,7,2 ', 4 '-tetrahydroxyisoflavanone) structural formula is:
。
The marine organisms that isoflavanone compounds of the present invention suppressed are biological for (but being not limited to) barnacle class.Preferably, said isoflavanone compounds can suppress biological the adhering to of barnacle class.Said isoflavanone compounds preferably suppresses the biological larva of barnacle class and adheres to.
The inventor has calculated 5,7-dihydroxy-2 '-methoxyl group-3 ', 4 '-methylene-dioxy isoflavanone, 5,7-dihydroxy-2 ', 4 '-dimethoxy isoflavanone and 5,7,2 ', 4 '-half of tetrahydroxy isoflavanone suppresses to adhere to concentration.Result of calculation shows that 3 kinds of compounds suppress to adhere to concentration EC to the half of the line barnacle young
50Measure the result and be respectively 3.5 ± 1.1 μ g/mL, 2.4 ± 0.9 μ g/mL and 2.1 ± 0.7 μ g/mL; It is active that The above results shows that 3 kinds of compounds all demonstrate preferably anti-biofouling, and wherein 5,7; 2 ', 4 '-activity of tetrahydroxy isoflavanone is the strongest.In addition; According to AVIelin etc. (referring to scientific and technical literature: Mary A.; Mary VI.; Rittschof D., Nagabhushanam R. Bacterial-barnacle interaction:potential of using juncellins and antibiotics to alter structure of bacterial communities.
J Chem. Ecol. 1993,19 (10): 2155-2167.), toxic effect is than (LC
50/ EC
50) be nontoxic anti-biofouling compound greater than the anti-biofouling compound more than 10.The toxic effect of the above-mentioned 3 kinds of compounds of warp test shows that than all greater than 10 these 3 kinds of compounds are nontoxic anti-biofouling compound.
As shown in Figure 1, the present invention also provides the preparation method of above-mentioned isoflavanone compounds.This method comprises the said compound of preparation from leopard cat tail bean plant (like wild kind beans).Preferably, preparation isoflavanone compounds from the root of wild kind beans plant, stem, leaf, fruit.Preferably, said method has following step:
(1) leaf of the open country kind beans of drying is pulverized, the leaf fragment of wild kind of beans;
(2) with the fragment soaked in solvent of wild kind beans leaf, get extract;
(3) extracting liquid filtering, concentrating under reduced pressure are got medicinal extract;
(4) medicinal extract is dispersed in the water, extracts with benzinum, ethyl acetate and n-butanol successively, after extract is drained, get petroleum ether extraction part medicinal extract, ethyl acetate extraction part medicinal extract, extracting n-butyl alcohol part medicinal extract respectively;
(5) get ethyl acetate extraction part medicinal extract through silica gel column chromatography, (gradient elution of volume ratio 1:0～2:1) obtains 14 components (Fr.1～Fr.14) with chloroform-methanol.
(6) Fr.4 is through silica gel column chromatography, and with benzinum: (gradient elution of volume ratio 15:1～2:1) obtains component Fr.4A～4G to ethyl acetate.Fr.4C is through silica gel column chromatography, and with benzinum: (gradient elution of volume ratio 15:1～4:1) obtains component Fr.4C-1～4 to ethyl acetate.Component Fr.4C-2 obtains compound through Sephadex LH-20 gel column chromatography (methyl alcohol) purifying
2Fr.4E is through silica gel column chromatography, and with benzinum: (gradient elution of volume ratio 10:1～2:1) obtains component Fr.4E-1～6 to ethyl acetate.Fr.4E-2 uses chloroform through Sephadex LH-20 gel column chromatography purifying: methyl alcohol (volume ratio 1:1) is eluant, eluent, uses recrystallizing methanol then, obtains compound
1Fr.4E-5 uses chloroform through Sephadex LH-20 gel column chromatography purifying: methyl alcohol (volume ratio 1:1) obtains compound for eluant, eluent
3
In step (2), described solvent available volume percentage is the methanol of 70% ~ 95% ethanol/water or 70% ~ 90% or 50% ~ 70% acetone, and reflux extracting time is each 2 hours, and refluxing extraction preferably repeats 3 times.
The present invention also provides the method for preparing antifouling paint, may further comprise the steps: 1) the fouling resistance composition is provided; And 2) the fouling resistance composition that step 1) is obtained mixes with film forming component, obtains antifouling paint.Wherein in said step 1), the fouling resistance composition can be the compound shown in the formula I, also can obtain like this: obtain extract with the wild kind beans plant of above-mentioned solvent extraction; With the gained extract through filter, concentrating under reduced pressure, process medicinal extract, with as said fouling resistance composition; Can also be with gained medicinal extract through the further separation and purification of above-mentioned column chromatography, obtain said isoflavanone compounds with as said fouling resistance composition.
The present invention also provides said isoflavanone compounds to be used for preventing the purposes of the coating of marine biofouling in preparation.Compound with anti-fouling activity of the present invention has antifouling effect, therefore can described compound with anti-fouling activity be used to prepare antifouling composition efficiently.
The present invention also provides a kind of method that is used to prevent marine biofouling, and it comprises: body structure surface applies antifouling paint of the present invention under water.
" submerged structure " includes, but is not limited to described in this paper: the submerged structure of drainpipe, underbody, screw, fish culture cage, harbour and offshore platform, submarine mine, buoy, submarine cable, power plant cooling pipe etc. borders on the sea.
For a better understanding of the present invention, below further explain or explanation content of the present invention, but these examples should not be understood that the restriction to protection domain of the present invention through specific embodiment.
Embodiment 1 wild kind beans plant extracts is active to the inhibition that the line kentrogon adheres to
Material source: wild kind beans are adopted in Kaiyuan City, Yunnan, and Tao Deding researcher is accredited as through Kunming Inst. of Botany, Chinese Academy of Sciences
Uraria clarkei(Clarke) Gagnep., sample are stored in Yunnan Institute for nationalitiesization and give birth to institute sample shop.
The preparation of wild kind beans extract: the open country kind beans leaf of drying is pulverized, respectively the leaf fragment of wild kind of beans; Then with the fragment of wild kind beans leaf with 95 volume % ethanol/water refluxing extraction 3 times, each 2 hours must extract; An open country kind beans extract is filtered respectively and becomes medicinal extract subsequent use with the Rotary Evaporators concentrating under reduced pressure.
Adopt suppressing the experimental model that line barnacle cyprids adheres to (can be referring to scientific and technical literature: Xu Y., He H. P., Qian P. Y, et al. Potent antifouling compounds produced by marine streptomyces.
Bioresource Technology. 2010,101 (4): the extract of 1331-1336) having tested the wild kind beans of leopard cat tail bean plant suppresses the ability that kentrogon adheres to.The march off into political wilderness anti-larva of kind beans extract of the concentration that adopts 24 well culture plates to be determined at 50 μ g/mL and 10 μ g/mL adheres to activity.Line adult barnacle (Darwin) picks up from intertidal zone, Hong Kong (22 ° of 19'N, 114 ° of 16'E).In the polystyrene plastics culture vessel of 12 L, put into the seawater that 8 L filter, then the line adult barnacle is put into container, placement lets it discharge larva, collects larva behind 2.5 h, and the larva in this stage is called naupiar larva (nauplius), does not have adhesive ability.Naupiar larva is put into the container that 8 L filtering seas (the filter membrane aperture is 0.22 μ m) is housed, bright in 24 ℃ of temperature and 15 h: aerobic culture under the dark periodicity of illumination of 9 h, and feeding angle hair diatom (
Chaetoceros gracilis Schutt), the collection larva is subsequent use later on to cultivate 3 days, and the larva in this stage is called cyprids (cypris), and adhesive ability is arranged.The extract of wild kind beans is mixed with methyl-sulfoxide (DMSO), be diluted to different concentration with the aseptic filtration seawater then.In each hole of 24 well culture plates, add 1.0 mL test fluid and 15 ± 3 cyprids, each concentration is all established 3 multiple holes.Equal-volume aseptic filtration seawater is done blank.24 well culture plates are bright in 24 ℃ of temperature and 15 h: as after cultivating 48 h under the dark periodicity of illumination of 9 h, to adhere to the number of larva in the microscopically statistics.Carry out statistical analysis with SPSS VIersion 11 data statistics softwares.
The result shows under the above-mentioned concentration, the ability that wild kind beans extract has remarkable inhibition line kentrogon to adhere to.
The result sees table 1:
The wild kind beans of embodiment 2 usefulness are further tested
Further test with a wild kind beans leaf plant.This is not that other plant of hint leopard cat tail Macroptilium does not have activity.
Using percent by volume respectively is that 70% acetone, 95% ethanol/water and 90% methanol make to extract solvent, repeats embodiment 1.
The result sees table 2:
Experimental result shows the methanol of acetone with 70%, 95% ethanol/water and 90% to be made to extract open country kind beans leaf 70% acetone extract, wild kind beans leaf 95% ethanol extract and wild kind beans leaf 90% methanolic extract that solvent obtained respectively to have significant anti-biofouling equally active, therefore makes to extract solvent with the acetone of variable concentrations or ethanol/water or methanol and can obtain the anti-biofouling active component in kind beans of open country equally.
Embodiment 3 is isolation identification anti-biofouling reactive compound from wild kind beans leaf
The leaf of the open country kind beans of drying is ground into the particle of particle diameter 0.1 ~ 0.5 cm size, uses 95% alcohol reflux 3 times then, each 2 hours; Extracting liquid filtering also desolvates with the Rotary Evaporators concentrating under reduced pressure and processes medicinal extract; Then medicinal extract is suspended in (per 100 g medicinal extract, 300 mL water) in the water; Use benzinum (with water volume ratio 1:1), ethyl acetate (with water volume ratio 1:1) and n-butanol (with water volume ratio 1:1) to extract successively; Boil off solvent with Rotary Evaporators again; Get extract 100 g, 70 g, 200 g respectively.
Get ethyl acetate extraction part medicinal extract (70 g) through silica gel column chromatography (100-200 order), (gradient elution of volume ratio 1:0 ~ 2:1) obtains 14 components (Fr.1 ~ Fr.14) with chloroform-methanol.Fr.4 (5.70 g) is through silica gel column chromatography, and with benzinum: (gradient elution of volume ratio 15:1～2:1) obtains component Fr.4A～4G to ethyl acetate.Fr.4C (1.18 g) is through silica gel column chromatography, and with benzinum: (gradient elution of volume ratio 15:1～4:1) obtains component Fr.4C-1～4 to ethyl acetate.Fr.4C-2 (0.38 g) obtains compound through Sephadex LH-20 gel column chromatography (methyl alcohol) purifying
2Fr.4E (1.69 g) is through silica gel column chromatography, and with benzinum: (gradient elution of volume ratio 10:1～2:1) obtains component Fr.4E-1～6 to ethyl acetate.Fr.4E-2 (0.33 g) uses chloroform through Sephadex LH-20 gel column chromatography purifying: methyl alcohol (volume ratio 1:1) is eluant, eluent, uses recrystallizing methanol then, obtains compound
1Fr.4E-5 (0.23 g) uses chloroform through Sephadex LH-20 gel column chromatography purifying: methyl alcohol (volume ratio 1:1) obtains compound for the eluant, eluent wash-out
3The isolation identification flow process of anti-biofouling active component is seen Fig. 1 in the wild kind beans leaf.
The chemical constitution of compound of the present invention with nuclear magnetic resoance spectrum (
1H NMR,
13C NMR, DEPT, COSY HSQC, HMBC), ESI-MS wave spectrograms such as (cation modes) identifies.According to analysis of compounds
1~
3Spectral data, and, be accredited as 5 respectively with reference to pertinent literature, 7-dihydroxy-2 '-methoxyl group-3 ', 4 '-methylene-dioxy isoflavanone, 5,7-dihydroxy-2 ', 4 '-dimethoxy isoflavanone and 5,7,2 ', 4 '-the tetrahydroxy isoflavanone.
Compound
1Physicochemical data: faint yellow flat crystal (methyl alcohol), ESI-MSm/z:353 [M+Na]
+ 1H-NMR?(400?MHz,?DMSO-
d 6 )?δ:?12.23?(1H,?s,?5-OH),?10.82?(1H,?s,?7-OH),?6.70?(1H,?d,?
J?=?8.0?Hz,?H-6′),?6.62(1H,?d,?
J?=?8.0?Hz,?H-5′),?6.02?(2H,?s,?H-6,?8),?5.91?(2H,?s,?-OCH
2O-),?4.39?(1H,?m,?H-2a),?4.34?(1H,?m,?H-2b),?4.31?(1H,?m,?H-3),?3.82?(3H,?s,?2′-OCH
3)。
13C-NMR?(100?MHz,?DMSO-
d 6 )?δ:?197.2?(C-4),?167.0?(C-7),?164.3?(C-5),?163.5?(C-9),?149.3?(C-4′),?141.8?(C-2′),?137.3?(C-3′),?123.9?(C-6′),?121.0?(C-1′),?103.4?(C-5′),?102.2?(C-10),?101.7?(-OCH
2O-),?96.5?(C-6),?95.3?(C-8),?70.3?(C-2),?59.6?(2′-OCH
3),?47.5?(C-3)。
Compound
2Physicochemical data: pale yellow powder (chloroform-methanol), ESI-MSm/z:339 [M+Na]
+ 1H-NMR?(400?MHz,?CDCl
3)?δ:?7.03?(1H,?d,?
J?=?8.0?Hz,?H-6′),?6.51?(1H,?d,?
J?=?2.4?Hz,?H-3′),?6.48?(1H,?dd,?
J?=?8.4,?2.4?Hz,?H-5′),?6.00?(1H,?s,?H-8),?5.95?(1H,?s,?H-6),?4.55?(1H,?m,?H-2a),?4.44?(1H,?m,?H-2b),?4.24?(1H,?m,?H-3),?3.82?(3H,?s,?OCH
3),?3.80?(3H,?s,?OCH
3)。
13C-NMR(100?MHz,?CDCl
3)?δ:?197.6?(C-4),?164.6?(C-7),?164.5?(C-9),?163.6?(C-5),?160.8?(C-4′),?158.4?(C-2′),?130.8?(C-6′),?115.0?(C-1′),?104.7?(C-5′),?103.4?(C-10),?99.2?(C-3′),?96.6?(C-6),?95.2?(C-8),?70.5?(C-2),?55.6?(4′-OCH
3),?55.4?(2′-OCH
3),?46.7?(C-3)。
Compound
3Physicochemical data: white powder (methyl alcohol), ESI-MSm/z:311 [M+Na]
+ 1H-NMR?(400?MHz,?CD
3OD)?δ:?6.87?(1H,?d,?
J?=?8.4?Hz,?H-6′),?6.35?(1H,?d,?
J?=?2.4?Hz,?H-3′),?6.30?(1H,?dd,?
J?=?8.4,?2.4?Hz,?H-5′),?5.91?(2H,?m,?H-6,?8),?4.58?(1H,?m,?H-2a),?4.40?(1H,?m,?H-2b),?4.21?(1H,?m,?H-3)。
13C-NMR?(100?MHz,?CD
3OD)?δ:?198.1(C-4),?166.7?(C-7),?164.4?(C-5),?163.8?(C-9),?157.8?(C-2′),?156.2?(C-4′),?130.6?(C-6′),?112.6?(C-1′),?106.4?(C-5′),?102.5?(C-3′),?102.4?(C-10),?95.7?(C-6),?94.6?(C-8),?70.1?(C-2),?46.6?(C-3)。
The anti-kentrogon that embodiment 4 measures said isoflavanone compounds adheres to activity
Adopt suppressing the experimental model that line barnacle cyprids adheres to (can be referring to scientific and technical literature: Xu Y., He H. P., Qian P. Y., et al. Potent antifouling compounds produced by marine streptomyces.
Bioresource Technology. 2010,101 (4): 1331-1336), the anti-kentrogon of test compounds adheres to activity.Line adult barnacle (Darwin) picks up from intertidal zone, Hong Kong (22 ° of 19'N, 114 ° of 16'E).In the polystyrene plastics culture vessel of 12 L, put into the seawater that 8 L filter, then the line adult barnacle is put into container, placement lets it discharge larva, collects larva behind 2.5 h, and the larva in this stage is called naupiar larva (nauplius), does not have adhesive ability.Naupiar larva is put into the container that 8 L filtering seas (the filter membrane aperture is 0.22 μ m) is housed, bright in 24 ℃ of temperature and 15 h: aerobic culture under the dark periodicity of illumination of 9 h, and feeding angle hair diatom (
Chaetoceros gracilis Schutt), the collection larva is subsequent use later on to cultivate 3 days, and the larva in this stage is called cyprids (cypris), and adhesive ability is arranged.3 kinds of isoflavanone compounds are dissolved in respectively in the methyl-sulfoxide (DMSO), are diluted to different concentration with the aseptic filtration seawater then.In each hole of 24 well culture plates, add 1.0 mL test fluid and 15 ± 3 cyprids, each concentration is all established 3 multiple holes.Equal-volume aseptic filtration seawater is done blank.24 well culture plates are bright in 24 ℃ of temperature and 15 h: as after cultivating 48 h under the dark periodicity of illumination of 9 h, to adhere to the number of larva in the microscopically statistics.Carry out statistical analysis with SPSS VIersion 11 data statistics softwares.3 kinds of isoflavanone compounds experimental results that anti-kentrogon adheres under variable concentrations are as shown in Figure 2.
Experimental result according to researchers' such as Rittschof method (referring to scientific and technical literature: Richard B. F.; DaVIid A. Z. F., Dan R. Molting of megalopae from the blue crab Callinectes sapidus:effects of offshore and estuarine cues.
Marine ecology progress series.1994,113:55-59) analyze.Can obtain the EC of 48 h according to experimental result
50(half suppresses to adhere to concentration, and promptly suppressing the larva adhesive rate is 50% o'clock pairing concentration of largest inhibition larva adhesive rate) is by EC
50Can know the height that the detection material anti-biofouling is active.And behind 24 h, calculate the mortality of larva, can obtain the LC of 24 h according to experimental result
50(half lethal concentration) is by LC
50/ EC
50(toxic effect ratio) can be known the toxicity size of detection material to kentrogon.Experiment analysis results shows 5,7-dihydroxy-2 '-methoxyl group-3 ', 4 '-methylene-dioxy isoflavanone, 5; 7-dihydroxy-2 ', 4 '-dimethoxy isoflavanone and 5,7; 2 ', 4 '-activity that the tetrahydroxy isoflavanone all has remarkable inhibition line kentrogon to adhere to, wherein 5; 7,2 ', 4 '-activity of tetrahydroxy isoflavanone is especially outstanding.Researchers such as AVIelin are (referring to scientific and technical literature: Mary A.; Mary VI.; Rittschof D., Nagabhushanam R. Bacterial-barnacle interaction:potential of using juncellins and antibiotics to alter structure of bacterial communities.
J Chem. Ecol. 1993,19 (10): point out that 2155-2167.) toxic effect is nontoxic anti-biofouling compound than greater than the anti-biofouling compound more than 10.The toxic effect of 3 kinds of compounds being tested shows that these 3 kinds of compounds suppress the line kentrogon and adhere to, but the line kentrogon is not had toxicity than all greater than 10.
The result sees table 3:
The preparation of embodiment 5 antifouling paints
Choose the anti-biofouling active component that the present invention relates to; Adopt the prior art for preparing antifouling paint; For example, active component is mixed or is spread in the polymer such as film forming natural resin, vinyl chloride acetate ethylene copolymer and other hydrolyzable, solvable or insoluble resin.Antifouling paint should discharge the effective active component of capacity and prevent biodeterioration to the surface.
The above is merely preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. the isoflavanone compounds is preventing that the submerged structure surface from receiving halobiontic adhering to and/or stained application, and the chemical structural formula of described isoflavanone compounds is the formula I:
In formula I, R
1, R
2, R
3, R
4, R
5Be respectively " H " or " OH " or " OCH
3".
2. according to the said a kind of isoflavanone compounds that is used to protect the submerged structure surface of claim 1, wherein said isoflavanone compounds is one or more in the compound shown in the formula II-formula IV:
5,7-dihydroxy-2 '-methoxyl group-3 ', 4 '-chemical constitution of methylene-dioxy isoflavanone, suc as formula II:
5,7-dihydroxy-2 ', 4 '-chemical constitution of dimethoxy isoflavanone, like formula III:
5,7,2 ', 4 '-chemical constitution of tetrahydroxy isoflavanone, suc as formula IV:
3. according to claim 1 or 2 each said a kind of isoflavanone compounds that are used to protect the submerged structure surface, in the application that prevents barnacle class biological attachment and/or stained submerged structure surface.
4. antifouling paint that is used to protect the submerged structure surface, it is characterized in that: antifouling paint comprises fouling resistance composition and film forming component, described fouling resistance composition is one or more in the isoflavanone compounds described in claim 1 or 2.
5. a kind of antifouling paint that is used to protect the submerged structure surface according to claim 4 is characterized in that: said film forming component is one or more in hydrolyzable, the solvable or insoluble resin.
6. according to claim 4 or 5 each said a kind of antifouling paints that are used to protect the submerged structure surface, preventing barnacle class biological attachment and/or stained submerged structure surface applications.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210045127 CN102613201B (en) | 2012-02-27 | 2012-02-27 | Isoflavanone compound for protecting underwater structure surface and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210045127 CN102613201B (en) | 2012-02-27 | 2012-02-27 | Isoflavanone compound for protecting underwater structure surface and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102613201A true CN102613201A (en) | 2012-08-01 |
| CN102613201B CN102613201B (en) | 2013-10-16 |
Family
ID=46553683
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210045127 Expired - Fee Related CN102613201B (en) | 2012-02-27 | 2012-02-27 | Isoflavanone compound for protecting underwater structure surface and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102613201B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153931A (en) * | 2015-09-25 | 2015-12-16 | 尚成荣 | Preprocessing agent for coating inner wall of solar energy power generating and heat storing device |
| CN112574610A (en) * | 2020-12-11 | 2021-03-30 | 浙江大学 | Coating capable of reducing fouling of enteromorpha and application method thereof |
| CN116376394A (en) * | 2023-03-20 | 2023-07-04 | 广东美涂士建材股份有限公司 | Environment-friendly marine microorganism fouling prevention coating and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08225409A (en) * | 1995-02-21 | 1996-09-03 | Kobe Steel Ltd | Agent and coating for controlling attachment of underwater organism |
| CN1882247A (en) * | 2003-11-13 | 2006-12-20 | 康普顿发展有限公司 | Molluscicidal and anti-barnacle compounds |
| CN101536687A (en) * | 2008-03-20 | 2009-09-23 | 香港科技大学 | Use of flavone and isoflavone derivative as anti-biofouling substances and method and paint for preventing marine biofouling |
-
2012
- 2012-02-27 CN CN 201210045127 patent/CN102613201B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08225409A (en) * | 1995-02-21 | 1996-09-03 | Kobe Steel Ltd | Agent and coating for controlling attachment of underwater organism |
| CN1882247A (en) * | 2003-11-13 | 2006-12-20 | 康普顿发展有限公司 | Molluscicidal and anti-barnacle compounds |
| CN101536687A (en) * | 2008-03-20 | 2009-09-23 | 香港科技大学 | Use of flavone and isoflavone derivative as anti-biofouling substances and method and paint for preventing marine biofouling |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153931A (en) * | 2015-09-25 | 2015-12-16 | 尚成荣 | Preprocessing agent for coating inner wall of solar energy power generating and heat storing device |
| CN112574610A (en) * | 2020-12-11 | 2021-03-30 | 浙江大学 | Coating capable of reducing fouling of enteromorpha and application method thereof |
| CN112574610B (en) * | 2020-12-11 | 2022-04-26 | 浙江大学 | Coating capable of reducing fouling of enteromorpha and application method thereof |
| CN116376394A (en) * | 2023-03-20 | 2023-07-04 | 广东美涂士建材股份有限公司 | Environment-friendly marine microorganism fouling prevention coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102613201B (en) | 2013-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101715770B (en) | Application of loop proline-3-hydroxy-2-aminobutyric acid in preventing and removing marine fouling organisms | |
| Xu et al. | Potent antifouling compounds produced by marine Streptomyces | |
| CN102093322A (en) | Application of osthole in preparation of marine antifouling paint | |
| WO2009115051A1 (en) | Antifouling method and composition using chromen-4-one derivatives | |
| CN102105542B (en) | Antifouling furan-2-one derivatives | |
| CN102613201B (en) | Isoflavanone compound for protecting underwater structure surface and application thereof | |
| EP2198713B1 (en) | Omaezallene and its use to prevent the attachment of barnacles to surfaces | |
| CN102757673B (en) | Amides is preventing the purposes in marine biofouling | |
| CN101724305B (en) | Application of cycle (proline-alanine) in preventing and removing marine fouling organism | |
| CN104592798B (en) | Application of the acetic acid orange acid amides in preventing and removing marine fouling organisms | |
| CN110724403A (en) | Application of quinazolinone alkaloid compound derived from marine fungi in preventing and removing marine fouling organisms | |
| JP2008504377A (en) | Environmentally friendly antifouling agent | |
| Li et al. | Investigation on the efficiency of a silicone antifouling coating in controlling the adhesion and germination of Ulva prolifera micro-propagules on rafts | |
| CN106810926B (en) | A kind of application of aporphine alkaloid | |
| CN102993151B (en) | Flavanol compound, and preparation method and application thereof | |
| CN102321089B (en) | Screw ring alkaloid compound, preparation method thereof and application in the aspect of marine organism fouling resistance | |
| CN103518722B (en) | Application of 17-oxymethyl-7-hydroxy-benzene-furan-chalcone in preparing marine fouling organism control agent | |
| CN110724149B (en) | Indole alkaloid dimer compound derived from marine fungi, preparation method and application of indole alkaloid dimer compound in marine fouling organism resistant control agent | |
| CN102613187A (en) | Application of flavane compound in preventing marine biofouling | |
| CN101717594B (en) | Application of loop proline-leucine in preventing and removing marine fouling organisms | |
| CN108056113B (en) | Component E separated from sargassum henryi ethyl acetate extract, preparation method thereof and application of component E in marine fouling organism prevention and removal | |
| CN101724306B (en) | Application of cycle proline-2-N-hydroxide radical-isoleucine in preventing and removing marine fouling organism | |
| CN110669370B (en) | Application of beauvericin from marine fungi in preventing and removing marine fouling organisms | |
| CN108484628A (en) | Application of the kusulactone class compound in preventing marine biofouling | |
| CN101230039B (en) | Compound having anti-fouling activity as well as extraction method and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131016 Termination date: 20150227 |
|
| EXPY | Termination of patent right or utility model |