CN102613201B - Isoflavanone compound for protecting underwater structure surface and application thereof - Google Patents
Isoflavanone compound for protecting underwater structure surface and application thereof Download PDFInfo
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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 includesbut 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 isoflavanone compounds and application thereof for the protection of the submerged structure surface.
Background technology
Marine fouling organism perches or is attached on boats and ships, buoy and the various Artificial facilities under water, and human marine economy activity is brought adverse effect.There is the marine fouling organism that seriously adheres to impact 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), 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.Marine fouling organism will be in case will produce serious harm in the marine facility surface attachment, the resistance that navigates by water as increasing ships; 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 and machinery malfunctioning; Absorb acoustic energy, make acoustic instrument subtract effect 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; Shellfish, algae contention adherance and bait etc. with cultivation.The harm that marine fouling organism brings causes huge economic loss to industries such as sea transport, aquacultures, 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.
Preventing and kill off of fouling organism mainly passed through physical measure, chemical means and biological method at present, or acts synergistically to realize anti-fouling purpose by above-mentioned several class methods.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 that is most widely used 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, the antifouling products such as organo-arsenic, organic lead, mercury oxide, organotin successively occur, basically solved the marine organisms attachment issue.After 20 century 70s, 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.Although organotin coating has broad spectrum activity aspect the anti-fouling biological attachment, can not be subjected to the pollutant effects such as water environment medium sulphide content and sulphate 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 one of chemical substance of introducing up to now marine environment Poisoning and harmfulness maximum, thereby various countries successively make laws, and forbids or limits the use of organo-tin compound in the ocean.The bill that International Maritime Organization (IMO) clearly proposes forbidding organo-tin compound from 2003 comes into effect, and completely forbids organo-tin compound by 2008 and makees antifouling composition.Cuprous oxide is a kind of marine antifoulant that is most widely used at present, it has antifouling activity to the overwhelming majority's animal class marine growth and most plant 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 preferably environmental acceptability 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 to environment.At present from ocean and terrestrial life, find many materials with anti-fouling activity, comprised the material of the types such as terpene, alkynes class, polycyclic compound, steroid, isothiocyanate.
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 ', the method of 5,7-trihydroxy-isoflavone also relates to and utilizes 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 flavone, 4 ', 5, the 7-trihydroxyflavone, 3 ', 4 ', 5,7-kaempferol and 5-flavonol are used for preventing the biodeterioration on submerged structure surface.
Summary of the invention
The use difficulty that the objective of the invention is to exist for anti-marine biofouling the deficiencies in the prior art and marine antifouling coating, efficient is low and have toxicity and the problem such as pollute, provide separate in the wild kind beans of Papillionoideae leopard cat tail bean plant from the natural products pulse family identify 3 kinds nontoxic and have an isoflavanone compounds of remarkable anti-fouling activity.Be to solve the above-mentioned problems in the prior art, the invention provides the purposes of isoflavanone compounds in preventing marine biofouling, be used for preventing the antifouling paint of marine biofouling and be used for preventing that the submerged structure surface is subject to 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, described isoflavanone compounds be 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:
Described a kind of isoflavanone compounds for the protection of the submerged structure surface is in the application that prevents barnacle class biological attachment and/or stained submerged structure surface.
A kind of antifouling paint for the protection of 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 for the protection of the submerged structure surface is characterized in that: described film forming component is one or more in hydrolyzable, the solvable or insoluble resin.
A kind of antifouling paint for the protection of the submerged structure surface is in the application that prevents barnacle class biological attachment and/or stained submerged structure surface.
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, easily degraded in marine environment, can not cause the pollution of water body environment, can not cause its enrichment in organism by the food chain transmission, environmentally friendly, safe.
2. the isoflavanone compounds among the present invention shows stronger inhibition biodeterioration activity, and the exploitation that can be fouling resistance coating or other fouling resistance product provides valuable lead compound, and good application prospect is arranged.
3. the Flavane compound among the present invention is 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, has reliable and stable source, and it is large to apply potentiality.
4. anti-biofouling substances provided by the invention, it is the Chemical Decomposition method that instructs by biological test, separation is identified out from wild kind beans, or utilize the structure-activity relationship analysis result from the compound in other source, to screen, experimental results show that compound involved in the present invention is the anti-biofouling compound of Nantural non-toxic.Utilizing the made anti-biofouling coating of described non-toxic compound is harmless to environment.
Description of drawings
Fig. 1 is that the activity of the active isoflavanone compounds of 3 kinds of anti-biofoulings described in the present invention is followed the trail of separation process figure;
Fig. 2 be 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 sample mean value and standard variance at least 3 shown in the figure;
Fig. 3 be 5,7-dihydroxy-2 ', 4 '-the dimethoxy isoflavanone to the line barnacle (
Balanus amphitrite) the inhibiting figure that adheres to of larva.Repeat sample 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 sample mean value and standard variance at least 3 shown in the figure.
Embodiment
Below the invention will be further described by the description of embodiment and with reference to accompanying drawing, 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 the scope of the present invention.
Isoflavanone compounds among the present invention can be naturally occurring compound, also can be artificial synthetic compound.
The kind of " antifouling paint " among the present invention can be the antifouling paint be used to preventing marine biofouling known in the art, such as: solubility body coating, automatic polishing copolymer class coating, non-adhesive-type coating, low surface energy anti-fouling paint, bonding formulation coating, bionical coating and natural anti-fouling agent coating etc. (can be referring to scientific and technical literature: Zhang Donghui etc., " Review on Anti-Fouling Coatings "
Modern coatings and application, the 5th phase of the 10th volume, 2007), as long as wherein contain fouling resistance composition described in film forming component and the present invention.
Ratio to the film forming component among the present invention and fouling resistance composition is not particularly limited, 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 " namely 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, reaches the southeast in the south from the warp of the west and 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, the effects such as carbuncle disappear.Pharmacological research shows that this platymiscium has anti-inflammatory, the effect such as anti-oxidant, antibacterial.
The inventor finds that solvent (such as the ethanol/water of the 90 volume %) extract of leopard cat tail bean plant (such as wild kind beans) has preferably anti-biofouling activity, and under biological activity test instructs, extract is carried out chemical constitution study, therefrom obtained preferably isoflavanone active component of anti-biofouling activity.Form from the structure of the isoflavanone compounds of the wild kind beans precursor structure by isoflavanone, other difference is substituting group and substituent position difference just.
(1) precursor structure of isoflavanone class:
(2) described compound can represent 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".
Described isoflavanone compounds mainly from wild kind beans, includes, but is not limited to: 5,7-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 suppresses are biological for (but being not limited to) barnacle class.Preferably, described isoflavanone compounds can suppress adhering to of barnacle class biology.The larva that described isoflavanone compounds preferably suppresses barnacle class biology adheres to.
The inventor 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
50Measurement result is 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 above-mentioned 3 kinds of compounds shows that than all greater than 10 these 3 kinds of compounds are nontoxic anti-biofouling compound after tested.
As shown in Figure 1, the present invention also provides the preparation method of above-mentioned isoflavanone compounds.The method comprise from leopard cat tail bean plant (such as wild kind beans), prepare as described in compound.Preferably, preparation isoflavanone compounds from the root of wild kind beans plant, stem, leaf, fruit.Preferably, described method has following step:
(1) leaf of the open country kind beans of drying is pulverized, got 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, reduced pressure concentration are got medicinal extract;
(4) medicinal extract is dispersed in water, extracts with benzinum, ethyl acetate and n-butanol successively, after extract is drained, get respectively petroleum ether portion medicinal extract, ethyl acetate extraction part medicinal extract, n-butanol portion medicinal extract;
(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, then uses recrystallizing methanol, 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 volume available percentage is the methanol/water of 70% ~ 95% ethanol/water or 70% ~ 90% or 50% ~ 70% acetone/water, 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 described 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 after filtration, reduced pressure concentration, make medicinal extract, with as described fouling resistance composition; Can also be with gained medicinal extract by the further separation and purification of above-mentioned column chromatography, obtain described isoflavanone compounds with as described fouling resistance composition.
The present invention also provides described isoflavanone compounds for the preparation of the purposes in the coating that prevents marine biofouling.Compound with anti-fouling activity of the present invention has antifouling effect, therefore can have the compound of anti-fouling activity for the preparation of efficient antifouling composition with described.
The present invention also provides a kind of method be used to preventing marine biofouling, and it comprises: body structure surface applies antifouling paint of the present invention under water.
Described " submerged structure " includes, but is not limited to herein: 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 and describe content of the present invention by specific embodiment, but these examples are not to be construed as limiting the scope of the invention.
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 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 become medicinal extract for subsequent use with the Rotary Evaporators reduced pressure concentration.
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 attachment activity 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.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 allows it discharge larva, collects larva behind 2.5 h, 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, and bright in 24 ℃ of temperature and 15 h: ventilation is cultivated under the dark periodicity of illumination of 9 h, and feeding angle hair diatom (
Chaetoceros gracilis Schutt), the collection larva is for 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), then be diluted to different concentration with the aseptic filtration seawater.Add 1.0 mL test fluid and 15 ± 3 cyprids in each hole of 24 well culture plates, 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 Software of Data Statistics.
The result shows under the above-mentioned concentration, the ability that wild kind beans extract has remarkable inhibition line kentrogon to adhere to.
The results are shown in 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.
Be that 70% acetone/water, 95% ethanol/water and 90% methanol/water make to extract solvent with percent by volume respectively, repeat embodiment 1.
The results are shown in Table 2:
Experimental result shows the methanol/water of acetone/water 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 obtains respectively to have equally a significant anti-biofouling active, therefore makes to extract solvent with the acetone/water of variable concentrations or ethanol/water or methanol/water and can obtain equally anti-biofouling active component in kind beans of open country.
Embodiment 3 separates evaluation 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, then uses 95% alcohol reflux 3 times, each 2 hours; Extracting liquid filtering is also made medicinal extract with the desolventizing of Rotary Evaporators reduced pressure concentration; Then medicinal extract is suspended in (per 100 g medicinal extract, 300 mL water) in the water, use successively 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, boil off solvent with Rotary Evaporators again, get respectively extract 100 g, 70 g, 200 g.
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, then uses recrystallizing methanol, 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 separation identity 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 nuclear magnetic resoance spectrum (
1H NMR,
13C NMR, DEPT, COSY HSQC, HMBC), the ESI-MS(cation mode) etc. wave spectrogram identify.According to analysis of compounds
1~
3Spectral data, and with reference to pertinent literature, be accredited as respectively 5,7-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)。
Embodiment 4 measures the anti-kentrogon attachment activity of described isoflavanone compounds
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 attachment activity of test compounds.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 allows it discharge larva, collects larva behind 2.5 h, 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, and bright in 24 ℃ of temperature and 15 h: ventilation is cultivated under the dark periodicity of illumination of 9 h, and feeding angle hair diatom (
Chaetoceros gracilis Schutt), the collection larva is for 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), then are diluted to different concentration with the aseptic filtration seawater.Add 1.0 mL test fluid and 15 ± 3 cyprids in each hole of 24 well culture plates, 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 Software of Data Statistics.3 kinds of isoflavanone compounds experimental results that anti-kentrogon adheres under variable concentrations as shown in Figure 2.
Experimental result according to the 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, namely suppress the larva adhesive rate for maximum suppress the larva adhesive rate 50% the time corresponding concentration), by EC
50The height of detection material anti-biofouling activity as can be known.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) as can be known detection material is big or small to the toxicity of 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 has remarkable inhibition line kentrogon to adhere to, wherein 5,7,2 ', 4 '-activity of tetrahydroxy isoflavanone is especially outstanding.The 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 testing 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 results are shown in Table 3:
The preparation of embodiment 5 antifouling paints
Choose the anti-biofouling active component that the present invention relates to, adopt prior art to prepare 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 only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (4)
1. the isoflavanone compounds is preventing that the submerged structure surface is subject to halobiontic adhering to and/or stained application, and described marine organisms are that the barnacle class is biological; Wherein said isoflavanone compounds is one or more in the compound shown in formula III-Shi IV:
2. antifouling paint for the protection of 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 the claim 1.
3. a kind of antifouling paint for the protection of the submerged structure surface according to claim 2 is characterized in that: described film forming component is one or more in hydrolyzable, the solvable or insoluble resin.
According to claim 2 or 3 each described a kind of antifouling paints for the protection of the submerged structure surface be applied in the surface that prevents barnacle class biological attachment and/or stained submerged structure.
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| 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 |
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| 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 |
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