CN106810926B - A kind of application of aporphine alkaloid - Google Patents
A kind of application of aporphine alkaloid Download PDFInfo
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- CN106810926B CN106810926B CN201710016820.3A CN201710016820A CN106810926B CN 106810926 B CN106810926 B CN 106810926B CN 201710016820 A CN201710016820 A CN 201710016820A CN 106810926 B CN106810926 B CN 106810926B
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- aporphine alkaloid
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
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Abstract
The invention discloses a kind of application of aporphine alkaloid, the application of the aporphine alkaloid is that the aporphine alkaloid is preparing the application in antifouling paint.The problems such as the purpose of the present invention is for existing for anti-marine biofouling the deficiencies in the prior art and marine antifouling coating using pollution caused by difficult, efficient low and toxicity, provides the separation from the sinomenium acutum platymiscium lobus cardiacus sinomenium acutum in natural products Hernandiaceae and identifies 3 kinds of aporphine alkaloids nontoxic and with significant anti-fouling activity.To solve the above-mentioned problems in the prior art, the present invention, which provides aporphine alkaloid, is preventing the purposes in marine biofouling, antifouling paint for preventing marine biofouling and preparation method thereof and for preventing submerged structure surface by the attachment of marine organisms and/or the method being stained.
Description
Technical field
The invention belongs to chemical technology fields, and in particular to a kind of application of aporphine alkaloid.
Background technique
With the increase of mankind's Activities of Ocean, the harm of marine fouling organism is increasingly by the attention of the mankind.Ocean is dirty
Damage biology be adhere to reproduction alow, submarine pipeline, oil platform, the netting gear of fishery and other all marine artificial facility surfaces
Harmful organism, be broadly divided into three categories: mushroom, attached plant and epizoite.Its representative 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. influences maximum to be an algae, Enteromorpha, barnacle, lime worm, bryozoan, ascidian etc. on ship.Marine fouling organism
Once attachment will generate serious harm on marine facility surface, such as increase the resistance of ships navigation；Make seawater cooling pipe and
The condenser pipe caliber of heat exchanger reduces or even completely plugged；Promote corrosion and leads to crevice corrosion；Make marine instrument and machine
Tool failure；Absorption sound energy, makes acoustic instrument reduction or failure；Increase the sectional area of marine building pile, column, increases wave and sea
The impact force of stream；Block mesh；Attachment base and bait etc. are fought for shellfish, the algae of cultivation.The harm of marine fouling organism bring
Huge economic loss is caused to industries such as sea transport, aquacultures.
Preventing and kill off for fouling organism mainly passes through physical measure, chemical means and biological method at present, or by above-mentioned several
Class method acts synergistically to realize anti-fouling purpose.Chemical means particularly may be divided into drug immersion method, paint coatings Protection Code,
Electrolysis anti-soil method and direct poisoning method etc..Wherein the method for coating antifouling paint is to use most commonly used method at present, and grasp
Make simplicity, anti-fouling effect is lasting, it is considered to be most efficient method.Cuprous oxide is a kind of ocean being most widely used at present
Anti-fouling agent, it has antifouling activity to most of animal class marine growth and most plant marine growths, but is stained to soft
Marine growth anti-fouling effect is bad, needs to add auxiliary anti-fouling agent to reach comprehensive anti-fouling effect.Also there is copper murder by poisoning to make
With especially largely being gathered in harbour in ocean, lead to seaweed mortality.Natural biological preparation usually has preferably
Environmental acceptability, majority can will not generate permanent biological accumulation, and from a wealth of sources with natural decomposition.From natural
It is expected to obtain low toxicity, efficient, wide spectrum marine active anti-fouling agent in product, thus the anti-fouling agent that substitution is toxic to environment.At present
Had found many substances with anti-fouling activity from ocean and terrestrial life, including terpene, acetylenic, polycyclic compound,
The substance of the types such as steroid, isothiocyanate.But it is yet far from satisfying the actual demand in market, therefore, exploitation
It is a kind of to can solve anti-fouling product and be very important.
Summary of the invention
The purpose of the present invention is to provide a kind of applications of aporphine alkaloid.
The object of the present invention is achieved like this, and the aporphine alkaloid is preparing the application in antifouling paint.
The purpose of the present invention is make for existing for anti-marine biofouling the deficiencies in the prior art and marine antifouling coating
The problems such as pollution caused by difficult, efficient low and toxicity, provide the sinomenium acutum platymiscium from natural products Hernandiaceae
Separation identifies 3 kinds of aporphine alkaloids nontoxic and with significant anti-fouling activity in lobus cardiacus sinomenium acutum.To solve existing skill
The above problem present in art, the present invention provide aporphine alkaloid prevent the purposes in marine biofouling, for preventing
Only antifouling paint of marine biofouling and preparation method thereof and for preventing submerged structure surface by the attached of marine organisms
And/or the method that is stained.
The invention has the following advantages:
1. the aporphine alkaloid in the present invention can be naturally occurring organic compound, and be non-toxic compound,
It is degradable in marine environment without toxic heavy metal, it not will cause the pollution of water body environment, will not be transmitted and be led by food chain
Its enrichment in organism is caused, it is environmentally friendly, it is highly-safe.
2. the aporphine alkaloid in the present invention shows stronger inhibition biodeterioration activity, can be applied for fouling resistance
The exploitation of material or other fouling resistance products provides valuable lead compound, there is good application prospect.
3. the aporphine alkaloid in the present invention is natural products, but its process for artificial is mature, acquiring way letter
Just, it is suitable for being mass produced, is not only restricted to the intracorporal content of biology, there is reliable and stable source, it is big to promote and apply potentiality.
4. anti-biofouling substances provided by the invention are the Chemical Decomposition methods instructed by biological test, from lobus cardiacus
Separation identifies in sinomenium acutum, or is screened from the compound in other sources using Structure-activity analysis result,
Experiments have shown that compound according to the present invention is the anti-biofouling compound of Nantural non-toxic.Utilize the non-toxic compound institute
Manufactured anti-biofouling coating is harmless to environment.
Detailed description of the invention
Fig. 1 is the tracking activity separation process of 3 kinds of heretofore described anti-biofouling activity aporphine alkaloids
Figure；
Fig. 2 be left-handed Actein to line barnacle (Balanus amphitrite) larva attachment inhibiting effect figure.
It is as shown in the figure at least three repeating sample average value and standard variance；
Fig. 3 be hernandine to line barnacle (Balanus amphitrite) larva attachment inhibiting effect figure.In figure
It show at least three repeating sample average value and standard variance；
Fig. 4 be dextrorotation Actein to line barnacle (Balanus amphitrite) larva attachment inhibiting effect figure.
It is as shown in the figure at least three repeating sample average value and standard variance.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is further illustrated, but is not subject in any way to the present invention
Limitation, based on present invention teach that it is made it is any transform or replace, all belong to the scope of protection of the present invention.
The application of the aporphine alkaloid is that the aporphine alkaloid is preparing answering in antifouling paint
With.
The antifouling paint is to prevent submerged structure surface by the attachment of marine organisms and/or the antifouling painting being stained
Material.
The marine organisms are barnacle class biology.
The aporphine alkaloid has a structure that
Wherein, R1, R2, R3For H, OH or OCH3。
The aporphine alkaloid is、WithIn
One or more.
Antifouling paint of the present invention is that the antifouling paint is in the application with the aporphine alkaloid
The antifouling paint that is prepared as anti-fouling activity ingredient of aporphine alkaloid.
The antifouling paint is to be mixed using aporphine alkaloid as anti-fouling activity ingredient with film forming component
Antifouling paint for preventing submerged structure surface from receiving the attachment of marine organisms and/or being stained.
The film forming component is one or more of hydrolyzable, solvable or insoluble resin.
The film forming component be alkyd resin, acrylic resin, chlorinated rubber resin, epoxy resin, silicone resin,
One or more of polyester, polyurethane and fluoropolymer.
The pollution resistance active constituent additional amount is the 0.1 ~ 20% of film forming component weight percent.
Aporphine alkaloid in the present invention can be naturally occurring compound, be also possible to artificial synthesized chemical combination
Object.
The type of " antifouling paint " in the present invention can be known in the art for preventing the anti-of marine biofouling
Dirty coating, such as: soluble ontology coating, automatic polishing copolymer class coating, non-adhesive-type coating, low surface energy anti-fouling paint,
Binding dosage form coating, simulated ecological and natural anti-fouling agent coating etc., (reference can be made to scientific and technical literature: Zhang Donghui etc., " antifouling paint is comprehensive
State ", modern coatings and coating, the 5th phase of volume 10,2007), as long as wherein containing film forming component and heretofore described anti-
It is stained ingredient.
The ratio of film forming component and fouling resistance ingredient in the present invention is not particularly limited, as long as fouling resistance ingredient contains
Amount is effective quantity.For example, the additional amount of fouling resistance ingredient can be the 0.1% ~ 20% of the weight of film forming component, preferably
1%~15%。
The term " effective quantity " being related in the present invention reaches the active constituent of fouling resistance effect in specific environment
Amount.
Heretofore described film forming component can be known in the art the antifouling paint for preventing marine biofouling
In film forming component, and can be one or more of hydrolyzable, solvable or insoluble resin；For example, can be alkyd
Resin, acrylic resin, chlorinated rubber resin, epoxy resin, silicone resin, polyester, polyurethane and fluoropolymer etc..
Aporphine alkaloid of the present invention is preferably from the sinomenium acutum platymiscium (such as lobus cardiacus sinomenium acutum) in Hernandiaceae
Isolated aporphine alkaloid.
The platymiscium whole world is distributed in the Eastern Hemisphere torrid zone, subtropical zone there are about 30 kinds.China shares 14 kind 1 within the border
6 mutation of subspecies, is distributed in the provinces and regions such as Yunnan, Sichuan, Guizhou, Guangxi, Guangdong, Hunan, Fujian and Taiwan.The platymiscium, which has, to disappear
Swell antipyretic, dispeling wind and dehumidification, removing blood stasis and acesodyne and treatment traumatic injury the effects of.
Inventor has found that solvent (such as ethanol/waters of the 90 volume %) extract of sinomenium acutum platymiscium (such as lobus cardiacus sinomenium acutum) has
Preferable anti-biofouling activity, and chemical constitution study is carried out to extract under biological activity test guidance, therefrom obtain
The preferable aporphine alkaloid ingredient of anti-biofouling activity.The structure of alkaloid compound from lobus cardiacus sinomenium acutum by
The precursor structure of aporphine alkaloid forms, and other differences are the position difference of substituent group and substituent group.
(1) precursor structure of aporphine alkaloid is as follows:
(2) compound can be indicated to flowering structure formula:
Wherein, R1, R2, R3For H, OH or OCH3。
The aporphine alkaloid is mainly from lobus cardiacus sinomenium acutum, including but not limited to: left-handed Actein, Katsuratree
Alkali and dextrorotation Actein.
The structural formula of left-handed Actein ((-)-actinodaphine) are as follows:
Hernandine (nandigerine), structural formula are as follows:
The structural formula of dextrorotation Actein ((+)-actinodaphine) are as follows:
The marine organisms that aporphine alkaloid of the present invention is inhibited are (but being not limited to) barnacle class biology.It is preferred that
Ground is that the aporphine alkaloid can inhibit the attachment of barnacle class biology.The aporphine alkaloid preferably inhibits rattan
The larva of pot class biology adheres to.
The present inventor calculates left-handed Actein, the half inhibition attachment concentration of hernandine and dextrorotation Actein.
Calculated result shows that 3 kinds of compounds inhibit attachment concentration EC to the half of the line barnacle young50Measurement result is respectively 3.62 ±
0.7 μ g/mL, 3.42 ± 0.5 μ g/mL and 3.80 ± 0.9 μ g/mL, the above results show that 3 kinds of compounds are all shown
Preferable anti-biofouling activity, and the anti-fouling activity of 3 kinds of compounds is relatively.In addition, according to the (ginseng such as AVIelin
See 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. Ecol1993,19 (10): 2155-2167.), poison
Effect is than (LC50/ EC50) it is greater than 10 or more anti-biofouling compound for nontoxic anti-biofouling compound.After tested above-mentioned 3
The toxic effect of kind compound shows that this 3 kinds of compounds are nontoxic anti-biofouling compound than both greater than 10.
The present invention also provides the preparation methods of above-mentioned aporphine alkaloid.This method includes from sinomenium acutum platymiscium (such as heart
Leaf sinomenium acutum) in prepare the compound.Preferably, aporphines are prepared from the root of lobus cardiacus sinomenium acutum plant, stem, leaf, fruit
Alkaloid.Preferably, the method has following step:
(1) root of dry lobus cardiacus sinomenium acutum is crushed, obtains the root fragment of lobus cardiacus sinomenium acutum；
(2) by the fragment soaked in solvent of lobus cardiacus cocculi, extracting solution is obtained；
(3) extracting solution is filtered, medicinal extract is concentrated under reduced pressure to obtain；
(4) medicinal extract is dispersed in water, is successively extracted with petroleum ether, ethyl acetate and n-butanol, extract liquor subtracts
After pressure distillation, petroleum ether portion medicinal extract, ethyl acetate extraction part medicinal extract, n-butanol portion medicinal extract are obtained respectively；
(5) take ethyl acetate extraction part medicinal extract through silica gel column chromatography, with chloroform-methanol (volume ratio 1:0~2:1) gradient
Afford 13 components (Fr.1~Fr.13).
(6) Fr.7 obtains component with methylene chloride: methanol (volume ratio 30:1 ~ 0:1) gradient elution through silica gel column chromatography
Fr.7a~7d.Fr.7c affords Fr.7c-1 ~ 6 through silica gel column chromatography, with methylene chloride: methanol (volume ratio 15:1).
Fr.7c-2 is with methanol: water (volume ratio 30:70) is mobile phase, and compound 1 is prepared through HPLC；Fr.7c-4 is with methanol: water
(volume ratio 25:75) is mobile phase, and compound 2 is prepared through HPLC；Fr.8 is through silica gel column chromatography, with methylene chloride: methanol
(volume ratio 30:1 ~ 0:1) gradient elution obtains component Fr.8a ~ 8h.Fr.8b is through silica gel column chromatography, with methylene chloride: methanol (body
Product is than 20:1) afford component Fr.8b-1 ~ 5.Fr.8b-2 is with methanol: water (volume ratio 61:39) is mobile phase, through HPLC system
It is standby to obtain compound 3.
In step (2), the solvent volume available percentage is 70% ~ 95% ethanol/water or 70% ~ 90% first
Alcohol/water or 50% ~ 70% acetone/water, reflux extracting time is every time 2 hours, and refluxing extraction is preferably repeated 3 times.
The present invention also provides the methods for preparing antifouling paint, comprising the following steps: 1) provides fouling resistance ingredient；And 2) will
The fouling resistance ingredient that step 1) obtains is mixed with film forming component, obtains antifouling paint.Wherein in the step 1), fouling resistance at
Dividing can be Formulas I compound represented, may also be obtained in that and obtains extracting solution with above-mentioned solvent extraction lobus cardiacus sinomenium acutum plant；
Gained extracting solution is filtered, is concentrated under reduced pressure, medicinal extract is made, using as the fouling resistance ingredient；Gained medicinal extract can also be led to
It crosses above-mentioned column chromatography further to isolate and purify, obtains the aporphine alkaloid using as the fouling resistance ingredient.
The present invention also provides the aporphine alkaloids to prepare the use in the coating for preventing marine biofouling
On the way.Compound of the present invention with anti-fouling activity has antifouling effect, therefore can have fouling resistance living described
The compound of property is used to prepare efficient anti-fouling agent.
The present invention also provides a kind of methods for preventing marine biofouling comprising: body structure surface coats under water
Antifouling paint of the invention.
" submerged structure " described herein includes but is not limited to: drainpipe, underbody, propeller, net of culture of fish
Case, the submerged structure of harbour and offshore platform, submarine mine, buoy, submarine cable, border on the sea power plant cooling pipe etc..
Case is embodied, the present invention will be further described below:
The inhibitory activity that 1 lobus cardiacus sinomenium acutum plant extracts of embodiment adheres to line kentrogon
Material source: lobus cardiacus sinomenium acutum is adopted in Luquan, Yunnan Province, through Kunming Inst. of Botany, Chinese Academy of Sciences Tao Deding researcher
It is accredited asUraria clarkei(Clarke) Gagnep., Saving specimen is in national medicine institute of Yunnan Institute for nationalities sample
Shop.
The preparation of lobus cardiacus sinomenium acutum extract: dry lobus cardiacus cocculi is crushed, and obtains the root fragment of lobus cardiacus sinomenium acutum respectively；So
The fragment of lobus cardiacus cocculi 90 % alcohol reflux of volume is extracted 3 times afterwards, obtains extracting solution within 2 hours every time；Lobus cardiacus sinomenium acutum is mentioned
Liquid is taken to filter and be concentrated under reduced pressure with Rotary Evaporators spare at medicinal extract respectively.
Using inhibit line barnacle cyprids attachment experimental model (reference can be made to scientific and technical literature: Xu Y., He H. P.,
Qian P. Y, et al. Potent antifouling compounds produced by marine
streptomyces. Bioresource Technology2010,101 (4): 1331-1336) test sinomenium acutum platymiscium
The extract of lobus cardiacus sinomenium acutum inhibits the ability of kentrogon attachment.It is measured using 24 well culture plates in 50 μ g/mL and 10 μ g/mL
Concentration under lobus cardiacus sinomenium acutum extract anti-larva attachment activity.Line adult barnacle (Darwin) pick up from Hong Kong (22 ° of 19'N,
114 ° of 16'E) intertidal zone.The seawater of 8 L filtering is put into the polystyrene plastics culture vessel of 12 L, then by line barnacle
Adult is put into container, and placement allows it to discharge larva, collects larva after 2.5 h, the larva in the stage is known as naupiar larva
(nauplius), without adhesive ability.Naupiar larva is put into the appearance equipped with 8 L filtering seas (filter sizes are 0.22 μm)
It is bright in 24 DEG C of temperature and 15 h in device: culture of ventilating under 9 h dark periodicity of illumination, and feeding angle hair diatom (Chaetoceros gracilis Schutt), collection larva is spare after culture 3 days, and the larva in the stage is known as cyprids (cypris), has
Adhesive ability.The extract of lobus cardiacus sinomenium acutum is mixed with dimethyl sulfoxide (DMSO), is then diluted to difference with aseptic filtration seawater
Concentration.1.0 mL test fluids and 15 ± 3 cyprids are added in each hole of 24 well culture plates, each concentration is equal
If 3 multiple holes.Isometric aseptic filtration seawater does blank control.24 well culture plates are bright in 24 DEG C of temperature and 15 h: 9 h are dark
After cultivating 48 h under periodicity of illumination, statistics adheres to the number of larva under the microscope.With 11 data statistics of SPSS VIersion
Software is for statistical analysis.
The result shows that lobus cardiacus sinomenium acutum extract has the ability for significantly inhibiting the attachment of line kentrogon under above-mentioned concentration.As a result
It is shown in Table 1.
The inhibiting effect that 1 lobus cardiacus sinomenium acutum root extract of table adheres to line kentrogon.
n=4
Embodiment 2 is further tested with lobus cardiacus sinomenium acutum
It is further tested with lobus cardiacus sinomenium acutum plant roots.This does not imply that the other plants of Sinomenium without activity.
It is respectively that 70% acetone/water, 80% ethanol/water and 90% methanol/water make Extraction solvent with percent by volume,
Repeat embodiment 1.It the results are shown in Table 2.The experimental results showed that being made with 70% acetone/water, 80% ethanol/water and 90% methanol/water
Extraction solvent distinguishes 70% acetone extract of lobus cardiacus cocculi, 80% ethanol extract of lobus cardiacus cocculi and lobus cardiacus sinomenium acutum obtained
90% methanolic extract of root equally has a significant anti-biofouling activity, therefore with the acetone/water or ethanol/water of various concentration
Or methanol/water makees Extraction solvent equally and can obtain the anti-biofouling active constituent in lobus cardiacus sinomenium acutum.
The inhibiting effect that 2 lobus cardiacus cocculi different solvents extract of table adheres to line kentrogon.
n = 4
Embodiment 3 separates identification anti-biofouling reactive compound from lobus cardiacus cocculi
The root of dry lobus cardiacus sinomenium acutum is ground into the particle of 0.1 ~ 0.5 cm size of partial size, then with 90% alcohol reflux 3
It is secondary, 2 hours every time；Extracting solution filtering simultaneously goes solvent that medicinal extract is made with Rotary Evaporators reduced pressure；Then medicinal extract is suspended in
In water (every 100 g medicinal extract, 300 mL water), successively use petroleum ether (with water volume ratio 1:1), ethyl acetate (with water volume ratio 1:1)
And n-butanol (with water volume ratio 1:1) is extracted, then boils off solvent with Rotary Evaporators, respectively 56 g of extract, 97
G, 92 g.
Take ethyl acetate extraction part medicinal extract (90 g) through silica gel column chromatography (100-200 mesh), with chloroform-methanol (volume
Than 1:0~2:1) gradient elution obtains 13 components (Fr.1~Fr.13).Fr.7 (8.1 g) uses dichloro through silica gel column chromatography
Methane: methanol (volume ratio 30:1 ~ 0:1) gradient elution obtains component Fr.7a ~ 7d.Fr.7c uses dichloromethane through silica gel column chromatography
Alkane: methanol (volume ratio 15:1) affords Fr.7c-1 ~ 6.Fr.7c-2 (1.1 g) is with methanol: water (volume ratio 30:70) is
Compound 1 is prepared through HPLC in mobile phase；Fr.7c-4 (0.9 g) is with methanol: water (volume ratio 25:75) is mobile phase,
Compound 2 is prepared through HPLC；Fr.8 (12 g) is through silica gel column chromatography, with methylene chloride: methanol (volume ratio 30:1 ~ 0:1)
Gradient elution obtains component Fr.8a ~ 8h.Fr.8b (2.1 g) is through silica gel column chromatography, with methylene chloride: methanol (volume ratio 20:
1) component Fr.8b-1 ~ 5 are afforded.Fr.8b-2 (0.7 g) is with methanol: water (volume ratio 61:39) is mobile phase, through HPLC
Compound 3 is prepared；The separation identity process of anti-biofouling active constituent is shown in Fig. 1 in lobus cardiacus cocculi.
The chemical structure of the compound of the present invention with nuclear magnetic resoance spectrum (1H NMR, 13C NMR, DEPT), ESI-MS(sun
Ion mode) etc. wave spectrograms identification.A left side is identified respectively as according to the spectral data of analysis of compounds 1 ~ 3, and with reference to pertinent literature
Revolve Actein, hernandine and dextrorotation Actein.
The physicochemical data of compound 1: colourless acicular crystal (methanol), the aobvious positive of bismuth potassium iodide, mp:205-206 DEG C.
ESI-MS m/z:312 [M+H]+, molecular formula: C18H17O4N。1H-NMR (400 MHz, CD3OD) δ: 7.67 (1H, s,
H-11), 6.70 (1H, s, H-8), 6.52 (1H, s, H-3), 6.06 (1H, s, OCH2O), 5.92 (1H,
s, OCH2O), 3.86(3H, s, 10-OCH3), 3.76 (1H, dd, J = 14.0, 4.8 Hz, H-6a), 3.28
(1H, dd, J = 10.0, 4.0 Hz, H-5a), 2.92 (1H, m, H-4a), 2.88 (1H, m, H-5b),
2.73 (1H, dd, J= 14.0, 4.8 Hz, H-7b), 2.58 (1H, m, H-4b), 2.56 (1H, t, J =
14.0 Hz, H-7a); 13C-NMR (100 MHz, CD3OD) δ:148.4 (C-2), 147.9 (C-10), 147.5
(C-9), 143.0 (C-1), 130.0 (C-7a), 128.2 (C-3a), 128.1 (C-3b), 124.0 (C-11a),
118.0 (C-11b), 116.1 (C-8), 112.3 (C-11), 108.0 (C-3), 102.0 (OCH2O), 56.7
(10-OCH3), 55.0 (C-6a), 44.2 (C-5), 37.0 (C-7), 29.9 (C-4)。
The physicochemical data of compound 2: yellow powder (methanol), the aobvious positive of bismuth potassium iodide, mp:208-209 DEG C; ESI-
MS m/z: 312 [M+H]+, molecular formula: C18H17O4N。1H-NMR (400 MHz, DMSO-d6) δ: 6.85 (1H, d, J
= 8.0 Hz H-8), 6.69 (1H, d, J = 8.0 Hz H-9), 6.63 (1H,s, H-3), 6.00 (1H, d, J
= 1.2 Hz, OCH2O), 5.86 (1H, d, J = 1.2 Hz, OCH2O), 3.78 (3H, s, 11-OCH3), 3.46
(1H, dd, J = 13.2, 3.6 Hz, H-6a), 3.12 (1H, dd, J = 10.0, 4.0 Hz, H-5a), 2.77
(1H, m, H-4a), 2.71(1H, m, H-5b), 2.67 (1H, dd, J = 13.2, 3.6 Hz, H-7b), 2.55
(1H, m, H-4b), 2.29 (1H, t, J = 13.2 Hz, H-7a); 13C-NMR (100 MHz, DMSO-d6) δ:
147.2 (C-11), 146.1 (C-2), 143.7 (C-10), 141.9 (C-1), 130.2 (C-3a), 129.8 (C-
7a), 126.5 (C-1b), 118.0 (C-8), 117.5 (C-11a), 113.8 (C-9), 110.9 (C-1a),
107.1 (C-3), 99.9 (OCH2O), 56.1 (11- OCH3), 54.1 (C-6a), 42.6 (C-5), 37.5 (C-
7), 29.0 (C-4)。
The physicochemical data of compound 3: white needle-like crystals (methanol), the aobvious positive of bismuth potassium iodide, mp:207-208 DEG C;
[α] = + 61o (c = 0.97, MeOH); ESI-MS m/z: 312 [M+H]+, molecular formula: C18H17O4N。1H-NMR
(400 MHz, CD3OD) δ: 7.41 (1H, s, H-11), 6.64 (1H, s, H-8), 6.52 (1H, s, H-3),
6.06 (1H, d, J = 1.2 Hz, OCH2O), 5.89 (1H, d, J =1.2 Hz, OCH2O), 3.98 (1H, dd,
J = 13.8, 4.8 Hz, H-6a), 3.74 (3H, s, 10-OCH3), 3.63 (1H, m, H-5b), 3.15 (2H,
m, H-4b and 5a), 2.91 (1H, m, H-7b), 2.83 (1H, m, H-4a), 2.77 (1H, m, H-7a);13C NMR (100 MHz , CD3OD) δ: 149.7 (C-10), 148.1 (C-2), 147.6 (C-1), 143.7 (C-
9), 126.3(C-7a), 125.3 (C-3a), 123.0 (C-3b), 121.0 (C-11a), 117.6 (C-1a),
116.0 (C-11), 111.9 (C-8), 107.7 (C-3), 102.6 (OCH2O), 56.4 (10- OCH3), 54.2
(C-6a), 42.6 (C-5), 33.6 (C-7), 26.3 (C-4)。
Embodiment 4 measures the anti-kentrogon attachment activity of the aporphine alkaloid
Using inhibit line barnacle cyprids attachment experimental model (reference can be made to scientific and technical literature: Xu Y., He H. P.,
Qian P. Y., et al. Potent antifouling compounds produced by marine
streptomyces. Bioresource Technology2010,101 (4): 1331-1336), the anti-rattan of compound is tested
Pot larva attachment activity.Line adult barnacle (Darwin) picks up from the intertidal zone Hong Kong (22 ° of 19'N, 114 ° of 16'E).In the poly- of 12 L
It is put into the seawater of 8 L filtering in polyglass culture vessel, then line adult barnacle is put into container, placement allows it to discharge
Larva collects larva after 2.5 h, and the larva in the stage is known as naupiar larva (nauplius), without adhesive ability.It will be without section children
Worm is put into the container equipped with 8 L filtering seas (filter sizes are 0.22 μm), bright in 24 DEG C of temperature and 15 h: 9 h dark light
It is cultivated according to ventilating under the period, and feeding angle hair diatom (Chaetoceros gracilis Schutt), it is collected after culture 3 days
Larva is spare, and the larva in the stage is known as cyprids (cypris), there is adhesive ability.3 kinds of aporphine alkaloids are distinguished
It is dissolved in dimethyl sulfoxide (DMSO), different concentration is then diluted to aseptic filtration seawater.In each hole of 24 well culture plates
1.0 mL test fluids of middle addition and 15 ± 3 cyprids, each concentration are all provided with 3 multiple holes.Isometric aseptic filtration seawater
Do blank control.It is 24 well culture plates are bright in 24 DEG C of temperature and 15 h: after cultivating 48 h under 9 h dark periodicity of illumination, micro-
The number of statistics attachment larva under mirror.It is for statistical analysis with 11 Software of Data Statistics of SPSS VIersion.3 kinds of aporphines
The experimental result of alkaloid anti-kentrogon attachment under various concentration is as in Figure 2-4.
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 it) is analyzed.The EC of 48 h can be obtained according to experimental result50(attachment concentration half-suppressed, i.e.,
Inhibition larva adhesive rate concentration corresponding when being the 50% of maximum suppression larva adhesive rate), by EC50It knows to detect substance antibiosis
Object is stained active height.And after 24 h, the mortality of larva is calculated, the LC of 24 h can be obtained according to experimental result50
(half lethal concentration), by LC50/EC50The toxicity size of detectable substance confrontation kentrogon known to (toxic effect ratio).Experiment analysis results
Show that left-handed Actein, hernandine and dextrorotation Actein have the activity for significantly inhibiting the attachment of line kentrogon, and 3
Kind compound activity is relatively.The researchers such as AVIelin (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. Ecol1993,19 (10): 2155-2167.) point out, toxic effect than be greater than 10 or more anti-biofouling compound
For nontoxic anti-biofouling compound.The toxic effect for the 3 kinds of compounds tested shows that this 3 kinds of compounds inhibit than both greater than 10
The attachment of line kentrogon, but there is no toxicity to line kentrogon.It the results are shown in Table 3.
The inhibiting effect that 33 kinds of aporphine alkaloids of table adhere to line kentrogon
| Sample number into spectrum | Sample ID | EC50 (µg/ml) | LC50 (µg/ml) | LC50/EC50 |
| 1 | Left-handed Actein | 3.62 ± 0.7 | > 40 | > 11.0 |
| 2 | Hernandine | 3.42 ± 0.5 | > 40 | > 11.7 |
| 3 | Dextrorotation Actein | 3.80 ± 0.9 | > 40 | > 10.5 |
n = 4, p<0.01
The preparation of 5 antifouling paint of embodiment
Anti-biofouling active constituent of the present invention is taken, using prior art preparation antifouling paint, for example, by active
Ingredient mixes or is spread in film forming natural resin, vinyl chloride acetate ethylene copolymer and other hydrolyzables, solvable or insoluble
In the polymer such as resin.Antifouling paint, which should release enough effective active constituents to surface, prevents biodeterioration.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (8)
1. a kind of application of aporphine alkaloid, it is characterised in that the aporphine alkaloid is in preparing antifouling paint
Using the aporphine alkaloid is、With
One or more of.
2. the application of aporphine alkaloid according to claim 1, it is characterised in that the antifouling paint is to prevent
Attachment and/or the antifouling paint that is stained of the submerged structure surface by marine organisms.
3. the application of aporphine alkaloid according to claim 2, it is characterised in that the marine organisms are barnacle
Class biology.
4. a kind of antifouling paint, it is characterised in that the antifouling paint is raw with any aporphine of claim 1 ~ 3
The antifouling paint that aporphine alkaloid in the application of alkaloids is prepared as anti-fouling activity ingredient.
5. antifouling paint according to claim 4, it is characterised in that the antifouling paint be using aporphine alkaloid as
Anti-fouling activity ingredient and film forming component are mixed and made into attachment and/or dirt for preventing submerged structure surface by marine organisms
The antifouling paint of damage.
6. antifouling paint according to claim 5, it is characterised in that the film forming component is hydrolyzable, solvable or insoluble tree
One or more of rouge.
7. according to the antifouling paint of claim 5 or 6, it is characterised in that the film forming component is alkyd resin, acrylic acid tree
One or more of rouge, chlorinated rubber resin, epoxy resin, silicone resin, polyester, polyurethane and fluoropolymer.
8. antifouling paint according to claim 5, it is characterised in that the pollution resistance active constituent additional amount is film forming component
The 0.1 ~ 20% of weight percent.
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