CN105153103B - A kind of preparation method of chloro polyketide and the application as marine antifoulant - Google Patents
A kind of preparation method of chloro polyketide and the application as marine antifoulant Download PDFInfo
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- CN105153103B CN105153103B CN201510359566.8A CN201510359566A CN105153103B CN 105153103 B CN105153103 B CN 105153103B CN 201510359566 A CN201510359566 A CN 201510359566A CN 105153103 B CN105153103 B CN 105153103B
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- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/76—Benzo[c]pyrans
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- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P17/00—Preparation of heterocyclic carbon compounds with only O, N, S, Se or Te as ring hetero atoms
- C12P17/02—Oxygen as only ring hetero atoms
- C12P17/06—Oxygen as only ring hetero atoms containing a six-membered hetero ring, e.g. fluorescein
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Abstract
A kind of preparation method of chloro polyketide and the application as marine antifoulant, Spawn incubation first is carried out to fungi Penicillium sp. (TA33 1) during preparation, fermented and cultured is carried out to the fungi again, gained mycelium chloroform methanol mixed liquor (1: 1) is extracted 3 times after being concentrated under reduced pressure, coarse extract is extracted with ethyl acetate 3 times to obtain；Ethyl acetate coarse extract carries out normal-phase silica gel column chromatography, the gel filtration chromatographies of Sephadex LH 20, HPLC high performance liquid chromatography successively, produces compound of formula I.The present invention provides a kind of marine organisms anti-fouling agent, it is characterised in that with the compound of formula I or its pharmaceutically acceptable salt of the present invention, for preventing and treating marine biofouling caused by barnacle attachment.
Description
Technical field
The present invention relates to a kind of preparation method of chloro polyketone (chlorinated polyketides) compound with answering
With there is extremely strong inhibitory activity to marine fouling organism barnacle Balanus amphitrite larvas more particularly to a kind of
Chloro polyketone and preparation method and application.
Background technology
Marine biofouling is that subduction is set in ocean for organic molecule, microorganism, animal, plant and their accessory substance
Apply the harmfulness accumulation on surface.This harmfulness accumulation frequently occurs in the surface for the ocean subduction facility do not protected, including
Sea-freight and the ship of tourism, naval's warship, heat exchanger, sea sensor and aquaculture base etc..Biodeterioration causes
Huge economic loss, only by taking USN's warship as an example, every year economic loss in this respect 18 to 26 hundred million dollars it
Between, and USN's warship quantity only accounts for the 0.5% of global ships quantity, therefore marine biofouling is extremely serious nature
Harm.Barnacle is representativeness biology very universal in fouling organism known today because of its very strong Adhering capacity.From 2008
After the year global use for eliminating poisonous anti-fouling agent organotin, finding safe and efficient marine antifoulant turns into urgent need solution in the world
Problem certainly.Marine natural products is considered as the important sources of novel sea anti-fouling agent.In fact, in the past few decades
The compound for much having strong anti-fouling activity is found that from sponge, the marine organisms such as coral and marine alga.However, from above-mentioned
The reactive compound found in macro-organism is due to being leveraged its potential application by the limitation measured.Marine microorganism
Due in the lab can with large scale fermentation, survivable natural environment, and as activity marine compound it is most important come
Source.However, in recent years there is not yet obtaining the chloro polyketide of important anti-fouling activity from the fungi of marine source
Use as anti-fouling agent.(J.A.Callow, M.E.Callow, Nat.Commun.2011,2,244-253；
C.M.Kirschner, A.B.Brennan, Annu.Rev.Mater.Res.2012,42,1-19；M.Schultz,
J.Bendick, E.Holm, W.Hertel, Biofouling 2011,27,87-98；N.Fusetani,
Nat.Prod.Rep.2004,21,94-104；N.Fusetani, Nat.Prod.Rep.2011,28,400-410；P.-
Y.Qian, Y.Xu, N.Fusetani, Biofouling 2010,26,223-234.)
The content of the invention
It is an object of the invention to provide a kind of preparation method and work of the chloro polyketide from coral fungi
For the application of marine antifoulant, it can meet the demand of prior art.Culture presevation information：Depositary institution's title：China
Microbiological Culture Collection administration committee common micro-organisms center；Depositary institution address：Yard 1, BeiChen xi Road, Chaoyang District, Beijing City
No. 3 Institute of Microorganism, Academia Sinica；Preservation date：On April 3rd, 2014；Deposit number：CGMCC8994；Classification And Nomenclature：
Penicillium sp.。
The present invention provides compound of formula I or its pharmaceutically acceptable salt：
Or its pharmaceutically acceptable salt.
Compound of formula I is selected from following compounds：
The present invention provides the preparation method of compound of formula I, it is characterised in that first to fungi in bacterium culture medium
Penicillium sp. (TA33-1) carry out Spawn incubation, then carry out fermented and cultured to the fungi in the fermentation medium, by institute
After mycelium chloroform-methanol mixed liquor (1: 1) extracts and is concentrated under reduced pressure for 3 times, coarse extract is extracted with ethyl acetate 3 times to obtain；Second
After acetoacetic ester coarse extract carries out normal-phase silica gel column chromatography, Sephadex LH-20 gel filtration chromatographies respectively, then it is efficient through HPLC
Liquid phantom preparing chromatogram, gained eluent is concentrated, as compound of formula I.
Bacterium culture medium preferably comprises glucose 0.1%-5.0% (percentage by weight, similarly hereinafter), ferment in above-mentioned preparation method
Female cream 0.01%-1%, peptone 0.01%-1%, agar 0.1%-3.0%, sodium chloride 0.05%-5%, remaining is water, training
Foster temperature is preferably 0-30 DEG C, and incubation time is preferably 3-15 days；Fermentation medium preferably comprises rice 1.0%-80.0% (weights
Measure percentage, similarly hereinafter), sodium chloride 0.05%-5%, remaining is water, and cultivation temperature is preferably 0-30 DEG C, and incubation time is preferably
10-60 days；The preferred 200-300 mesh silica gel of stationary phase that described normal-phase silica gel column chromatography uses, mobile phase preferred volume ratio are
5%-60% ethyl acetate-light petrol mixed solvent；The mobile phase that the Sephadex LH-20 gel filtration chromatographies use is excellent
It is chloroform: methanol=1: 1 mixed solvent to select volume ratio；The chromatographic column used in the HPLC high performance liquid preparative chromatographies is this
Field routine ODS C18 posts, preferably 10 × 250mm of Kromasil, 5 μm, flow velocity is preferably 1.0-5.0mL/min, mobile phase
Preferred volume ratio is 50%-80% Methanol+Water.
The chloro polyketide that the present invention obtains from coral fungi is to marine fouling organism barnacle Balanus
Amphitrite larvas have extremely strong inhibitory activity, available for marine antifoulant is developed, have a extensive future.
Another embodiment of the present invention provides compound of formula I or its pharmaceutically acceptable salt is preparing marine antifoulant
In application.
Term " pharmaceutically acceptable salt " refers to the addition of atoxic inorganic or organic acid and/or alkali in the present invention
Salt.Reference can be made to " Salt selection for basic drugs ", Int.J.Pharm. (1986), 33,201-217.
Embodiment
For the ease of a further understanding of the present invention, examples provided below has done more detailed description to it.But
It is that these embodiments only are not used for limiting the scope of the present invention or implementation principle, reality of the invention for being better understood from inventing
The mode of applying is not limited to herein below.
Embodiment 1
(1) coral source fungi Penicillium sp. (TA33-1) Spawn incubation
Culture medium used in Spawn incubation contains glucose 1.0% (percentage by weight, similarly hereinafter), yeast extract 0.2%, albumen
Peptone 0.2%, agar 1.0%, sodium chloride 3.0%, remaining is water, test tube slant is made during use, fungal bacterial strain is trained at 30 DEG C
Support 3 days.
(2) coral source fungi Penicillium sp. (TA33-1) fermentation
Culture medium used in fermented and cultured contains rice 40.0% (percentage by weight, similarly hereinafter), sodium chloride 3.0%, remaining
For water；Fungal bacterial strain is cultivated 30 days in 28 DEG C.
(3) the extraction separation of compound of formula I
The mycelium for taking 80 bottles of steps (2) to obtain, extracted 3 times after being concentrated under reduced pressure, used with chloroform-methanol mixed liquor (1: 1)
Ethyl acetate extracts 3 times to obtain coarse extract；Ethyl acetate coarse extract carries out normal-phase silica gel column chromatography (stationary phase 200- respectively
300 mesh silica gel；Mobile phase is 70% ethyl acetate/petroleum ether mixed solvent, volume ratio), Sephadex LH-20 gel column layers
After analysing (chloroform: methanol=1: 1 mixed solvent, volume ratio), then (chromatographic column is through the separation of HPLC high performance liquid preparative chromatographies
Kromasil 10 × 250mm, 5 μm, flow velocity 2.0mL/min, mobile phase is 90% Methanol+Water, volume ratio),
Gained eluent is concentrated, obtains yellow solid, as compound of formula I.
The structural identification data of compound of formula I：
Yellow solid；ESI-MS m/z 390.95[M+H]+；Nuclear magnetic resonance
Hydrogen is composed1HNMR (600MHz, CDCl3)δH7.94 (1H, s, H-1), 7.07 (1H, d, J=15.6Hz, H-10), 6.65 (1H, s,
H-4), 6.09 (1H, d, J=15.6Hz, H-9), 5.71 (1H, d, J=9.6Hz, H-12), 2.49 (1H, m, H-13), 2.17
(3H, s, H-20), 1.85 (3H, s, H-17), 1.57 (3H, s, H-18), 1.44 (1H, m, H-14), 1.34 (1H, m, H-14),
1.02 (3H, d, J=6.6Hz, H-16), 0.87 (3H, t, J=7.2Hz, H-15)；Carbon-13 nmr spectra13C NMR (150MHz,
CDCl3) δ C 191.9 (C6), 186.0 (C8), 170.2 (COCH3), 158.2 (C3), 152.7 (C1), 148.9 (C12),
143.0 (C10), 138.8 (C4a), 132.1 (C11), 115.8 (C9), 114.7 (C5), 110.9 (C8a), 106.4 (C4),
84.7 (C7), 35.2 (C13), 30.2 (C14), 22.6 (C18), 20.3 (C16), 20.1 (COCH3), 12.5 (C17), 12.0
(C15).
Embodiment 2
(1) coral source fungi Penicillium sp. (TA33-1) Spawn incubation
Culture medium used in Spawn incubation contains glucose 0.1%-5.0% (percentage by weight, similarly hereinafter), yeast extract
0.01%-1%, peptone 0.01%-1%, agar 0.1%-3.0%, sodium chloride 0.05%-5%, remaining is water, during use
Test tube slant is made, fungal bacterial strain is cultivated 3-15 days at 0-30 DEG C.
(2) coral source fungi Penicillium sp. (TA33-1) fermentation
Culture medium used in fermented and cultured contains rice 1.0%-80.0% (percentage by weight, similarly hereinafter), sodium chloride
0.05%-5%, remaining is water, and fungal bacterial strain is cultivated 10-60 days in 0-30 DEG C.
(3) the extraction separation of compound of formula I
Take obtained by 10-60 bottles step (2) that gained mycelium chloroform-methanol mixed liquor (1: 1) 3 decompressions of extraction is dense
After contracting, coarse extract is extracted with ethyl acetate 3 times to obtain；Normal-phase silica gel column chromatography is carried out respectively after the concentration of ethyl acetate coarse extract
(stationary phase is this area routine purification on normal-phase silica gel, and mobile phase is 15%-40% ethyl acetate-light petrol mixed solvent, volume
Than), after Sephadex LH-20 gel filtration chromatographies (mobile phase is chloroform: methanol=1: 1 mixed solvent, volume ratio), then pass through
(chromatographic column is this area routine ODS C18 posts to HPLC high performance liquid preparative chromatographies, flow velocity 1.0-5.0mL/min, and mobile phase is
50%-80% Methanol+Water, volume ratio), gained eluent is concentrated, obtains yellow solid, as compound of formula I.
The structural identification data of its compounds of formula I is consistent with corresponding data in embodiment 1.
Other Spawn incubations, the fermentation condition not particularly pointed out in embodiment 1-2, and normal phase silica gel column chromatography separation,
Other experimental operating conditions such as the separation of Sephadex LH-20 gel filtration chromatographies, high performance liquid chromatography separation are this area routine
Experimental operating conditions, those skilled in the art can reasonably be selected according to being actually needed.
Embodiment 3
To coral source fungi Penicillium sp. (TA33-1) progress Spawn incubations in bacterium culture medium, then
Fermented and cultured is carried out to the fungi in fermentation medium, by gained filtering fermentation liquor, thalline is removed, after filtrate is concentrated, uses second
Acetoacetic ester extracts；After carrying out normal-phase silica gel column chromatography, Sephadex LH-20 gel filtration chromatographies respectively after extract concentration, then pass through
HPLC high performance liquid preparative chromatographies, gained eluent is concentrated, obtain yellow solid, as compound of formula I, its structural identification data
It is consistent with corresponding data in embodiment 1.Contain glucose, yeast extract, peptone, agar, thick in wherein described bacterium culture medium
Sea salt, water, rice, coarse sea salt, peptone, water are contained in the fermentation medium；Described chromatographic isolation is normal phase silicagel column
Chromatographic isolation, Sephadex LH-20 gel filtration chromatographies and high performance liquid chromatography separation.
In order to explore the method for being widely applied to prepare formula I, bacterium culture medium in the present embodiment,
The addition of each composition in fermentation medium, add in conventional ratio in this area or add in any proportion, during chromatographic isolation
The selection of the specification of used silica gel, the specification of Sephadex LH-20 gels, the model of chromatographic column and eluting solvent, is ability
The conventional selection in domain.Test result indicates that the preparation method of above-mentioned conventional selection, the yellow solid that can be invented, i.e. Formulas I
Compound, its structural identification data is consistent with corresponding data in embodiment 1, only exists individual compound in purity and yield side
The fine difference in face.
Embodiment 1-3 result shows, according to the conventional Spawn incubation in this area, fermentation condition, conventional purification on normal-phase silica gel
Pillar layer separation, the separation of Sephadex LH-20 gel column chromatographies, the condition of high performance liquid chromatography separation are to coral source fungi
Penicillium sp. (TA33-1) carry out Spawn incubation, ferment, isolate and purify, and can obtain the chemical combination of formula I structures
Thing.The preparation method of formula I, the method described in preferred embodiment 1-2.
Embodiment 4
The compound of formula I of the present invention is tested according to following document barnacle Balanus amphitrite larvas attachment activity
Method is tested：Thiyagarajan, V.；Harder, T.；Qiu, J.W.；Qian, P.Y.Mar.Biol. (Berlin) 2003,
143,543-554.
The compound of formula I of the present invention has extremely strong inhibitory activity, its EC to the attachment of barnacle B.amphitrite larvas50Value
For 5.63 μ g/mL, and there is very high security, its LC50More than 50 μ g/mL.Above-mentioned activity is much better than USN's regulation
Potential natural anti-fouling compound EC50The μ g/mL of value 25 standard.This shows compound of formula I or its is pharmaceutically acceptable
Salt can be used for the marine antifoulant for preparing high-efficiency low-toxicity, and coral source fungi Penicillium sp. (TA33-1) can enter
Row large scale fermentation produces, and ensure that the natural origin of compound of formula I, has broad application prospects.
Claims (1)
1. the chloro polyketide or its pharmaceutically acceptable salt of a kind of Formulas I structure are preparing anti-barnacle marine antifoulant side
The application in face,
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| CN106749306B (en) * | 2016-11-30 | 2019-06-07 | 厦门大学 | The application of nancoin and its derivative as marine antifoulant |
| CN108101878B (en) * | 2016-12-22 | 2021-04-09 | 扬州大学 | Azaphilones compounds in marine fungus HK1-6 and application thereof as MRSA resistant drugs |
| CN108676066B (en) * | 2018-05-29 | 2021-09-10 | 深圳大学 | Application and preparation method of compound Malformin C |
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