CN104031955A - Preparation method of dihydroquinolinone alkaloid compound and application thereof as sea antifouling composition - Google Patents
Preparation method of dihydroquinolinone alkaloid compound and application thereof as sea antifouling composition Download PDFInfo
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- CN104031955A CN104031955A CN201410254857.6A CN201410254857A CN104031955A CN 104031955 A CN104031955 A CN 104031955A CN 201410254857 A CN201410254857 A CN 201410254857A CN 104031955 A CN104031955 A CN 104031955A
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Abstract
The invention discloses a preparation method of a dihydroquinolinone alkaloid compound and an application thereof as a sea antifouling composition. The preparation method comprises the steps: during preparation, firstly performing strain culturing on fungus Scopulariopsis sp. (TA01-33), then performing fermental cultivation on the fungus, filtering to remove a thallus, and after concentrating filtrate, extracting with ethyl acetate; sequentially performing normal phase column chromatography on silica gel, Sephadex LH-20 gel column chromatography, and HPLC (High Performance Liquid Chromatography) to obtain the compound shown in a formula I. The invention provides a sea antifouling composition, which is characterized in that the compound shown as the formula I or a salt thereof, provided by the invention is used as an effective ingredient, and used for controlling sea organism antifouling caused by attachment of barnacles.
Description
Technical field
The present invention relates to preparation method and the application of a kind of dihydro-quinolinone (dihydroquinolone) alkaloid compound, particularly relate to a kind of preparation method and application marine fouling organism barnacle Balanus amphitrite larva to the dihydro-quinolinone alkaloid compound of extremely strong inhibition activity.
Background technology
Marine biofouling is that organic molecule, microorganism, animal, plant and their by product gather in the hazardness on subduction facility surface, ocean.This hazardness is gathered the surface that often occurs in the ocean subduction facility that there is no protection, comprises the boats and ships of sea-freight and tourism, naval's warship, heat exchanger, sea sensor and aquaculture base etc.Biodeterioration has caused huge financial loss, only taking United States Navy's warship as example, annual financial loss is in this respect between 18 to 2,600,000,000 dollars, and United States Navy's warship quantity only accounts for 0.5% of global ships quantity, and therefore marine biofouling is extremely serious natural hazard.Barnacle because of its very strong ability of sticking be representativeness biology very general in fouling organism known today.Cancelled after the use of poisonous stain control agent organotin from the whole world in 2008, finding marine antifoulant safely and efficiently becomes the problem of being badly in need of in the world solution.Marine natural product is considered to the important sources of novel sea stain control agent.In fact, in the past few decades in from sponge, in the marine organisms such as coral and marine alga, found much to have the compound of strong anti-fouling activity.But the active compound of finding from above-mentioned macro-organism has affected its potential application greatly owing to being subject to quantitative limitation.Marine microorganism is due to can large scale fermentation in laboratory, survivable physical environment, and become the most important source of activity marine compound.But, there is not yet in recent years the dihydro-quinolinone alkaloid compound that obtains important anti-fouling activity from marine microorganism as the use of stain control 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，Biofouling2011，27，87-98；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，Biofouling2010，26，223-234。)
Summary of the invention
The object of the present invention is to provide a kind of preparation method of the dihydro-quinolinone alkaloid compound that derives from thalassiomycetes with as the application of marine antifoulant, it can meet the demand of prior art.Culture presevation information: depositary institution's title: China Committee for Culture Collection of Microorganisms's common micro-organisms center; Depositary institution address: No. 3, Yard 1, BeiChen xi Road, Chaoyang District, Beijing City Institute of Microorganism, Academia Sinica; Preservation date: on December 17th, 2012; Deposit number: CGMCC6959; Classification And Nomenclature: Scopulariopsis sp..
The invention provides formula I compound or its pharmacy acceptable salt:
R in formula I
1for OH, R
2for H; Or R
1for H, R
2for OH.
Formula I compound is selected from following compounds:
The invention provides the preparation method of formula I compound, it is characterized in that first in bacterium culture medium, carrying out spawn culture to separating from the endogenetic fungus Scopulariopsis of gorgonian Carijoa sp. sp. (TA01-33), in fermention medium, this fungi is carried out to fermentation culture again, then by gained filtering fermentation liquor, remove thalline, after filtrate is concentrated, be extracted with ethyl acetate; After extraction liquid is concentrated, carry out respectively after purification on normal-phase silica gel column chromatography, Sephadex LH-20 gel filtration chromatography, then through HPLC high performance liquid preparative chromatography, gained elutriant is concentrated, be formula I compound.
In above-mentioned preparation method, bacterium culture medium preferably contains glucose 0.1%-5.0% (weight percent, yeast extract paste 0.01%-1%, peptone 0.01%-1%, agar 0.1%-3.0%, sodium-chlor 0.05%-5% down together),, all the other are water, culture temperature is preferably 0-30 DEG C, and incubation time is preferably 3-15 days; Fermention medium preferably contains glucose 0.1%-5.0% (weight percent, yeast extract paste 0.01%-1%, peptone 0.01%-1%, sodium-chlor 0.05%-5% down together),, all the other are water, and culture temperature is preferably 0-30 DEG C, and incubation time is preferably 10-60 days; The preferred 200-300 order of the stationary phase silica gel that described purification on normal-phase silica gel column chromatography adopts, ethyl acetate-sherwood oil mixed solvent that moving phase preferred volume ratio is 15%-40%; The moving phase preferred volume ratio that described Sephadex LH-20 gel filtration chromatography adopts is sherwood oil: chloroform: methyl alcohol=2: the mixed solvent of 1: 1; The chromatographic column adopting in described HPLC high performance liquid preparative chromatography is this area conventional ODS C18 post, is preferably Kromasil10 × 250mm, 7 μ m, and flow velocity is preferably 1.0-5.0mL/min, the Methanol+Water that moving phase preferred volume ratio is 50%-80%.
The dihydro-quinolinone alkaloid compound that the present invention obtains from thalassiomycetes has extremely strong inhibition activity to marine fouling organism barnacle Balanus amphitrite larva, can be used for developing marine antifoulant, has a extensive future.
Another embodiment of the present invention provides formula I compound or its pharmacy acceptable salt in the application of preparing in marine antifoulant.
Term in the present invention " pharmacy acceptable salt " refers to the additive salt of atoxic inorganic or organic acid and/or alkali.Can be referring 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, the embodiment providing has below done more detailed description to it.But these embodiment are only not used for limiting scope of the present invention or implementation principle for better understanding invention, and embodiments of the present invention are not limited to following content.
Embodiment 1
(1) spawn culture of gorgonian endogenetic fungus Scopulariopsis sp. (TA01-33)
Spawn culture substratum used contains glucose 1.0% (weight percent, yeast extract paste 0.2%, peptone 0.2%, agar 1.0%, sodium-chlor 3.0% down together),, all the other are water, make test tube slant when use, and fungal bacterial strain is cultivated 5 days at 30 DEG C.
(2) fermentation of gorgonian endogenetic fungus Scopulariopsis sp. (TA01-33)
Fermentation culture substratum used contains glucose 1.0% (weight percent, lower same), yeast extract paste 0.2%, peptone 0.2%, sodium-chlor 3.0%, and all the other are water; Fungal bacterial strain is cultivated 60 days in 28 DEG C.
(3) extraction of formula I compound separates
Get the filtering fermentation liquor that 10L step (2) obtains, remove thalline, after filtrate is concentrated, with isopyknic ethyl acetate extraction 5 times; (stationary phase is 200-300 order silica gel after extraction liquid is concentrated, to carry out respectively purification on normal-phase silica gel column chromatography; Moving phase is 30% ethyl acetate/petroleum ether mixed solvent, volume ratio), Sephadex LH-20 gel filtration chromatography (sherwood oil: chloroform: methyl alcohol=2: the mixed solvent of 1: 1, volume ratio) after, through the separation of HPLC high performance liquid preparative chromatography, (chromatographic column is Kromasil10 × 250mm again, 7 μ m, flow velocity is 2.0mL/min, moving phase is 75% Methanol+Water, volume ratio), gained elutriant is concentrated, obtain colourless crystallization (compound 1 and 2), be formula I compound.
The structural identification data of formula I compound:
Aflaquinolone F (1)
: clear crystal; Specific rotation light value [α]
25 d=-3.4 (c0.076, MeOH);
1h NMR (600MHz, DMSO-d
6, δ, ppm, J/Hz) and δ 10.30 (s, 1-NH), 7.40 (dd, 8.4,1.8, H-12/16), 7.35 (dd, 7.2,6.6, H-13/15), 7.28 (tt, 7.2,1.2, H-14), 7.21 (td, 7.5,1.2, H-8), 6.92 (dd, 7.8,1.2Hz, H-9), 6.86 (td, 7.6,1.2Hz, H-7), 6.65 (dd, 7.8,1.2Hz, H-6), 4.56 (s, H-3).
13c NMR (150MHz, DMSO-d
6, δ, ppm): 170.5 (C, C-2), 141.8 (C, C-11), 137.3 (C, C-10), 129.3 (C, C-5), 128.8 (CH, C-8), 128.2 (CH, C-6), 127.7 (CH, C-13/15), 127.1 (CH, C-12/16), 126.9 (C-14), 122.0 (CH, C-7), 115.4 (CH, C-9), 77.0 (C, C-4), (74.4 CH, C-3); Mass spectrum EIMSm/z:255[M]
+.
Aflaquinolone G (2)
clear crystal; Specific rotation light value [α]
25 d=+162.7 (c0.011, MeOH);
1h NMR (300MHz, acetone-d
6, δ, ppm, J/Hz): 9.53 (s, 1-NH), 7.62 (dd, 7.5,1.2H-6), 7.36, (m, H-12/16), 7.29 (td, 7.8,1.5, H-8), 7.23-7.16 (m, H-13/15, H-14), 7.10 (td, 7.5,1.6, H-7), 7.04 (d, 7.8, H-9), 4.62 (s, H-3);
13c NMR (75MHz, acetone-d
6): 170.4 (C, C-2), 141.2 (C, C-11), 135.6 (C, C-10), 131.4 (C, C-5), 129.0 (CH, C-8), 127.6 (CH, C-13/15, C-14), 127.4 (CH, C-12/16), 126.8 (CH, C-6), 123.6 (CH, C-7), 115.9 (CH, C-9), 77.2 (C, C-4), 75.6 (CH, C-3); Mass spectrum EIMSm/z:255[M]
+.
Embodiment 2
(1) spawn culture of gorgonian endogenetic fungus Scopulariopsis sp. (TA01-33)
Spawn culture substratum used contains glucose 0.1%-5.0% (weight percent, yeast extract paste 0.01%-1%, peptone 0.01%-1%, agar 0.1%-3.0%, sodium-chlor 0.05%-5% down together),, all the other are water, when use, make test tube slant, fungal bacterial strain is cultivated 3-15 days at 0-30 DEG C.
(2) fermentation of gorgonian endogenetic fungus Scopulariopsis sp. (TA01-33)
Fermentation culture substratum used contains glucose 0.1%-5.0% (weight percent, yeast extract paste 0.01%-1%, peptone 0.01%-1%, sodium-chlor 0.05%-5% down together),, all the other are water, and fungal bacterial strain is cultivated 10-60 days in 0-30 DEG C.
(3) extraction of formula I compound separates
Get the filtering fermentation liquor of 5-50L step (2) gained, remove thalline, filtrate is concentrated after, with the ethyl acetate extraction of 1-3 times of volume 2-5 time, (stationary phase is the conventional purification on normal-phase silica gel in this area after extraction liquid is concentrated, to carry out respectively purification on normal-phase silica gel column chromatography, moving phase is ethyl acetate-sherwood oil mixed solvent of 15%-40%, volume ratio), (moving phase is sherwood oil to Sephadex LH-20 gel filtration chromatography: chloroform: methyl alcohol=2: the mixed solvent of 1: 1, volume ratio) after, through HPLC high performance liquid preparative chromatography, (chromatographic column is this area conventional ODS C18 post again, flow velocity is 1.0-5.0mL/min, moving phase is the Methanol+Water of 50%-80%, volume ratio), gained elutriant is concentrated, obtain colourless crystallization (compound 1 and 2), be formula I compound.The structural identification data of its Chinese style I compound are consistent with corresponding data in embodiment 1.
Other spawn culture, the fermentation condition that in embodiment 1-2, specifically do not indicate, and other experimental implementation conditions such as normal phase silica gel column chromatography separation, the separation of Sephadex LH-20 gel filtration chromatography, high performance liquid chromatography separation are the experimental implementation condition of this area routine, those skilled in the art can according to actual needs, reasonably select.
Embodiment 3
In bacterium culture medium, thalassiomycetes Scopulariopsis sp. (TA01-33) is carried out to spawn culture, in fermention medium, this fungi is carried out to fermentation culture again, by gained filtering fermentation liquor, remove thalline, after filtrate is concentrated, be extracted with ethyl acetate; After extraction liquid is concentrated, carry out respectively after purification on normal-phase silica gel column chromatography, Sephadex LH-20 gel filtration chromatography, again through HPLC high performance liquid preparative chromatography, gained elutriant is concentrated, obtain 2 clear crystals (compound 1 and 2), be formula I compound, its structural identification data are consistent with corresponding data in embodiment 1.In wherein said bacterium culture medium, contain glucose, yeast extract paste, peptone, agar, thick sea salt, water, in described fermention medium, contain rice, thick sea salt, peptone, water; Described chromatographic separation is that normal phase silica gel column chromatography separates, Sephadex LH-20 gel filtration chromatography separates and separates with high performance liquid chromatography.
In order to explore the method that is applicable to widely prepare formula I compound of the present invention, the interpolation of each composition in bacterium culture medium, fermention medium in the present embodiment, all add or add in any proportion in conventional ratio in this area, specification, the model of chromatographic column and the selection of eluting solvent of the specification of used silica gel, Sephadex LH-20 gel when chromatographic separation, the routine that is this area is selected.Experimental result shows, the above-mentioned conventional preparation method who selects all can obtain 2 clear crystals of invention, i.e. formula I compound, and its structural identification data are consistent with corresponding data in embodiment 1, only have the fine difference of individual compound aspect purity and yield.
The result of embodiment 1-3 shows, according to the spawn culture of this area routine, fermentation condition, the condition that conventional normal phase silica gel column chromatography separates, Sephadex LH-20 gel column chromatography separates, high performance liquid chromatography separates is carried out spawn culture, fermentation, separation and purification to thalassiomycetes Scopulariopsis sp. (TA01-33), all can obtain the compound of formula I structure of the present invention.The preparation method of formula I compound of the present invention, the method for recording in preferred embodiment 1-2.
Embodiment 4
Formula I compound of the present invention is tested according to following literature method test barnacle Balanus amphitrite larva attachment activity: Thiyagarajan, V.; Harder, T.; Qiu, J.W.; Qian, P.Y.Mar.Biol. (Berlin) 2003,143,543-554.
1 and 2 pairs of barnacle B.amphitrite larvas of compound of the present invention adhere to and have extremely strong inhibition activity, its EC
s0value is 0.22 and 22.5 μ g/mL, its median lethal concentration (LC
50) be all greater than 50 μ g/mL, show that the inhibition activity that kentrogon is adhered to is high, and low to the toxicity of kentrogon, there is the feature of high-efficiency low-toxicity.
The invention provides a kind of marine organisms stain control agent, it is characterized in that using formula I dihydro-quinolinone alkaloid compound or its salt as effective constituent, adhere to for preventing and treating barnacle the marine biofouling causing, and raw material can carry out scale operation by fungi fermentation, be not subject to resource limit, therefore have a extensive future.
Claims (6)
1. the preparation method of the dihydro-quinolinone alkaloid compound of a formula I structure, it is characterized in that comprising the following steps: first in bacterium culture medium, fungi Scopulariopsis sp. (TA01-33) is carried out to spawn culture, in fermention medium, this fungi is carried out to fermentation culture again, by gained filtering fermentation liquor, remove thalline, after filtrate is concentrated, be extracted with ethyl acetate; After extraction liquid is concentrated, carry out respectively after purification on normal-phase silica gel column chromatography, Sephadex LH-20 gel filtration chromatography, then through HPLC high performance liquid preparative chromatography, gained elutriant is concentrated, obtain formula I compound; Its Chinese style I compound structure is:
r
1for OH, R
2for H; Or R
1for H, R
2for OH; In wherein said bacterium culture medium, contain glucose, yeast extract paste, peptone, agar, thick sea salt, water; In described fermention medium, contain glucose, yeast extract paste, peptone, agar, thick sea salt, water; Described chromatographic separation is that normal phase silica gel column chromatography separates, Sephadex LH-20 gel filtration chromatography separates and separates with high performance liquid chromatography.
2. preparation method as claimed in claim 1, it is characterized in that described bacterium culture medium preferably contains glucose 0.1%-5.0%, yeast extract paste 0.01%-1%, peptone 0.01%-1%, agar 0.1%-3.0%, sodium-chlor 0.05%-5%, all the other are water, above-mentioned percentage composition is all weight percentage, culture temperature is preferably 0-30 DEG C, and incubation time is preferably 3-15 days.
3. preparation method as claimed in claim 1, it is characterized in that described fermention medium preferably contains glucose 0.1%-5.0%, yeast extract paste 0.01%-1%, peptone 0.01%-1%, sodium-chlor 0.05%-5%, all the other are water, above-mentioned percentage composition is all weight percentage, culture temperature is preferably 0-30 DEG C, and incubation time is preferably 10-60 days.
4. the preparation method as described in claim 2-3 any one, is characterized in that the stationary phase that described purification on normal-phase silica gel column chromatography adopts is 200-300 order silica gel, and moving phase is that volume ratio is ethyl acetate-sherwood oil mixed solvent of 15%-40%; The moving phase that described SephadexLH-20 gel filtration chromatography adopts is that volume ratio is sherwood oil: chloroform: methyl alcohol=2: the mixed solvent of 1: 1; The chromatographic column adopting in described HPLC high performance liquid preparative chromatography is Kromasil10 × 250mm, 7 μ m, and flow velocity is 1.0-5.0mL/min, moving phase is the Methanol+Water of volume ratio 50%-80%.
5. a marine organisms stain control agent, is characterized in that it contains formula I compound claimed in claim 1 or its pharmacy acceptable salt as effective constituent.
6. formula I compound claimed in claim 1 or its pharmacy acceptable salt are in the application of preparing in marine antifoulant.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108658975A (en) * | 2017-03-28 | 2018-10-16 | 中国海洋大学 | A kind of nitrogenous compound and preparation method thereof and application as marine antifoulant |
| CN108658974A (en) * | 2017-03-28 | 2018-10-16 | 中国海洋大学 | A kind of lactam analog compound and its preparation method and application |
| CN108658973A (en) * | 2017-03-28 | 2018-10-16 | 中国海洋大学 | A kind of lactam analog compound and preparation method thereof and purposes as marine antifoulant |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554018A (en) * | 2013-10-17 | 2014-02-05 | 中国海洋大学 | Dihydroquinolone alkaloid compound as well as crystal, preparation method and application thereof as marine anti-fouling agent |
| CN103554090A (en) * | 2013-10-15 | 2014-02-05 | 中国海洋大学 | Terpenoid dihydroquinolone alkaloid compound as well as crystal, preparation method and application thereof as marine anti-fouling agent |
| CN103570744A (en) * | 2013-04-07 | 2014-02-12 | 中国海洋大学 | Quinazoline alkaloid compound, preparation method thereof and application of quinazoline alkaloid compound as tumor cell growth inhibitor |
-
2014
- 2014-06-06 CN CN201410254857.6A patent/CN104031955B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103570744A (en) * | 2013-04-07 | 2014-02-12 | 中国海洋大学 | Quinazoline alkaloid compound, preparation method thereof and application of quinazoline alkaloid compound as tumor cell growth inhibitor |
| CN103554090A (en) * | 2013-10-15 | 2014-02-05 | 中国海洋大学 | Terpenoid dihydroquinolone alkaloid compound as well as crystal, preparation method and application thereof as marine anti-fouling agent |
| CN103554018A (en) * | 2013-10-17 | 2014-02-05 | 中国海洋大学 | Dihydroquinolone alkaloid compound as well as crystal, preparation method and application thereof as marine anti-fouling agent |
Non-Patent Citations (3)
| Title |
|---|
| SCOTT A. NEFF: "Aflaquinolones A–G: Secondary Metabolites from Marine and Fungicolous Isolates of Aspergillus Spp.", 《J NAT PROD.》 * |
| 周世伟等: "天然产物防除海洋污损生物的研究进展", 《天然产物研究与开发》 * |
| 胥汝芳: "柳珊瑚来源的一株真菌中生物碱化合物及其生物活性", 《中国优秀硕士学位论文全文数据库，医药卫生科技辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108658975A (en) * | 2017-03-28 | 2018-10-16 | 中国海洋大学 | A kind of nitrogenous compound and preparation method thereof and application as marine antifoulant |
| CN108658974A (en) * | 2017-03-28 | 2018-10-16 | 中国海洋大学 | A kind of lactam analog compound and its preparation method and application |
| CN108658973A (en) * | 2017-03-28 | 2018-10-16 | 中国海洋大学 | A kind of lactam analog compound and preparation method thereof and purposes as marine antifoulant |
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