CN111606878A - Cadinane derivative and preparation and application thereof - Google Patents
Cadinane derivative and preparation and application thereof Download PDFInfo
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- CN111606878A CN111606878A CN202010448394.2A CN202010448394A CN111606878A CN 111606878 A CN111606878 A CN 111606878A CN 202010448394 A CN202010448394 A CN 202010448394A CN 111606878 A CN111606878 A CN 111606878A
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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- C12P17/00—Preparation of heterocyclic carbon compounds with only O, N, S, Se or Te as ring hetero atoms
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Abstract
The invention relates to the field of algae inhibitors, in particular to a cadinane derivative derived from seaweed endophytic fungi, a preparation method thereof and application thereof in algae inhibition. The preparation method comprises inoculating Trichoderma viride (Trichoderma virens) RR-dl-6-8 of algae endophytic fungi into a fungus culture medium for fermentation culture, and separating and purifying the fermentation product to obtain the cadinane derivative shown in formula (I). The compound obtained by the invention has half inhibitory concentration of 1.5 microgram/ml on microalgae through a microalgae inhibition activity experiment.
Description
Technical Field
The invention relates to the field of algae inhibitors, in particular to a cadinane derivative derived from seaweed endophytic fungi, a preparation method thereof and application thereof in algae inhibition.
Background
After 2000, China enters the high-incidence period of red tide, and the incidence frequency and the harm degree of the red tide are obviously increased. The main harm forms of red tide are four, namely, the ecological balance of the ocean is destroyed; secondly, marine fishery resources are damaged; thirdly, the health of human beings is harmed; and fourthly, the development of marine tourism industry is influenced. Red tide disasters seriously affect the development of marine fishery, offshore travel and marine economy. Statistically, the economic loss caused by red tide is more than 10 billion yuan each year. The scientific and effective prevention and treatment of red tide is one of the worldwide problems.
At present, the prevention and treatment strategy of red tide is to prevent the eutrophication of seawater, and also to inhibit the development of red tide organisms, namely red tide algae, and the method for inhibiting the development of the red tide algae is mainly chemical treatment. Although chemical agents such as copper sulfate, chlorine gas, etc. rapidly and effectively kill or inhibit harmful algae or inhibit their growth and reproduction, there are problems of damage to non-red tide organisms, drug residues, secondary pollution to the environment, etc.
Disclosure of Invention
The invention aims to provide a cadinane derivative, and preparation and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a cadinane derivative has a structure shown in formula (I)
A method for preparing a cadinane derivative comprises inoculating Trichoderma viride (Trichoderma virens) RR-dl-6-8 into a fungus culture medium, fermenting, and purifying the fermentation product to obtain the cadinane derivative shown in formula (I); the Trichoderma viride (Trichoderma virens) RR-dl-6-8 is preserved in the China Center for Type Culture Collection (CCTCC) in 2018, 6 months and 27 days, and the preservation number is CCTCC M2018406.
The method specifically comprises the following steps:
1) inoculating Trichoderma viride (Trichoderma virens) RR-dl-6-8 into a fungus culture medium, fermenting for 10-60 days, extracting by an organic solvent and concentrating to obtain a crude extract;
2) subjecting the crude extract obtained in the step 1) to silica gel column chromatography, performing gradient elution by using an organic solvent, collecting eluent, and detecting the eluent by thin layer chromatography;
3) collecting the eluted components in the step 2), and sequentially carrying out reversed phase silica gel column chromatography, gel column chromatography and preparative thin layer chromatography for separation and purification to obtain the cadinane derivative shown as the formula (I).
The fungus culture medium in the step 1) is a rice solid culture medium, a jerusalem artichoke glucose liquid culture medium or a potato glucose liquid culture medium.
The organic solvent extract is one or more of ethyl acetate, petroleum ether, n-hexane, cyclohexane, dichloromethane, methanol, ethanol, propanol or isopropanol.
The organic solvent in the step 2) is one or more of petroleum ether-ethyl acetate, petroleum ether-ethanol, petroleum ether-propanol, petroleum ether-isopropanol, dichloromethane-ethyl acetate, dichloromethane-methanol, dichloromethane-ethanol, dichloromethane-propanol and dichloromethane-isopropanol in a volume ratio of 50-0: 1.
The developing solvent for thin layer chromatography is one or more of petroleum ether-ethyl acetate, petroleum ether-ethanol and dichloromethane-methanol in a volume ratio of 100-0: 1.
The reverse phase silica gel column chromatography eluent in the step 3) is water-methanol or water-ethanol with the volume ratio of 5-0: 1; the eluent of the gel column chromatography is dichloromethane-methanol or dichloromethane-ethanol with the volume ratio of 2-0: 1; the thin layer chromatography developing solvent is prepared from dichloromethane-methanol or petroleum ether-ethanol with the volume ratio of 30-0: 1.
An application of a cadinane derivative in preparing an algicide for microalgae.
The algistat can be used as one or more of red tide heterocurvulus and prorocentrum donghaiense causing red tide hazards.
The invention has the following advantages: the invention obtains the cadinane derivative by fermenting, extracting and separating Trichoderma viride (Trichoderma virens) RR-dl-6-8 separated from marine red algae, namely, Arthrospira matsuensis, wherein half inhibition concentrations of the compound to red tide heterocurvulus and east sea protozobium which can cause red tide are respectively 1.5 microgram/ml and 2.4 microgram/ml through a microalgae inhibition activity experiment.
The specific implementation mode is as follows:
the invention is further illustrated below with reference to the examples of embodiment.
Example 1
The structure of the cadinane derivative derived from the seaweed endophytic fungi is shown as a formula (I).
The compound has the following physicochemical and spectral characteristics:
colorless oil, specific optical rotation [ α]20 D122(c 0.050, MeOH); nuclear magnetic resonance hydrogen spectrum (deuterium substituted chloroform as solvent)H0.96d (6.8),1.14d (7.4),1.28dddd (13.0,13.0,11.4,4.5),1.36dddd (13.0,13.0,10.6,3.6),1.58m,1.63m,1.85ddd (11.4,6.3,6.3),1.89dd (8.7,3.5),2.04m,2.37ddd (17.4,7.2,1.8),2.66ddd (17.4,5.5,1.6),2.73m,3.55dd (10.4,8.3),3.74s,4.09 (8.3 ),4.15ddd (8.7,7.2,5.5),6.93dd (1.8, 1.6); nuclear magnetic resonance carbon spectrum (deuterated chloroform as solvent)C11.6CH3,21.0CH3,23.4CH2,27.5CH2,29.9CH,35.2CH2,36.8CH,43.8CH,48.9CH,52.0CH3,68.5CH,71.8CH285.5C,126.8C,143.3CH, 167.4C; high resolution mass spectrometry [ M ]]+m/z 280.1676, calculated 280.1675.
Example 2
A process for the preparation of a cadinane derivative of the formula (I):
taking good Trichoderma viride (Trichoderma virens) RR-dl-6-8 strain growing on a plate, cutting into small pieces, inoculating the small pieces into a rice solid culture medium, putting 50 g of the rice solid culture medium into each 1L triangular flask, standing and fermenting for 40 days at room temperature in 200 bottles, extracting for three times by using ethyl acetate, concentrating under reduced pressure, and obtaining 134.6 g of crude extract after concentrating.
The rice solid medium comprises 500 g of rice, 6 g of peptone, 500 ml of distilled water and 500 ml of aged seawater per liter.
Trichoderma viride (Trichoderma virens) RR-dl-6-8 strain was deposited in the China center for type culture Collection CCTCC at 27 months 6 in 2018, address: the preservation number of the university of Wuhan, China is CCTCC M2018406, the university of Wuhan is classified and named as Trichoderma virens, and the plant number is RR-dl-6-8.
Subjecting the crude extract to 100-mesh 200-mesh silica gel column chromatography, performing gradient elution with petroleum ether-ethyl acetate and dichloromethane-methanol in volume ratios of 50:1, 20:1, 10:1, 5:1, 2:1, 1:1 to 0:1 and 20:1, 10:1, 5:1, 2:1 to 0:1 in sequence, collecting eluates respectively, detecting the collected components by Thin Layer Chromatography (TLC) (dichloromethane-methanol in volume ratio of 50-1:1 is developed, and anisaldehyde-sulfuric acid is developed), judging and combining the same or similar parts according to Rf value to obtain 8 components (1-8).
Developing component 5 with Rf value of 0.5-0.6 (volume ratio of 20:1 dichloromethane-methanol, anisaldehyde-sulfuric acid color development), that is, eluting component with petroleum ether-ethyl acetate gradient of volume ratio of 1:1, sequentially passing through reversed phase C18Silica gel column, SephadexLH-20 gel column and preparative thin layer chromatography. Inverse phase C18Eluting with silica gel column chromatography with 11:9 water-methanol by TLC detection (dichloromethane-methanol at 20:1 volume ratio for development, anisaldehyde-sulfuric acid for color development), and collecting the grey anisaldehyde-sulfuric acid component; collecting eluate of the fraction by Sephadex LH-20 gel column chromatography, detecting by TLC (dichloromethane-methanol at volume ratio of 20:1 is developed, anisaldehyde-sulfuric acid is developed), and collecting the grey fraction of anisaldehyde-sulfuric acid; collecting fractions, performing thin layer chromatography, and collecting fraction with Rf value of 0.5-0.6 (1.0 mg) with dichloromethane-methanol at volume ratio of 20:1 as developing agent. The compound is determined to be pure by thin layer chromatography detection (volume ratio is 20:1 dichloromethane-methanol development, anisaldehyde-sulfuric acid color development) and shows single gray spots. The structure of the derivative is identified as a cadinane derivative through spectral analysis, and the structural formula is shown as (I).
Example 3
The difference from the embodiment 2 is that
Collecting good Trichoderma viride (Trichoderma virens) RR-dl-6-8 strain growing on the plate, cutting into small pieces, inoculating into Jerusalem artichoke glucose liquid culture medium, placing 300 ml of culture medium in each 1L triangular flask, standing and fermenting for 30 days at room temperature, extracting with dichloromethane for three times, concentrating under reduced pressure, and concentrating to obtain 100 g of crude extract.
The jerusalem artichoke glucose liquid culture medium comprises 500 ml of boiling juice containing 200 g of jerusalem artichoke tubers per liter, 20 g of glucose, 5 g of peptone and 500 ml of aged seawater.
Subjecting the crude extract to 200-300 mesh silica gel column chromatography, gradient eluting sequentially with petroleum ether-ethanol at volume ratio of 50:1, 30:1, 15:1, 10:1, 5:1, 2:1, 1:1 to 0:1, collecting eluates respectively, detecting with thin layer chromatography (petroleum ether-ethanol at volume ratio of 50-0:1 is developed, and anisaldehyde-sulfuric acid is developed), and judging and combining the same or similar parts according to Rf value to obtain 8 components (1-8).
Developing the component 3 with Rf value of 0.5-0.6 (petroleum ether-ethanol with volume ratio of 12:1, and anisaldehyde-sulfuric acid developing), that is, the component eluted by petroleum ether-ethanol with volume ratio of 15:1, sequentially passing through reversed phase C18Silica gel column, Sephadex LH-20 gel column and preparative thin layer chromatography. Inverse phase C18Silica gel column chromatography eluent is water-ethanol with volume ratio of 3:2, TLC detection (petroleum ether-ethanol with volume ratio of 12:1 is developed, anisaldehyde-sulfuric acid is developed), and anisaldehyde-sulfuric acid is collected to give gray component; collecting eluate after Sephadex LH-20 gel column chromatography, detecting by TLC (petroleum ether-ethanol development at volume ratio of 12:1, and anisaldehyde-sulfuric acid color development), and collecting the grey anisaldehyde-sulfuric acid component; collecting the components, performing thin layer chromatography, using petroleum ether-ethanol with a volume ratio of 12:1 as a developing agent, and collecting the components with Rf value of 0.5-0.6 to obtain the cadinane derivative shown in formula (I).
Example 4
Microalgae inhibition activity experiment:
specifically, the method comprises activating microalgae to be tested, collecting microalgae in logarithmic growth phase, and diluting with sterilized f/2 culture medium to a certain cell concentration (about 5 × 10)4One/ml), take 96-well plate, add 195 microliter algae solution per well as test culture plate. The sample group and the control group were each set in triplicate, and 5. mu.l of a 4 mg/ml solution of the compound in dimethyl sulfoxide (dimethyl sulfoxide) (II)DMSO), blank control with 5 microliters of solvent, positive control with 5 microliters of K at a concentration of 4 mg/ml2Cr2O7And (3) solution. The culture temperature is 20 ℃, the illumination intensity is 2000Lux, and the light-dark ratio is 14:10 (h), and the culture is carried out for 24 h. The microalgae to be tested are red tide heterocurvula and prorocentrum donghaiense.
Counting microalgae in each experimental group under a microscope by using a blood counting plate. For the experimental group with the inhibition rate of more than 50%, the half inhibition concentration IC is further calculated50The value is obtained. The prepared compound solutions with final concentrations of 4 mg/ml were sequentially diluted to finally obtain 15 groups of sequentially reduced concentrations of components (1000, 500, 200, 100, 50, 20, 10, 5, 2,1, 0.5, 0.25, 0.125, 0.0625, 0.03125 μ g/ml). Observing and calculating microalgae inhibition rate of the compound under each concentration gradient, taking at least 5 concentration gradients with the inhibition rate between 0 and 100, and calculating IC50The value is obtained.
The experimental results are as follows: the obtained cadinane derivative has half inhibitory concentrations of 1.5 microgram/ml and 2.4 microgram/ml for red tide heterocurvatia and prorocentrum donghaiense, and has effects of inhibiting red tide heterocurvatia and prorocentrum donghaiense.
Claims (8)
1. A cadinane derivative characterized by: the structure of the cadinane derivative is shown as the formula (I)
2. A process for producing the cadinane derivative according to claim 1, which comprises: inoculating Trichoderma viride (Trichoderma virens) RR-dl-6-8 into a fungus culture medium for fermentation culture, and purifying a fermentation product to obtain the cadinane derivative shown in the formula (I); the Trichoderma viride (Trichoderma virens) RR-dl-6-8 is preserved in the China Center for Type Culture Collection (CCTCC) in 2018, 6 months and 27 days, and the preservation number is CCTCC M2018406;
3. the process for the preparation of a cadinane derivative according to claim 2, which comprises the steps of:
1) inoculating Trichoderma viride (Trichoderma virens) RR-dl-6-8 into a fungus culture medium, fermenting for 10-60 days, extracting by an organic solvent and concentrating to obtain a crude extract;
2) subjecting the crude extract obtained in the step 1) to silica gel column chromatography, performing gradient elution by using an organic solvent, collecting eluent, and detecting the eluent by thin layer chromatography;
3) collecting the eluted components in the step 2), and sequentially carrying out reversed phase silica gel column chromatography, gel column chromatography and preparative thin layer chromatography for separation and purification to obtain the cadinane derivative shown as the formula (I).
4. A process for the preparation of a cadinane derivative according to claim 3, wherein: the fungus culture medium in the step 1) is a rice solid culture medium, a jerusalem artichoke glucose liquid culture medium or a potato glucose liquid culture medium;
the organic solvent extract is one or more of ethyl acetate, petroleum ether, n-hexane, cyclohexane, dichloromethane, methanol, ethanol, propanol or isopropanol.
5. A process for the preparation of a cadinane derivative according to claim 3, wherein: the organic solvent in the step 2) is one or more of petroleum ether-ethyl acetate, petroleum ether-ethanol, petroleum ether-propanol, petroleum ether-isopropanol, dichloromethane-ethyl acetate, dichloromethane-methanol, dichloromethane-ethanol, dichloromethane-propanol and dichloromethane-isopropanol in a volume ratio of 50-0: 1.
6. A process for the preparation of a cadinane derivative according to claim 3, wherein: the reverse phase silica gel column chromatography eluent in the step 3) is water-methanol or water-ethanol with the volume ratio of 5-0: 1; the eluent of the gel column chromatography is dichloromethane-methanol or dichloromethane-ethanol with the volume ratio of 2-0: 1; the thin layer chromatography developing solvent is prepared from dichloromethane-methanol or petroleum ether-ethanol with the volume ratio of 30-0: 1.
7. Use of the cadinane derivative of claim 1, wherein: the application of the cadinane derivative in preparing an algistat for microalgae is provided.
8. Use of a cadinane derivative according to claim 7, wherein: the microalgae are red tide heterocurvula and/or prorocentrum donghaiense causing red tide hazards.
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