CN111635316B - Chlorine-containing sesquiterpene derivative and preparation and application thereof - Google Patents
Chlorine-containing sesquiterpene derivative and preparation and application thereof Download PDFInfo
- Publication number
- CN111635316B CN111635316B CN202010447820.0A CN202010447820A CN111635316B CN 111635316 B CN111635316 B CN 111635316B CN 202010447820 A CN202010447820 A CN 202010447820A CN 111635316 B CN111635316 B CN 111635316B
- Authority
- CN
- China
- Prior art keywords
- chlorine
- dichloromethane
- ethanol
- petroleum ether
- culture medium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C69/757—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/62—Carboxylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The invention relates to the field of algae inhibiting agents, in particular to a chlorine-containing sesquiterpene derivative derived from algal 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 marine algae endophytic fungus into a fungus culture medium for fermentation culture, and separating and purifying the fermentation product to obtain the chlorine-containing sesquiterpene derivative shown in formula (I). The half inhibition concentration of the compound on microalgae obtained by the chlorine-containing sesquiterpene derivative through a microalgae inhibition activity experiment can reach 0.83 microgram/ml.
Description
Technical Field
The invention relates to the field of algae inhibiting agents, in particular to a chlorine-containing sesquiterpene derivative derived from algal endophytic fungi, a preparation method thereof and application thereof in algae inhibition.
Background
Worldwide, offshore red tide disasters are increasingly aggravated, and the development of marine fishery, offshore tourism and marine economy is seriously hindered. The main harmful forms of red tide mainly include damage to marine ecological balance, damage to marine fishery resources, damage to human health and influence on the development of marine tourism. There are about 300 species of microalgae that can induce red tide in the ocean, and there are about 80 species of toxic red tide algae. The scientific and effective prevention and treatment of red tide is one of the worldwide problems. The prevention and control 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. can rapidly and effectively kill or inhibit harmful algae or inhibit the growth and reproduction thereof, there are problems of harm to non-red tide organisms, drug residues, secondary pollution to the environment, etc.
Compared with the traditional chemical agents used in the treatment of the red tide, the marine organism-derived natural medicine has the advantages of strong pertinence, high safety, obvious activity and environmental friendliness, and provides a new idea for solving the problem of prevention and treatment of the red tide caused by red tide algae at present.
Disclosure of Invention
The invention aims to provide chlorine-containing sesquiterpene derivatives, and preparation and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a chloro-sesquiterpene derivative has a structure shown in formula (I)
A method for preparing chlorine-containing sesquiterpene derivatives comprises inoculating Trichoderma viride (Trichoderma virens) RR-dl-6-8 in fungus culture medium, fermenting, and purifying to obtain chlorine-containing sesquiterpene derivatives represented by 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 chlorinated sesquiterpene derivative shown in 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 chlorine-containing sesquiterpene derivative in preparing microalgae algistat.
The algistat can be used as one or more of red tide heterocurvatia, strong prorocentrum or prorocentrum donghaiense which cause red tide hazards.
The invention has the following advantages: the chlorine-containing sesquiterpene derivative is obtained by extracting and separating Trichoderma viride (Trichoderma virens) RR-dl-6-8 fermentation separated from marine red algae, namely, the pine node algae, and half inhibitory concentrations of the compound to red tide heterocurvulus, strong pre-ditch algae and east sea protozobium which can cause red tide are respectively 0.87 microgram/ml, 1.5 microgram/ml and 0.83 microgram/ml through a microalgae activity inhibition 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 chlorine-containing sesquiterpene 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 [ alpha ]] 20 D 42(c 0.74, MeOH); hydrogen nuclear magnetic resonance spectrum (deuterated chloroform as solvent) delta H 0.74d (6.9),0.89d (6.9),1.13ddd (14.1,13.9,12.3,3.4),1.32ddd (12.3,10.5,3.2,3.2),1.40ddd (13.9,13.2,3.5),1.63m,1.69dddd (14.1,3.6,3.5,3.2),2.37ddd (13.2,3.6,3.4),2.75d (11.8),2.81ddd (11.8,10.5,10.4),3.63s,3.77s,3.88s,4.31s,6.42d (10.4); nuclear magnetic resonance carbon spectrum (deuterated chloroform as solvent) delta C 15.6CH 3 ,20.4CH 2 ,21.5CH 3 ,28.3CH,35.5CH 2 ,40.2CH,46.4CH,48.6CH 2 ,52.2CH 3 ,52.5CH 3 ,57.5CH 2 57.6CH,72.4CH,133.7C,144.4CH,167.5C, 173.6C; high resolution mass spectrometry [ M ]] + m/z 362.1497, calculated 362.1496.
Example 2
A preparation method of chlorine-containing sesquiterpene derivatives shown in a formula (I) comprises the following steps:
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 is named as Trichoderma virens by classification, and the strain 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 the component 5 with Rf value of 0.6-0.7 (developing with dichloromethane-methanol at volume ratio of 20:1, and developing with anisaldehyde-sulfuric acid), that is, sequentially subjecting the component eluted with petroleum ether-ethyl acetate at volume ratio of 1:1 to reversed phase C 18 Silica gel column, Sephadex LH-20 gel column and preparative thin layer chromatography. Inverse phase C 18 Silica gel column chromatography eluent is water-methanol with volume ratio of 3:2, TLC detection (dichloromethane-methanol with volume ratio of 20:1 is developed, anisaldehyde-sulfuric acid is developed), and anisaldehyde-sulfuric acid is collected to generate grey components; 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 with dichloromethane-methanol at volume ratio of 20:1 as developing agent, and collecting fraction with Rf value of 0.6-0.7 as compound (72.3 mg) shown in formula (I). Detecting by thin layer chromatography (volume ratio of 20:1 dichloromethane-methanol development, anisaldehyde-sulfuric acid color development), and determining as pure compound in the form of single gray spot. The structure is identified as a chlorine-containing sesquiterpene derivative through spectral analysis, and the structural formula is shown as (I).
Example 3
The difference from the embodiment 2 lies in
Taking good Trichoderma viride (Trichoderma virens) RR-dl-6-8 strain growing on a flat plate, cutting into small pieces, inoculating into a jerusalem artichoke glucose liquid culture medium, putting 300 ml of culture medium into each 1L triangular flask, standing and fermenting for 30 days at room temperature in 200 bottles, then extracting for three times by using dichloromethane, concentrating under reduced pressure, and obtaining 100 g of crude extract after concentrating.
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, performing gradient elution sequentially with petroleum ether-ethanol at volume ratios of 50:1, 30:1, 15:1, 10:1, 5:1, 2:1, and 1:1 to 0:1, collecting eluates respectively, detecting by 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 0.6-0.7 (petroleum ether-ethanol with volume ratio of 12:1, developing with anisaldehyde-sulfuric acid), that is, the component eluted by petroleum ether-ethanol with volume ratio of 15:1, sequentially passing through reversed phase C 18 Silica gel column, Sephadex LH-20 gel column and preparative thin layer chromatography. Inverse phase C 18 Silica gel column chromatography eluent is water-ethanol with volume ratio of 2:1, 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 components, performing thin layer chromatography, taking petroleum ether-ethanol with a volume ratio of 12:1 as a developing solvent, and collecting components with an Rf value of 0.6-0.7 to obtain the chlorine-containing sesquiterpene 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) 4 One/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, the sample group was added 5. mu.l of a 4 mg/ml compound solution in dimethyl sulfoxide (DMSO) as the solvent, the blank group was added 5. mu.l of a solvent, and the positive control group was added 5. mu.l of K in 4 mg/ml concentration 2 Cr 2 O 7 And (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. Wherein the microalgae to be tested are red tide heterocurvulus, robusta prokaryote 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 calculated 50 The 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 of 0-100, and calculating IC 50 The value is obtained.
The experimental results are as follows: the obtained chlorinated sesquiterpene derivatives have half inhibitory concentrations of 0.87 microgram/ml, 1.5 microgram/ml and 0.83 microgram/ml for Heterocurus ruber, Praenopsis robusta and Prorocentrum donghaiense, respectively, and have effects of inhibiting Heterocurus ruber, Praenopsis robusta and Prorocentrum donghaiense.
Claims (8)
1. A chloro-sesquiterpene derivative, which is characterized in that: the structure of the chlorine-containing sesquiterpene derivative is shown as the formula (I)
2. A process for the preparation of chloro-sesquiterpene derivatives according to claim 1, wherein: inoculating Trichoderma viride (Trichoderma virens) RR-dl-6-8 into a fungus culture medium for fermentation culture, and purifying a fermentation product to obtain chlorine-containing sesquiterpene 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;
3. the process for the preparation of chlorinated sesquiterpene derivatives according to claim 2, comprising the specific steps of:
1) inoculating Trichoderma viride (Trichoderma virens) RR-dl-6-8 into a fungus culture medium, fermenting for 10-60 days, extracting by using 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 chlorinated sesquiterpene derivative shown in the formula (I).
4. The process for the preparation of chlorine-containing sesquiterpene derivatives of 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. The process for the preparation of chlorine-containing sesquiterpene derivatives of claim 3, wherein: the eluent in the step 2) is one or more groups 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. The process for the preparation of chlorine-containing sesquiterpene derivatives of 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 a chloro-sesquiterpene derivative according to claim 1, wherein: the chlorine-containing sesquiterpene derivative is applied to preparing the algae inhibitor of the microalgae.
8. Use of chlorine-containing sesquiterpene derivatives according to claim 7 wherein: the algistat can inhibit one or more of red tide heterocurvula, robusta or prorocentrum donghaiense which are harmful to red tide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010447820.0A CN111635316B (en) | 2020-05-25 | 2020-05-25 | Chlorine-containing sesquiterpene derivative and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010447820.0A CN111635316B (en) | 2020-05-25 | 2020-05-25 | Chlorine-containing sesquiterpene derivative and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111635316A CN111635316A (en) | 2020-09-08 |
| CN111635316B true CN111635316B (en) | 2022-09-30 |
Family
ID=72324783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010447820.0A Active CN111635316B (en) | 2020-05-25 | 2020-05-25 | Chlorine-containing sesquiterpene derivative and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111635316B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108383707A (en) * | 2018-04-23 | 2018-08-10 | 中国科学院烟台海岸带研究所 | A kind of daucane sesquiterpenoids and its preparation and application |
| CN109956883A (en) * | 2019-04-26 | 2019-07-02 | 中国科学院烟台海岸带研究所 | A kind of acetylation flores aurantii containing azo-cycle alkane type sesquiterpene derivative and its preparation and application |
-
2020
- 2020-05-25 CN CN202010447820.0A patent/CN111635316B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108383707A (en) * | 2018-04-23 | 2018-08-10 | 中国科学院烟台海岸带研究所 | A kind of daucane sesquiterpenoids and its preparation and application |
| CN109956883A (en) * | 2019-04-26 | 2019-07-02 | 中国科学院烟台海岸带研究所 | A kind of acetylation flores aurantii containing azo-cycle alkane type sesquiterpene derivative and its preparation and application |
Non-Patent Citations (4)
| Title |
|---|
| Sesquiterpenes with Phytopathogenic Fungi Inhibitory Activities from Fungus Trichoderma virens from Litchi chinensis Sonn.;Zhibo Hu et al.;《Journal of Agricultural and Food Chemistry》;20190903;第67卷;第10646-10652页 * |
| Sesquiterpenoids from the Endophytic Fungus Rhinocladiella similis;Shuai Liu et al.;《Journal of Natural Products》;20190502;第82卷;第1055-1062页 * |
| 四株海洋藻栖木霉次生代谢产物的结构与活性研究;宋银平;《中国博士学位论文全文数据库基础科学辑》;20190930;第A006-105页 * |
| 松节藻来源长枝木霉DL5-4化学成分及其生物活性研究;邹积雪等;《化学与生物工程》;20190320;第36卷(第3期);第13-17页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111635316A (en) | 2020-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108467337B (en) | Sesquiterpene enol compound and preparation and application thereof | |
| CN109503414B (en) | Nitrogenous ring nerolidine type sesquiterpene derivative and preparation and application thereof | |
| CN108383707B (en) | Carotene sesquiterpene compound and preparation and application thereof | |
| CN108484363B (en) | Sesquiterpene triol compound and preparation and application thereof | |
| CN107586721B (en) | Benzophenone compound with antioxidant activity and preparation method and application thereof | |
| CN109503535B (en) | Bicyclic ring nerolidine type sesquiterpene derivative and preparation and application thereof | |
| CN108373457B (en) | Epoxy sesquiterpenoids and preparation and application thereof | |
| CN109956883B (en) | Acetylated nitrogenous ring nerolidine type sesquiterpene derivative and preparation and application thereof | |
| CN109503413B (en) | Monocyclic ring nerolidine type sesquiterpene derivative and preparation and application thereof | |
| CN109988180B (en) | Diketopiperazine derivative and preparation and application thereof | |
| CN111635316B (en) | Chlorine-containing sesquiterpene derivative and preparation and application thereof | |
| CN109503428B (en) | Cyclonerane hydroxamic acid derivative and preparation and application thereof | |
| CN110862371B (en) | Polycyclic polyketone compound, preparation method thereof and application thereof in preparation of antibacterial drugs | |
| CN108467398B (en) | Diketopiperazine compound and preparation and application thereof | |
| CN116926143A (en) | Aromatic polyketone compound and preparation method and application thereof | |
| CN111606878B (en) | Cadinane derivative and preparation and application thereof | |
| CN110003041B (en) | Cyclonerane acylated derivative and preparation and application thereof | |
| CN109678749B (en) | Cyclonerane type sesquiterpene amide and preparation and application thereof | |
| CN111662257B (en) | Benzencadinane derivative, and preparation and application thereof | |
| CN108640832B (en) | Cadinane sesquiterpenoids, and preparation and application thereof | |
| CN109627192B (en) | Cyclonerane type sesquiterpene derivative and preparation and application thereof | |
| CN113444131B (en) | N-acetylglucosamine compounds, and preparation method and application thereof | |
| CN112111409A (en) | Penicillium oxalicum and application thereof | |
| CN113621526A (en) | Marine fungus Aspergillus versicolor M-7-SW9, mixed source terpenoid and extraction method and application thereof | |
| CN112107602B (en) | A pair of twin-nitrogen containing alkaloid enantiomers, preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |