CN105601638A - Chlorophyllin derivative and preparation method thereof and application of chlorophyllin derivative to bacteriostasis and insect disinfestation - Google Patents
Chlorophyllin derivative and preparation method thereof and application of chlorophyllin derivative to bacteriostasis and insect disinfestation Download PDFInfo
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- CN105601638A CN105601638A CN201610060252.2A CN201610060252A CN105601638A CN 105601638 A CN105601638 A CN 105601638A CN 201610060252 A CN201610060252 A CN 201610060252A CN 105601638 A CN105601638 A CN 105601638A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
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- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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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
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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Abstract
The invention relates to a chlorophyllin derivative and a preparation method thereof and application of the chlorophyllin derivative serving as a photosensitive bacteriostatic agent and insecticide to bacteriostasis and insect disinfestation. The chemical structure general formula of the derivative is shown as follows. According to the derivative, silkworm excrement serves as a raw material, chlorophyll is extracted from the silkworm excrement and is heated and hydrolyzed under a concentrated alkali condition, metallic magnesium ions are removed under an acidic condition, hydrophobic phytol side chains are removed through hydrolysis, and then the chlorophyllin derivative is obtained after modification. The chlorophyllin derivative is high in photosensitivity and high in quantum yield, and has 2 or 3 wavelengths to be selected, the selectivity of anti-pathogen microorganisms of a photosensitizer is improved, and obvious inhabitation and poisoning effects are achieved for bacillus subtilis, escherichia coli, forestry pathogens (fusarium oxysporum) and gypsy moths; the chlorophyllin derivative can be degraded in an environment, cannot pollute the environment, and is a true environment-friendly plant source bacteriostatic agent and insecticide. The general formula is shown in the description.
Description
Technical field
The present invention relates to a kind of phyllins, particularly relate to a kind of chlorophyllin derivative, its preparation method and as photosensitive bacteriostatic agent, photosensitiveThe application of pesticide.
Background technology
The required chlorophyll of human survival belongs to magnesium porphyrin compound, after the magnesium ion at chlorophyll porphyrin ring center is replaced with other metal ionTo phyllins product, as Copper chlorophyllin sodium salt, calcium chlorophyllin sodium salt, sodium cobalt chlorophyllin salt, iron chlorophyllin sodium salt etc., have good paintedEffect, promote hematopoiesis, protect the liver, antimicrobial, promote the biological natures such as wound and ulcer healing and anti-sudden change and unique pharmacological function, be easy to byAbsorption of human body, and have no side effect, be widely used in medicine, food, daily-use chemical industry and clinical. Some derivative of chlorophyll or effectively lightQuick dose, for example in light power tumor therapy as sensitising agent. Prove that porphyrin can accumulate in tumor tissues, in the time of irradiation tumor tissues,Due to porphyrin extinction on the spot, so determine that its fluorescence position just becomes a kind of method of lesion detection.
Light power antimicrobial chemical therapy (PhotodynamicAntimicrobialChemotherapy, PACT) is in conjunction with photosensitizer molecule and visibleThe active oxygen species that light produces carries out deactivation a kind of antibiotic method to pathogenic microorganism, the PDT of its mechanism of action and cancer is similar, but rightThe research of PACT and application are forgotten by people gradually because of antibiotic discovery, are not well applied. Sensitising agent is at light power antimicrobial chemicalIn therapy, occupy considerable status. Sensitising agent, under aerobic and illumination condition, can absorb photon, first transits to singlet state, alters between being thenTo triplet, and substrate generation electronics or hydrogen atom transfer, produce free radical or radical ion, then kill order by the oxidation to substrateMark molecule.
In recent years, due to the caused toxic and side effect of abuse of antibiotics, the destruction of natural microorganisms group and the appearance of drug-fast bacteria, make antibioticDrug effect reduces gradually, and directly and serious harm health indirectly and environment. Thereby, if can, taking natural plants as raw material, extract leaf greenElement, and to its modification, make novel degradable chlorophyll base photosensitizer, and be applied to antibacterial, desinsection field, seem particularly important.
Summary of the invention
Object of the present invention aims to provide a kind of chlorophyllin derivative, its preparation method and the application as photosensitive bacteriostatic agent, photosensitive pesticide. ThisChlorophyll is extracted in bright employing from silkworm excrement, and then heating hydrolysis under concentrated base condition sloughs magnesium metal ion under acid condition, simultaneously by hydrolysisRemove the green phytol side chain of hydrophobicity leaf, and and then its modification is obtained to chlorophyllin derivative. This chlorophyllin derivative light sensitivity is high, quantum yield is high,Have 2-3 wavelength available simultaneously, improved the selective of sensitising agent resisting pathogenic microbes.
In order to realize foregoing invention object, the present invention has adopted following technical scheme:
Chlorophyllin derivative of the present invention, its chemical structure of general formula is as follows,
Wherein, R1、R2、R3Be selected from hydrogen atom, alkyl, carboxyl ,-OH or-NH2Group, R1、R2、R3Can be the same or different.
Preferably, R1For OCH3，R2For OCH3,R3For CH3; Or R1For NH2，R2For NH2,R3For H.
The preparation method of chlorophyllin derivative of the present invention, comprises the steps:
(1) taking silkworm excrement as raw material, extract chlorophyll a, after fully dissolving, add concentrated alkali solution in solvent, the water bath with thermostatic control that is placed in uniform temperature is stirredMix certain hour, after it is fully hydrolyzed, leave standstill;
(2) the sediment suction filtration that will obtain from step (1), is dissolved in the water, and uses petroleum ether extraction 3-5 time; Adjust molten with certain density acid againThe pH=1 left and right of liquid, room temperature is placed 2 hours, has Precipitation, crosses leaching precipitation, with distilled water washing precipitation 1-2 time, blackish greenly dryChlorophyllin solid;
(3) by the further esterification of chlorophyllin or the amidatioon of step (2) gained, obtain corresponding chlorophyllin derivative.
Preferably, in described step (3), described chlorophyllin reacts under acid catalysis with methyl alcohol, obtains R1For OCH3，R2For OCH3,R3For CH3Chlorophyllin Ester derivative.
Preferably, in described step (3), described chlorophyllin reacts with ammoniacal liquor, obtains R1For NH2，R2For NH2,，R3For the chlorophyllin of HAmide derivatives.
Chlorophyllin derivative of the present invention is as the purposes of photosensitive bacteriostatic agent, photosensitive pesticide, and preferred, this chlorophyllin derivative is used for the treatment of partBacterium infects, and control forestry pathogen, forest disease and pest, also can be used in coating, to reduce the environment of load of microorganisms sensitivity.
Beneficial effect of the present invention is:
1. the present invention, taking silkworm excrement as raw material, makes chlorophyllin derivative, and this chlorophyllin derivative is more satisfactory photosensitive bacteriostatic agent, pesticide, itLight sensitivity is high, quantum yield is high, have 2-3 wavelength available simultaneously, has improved the selective of sensitising agent resisting pathogenic microbes, damage by forest-insects;
2. chlorophyllin derivative is equal to bacillus subtilis, Escherichia coli, forestry pathogen (Fusarium oxysporum) and injurious forest-insect (gypsymoth) etc.There is obvious inhibition;
3. chlorophyllin derivative degradable in environment, does not pollute the environment, and is that environmental protection type plant source is truly antibacterial, pesticide, is oneA little germs, the resistance to the action of a drug problem of insect to existing antiseptic, pesticide, find a kind of new solution;
4. synthetic route is fairly simple, and ultimate yield is higher, can greatly reduce costs.
Detailed description of the invention
Below in conjunction with specific embodiment, further set forth the present invention. Should be understood that these embodiment are only not used in and limit this for the present invention is describedBright scope. In addition should be understood that those skilled in the art can make various changes or modifications the present invention after reading the content of the present invention's instruction,These equivalent form of values fall within the application's appended claims limited range equally.
Specific embodiment 1: chlorophyllin synthetic
(1) take silkworm excrement chlorophyll primary extract 1g, add 10mL acetone solution, stir 30min, add concentrated NaOH solution 20ml, be placed in 50 DEG CWater bath with thermostatic control in stir 2h, after it is fully hydrolyzed, leave standstill 2h;
(2) the sediment suction filtration that will obtain from step (1), is dissolved in 30mL water, uses 30mL petroleum ether extraction three times; Use again 18% HClThe pH=1 left and right of adjusting solution, room temperature is placed 2 hours, has Precipitation, crosses leaching precipitation, uses distilled water washing precipitation, blackish greenly drySolid. By efficient liquid phase chromatographic analysis, by with the comparing of standard items, the content that can record chlorophyllin in product is 62.60%.
Specific embodiment 2: Chlorophyllin Ester derivative synthetic
(1) take silkworm excrement chlorophyll primary extract 2g, add 25mL acetone solution, stir 30min, add concentrated NaOH solution 40ml, be placed in 50 DEG CWater bath with thermostatic control in stir 2h, after it is fully hydrolyzed, leave standstill 2h;
(2) the sediment suction filtration that will obtain from step (1), is dissolved in 60mL water, uses petroleum ether extraction three times; Adjust molten with 18% HCl againThe pH=1 left and right of liquid, room temperature is placed 2 hours, has Precipitation, crosses leaching precipitation, uses distilled water washing precipitation, is dried to obtain blackish green chlorophyllinSolid;
(3) take the chlorophyllin solid 1g in step (2), add 40mL methyl alcohol, appropriate sulfuric acid catalyst, be heated to 40 DEG C of reaction 2h, reactionAfter complete, rotary evaporation is removed methyl alcohol, and gained crude product, through column chromatography purification, obtains R1For OCH3，R2For OCH3,R3For CH3ChlorophyllinEster derivant.
Specific embodiment 3: chlorophyllin amide derivatives synthetic
(1) take silkworm excrement chlorophyll primary extract 1g, add 10mL acetone solution, stir 30min, add concentrated NaOH solution 20ml, be placed in 50～60 DEG CWater bath with thermostatic control in stir 2h, after it is fully hydrolyzed, leave standstill 2h;
(2) by the sediment suction filtration obtaining, be dissolved in 30mL water from upper step, use 30mL petroleum ether extraction three times; Adjust with 18% HCl againThe pH=1 left and right of whole solution, room temperature is placed 2 hours, has Precipitation, crosses leaching precipitation, uses distilled water washing precipitation, is dried to obtain blackish green leafGreen acids solid;
(3) take the chlorophyllin solid 0.5g in step (2), add 30mL ammoniacal liquor, be heated to 60 DEG C of reaction 2h, after having reacted, rotary evaporation removesDeammoniation water, gained crude product, through ethyl acetate extraction, washing, column chromatography purification, obtains R1For NH2，R2For NH2，R3For the chlorophyllin of HAmide derivatives.
Specific embodiment 4: the bacteriostatic experiment of chlorophyllin derivative to Fusarium oxysporum
Selecting forestry pathogen-Fusarium oxysporum is research object, adopts growth rate method to measure chlorophyllin, Chlorophyllin Ester derivative, chlorophyllinThe bacteriostasis rate of amide derivatives to Fusarium oxysporum, taking raw material chlorophyll as comparison other.
Fusarium oxysporum is activated on PDA culture medium, grow after 7 days, beat and get bacterium piece from its colony edge with card punch (Φ 10.0mm);Then the pastille PDA culture medium central authorities of the variable concentrations processing that pre-sets of access, mycelia faces up, and covers ware lid, seals with sealed membrane.Every processing repeats 3 times, and the incubator that is placed in 25 DEG C is cultivated, and in inoculation, within latter 7 days, with the vertical survey of right-angled intersection method, it processes colony diameter. SurveyDetermine result as shown in table 1.
The bacteriostatic experiment data of table 1 chlorophyllin derivative to Fusarium oxysporum
As can be seen from Table 1, raw material chlorophyll is without bacteriostatic activity, and chlorophyllin, Chlorophyllin Ester derivative, chlorophyllin amide derivatives are to sharp spore sickleIt is active that cutter bacterium has obvious inhibition, especially strong to the bacteriostatic activity of Fusarium oxysporum with Chlorophyllin Ester derivative, chlorophyllin amide derivatives.
Specific embodiment 5: the bacteriostatic experiment of chlorophyllin derivative to bacillus subtilis, two kinds of bacteriums of EHEC
First two kinds of bacteriums of bacillus subtilis, EHEC that preserve choice experiment chamber are research object, observe chlorophyllin derivative illumination,The impact of the growing state on bacterium under dark condition. Specific experiment result is referring to table 2.
The photosensitive activity of table 2 chlorophyllin derivative to bacterium
Known by table 2 data analysis, raw material chlorophyll is to the equal unrestraint effect of above-mentioned two kinds of bacteriums, under illumination condition, and chlorophyllin, chlorophyllinEster derivant, chlorophyllin amide derivatives all have obvious inhibitory action to EHEC and bacillus subtilis, but under dark condition of culture, leafThe bacteriostasis of green acids, Chlorophyllin Ester derivative, chlorophyllin amide derivatives weakens, and shows chlorophyllin, Chlorophyllin Ester derivative, chlorophyllin acid amidesDerivative is photosensitive bacteriostatic agent. Wherein, the bacteriostatic activity of Chlorophyllin Ester derivative, chlorophyllin amide derivatives is better than chlorophyllin.
Specific embodiment 6: the insecticidal test of chlorophyllin derivative to gypsymoth
Experimental selection gypsymoth is research object, adopts injection to measure chlorophyllin, Chlorophyllin Ester derivative, chlorophyllin amide derivatives to gypsymothPoisoning effect, taking raw material chlorophyll as comparison other. Draw a certain amount of chlorophyllin derivative with micro syringe and be injected in gypsymoth pronotaryPlace, 30 of each product injections, examination worm is raised in glass jar, to not implementing on the same group photo-irradiation treatment. Chlorophyllin, Chlorophyllin Ester derivative, leafGreen acids amide derivatives all has obvious poisoning effect to gypsymoth, in table 3.
The insecticidal test data of table 3 chlorophyllin derivative to gypsymoth
Claims (8)
1. a chlorophyllin derivative, is characterized in that, the chemical structure of general formula of this chlorophyllin derivative is as follows,
Wherein, R1、R2、R3Be selected from hydrogen atom, alkyl, carboxyl ,-OH or-NH2Group, R1、R2、R3Can be the same or different.
2. chlorophyllin derivative according to claim 1, is characterized in that, described R1For OCH3，R2For OCH3,R3For CH3。
3. chlorophyllin derivative according to claim 1, is characterized in that, described R1For NH2，R2For NH2,R3For H.
4. the preparation method of chlorophyllin derivative according to claim 1, is characterized in that, comprises the steps:
(1) taking silkworm excrement as raw material, extract chlorophyll a, after fully dissolving, add concentrated alkali solution in solvent, the water bath with thermostatic control that is placed in uniform temperature is stirredMix certain hour, after it is fully hydrolyzed, leave standstill;
(2) by the sediment suction filtration obtaining from upper step, be dissolved in the water, use petroleum ether extraction 3-5 time; Adjust solution with certain density acid againAbout pH=1, room temperature is placed 2 hours, has Precipitation, crosses leaching precipitation, with distilled water washing precipitation 1-2 time, is dried to obtain blackish green chlorophyllinSolid;
(3) by the further esterification of chlorophyllin or the amidatioon of step (2) gained, obtain corresponding chlorophyllin derivative.
5. the preparation method of chlorophyllin derivative according to claim 4, is characterized in that, in described step (3), described chlorophyllin and methyl alcohol existUnder acid catalysis, react, obtain R1For OCH3，R2For OCH3,R3For CH3Chlorophyllin Ester derivative.
6. the preparation method of chlorophyllin derivative according to claim 4, is characterized in that, in described step (3), and described chlorophyllin and ammoniacal liquorReaction, obtains R1For NH2，R2For NH2,R3For the chlorophyllin amide derivatives of H.
7. chlorophyllin derivative according to claim 1 is as the purposes of photosensitive bacteriostatic agent, photosensitive pesticide.
8. the purposes of chlorophyllin derivative according to claim 7, is characterized in that, this chlorophyllin derivative is used for the treatment of localized bacterial infection, anti-Control forestry pathogen, forest disease and pest, also can be used in coating, to reduce the environment of load of microorganisms sensitivity.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107028250A (en) * | 2017-04-25 | 2017-08-11 | 漯河医学高等专科学校 | Antibacterial mask filter disc |
| CN110151582A (en) * | 2019-04-02 | 2019-08-23 | 陈云 | A kind of deodorization is antibacterial and repairs the function spray and its preparation and application of mucous membrane |
| CN110476979A (en) * | 2019-09-05 | 2019-11-22 | 青岛金尔农化研制开发有限公司 | A kind of Recompounded pesticide for preventing and treating wheat scab |
| CN113634141A (en) * | 2020-04-27 | 2021-11-12 | 万华化学集团股份有限公司 | Preparation method of polyamide composite reverse osmosis membrane, reverse osmosis membrane and application of reverse osmosis membrane |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107028250A (en) * | 2017-04-25 | 2017-08-11 | 漯河医学高等专科学校 | Antibacterial mask filter disc |
| CN110151582A (en) * | 2019-04-02 | 2019-08-23 | 陈云 | A kind of deodorization is antibacterial and repairs the function spray and its preparation and application of mucous membrane |
| CN110476979A (en) * | 2019-09-05 | 2019-11-22 | 青岛金尔农化研制开发有限公司 | A kind of Recompounded pesticide for preventing and treating wheat scab |
| CN113634141A (en) * | 2020-04-27 | 2021-11-12 | 万华化学集团股份有限公司 | Preparation method of polyamide composite reverse osmosis membrane, reverse osmosis membrane and application of reverse osmosis membrane |
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