CN105601638B - A kind of chlorophyllin derivative and preparation method thereof, as the application of photosensitive bacteriostatic agent and light sensitive pesticides - Google Patents
A kind of chlorophyllin derivative and preparation method thereof, as the application of photosensitive bacteriostatic agent and light sensitive pesticides Download PDFInfo
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- CN105601638B CN105601638B CN201610060252.2A CN201610060252A CN105601638B CN 105601638 B CN105601638 B CN 105601638B CN 201610060252 A CN201610060252 A CN 201610060252A CN 105601638 B CN105601638 B CN 105601638B
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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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- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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Abstract
本发明涉及一种叶绿酸衍生物、其制备方法及作为光敏抑菌剂、杀虫剂在抑菌、杀虫方面的应用，该衍生物的化学结构通式如下所示，其是以蚕砂为原料，从中提取叶绿素，在浓碱条件下加热水解，然后在酸性条件下脱去金属镁离子，同时通过水解去除疏水性叶绿植醇侧链，并进而对其改性得到的。该叶绿酸衍生物光敏性高、量子产率高，同时拥有2‑3个波长可供选择，提高了光敏剂抗病原微生物的选择性，对枯草芽孢杆菌、大肠杆菌、林业病原菌(尖孢镰刀菌)和舞毒蛾均有明显的抑制、毒杀效果，在环境中可降解，不会污染环境，是真正意义上的环保型植物源抑菌、杀虫剂。 The invention relates to a chlorophyllin derivative, its preparation method and its application as a photosensitive bacteriostatic agent and insecticide in the aspects of bacteriostasis and insecticide. The general chemical structure of the derivative is as follows. Sand is used as raw material, from which chlorophyll is extracted, heated and hydrolyzed under concentrated alkali conditions, and then metal magnesium ions are removed under acidic conditions, and the hydrophobic phytol side chain is removed by hydrolysis, and then modified. The chlorophyllin derivative has high photosensitivity, high quantum yield, and has 2-3 wavelengths to choose from, which improves the selectivity of photosensitizers against pathogenic microorganisms, and is effective against Bacillus subtilis, Escherichia coli, and forestry pathogens (Sharp Fusarium sporogenes) and gypsy moth have obvious inhibitory and poisonous effects, are degradable in the environment, and will not pollute the environment. They are truly environmentally friendly plant-source bacteriostatic and insecticides.
Description
Technical field
The present invention relates to a kind of phyllins, more particularly to a kind of chlorophyllin derivative, preparation method and work
For the application of photosensitive bacteriostatic agent, light sensitive pesticides.
Background technology
Chlorophyll needed for human survival belongs to magnesium porphyrin compound, by the magnesium ion at chlorophyll porphyrin ring center with other
Metal ion substitution after obtain phyllins product, as Copper chlorophyllin sodium salt, calcium chlorophyllin sodium salt, sodium cobalt chlorophyllin salt,
Iron chlorophyllin sodium salt etc. has excellent coloring effect, promotes hematopoiesis, liver protection, antimicrobial, promotion wound and ulcer healing and resists
Mutation etc. biological natures and unique pharmacological function, be easily absorbed by the body, and have no toxic side effect, be widely used in medicine,
Food, daily-use chemical industry and clinic.The certain derivatives of chlorophyll or effective photosensitizer, such as make in light power tumor therapy
For photosensitizer.Being proved porphyrin can accumulate in tumor tissues, when irradiating tumor tissues, due to porphyrin extinction on the spot,
So determining its fluorescent places just becomes a kind of method of lesion detection.
Light power antimicrobial chemical therapy (Photodynamic Antimicrobial Chemotherapy, PACT) is knot
Close a kind of antibiotic method that the active oxygen species that photosensitizer molecule and visible light generate inactivate pathogenic microorganism, effect
Mechanism is similar with the photodynamic therapy of cancer, but research to PACT and application are gradually lost by people because of the discovery of antibiotic
Forget, is not applied well.Photosensitizer occupies considerable status in light power antimicrobial chemical therapy.Photosensitizer exists
Under aerobic and illumination condition, photon can be absorbed, transits to singlet state first, triplet is channeled between being then and electricity occurs for substrate
Son or Hydrogen transfer, generate free radicals or radical ion, then pass through and kill target molecule to the oxidation of substrate.
In recent years, the toxic side effect caused by abuse of antibiotics, the destruction of natural microorganisms group and drug-fast bacteria
Appearance, so that the drug effect of antibiotic is continuously decreased, and both directly and indirectly seriously endanger health and environment.Thus,
If chlorophyll can be extracted, and be modified to it using natural plants as raw material, novel degradable chlorophyll base photosensitizer is made, and will
It is applied to antibacterial, desinsection field, then is particularly important.
Invention content
The purpose of the present invention is intended to provide a kind of chlorophyllin derivative, preparation method and as photosensitive bacteriostatic agent, photosensitive
The application of insecticide.The present invention heats hydrolysis, then in acid condition using chlorophyll is extracted from silkworm excrement under the conditions of concentrated base
Under slough metal magnesium ion, while the green phytol side chain of hydrophobicity leaf is removed by hydrolysis, and be modified that obtain leaf green to it in turn
Acid derivative.Chlorophyllin derivative light sensitivity is high, quantum yield is high, while it is available to possess 2-3 wavelength, improves light
The selectivity of quick dose of resisting pathogenic microbes.
In order to achieve the above-mentioned object of the invention, present invention employs following technical solutions：
The chlorophyllin derivative of the present invention, chemical structure of general formula is as follows,
Wherein, R1、R2、R3Selected from hydrogen atom, alkyl, carboxyl ,-OH or-NH2Group, R1、R2、R3Can it is identical can also
Difference excludes R1=R2=OH, R3=H；R1=R2=OCH3,R3=CH3Compound.
Preferably, R1For NH2, R2For NH2,R3For H.
The preparation method of the chlorophyllin derivative of the present invention, includes the following steps：
(1) using silkworm excrement as raw material, chlorophyll a is extracted, in a solvent fully after dissolving, concentrated alkali solution is added, is placed in certain
Certain time is stirred in the water bath with thermostatic control of temperature, after it is fully hydrolyzed, is stood；
(2) sediment that will be obtained from step (1) filters, and is dissolved in the water, with petroleum ether extraction 3-5 times；Again with one
The pH=1 or so for determining the acid adjustment solution of concentration, is placed at room temperature for 2 hours, there is Precipitation, filter to take precipitation, washed with distillation
Wash precipitation 1-2 times, dry blackish green chlorophyllin solid；
(3) by further esterification or the amidation of the chlorophyllin obtained by step (2), corresponding chlorophyllin derivative is obtained.
Preferably, in the step (3), the chlorophyllin is reacted with ammonium hydroxide, obtains R1For NH2, R2For NH2, R3For H's
Chlorophyllin amide derivatives.
Purposes of the chlorophyllin derivative of the present invention as photosensitive bacteriostatic agent, light sensitive pesticides, it is preferred that the chlorophyllin spreads out
Biology is for treating localized bacterial infection, prevention forestry pathogen, forest disease and pest, it can also be used in coating, to reduce micro- life
The environment of object load-sensitive.
The beneficial effects of the present invention are：
1. the present invention using silkworm excrement as raw material, is made chlorophyllin derivative, which is more satisfactory photosensitive
Bacteriostatic agent, insecticide, its light sensitivity is high, quantum yield is high, while it is available to possess 2-3 wavelength, improves photosensitizer and resists
The selectivity of pathogenic microorganism, damage by forest-insects；
2. chlorophyllin derivative does harm to bacillus subtilis, Escherichia coli, forestry pathogen (Fusarium oxysporum) and forest
Worm (gypsymoth) etc. has apparent inhibition；
3. chlorophyllin derivative is degradable in the environment, do not pollute the environment, is environmental protection type plant source truly
Antibacterial, insecticide is some germs, pest to the resistance problems of existing antiseptic, insecticide, finds a kind of new solution and does
Method；
4. synthetic route is fairly simple, ultimate yield is higher, can substantially reduce cost.
Specific implementation mode
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content that the present invention lectures, those skilled in the art
The present invention can be made various changes or modifications, such equivalent forms are equally fallen within defined by the application the appended claims
Range.
Specific embodiment 1：The synthesis of chlorophyllin
(1) silkworm excrement chlorophyll primary extract 1g is weighed, 10mL acetone solutions are added, stirs 30min, concentrated NaOH solution is added
20ml is placed in 50 DEG C of water bath with thermostatic control and stirs 2h, after it is fully hydrolyzed, stands 2h；
(2) sediment that will be obtained from step (1) filters, and is dissolved in 30mL water, three times with 30mL petroleum ether extractions；Again
The pH=1 or so of solution is adjusted with 18% HCl, 2 hours is placed at room temperature for, there is Precipitation, filter to take precipitation, washed with distillation
Wash precipitation, dry dark green solid.It can be measured in product by the comparison with standard items by efficient liquid phase chromatographic analysis
The content of chlorophyllin is 62.60%.
Specific embodiment 2：The synthesis of Chlorophyllin Ester derivative
(1) silkworm excrement chlorophyll primary extract 2g is weighed, 25mL acetone solutions are added, stirs 30min, concentrated NaOH solution is added
40ml is placed in 50 DEG C of water bath with thermostatic control and stirs 2h, after it is fully hydrolyzed, stands 2h；
(2) sediment that will be obtained from step (1) filters, and is dissolved in 60mL water, three times with petroleum ether extraction；It uses again
The pH=1 or so of 18% HCl adjustment solution, is placed at room temperature for 2 hours, there is Precipitation, filter to take precipitation, be washed with distilled water
Precipitation, dry blackish green chlorophyllin solid；
(3) the chlorophyllin solid 1g in step (2) is weighed, 40mL methanol, moderate amount of sulfuric acid catalyst is added, is heated to 40 DEG C
2h is reacted, after having reacted, rotary evaporation removes methanol, and the purifying of gained crude by column chromatography obtains R1For OCH3, R2For OCH3,
R3For CH3Chlorophyllin Ester derivative.
Specific embodiment 3：The synthesis of chlorophyllin amide derivatives
(1) silkworm excrement chlorophyll primary extract 1g is weighed, 10mL acetone solutions are added, stirs 30min, concentrated NaOH solution is added
20ml is placed in 50~60 DEG C of water bath with thermostatic control and stirs 2h, after it is fully hydrolyzed, stands 2h；
(2) sediment obtained from upper step is filtered, is dissolved in 30mL water, three times with 30mL petroleum ether extractions；Again
The pH=1 or so of solution is adjusted with 18% HCl, 2 hours is placed at room temperature for, there is Precipitation, filter to take precipitation, washed with distillation
Wash precipitation, dry blackish green chlorophyllin solid；
(3) the chlorophyllin solid 0.5g in step (2) is weighed, 30mL ammonium hydroxide is added, 60 DEG C of reaction 2h is heated to, has reacted
Afterwards, rotary evaporation removes ammonium hydroxide, and gained crude product is extracted through ethyl acetate, washed, column chromatography purifies, and obtains R1For NH2, R2For
NH2, R3For the chlorophyllin amide derivatives of H.
Specific embodiment 4：Bacteriostatic experiment of the chlorophyllin derivative to Fusarium oxysporum
It is research object to select forestry pathogen-Fusarium oxysporum, and chlorophyllin, Ye Lv are measured using growth rate method
Acid ester derivant, chlorophyllin amide derivatives are to the bacteriostasis rate of Fusarium oxysporum, using raw material chlorophyll as comparison other.
Fusarium oxysporum is activated in PDA culture medium, after growth 7 days, with card punch (Φ 10.0mm) from its bacterium colony
Edge, which is beaten, takes fungus block；Then the drug containing PDA culture medium center of the various concentration processing pre-set is accessed, mycelia is face-up,
Ware lid is covered, is sealed with sealed membrane.Often processing is repeated 3 times, and is placed in 25 DEG C of incubator and is cultivated, uses cross within 7 days after inoculation
Its processing colony diameter of interior extrapolation method vertical measurement.Measurement result is as shown in table 1.
Bacteriostatic experiment data of the 1 chlorophyllin derivative of table to Fusarium oxysporum
As it can be seen from table 1 raw material chlorophyll is without bacteriostatic activity, and chlorophyllin, Chlorophyllin Ester derivative, chlorophyllin amide
Derivative has apparent inhibitory activity to Fusarium oxysporum, especially with Chlorophyllin Ester derivative, chlorophyllin amide derivatives to point
The bacteriostatic activity of fusarium oxysporum is strong.
Specific embodiment 5：Bacteriostatic experiment of the chlorophyllin derivative to two kinds of bacillus subtilis, escherichia coli bacteriums
Two kinds of bacillus subtilis, escherichia coli bacteriums of choice experiment room preservation first are research object, observe leaf
Influence of the green acids derivative under illumination, dark condition to the growing state of bacterium.Specific experiment result is referring to table 2.
Photosensitive activity of the 2 chlorophyllin derivative of table to bacterium
By 2 data analysis of table it is found that raw material chlorophyll acts on the equal unrestraint of above two bacterium, in illumination condition
Under, chlorophyllin, Chlorophyllin Ester derivative, chlorophyllin amide derivatives have significantly escherichia coli and bacillus subtilis
Inhibiting effect, but under the conditions of light culture, chlorophyllin, Chlorophyllin Ester derivative, chlorophyllin amide derivatives bacteriostasis subtract
It is weak, show that chlorophyllin, Chlorophyllin Ester derivative, chlorophyllin amide derivatives are photosensitive bacteriostatic agent.Wherein, Chlorophyllin Ester derives
Object, chlorophyllin amide derivatives bacteriostatic activity be better than chlorophyllin.
Specific embodiment 6：Insecticidal test of the chlorophyllin derivative to gypsymoth
Experimental selection gypsymoth is research object, and chlorophyllin, Chlorophyllin Ester derivative, chlorophyllin acyl are measured using injection method
Amine derivative is to the poisoning effect of gypsymoth, using raw material chlorophyll as comparison other.A certain amount of leaf is drawn with micro syringe
Green acids derivative is injected at gypsymoth pronotary, each injections 30, and test worm is raised in glass jar, to different groups
Implement photo-irradiation treatment.Chlorophyllin, Chlorophyllin Ester derivative, chlorophyllin amide derivatives have gypsymoth apparent poisoning effect
It answers, is shown in Table 3.
Insecticidal test data of the 3 chlorophyllin derivative of table to gypsymoth
Claims (4)
1. a kind of chlorophyllin derivative, which is characterized in that the chemical structure of general formula of the chlorophyllin derivative is as follows,
Wherein, R1For NH2, R2For NH2,R3For H.
2. the preparation method of chlorophyllin derivative according to claim 1, which is characterized in that include the following steps：
(1) using silkworm excrement as raw material, chlorophyll a is extracted, in a solvent fully after dissolving, concentrated alkali solution is added, is placed in certain temperature
Water bath with thermostatic control in stir certain time, after it is fully hydrolyzed, stand；
(2) sediment obtained from upper step is filtered, is dissolved in the water, with petroleum ether extraction 3-5 times；A certain concentration is used again
Acid adjustment solution pH=1 or so, be placed at room temperature for 2 hours, there is Precipitation, filter to take precipitation, be washed with distilled water precipitation
1-2 times, dry blackish green chlorophyllin solid；
(3) chlorophyllin obtained by step (2) is reacted with ammonium hydroxide, obtains R1For NH2, R2For NH2,R3Spread out for the chlorophyllin amide of H
Biology.
3. purposes of the chlorophyllin derivative according to claim 1 as photosensitive bacteriostatic agent, light sensitive pesticides.
4. the purposes of chlorophyllin derivative according to claim 3, which is characterized in that the chlorophyllin derivative is for preventing
Forestry pathogen, forest disease and pest, it can also be used in coating, to reduce the environment of load of microorganisms sensitivity.
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| JP2015522554A (en) | 2012-06-04 | 2015-08-06 | サンコー・エナジー・インコーポレーテッド | Formulation containing paraffin oil and anti-settling agent |
| CN107028250A (en) * | 2017-04-25 | 2017-08-11 | 漯河医学高等专科学校 | Antibacterial mask filter disc |
| WO2020163964A1 (en) | 2019-02-15 | 2020-08-20 | Suncor Energy Inc. | The use of protoporphyrin ix derivatives to improve the health of plants |
| 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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| CN100503610C (en) * | 2006-02-28 | 2009-06-24 | 中国人民解放军第二军医大学 | Benzophyllogreen porphyrin photosensitizer and its preparation method and use |
| CN102093369B (en) * | 2011-01-28 | 2012-11-14 | 武汉联合药业有限责任公司 | Method for extracting chlorophyll and preparing sodium ferrous chlorophyll from silkworm excrement |
| CA2846011C (en) * | 2011-08-23 | 2019-10-15 | Yeda Research And Development Co.Ltd. | (bacterio)chlorophyll photosensitizers for treatment of eye diseases and disorders |
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