阅读说明：本技术 一种脱氢枞胺(取代)苯甲醛Schiff碱衍生物的用途 (Application of dehydroabietylamine (substituted) benzaldehyde Schiff base derivative ) 是由 饶小平 翟兆兰 许吉 宋湛谦 商士斌 于 2019-09-30 设计创作，主要内容包括：本发明公开了一种脱氢枞胺(取代)苯甲醛Schiff碱衍生物的用途,用于木材防腐。本发明脱氢枞胺(取代)苯甲醛Schiff碱衍生物,可对灰葡萄孢、腐皮镰孢、禾谷镰孢、尖孢镰孢、芸苔链格孢和采绒革盖菌等均起到有效的抑制作用,可直接用于木材防腐或用于制备木材防腐剂；原料来源广泛,成本低廉,具有天然、无毒、可再生等优势。(The invention discloses an application of a dehydroabietylamine (substituted) benzaldehyde Schiff base derivative for wood preservation. The dehydroabietylamine (substituted) benzaldehyde Schiff base derivative can effectively inhibit botrytis cinerea, fusarium solani, fusarium graminearum, fusarium oxysporum, alternaria brassicae, coriolus versicolor and the like, and can be directly used for wood preservation or used for preparing wood preservatives; the raw materials have wide sources and low cost, and have the advantages of being natural, non-toxic, renewable and the like.)

1. The application of the dehydroabietylamine (substituted) benzaldehyde Schiff base derivative is characterized in that: it is used for wood preservation.

2. The use of a dehydroabietylamine (substituted) benzaldehyde Schiff base derivative according to claim 1, wherein: the method is used for preparing the wood preservative.

3. Use of the dehydroabietylamine (substituted) benzaldehyde Schiff base derivative according to claim 1 or 2, wherein: the concentration of the dehydroabietylamine (substituted) benzaldehyde Schiff base derivative is 11.25-180 mu g/mL.

4. Use of the dehydroabietylamine (substituted) benzaldehyde Schiff base derivative according to claim 1 or 2, wherein: the structural formula of the dehydroabietylamine (substituted) benzaldehyde Schiff base derivative is as follows:

wherein R is₂Is composed of

5. The use of a dehydroabietylamine (substituted) benzaldehyde Schiff base derivative according to claim 4, wherein: r₂Is composed ofThe dehydroabietylamine (substituted) benzaldehyde Schiff base derivative is used for inhibiting botrytis cinerea and fusarium graminearum; r₂Is composed ofUse for inhibiting botrytis cinerea, fusarium solani, alternaria brassicae, fusarium graminearum and fusarium oxysporum; r₂Is composed ofThe dehydroabietylamine (substituted) benzaldehyde Schiff base derivative is used for inhibiting botrytis cinerea, alternaria brassicae and fusarium graminearum; r₂Is composed ofThe dehydroabietylamine (substituted) benzaldehyde Schiff base derivative of (1) is used for inhibiting botrytis cinerea and alternaria brassicae; r₂Is composed ofThe dehydroabietylamine (substituted) benzaldehyde Schiff base derivative of (1) is used for inhibiting botrytis cinerea and alternaria brassicae; r₂Is composed ofThe dehydroabietylamine (substituted) benzaldehyde Schiff base derivative is used for inhibiting botrytis cinerea and fusarium graminearum.

6. The use of a dehydroabietylamine (substituted) benzaldehyde Schiff base derivative according to claim 4, wherein: r₂Is composed of

7. The use of a dehydroabietylamine (substituted) benzaldehyde Schiff base derivative according to claim 6, wherein: r₂Is composed of

8. The use of a dehydroabietylamine (substituted) benzaldehyde Schiff base derivative according to claim 7, wherein: r₂Is composed ofThe concentration of the dehydroabietylamine (substituted) benzaldehyde Schiff base derivative is 11.25 +/-2 mu g/mL, R₂Is composed ofThe concentration of the dehydroabietylamine (substituted) benzaldehyde Schiff base derivative is 22.5 +/-2 mu g/mL, R₂Is composed ofThe concentration of the dehydroabietylamine (substituted) benzaldehyde Schiff base derivative is 11.25 +/-2 mu g/mL, R₂Is composed ofThe concentration of the dehydroabietylamine (substituted) benzaldehyde Schiff base derivative of (1) was 45. + -.2. mu.g/mL.

9. The use of a dehydroabietylamine (substituted) benzaldehyde Schiff base derivative according to claim 7, wherein: r₂Is composed of

Technical Field

The invention relates to an application of a dehydroabietylamine (substituted) benzaldehyde Schiff base derivative, belonging to the field of wood preservation.

Background

As a renewable biomass material, the wood has the characteristics of no toxicity, no pollution, beautiful appearance, easy processing and the like, is widely used as building and decoration materials all the time, and is a green natural product which is well favored by people. However, the wood contains abundant cellulose, provides nutrients for wood decay fungi and the like under the condition of proper temperature and humidity, is easy to be eroded and decayed by the fungi, shortens the service life of the wood and causes the loss of the wood in the aspects of economic value and use value. The method for performing preservative treatment on the wood is an important way and means for prolonging the service life of the wood, improving the utilization level of the wood and saving wood resources. Therefore, research and development of techniques for preservation of wood and the like have been receiving wide attention.

Disclosure of Invention

The invention provides an application of a dehydroabietylamine (substituted) benzaldehyde Schiff base derivative, which can effectively inhibit botrytis cinerea, Fusarium solani, Fusarium graminearum, Fusarium oxysporum, Alternaria brassicae, Coriolus versicolor and the like, and can be used for wood preservation; the dehydroabietylamine (substituted) benzaldehyde Schiff base derivative is prepared from renewable resource rosin, and has the advantages of being natural, non-toxic, renewable and the like.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

an application of dehydroabietylamine (substituted) benzaldehyde Schiff base derivative in preservation of wood.

The bacteriostatic agent has strong selectivity on strains, the difference of the inhibitory effect of the same product on different strains is obvious, and the applicant finds that the dehydroabietylamine (substituted) benzaldehyde Schiff base derivative can effectively inhibit botrytis cinerea, fusarium solani, fusarium graminearum, fusarium oxysporum, alternaria brassicae, coriolus versicolor and the like, and can be used for wood preservation.

The dehydroabietylamine (substituted) benzaldehyde Schiff base derivative can be directly used for wood preservation and can also be used for preparing wood preservatives.

In order to improve the anticorrosion effect, the concentration of the dehydroabietylamine (substituted) benzaldehyde Schiff base derivative is 11.25-180 mu g/mL when the derivative is used. The applicant finds that the concentration of the dehydroabietylamine (substituted) benzaldehyde Schiff base derivative and the antibacterial effect are not in a simple proportional relationship, and the antibacterial rate is increased, reduced and increased along with the increase of the concentration.

The structural formula of the dehydroabietylamine (substituted) benzaldehyde Schiff base derivative is as follows:in order to further secure the wood preservative effect, preferably, R₂Is composed of

The different dehydroabietylamine (substituted) benzaldehyde Schiff base derivatives can also be used for inhibiting specific pathogenic fungi to meet the requirements of different occasions, wherein R is₂Is composed ofThe dehydroabietylamine (substituted) benzaldehyde Schiff base derivative is used for inhibiting botrytis cinerea and fusarium graminearum; r₂Is composed ofFor inhibiting botrytis cinerea, fusarium solani, alternaria brassicae, fusarium graminearum and fusarium oxysporum; r₂Is composed ofThe dehydroabietylamine (substituted) benzaldehyde Schiff base derivative is used for inhibiting botrytis cinerea, alternaria brassicae and fusarium graminearum; r₂Is composed ofThe dehydroabietylamine (substituted) benzaldehyde Schiff base derivative of (1) is used for inhibiting Botrytis cinerea and Alternaria brassicae; r₂Is composed ofThe dehydroabietylamine (substituted) benzaldehyde Schiff base derivative of (1) is used for inhibiting Botrytis cinerea and Alternaria brassicae; r₂Is composed ofThe dehydroabietylamine (substituted) benzaldehyde Schiff base derivative is used for inhibiting botrytis cinerea and fusarium graminearum.

In order to further enhance the effect of wood preservation, the structural formula of the dehydroabietylamine (substituted) benzaldehyde Schiff base derivative is preferably R₂Is composed of More preferably, R₂Is composed of R₂Is composed ofThe inhibition rate of the dehydroabietylamine (substituted) benzaldehyde Schiff base derivative on botrytis cinerea and alternaria brassicae is 100 percent, R is₂Is composed ofThe inhibition rate of the dehydroabietylamine (substituted) benzaldehyde Schiff base derivative on Fusarium solani and Alternaria brassicae is 100 percent, R₂Is prepared byThe inhibition rate of the dehydroabietylamine (substituted) benzaldehyde Schiff base derivative on part of pathogenic fungi also reaches 100%. Even more preferably, R₂Is composed of

In order to take account of cost and bacteriostatic efficiency, it is preferable that R is used when R is used₂Is composed ofThe concentration of the dehydroabietylamine (substituted) benzaldehyde Schiff base derivative is 11.25 +/-2 mu g/mL, R₂Is composed ofThe concentration of the dehydroabietylamine (substituted) benzaldehyde Schiff base derivative is 22.5 +/-2 mu g/mL, R₂Is composed ofThe concentration of the dehydroabietylamine (substituted) benzaldehyde Schiff base derivative is 11.25 +/-2 mu g/mL, R₂Is composed ofThe concentration of the dehydroabietylamine (substituted) benzaldehyde Schiff base derivative of (1) was 45. + -.2. mu.g/mL. That is, the substitution position and type of the halogen atom on the benzene ring will affect the concentration for optimal bacteriostatic activity. The dehydroabietylamine (substituted) benzaldehyde Schiff base derivative can be diluted and directly used for wood preservation, and can also be used for preparing wood preservatives after being compounded with other substances as an effective component.

The prior art is referred to in the art for techniques not mentioned in the present invention.

The dehydroabietylamine (substituted) benzaldehyde Schiff base derivative can effectively inhibit botrytis cinerea, fusarium solani, fusarium graminearum, fusarium oxysporum, alternaria brassicae, coriolus versicolor and the like, and can be directly used for wood preservation or used for preparing wood preservatives; the raw materials have wide sources and low cost, and have the advantages of being natural, non-toxic, renewable and the like.

Drawings

FIG. 1 shows the bacteriostatic activity of dehydroabietylamine (substituted) benzaldehyde Schiff base derivatives on Botrytis cinerea at different concentrations;

FIG. 2 is a graph showing the bacteriostatic activity of dehydroabietylamine (substituted) benzaldehyde Schiff base derivatives against Fusarium solani at different concentrations;

FIG. 3 is a graph showing the bacteriostatic activity of dehydroabietylamine (substituted) benzaldehyde Schiff base derivatives against Fusarium graminearum at various concentrations;

FIG. 4 shows the bacteriostatic activity of dehydroabietylamine (substituted) benzaldehyde Schiff base derivatives against Alternaria brassicae at different concentrations;

FIG. 5 is a graph showing the bacteriostatic activity of dehydroabietylamine (substituted) benzaldehyde Schiff base derivatives against Fusarium oxysporum at various concentrations;

FIG. 6 shows the bacteriostatic activity of dehydroabietylamine (substituted) benzaldehyde Schiff base derivatives against Coriolus versicolor at different concentrations.

Detailed Description

In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.

1. Sample preparation: the dehydroabietylamine (substituted) benzaldehyde Schiff base derivative has a structural formula as follows:for convenience of statistics, according to R₂The sample dehydroabietylamine (substituted) benzaldehyde Schiff base derivatives were numbered as shown in table 1 below.

TABLE 1 Dehydroabietylamine (substituted) benzaldehyde Schiff base derivative numbering

2. Pathogenic fungi: selecting the fungal pathogens which are easy to cause wood decay and have representative characteristics: botrytis cinerea (CGMCC 3.3790), Fusarium solani (CGMCC 3.2889), Fusarium graminearum (CGMCC3.4733), Fusarium oxysporum (CGMCC 3.3633), Alternaria brassicolo (CGMCC 3.7805) and Coriolus versicolor (CFCC5336), the 6 test phytopathogenic fungi being supplied by the China general Microbiological Culture Collection Center (general Microbiological Culture Collection Center) and the China Forestry Microbiological Culture Collection Center (China general Microbiological Culture Collection Center);

3. other reagents: absolute ethyl alcohol, glucose, agar and cycloheximide are analytically pure;

4. preparation of a culture medium:

preparation of Potato Dextrose Agar (PDA) medium: accurately weighing 200g of potatoes, cleaning, peeling, cutting into small pieces, pouring 1000ml of boiled distilled water (100 ℃) into the small pieces for water boiling, continuously stirring in the water boiling process to prevent the potatoes from sticking to a pot, and filtering potato residues to obtain potato filtrate when the potatoes are boiled to be fragile under light pressure; heating potato filtrate with slow fire to boil, adding 20g glucose, stirring until glucose is completely dissolved, adding 18g agar, stirring, preventing sticking, reducing fire power, and stopping fire when the liquid is clear and transparent to obtain PDA culture medium.

5. Activation of pathogenic fungi:

(1) and (3) sterilization: the cleaned culture dish, inoculating needle, PDA culture medium, etc. are placed in autoclave (HVE-50 autoclave, Wayuejing instruments Co., Ltd.), and sterilized at 0.1Mpa and 121 deg.C for 22 min.

(2) Plate preparation: placing sterilized culture medium and apparatus on clean bench (SW-CJ-1FD clean bench, Suzhou Antai air technology Co., Ltd.), irradiating with ultraviolet lamp for 15min, closing the ultraviolet lamp, and blowing for 10 min; pouring the non-solidified culture medium into empty dishes, pouring about 20mL of the culture medium into each dish, flatly placing the culture medium, and inoculating the culture medium after complete condensation; the name and date of the inoculum is marked.

(3) Inoculation: picking out pathogenic fungi hypha stored in a test tube by using an inoculating needle, inoculating the hypha on a flat plate by adopting a marking method without scratching agar, and sealing a dish opening by using a sealing film after inoculation so as to prevent external pollution from entering;

(4) culturing: the inoculated fungus plate is put into an incubator (PQX-380D multi-section programmable artificial climate box (incubator) of Ningbo southeast instruments Co., Ltd.) at 28 ℃, and is cultured in dark until obvious bacterial colonies are formed.

6. And (3) determining the bacteriostatic activity of each sample:

6.1 primary determination of bacteriostatic activity, and respectively carrying out the following operations on each sample:

accurately weighing 36mg of sample, using absolute ethyl alcohol to fix the volume to 10mL, and preparing the sample solution to be detected with the concentration of 3.6 mg/mL. Setting the final concentration of the sample in each culture dish to be 180 mug/mL, taking absolute ethyl alcohol as a solvent control, taking an cycloheximide aqueous solution with the same concentration as the solution to be detected as a positive control, taking a pure PDA culture medium as a blank control, and determining the inhibitory activity of the sample solution on the pathogenic fungi by adopting a growth rate method.

In a clean bench, 9mL of sample solution to be tested is transferred by a sterilized gun head, filtered by a 0.22 μm sterile filter head and then mixed with 171mL of PDA culture medium at 40 ℃ by gentle shaking to obtain the PDA culture medium (180 μ g/mL) containing samples. 10mL of PDA culture medium containing samples is poured into each culture dish, the culture dishes are rotated to evenly spread the culture medium, and the culture medium is marked, cooled and solidified for standby. The solvent control and the positive control were performed as above.

And inoculating the activated pathogenic fungi into each culture dish, wherein all the pathogenic fungi are inoculated within the same day. After inoculation, the strain is placed into an incubator for culturing for 10d, when the strain is cultured to the 2 nd, 4 th, 6 th, 8 th and 10 th days, the colony growth diameter of the pathogenic fungi is measured by a cross method, the data is recorded, the result is shown in the table 2, and the inhibition rate is calculated according to the following formula:

TABLE 2 Primary assay for Dehydroabietylamine (substituted) benzaldehyde Schiff base derivatives bacteriostatic Activity

The percentage in table 2 above is the inhibition rate, and as can be seen from table 2, each dehydroabietylamine (substituted) benzaldehyde Schiff base derivative has better bacteriostatic activity against 6 pathogenic fungi and can be used for wood preservation; and the inhibition rate of the sample No. 1 to the botrytis cinerea is more than 90% after 2 days, and the inhibition rate to the fusarium graminearum is more than 80%; 2. the inhibition rates of the No. 7 and No. 8 samples to Botrytis cinerea, Fusarium solani, Alternaria brassicae, Fusarium graminearum and Fusarium oxysporum are both more than 80%, and the inhibition rates of the No. 8 samples to Fusarium solani and Alternaria brassicae are both 100% and are equivalent to the inhibition activities of positive control cycloheximide to Fusarium solani and Alternaria brassicae; the inhibition rate of the sample No. 4 to the botrytis cinerea and the alternaria brassicae is 100 percent, and is equivalent to the inhibition activity of cycloheximide to the botrytis cinerea and the alternaria brassicae.

6.2 further determination of bacteriostatic activity:

selecting No. 4, 6-8 samples of the dehydroabietylamine (substituted) benzaldehyde Schiff base derivative with good inhibitory activity on 6 different pathogenic fungi, and respectively carrying out the following operations on each sample: sample solutions with final concentrations of 100, 50, 25 and 12.5 mu g/mL of samples in each culture dish are prepared by a double dilution method, and absolute ethyl alcohol is also used as a solvent control, an aqueous solution of cycloheximide with the same concentration as the solution to be detected is used as a positive control, and a pure PDA culture medium is used as a blank control. The same sample was inoculated with six pathogenic fungi of Botrytis cinerea, Coriolus versicolor, Fusarium solani, Fusarium oxysporum, Alternaria brassicae and Fusarium graminearum respectively under a concentration gradient, three replicate groups were set up for each experiment, the growth diameter of each bacterium was measured during the culture in an incubator at 28 ℃ for 10 days, the average diameter and the inhibition rate were calculated, and the results are shown in FIGS. 1 to 6, in which 4, 6, 7 and 8 represent sample No. 4, sample No. 6, sample No. 7 and sample No. 8, respectively.

As shown in FIGS. 1-6, the four samples have good inhibitory activity against 6 different pathogenic fungi at different concentrations, and sample No. 4 has the highest inhibitory rate against 6 different pathogenic fungi at 11.25 μ g/mL; the sample No. 6 has the highest inhibition rate to 6 different pathogenic fungi under 22.5 mu g/mL, and the inhibition rates are all 95 percent; the sample No. 7 integrates the inhibition rates on 6 different pathogenic fungi, and the inhibition rate is preferably about 11.25, and the inhibition rate is the lowest at 25 mu g/mL; sample No. 8 showed the highest inhibition of 6 different pathogenic fungi at 45. mu.g/mL.