新型含氮、硫、磷壳聚糖衍生物的制备、抑菌活性与机理初探
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摘要
传统化学农药的长期和不合理使用，给环境和人类健康带来了巨大的威胁。因此，开发新型生物杀菌剂的需求已越来越迫切。壳聚糖是一类有着广谱抑菌活性的天然多糖，其生物相容性好、易降解、无毒，因而作为一种可再生资源在农业领域受到了越来越多的关注。然而，壳聚糖的抑菌活性有限，这限制了其应用。而通过对壳聚糖进行化学改性是一种可以提高其抑菌活性的有效方法。
本论文以壳聚糖为骨架，通过定位导入、接枝共聚技术接入高活性基团制备了9类共30个含氮、硫、磷壳聚糖衍生物，并对制备的壳聚糖衍生物采用红外光谱、核磁波谱、元素分析、X射线衍射、差示扫描量热、扫描电镜等分析手段对其理化性质进行全面解析，确定了其取代位置、取代度、热力学性质、晶体性质等。通过抑菌活性筛选，研究了壳聚糖衍生物的抑菌活性和杀菌谱，并筛选出2种壳聚糖衍生物进行抑菌机理探讨。主要研究结果如下：
1.制备了3种壳聚糖1,2,4-三唑衍生物。壳聚糖1,2,4-三唑衍生物相比其合环前产物酰基硫脲壳聚糖，抑菌活性和溶解性明显提高。抑菌活性结果表明：三唑环上取代基的电负性和空间位阻对抑菌活性影响很大，甲基强于氯甲基，强于苯基。制备了2种新型壳聚糖1,2,3-三唑衍生物。抑菌结果表明：壳聚糖苯甲酸酯-1,2,3-三唑(PhTACS)活性强于壳聚糖烟酸酯-1,2,3-三唑(PyTACS)。
2.制备了9种壳聚糖酰基卤代苯缩氨基硫脲衍生物。抑菌结果表明：壳聚糖酰基缩卤代苯氨基硫脲衍生物中，氯乙酰基缩卤代苯氨基硫脲强于乙酰基，强于苯甲酰基；卤代苯中氯原子强于氟原子，强于三氟甲基。卤代苯中氯原子强于氟原子，强于三氟甲基。制备了7种壳聚糖烷基(取代苯基)缩氨基硫脲衍生物。抑菌结果表明：壳聚糖烷基(取代苯基)缩氨基硫脲衍生物中，含取代苯基的衍生物抑菌活性要明显强于带烷基的衍生物；苯环上的取代基供电性越强，活性越高。制备了2种壳聚糖二硫代氨基甲酸酯衍生物并测定了其抑菌活性。结果表明壳聚糖二硫代氨基甲酸甲酯的抑菌活性要强于甲酸乙酯。制备了2种壳聚糖二硫代氨基甲酸盐衍生物并研究了其抑菌活性。结果表明：壳聚糖硫代氨基甲酸盐，其溶解性比壳聚糖显著提高，但抑菌活性却没有明显提高，说明溶解度不是影响壳聚糖及其衍生物的决定因素。此外，硫代氨基甲酸氨盐的活性要强于三乙烯二胺盐。
3.制备了壳聚糖α-氨基丁基膦酸乙酯(α-APEPCS)，抑菌结果表明：壳聚糖a-氨基苯氧基嘧啶膦酸酯衍生物具有很好的抑菌效果和杀菌谱。制备了2种壳聚糖a-氨基苯氧基嘧啶膦酸酯衍生物。抑菌结果表明：制备的壳聚糖a-氨基苯氧基嘧啶膦酸酯衍生物均具有很好的抑菌效果和杀菌谱，在250μg/mL下对黄瓜枯萎病原真菌、芦笋茎枯病原真菌、葱紫斑病原真菌的抑菌活性可达100%，明显强于阳性对照三唑酮和多抗霉素。制备了2种壳聚糖α-氨基呋喃基膦酸酯类衍生物，制备的衍生物的溶解性和抑菌性均有很大提升。构效关系表明壳聚糖α-氨基膦酸酯，膦酸乙酯活性稍好。
4.通过对含氮、硫、磷壳聚糖衍生物的抑菌活性筛选，发现含磷壳聚糖衍生物的溶解性和抑菌活性均要强于含氮和硫的壳聚糖衍生物。由于壳聚糖α-氨基丁基膦酸乙酯(α-APEPCS)和壳聚糖α-氨基呋喃基膦酸乙酯(α-AFEPCS)合成更简便、所用原料成本更低，因此选择其进行抑菌机理的探讨。
5.以α-APEPCS和α-AFEPCS为研究对象，探讨了其对黄瓜枯萎病原真菌和茶炭疽病原真菌细胞壁和细胞膜结构和功能的影响及对代谢中间产物丙酮酸合成的影响。主要结论如下：描电镜显示，100μg/mL下，α-APEPCS和α-AFEPCS就能对病菌菌丝造成严重破坏，使菌丝部分或全部破裂；而多抗霉素处理的菌丝只是发生变形，壳聚糖处理的菌丝超微结构变化不大；α-APEPCS、α-AFEPCS、壳聚糖、多抗霉素均能改变菌丝细胞膜的通透性，其中多抗霉素处理后的菌液电导率变化最快；用α-APEPCS、α-AFEPCS、壳聚糖、多抗霉素处理24小时后的菌液中可溶性蛋白量均有所增加，说明药液破坏了细胞膜的结构，使蛋白等大分子溢出，其中α-APEPCS处理的蛋白溢出量最大。用α-APEPCS、α-AFEPCS、壳聚糖、多抗霉素处理24小时后的菌液中丙酮酸含量均有降低，说明各药液均抑制了病菌重要的代谢中间产物丙酮酸的合成。
本论文制备并筛选出了5种抑菌活性较好、有着潜在应用前景的壳聚糖衍生物，初步探讨了其作用机理。制备的壳聚糖衍生物保持了壳聚糖的基本骨架，因此可能会具有壳聚糖特有的生物相容性好、易于降解、毒性低的优点。此外，上述壳聚糖衍生物与市场上常用的杀菌剂三唑酮和多抗霉素相比，杀菌谱明显不同，这对研制新型低毒、无交互抗性的海洋生物农药进而代替部分高毒化学农药，实现海洋生物资源的高值化利用方面无疑有着十分重要的意义。
The frequent and wide application of traditional fungicides has caused serious problems such as environmental pollution and threats to human health. Therefore, it is critically necessary to discover new biofungicidal alternatives. Chitosan is one kind of natural polysaccharide and it is proved to have broad-spectrum antifungal activity. Chitosan possesses good biocompatibility, biodegradability, and non-toxicity. Hence, it has attracted much attention in the field of agriculture. However, chitosan can not be used directly as a fungicide due to its relatively low antifungal activity. Hence, many strategies were proposed to overcome these limitations. A widely used approach is the chemical modification of chitosan.
In this study, nine kinds of chitosan derivatives were designed via localization of import active group and strategy of graft copolymerization. Totally,30target derivatives were obtained. Their structures were confirmed by FT-IR, NMR, elemental analysis, XRD, DSC, and SEM to determine position and degree of substitution, crystal properties, and thermodynamic properties. Antifungal activity of them against R. solani, A. solani, P. piricola Nose, S. solani, P. asparagi, F. oxysporum, A. porri, G. theae-sinensis was tested. And two of the chitosan derivatives were selected to study mechanism of action. The major findings and results were listed as follows:
1. Three new1,2,4-triazole chitosan derivatives were prepared via cyclization of acyl thiourea chitosan. Their solubility and antifungal activity improved after chemical modification chitosan. Antifungal results exhibited the activity was greatly influenced by electronegativity of substituents in triazole and steric effect. The inhibitory effect followed a sequence of methyl＞methyl chloride＞phenyl. Two new1,2,3-triazole chitosan derivatives were prepared via “Click Chemistry”. Antifungal results showed PhTACS had a better inhibitory effect than PyTACS.
2. Nine acyl halogenated phenyl-thiosemicarbazone chitosan derivativess were prepared. The inhibitory effect followed a sequence of chloroacetyl thiosemicarbazone＞acetyl thiosemicarbazone＞benzoyl thiosemicarbazone. Various substituents of aromatic ring in chitosan derivatives had distinct impacts on antifungal activity: Cl＞F＞CF3. Seven alkyl(substituted phenyl) thiosemicarbazone were obtained and the antifungal activity was studied. It was found that the chitosan derivatives with substituted phenyl had stronger inhibitory effect than those with alkyl Strong electron contributing group at phenyl was helpful to enhance the antifungal properties. Two alkyl dithiocarbamates chitosan derivatives were prepared and their antifungal activity was evaluated. The results showed methyl dithiocarbamates chitosan was more effective than ethyl dithiocarbamates chitosan. Two dithiocarbamates chitosan salts were prepared and their antifungal activity was studied. Their solubility obviously improved after chemical modification but the antifungal activity enhanced slightly. It indicated that solubility was not a decisive factor for antifungal activity. Additionally, dithiocarbamate chitosan (ADTCCS) was more effective than triethylene diamine dithiocarbamate chitosan (TEDADTCCS).
3. The derivative α-amino-n-propyl-o,o-diethyl phosphonate chitosan was obtained, antifungal results showed it had good activity. Two α-amino-2-(p-tolyloxy)pyrimidine phosphonate chitosan were prepared. All the chitosan derivatives had excellent and broad-spectrum antifungal activity. At250μg/mL, the derivatives inhibited growth of P. asparagi, F. oxysporum and A. porri at100%, and they were much stronger than triadimefon and polyoxin. Two α-amino-furanyl phosphonate chitosan derivatives were prepared via one pot synthesis under microwave assisted and solvent-free conditions. Their solubility and antifungal activity greatly enhanced after modification. The structure-activity relationship showed that α-amino-furanyl ethyl phosphonate chitosan was slightly effective than α-amino-furanyl methyl phosphonate chitosan.
4. It was found that solubility and antifungal activity of phosphor-containing chitosan derivatives was much better than (nitrogen and sulfur)-containing chitosan based on the antifunal screening results. Considering the preparation of α-APEPCS and α-AFEPCS was simpler and their raw material was cheaper, they were selected to study the mechanism of action.
5. In order to investigate the antifungal mechanisms of chitosan and its derivatives, we examined their effects on hyphal morphology, membrane permeability, pyruvate, chitosan, and soluble protein in F. oxysporum and G. theae-sinensis. SEM obversation showed that the hyphal treated with α-APEPCS and α-AFEPCS was serious damaged, part or all of the hyphal cracked at100μg/mL While the hyphal treated with polyoxin only had a slight deformation and the hyphal treated with chitosan had no obvious change. The relative permeability rates of the cell membrane treated with samples were all higher than that of blank control. The results showed that the cell membrane of fungi incubated with the samples was destroyed. And the relative permeability rates of the cell membrane treated with polyoxin changed fastest. The mycelial soluble protein content that was treated by the samples after24h was higher than the blank control, it also indicated the cell membrane of fungi was destroyed, and the mycelia soluble protein content for α-APEPCS was higher than the others. The mycelial pyruvate content of the fungi treated with the samples reduced after24h, it might be attributed to the fact that the derivatives can inhibit the activity of lactate dehydrogenase (LDH), thereby inducing the decrease of the pyruvate content.
In the study, five chitosan derivatives with greatly enhanced activity were selected via antifungal screening. Their mechanism of action was preliminary studied. The new obtained chitosan derivatives may have a good biocompatibility, biodegradability, and non-toxicity because they retained the skeleton structure of chitosan. Moreover, the derivatives had a different antifungal spectrum compared with triadimefon and polyoxin. All the above results described here lend themselves to find novel low-toxicity and no-cross-resistance marine fungicides. And it is important to explore marine biological resources technology of high-value line.
本论文以壳聚糖为骨架，通过定位导入、接枝共聚技术接入高活性基团制备了9类共30个含氮、硫、磷壳聚糖衍生物，并对制备的壳聚糖衍生物采用红外光谱、核磁波谱、元素分析、X射线衍射、差示扫描量热、扫描电镜等分析手段对其理化性质进行全面解析，确定了其取代位置、取代度、热力学性质、晶体性质等。通过抑菌活性筛选，研究了壳聚糖衍生物的抑菌活性和杀菌谱，并筛选出2种壳聚糖衍生物进行抑菌机理探讨。主要研究结果如下：
1.制备了3种壳聚糖1,2,4-三唑衍生物。壳聚糖1,2,4-三唑衍生物相比其合环前产物酰基硫脲壳聚糖，抑菌活性和溶解性明显提高。抑菌活性结果表明：三唑环上取代基的电负性和空间位阻对抑菌活性影响很大，甲基强于氯甲基，强于苯基。制备了2种新型壳聚糖1,2,3-三唑衍生物。抑菌结果表明：壳聚糖苯甲酸酯-1,2,3-三唑(PhTACS)活性强于壳聚糖烟酸酯-1,2,3-三唑(PyTACS)。
2.制备了9种壳聚糖酰基卤代苯缩氨基硫脲衍生物。抑菌结果表明：壳聚糖酰基缩卤代苯氨基硫脲衍生物中，氯乙酰基缩卤代苯氨基硫脲强于乙酰基，强于苯甲酰基；卤代苯中氯原子强于氟原子，强于三氟甲基。卤代苯中氯原子强于氟原子，强于三氟甲基。制备了7种壳聚糖烷基(取代苯基)缩氨基硫脲衍生物。抑菌结果表明：壳聚糖烷基(取代苯基)缩氨基硫脲衍生物中，含取代苯基的衍生物抑菌活性要明显强于带烷基的衍生物；苯环上的取代基供电性越强，活性越高。制备了2种壳聚糖二硫代氨基甲酸酯衍生物并测定了其抑菌活性。结果表明壳聚糖二硫代氨基甲酸甲酯的抑菌活性要强于甲酸乙酯。制备了2种壳聚糖二硫代氨基甲酸盐衍生物并研究了其抑菌活性。结果表明：壳聚糖硫代氨基甲酸盐，其溶解性比壳聚糖显著提高，但抑菌活性却没有明显提高，说明溶解度不是影响壳聚糖及其衍生物的决定因素。此外，硫代氨基甲酸氨盐的活性要强于三乙烯二胺盐。
3.制备了壳聚糖α-氨基丁基膦酸乙酯(α-APEPCS)，抑菌结果表明：壳聚糖a-氨基苯氧基嘧啶膦酸酯衍生物具有很好的抑菌效果和杀菌谱。制备了2种壳聚糖a-氨基苯氧基嘧啶膦酸酯衍生物。抑菌结果表明：制备的壳聚糖a-氨基苯氧基嘧啶膦酸酯衍生物均具有很好的抑菌效果和杀菌谱，在250μg/mL下对黄瓜枯萎病原真菌、芦笋茎枯病原真菌、葱紫斑病原真菌的抑菌活性可达100%，明显强于阳性对照三唑酮和多抗霉素。制备了2种壳聚糖α-氨基呋喃基膦酸酯类衍生物，制备的衍生物的溶解性和抑菌性均有很大提升。构效关系表明壳聚糖α-氨基膦酸酯，膦酸乙酯活性稍好。
4.通过对含氮、硫、磷壳聚糖衍生物的抑菌活性筛选，发现含磷壳聚糖衍生物的溶解性和抑菌活性均要强于含氮和硫的壳聚糖衍生物。由于壳聚糖α-氨基丁基膦酸乙酯(α-APEPCS)和壳聚糖α-氨基呋喃基膦酸乙酯(α-AFEPCS)合成更简便、所用原料成本更低，因此选择其进行抑菌机理的探讨。
5.以α-APEPCS和α-AFEPCS为研究对象，探讨了其对黄瓜枯萎病原真菌和茶炭疽病原真菌细胞壁和细胞膜结构和功能的影响及对代谢中间产物丙酮酸合成的影响。主要结论如下：描电镜显示，100μg/mL下，α-APEPCS和α-AFEPCS就能对病菌菌丝造成严重破坏，使菌丝部分或全部破裂；而多抗霉素处理的菌丝只是发生变形，壳聚糖处理的菌丝超微结构变化不大；α-APEPCS、α-AFEPCS、壳聚糖、多抗霉素均能改变菌丝细胞膜的通透性，其中多抗霉素处理后的菌液电导率变化最快；用α-APEPCS、α-AFEPCS、壳聚糖、多抗霉素处理24小时后的菌液中可溶性蛋白量均有所增加，说明药液破坏了细胞膜的结构，使蛋白等大分子溢出，其中α-APEPCS处理的蛋白溢出量最大。用α-APEPCS、α-AFEPCS、壳聚糖、多抗霉素处理24小时后的菌液中丙酮酸含量均有降低，说明各药液均抑制了病菌重要的代谢中间产物丙酮酸的合成。
本论文制备并筛选出了5种抑菌活性较好、有着潜在应用前景的壳聚糖衍生物，初步探讨了其作用机理。制备的壳聚糖衍生物保持了壳聚糖的基本骨架，因此可能会具有壳聚糖特有的生物相容性好、易于降解、毒性低的优点。此外，上述壳聚糖衍生物与市场上常用的杀菌剂三唑酮和多抗霉素相比，杀菌谱明显不同，这对研制新型低毒、无交互抗性的海洋生物农药进而代替部分高毒化学农药，实现海洋生物资源的高值化利用方面无疑有着十分重要的意义。
The frequent and wide application of traditional fungicides has caused serious problems such as environmental pollution and threats to human health. Therefore, it is critically necessary to discover new biofungicidal alternatives. Chitosan is one kind of natural polysaccharide and it is proved to have broad-spectrum antifungal activity. Chitosan possesses good biocompatibility, biodegradability, and non-toxicity. Hence, it has attracted much attention in the field of agriculture. However, chitosan can not be used directly as a fungicide due to its relatively low antifungal activity. Hence, many strategies were proposed to overcome these limitations. A widely used approach is the chemical modification of chitosan.
In this study, nine kinds of chitosan derivatives were designed via localization of import active group and strategy of graft copolymerization. Totally,30target derivatives were obtained. Their structures were confirmed by FT-IR, NMR, elemental analysis, XRD, DSC, and SEM to determine position and degree of substitution, crystal properties, and thermodynamic properties. Antifungal activity of them against R. solani, A. solani, P. piricola Nose, S. solani, P. asparagi, F. oxysporum, A. porri, G. theae-sinensis was tested. And two of the chitosan derivatives were selected to study mechanism of action. The major findings and results were listed as follows:
1. Three new1,2,4-triazole chitosan derivatives were prepared via cyclization of acyl thiourea chitosan. Their solubility and antifungal activity improved after chemical modification chitosan. Antifungal results exhibited the activity was greatly influenced by electronegativity of substituents in triazole and steric effect. The inhibitory effect followed a sequence of methyl＞methyl chloride＞phenyl. Two new1,2,3-triazole chitosan derivatives were prepared via “Click Chemistry”. Antifungal results showed PhTACS had a better inhibitory effect than PyTACS.
2. Nine acyl halogenated phenyl-thiosemicarbazone chitosan derivativess were prepared. The inhibitory effect followed a sequence of chloroacetyl thiosemicarbazone＞acetyl thiosemicarbazone＞benzoyl thiosemicarbazone. Various substituents of aromatic ring in chitosan derivatives had distinct impacts on antifungal activity: Cl＞F＞CF3. Seven alkyl(substituted phenyl) thiosemicarbazone were obtained and the antifungal activity was studied. It was found that the chitosan derivatives with substituted phenyl had stronger inhibitory effect than those with alkyl Strong electron contributing group at phenyl was helpful to enhance the antifungal properties. Two alkyl dithiocarbamates chitosan derivatives were prepared and their antifungal activity was evaluated. The results showed methyl dithiocarbamates chitosan was more effective than ethyl dithiocarbamates chitosan. Two dithiocarbamates chitosan salts were prepared and their antifungal activity was studied. Their solubility obviously improved after chemical modification but the antifungal activity enhanced slightly. It indicated that solubility was not a decisive factor for antifungal activity. Additionally, dithiocarbamate chitosan (ADTCCS) was more effective than triethylene diamine dithiocarbamate chitosan (TEDADTCCS).
3. The derivative α-amino-n-propyl-o,o-diethyl phosphonate chitosan was obtained, antifungal results showed it had good activity. Two α-amino-2-(p-tolyloxy)pyrimidine phosphonate chitosan were prepared. All the chitosan derivatives had excellent and broad-spectrum antifungal activity. At250μg/mL, the derivatives inhibited growth of P. asparagi, F. oxysporum and A. porri at100%, and they were much stronger than triadimefon and polyoxin. Two α-amino-furanyl phosphonate chitosan derivatives were prepared via one pot synthesis under microwave assisted and solvent-free conditions. Their solubility and antifungal activity greatly enhanced after modification. The structure-activity relationship showed that α-amino-furanyl ethyl phosphonate chitosan was slightly effective than α-amino-furanyl methyl phosphonate chitosan.
4. It was found that solubility and antifungal activity of phosphor-containing chitosan derivatives was much better than (nitrogen and sulfur)-containing chitosan based on the antifunal screening results. Considering the preparation of α-APEPCS and α-AFEPCS was simpler and their raw material was cheaper, they were selected to study the mechanism of action.
5. In order to investigate the antifungal mechanisms of chitosan and its derivatives, we examined their effects on hyphal morphology, membrane permeability, pyruvate, chitosan, and soluble protein in F. oxysporum and G. theae-sinensis. SEM obversation showed that the hyphal treated with α-APEPCS and α-AFEPCS was serious damaged, part or all of the hyphal cracked at100μg/mL While the hyphal treated with polyoxin only had a slight deformation and the hyphal treated with chitosan had no obvious change. The relative permeability rates of the cell membrane treated with samples were all higher than that of blank control. The results showed that the cell membrane of fungi incubated with the samples was destroyed. And the relative permeability rates of the cell membrane treated with polyoxin changed fastest. The mycelial soluble protein content that was treated by the samples after24h was higher than the blank control, it also indicated the cell membrane of fungi was destroyed, and the mycelia soluble protein content for α-APEPCS was higher than the others. The mycelial pyruvate content of the fungi treated with the samples reduced after24h, it might be attributed to the fact that the derivatives can inhibit the activity of lactate dehydrogenase (LDH), thereby inducing the decrease of the pyruvate content.
In the study, five chitosan derivatives with greatly enhanced activity were selected via antifungal screening. Their mechanism of action was preliminary studied. The new obtained chitosan derivatives may have a good biocompatibility, biodegradability, and non-toxicity because they retained the skeleton structure of chitosan. Moreover, the derivatives had a different antifungal spectrum compared with triadimefon and polyoxin. All the above results described here lend themselves to find novel low-toxicity and no-cross-resistance marine fungicides. And it is important to explore marine biological resources technology of high-value line.
引文
[1]王爱勤.甲壳素化学[M].第一版.北京:科学出版社,2008:9-10.
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