烟台近海海域典型污损生物调查及其防除研究
刘苏静
学位类型博士
导师夏传海
2016-05-17
学位授予单位中国科学院大学
学位授予地点北京
关键词污损生物 Biofouling Organism 海洋防污剂 Antifouling Agent 吲哚 Indoles 构效关系 Structure-activity Relationship 快速评价 Rapid Evaluation
摘要海洋生物污损是人类从事海洋活动面临的重大挑战之一。如何有效解决海洋生物污损问题是人类开发利用海洋资源必须解决的一个难题。目前,在众多海洋生物污损的防除技术中,涂装海洋防污涂料是最经济、最方便、最有效的措施之一。然而,有机锡(TBT)、滴滴涕(DDT)被禁用后,低毒、高效、绿色、安全的环境友好型海洋防污涂料的开发是目前海洋污损防除领域研究的热点之一。
本论文通过对烟台近海海域污损生物的调查,了解烟台近海海域主要污损生物季节变化特征;在此基础上,对常见的几种海洋防污剂(辣椒碱、Sea-Nine 211等)开展防污活性研究,比较和筛选适合烟台近海海域污损生物防除的海洋防污剂;以吲哚类化合物为研究对象,开展吲哚类化合物活性研究,阐述结构-效应的关系,筛选结构简单、活性高、易于开发的抗污先导化合物;同时,针对防污剂的活性评价,比较几种用于海洋防污材料评价的生物模型,开展并建立卤虫的实验室快速评价方法。得出的主要结论如下:
海上挂板共鉴定分类大型污损生物 34 种,主要有优势物种为东方缝栖蛤、草苔虫、紫贻贝、藤壶、大室膜孔苔虫、牡蛎、麦秆虫、华美盘管虫、中胚花筒螅等。该海域全年都有污损生物附着,月板附着生物量为 2.8 ~1500 g/m2;污损生物附着高峰期为 5-11 月份,夏秋季节污损生物种类及数量最多(5984.3 g/m2,23 种;10231.5 g/m2,22 种)。
利用室内生物学方法及海上挂板实验对几种常见海洋防污剂进行活性评价,2,4,6-三氯苯基马来酰亚胺(TCPM)、Sea-Nine 211、吡啶硫酮类化合物的防污效果较好,说明这些化合物适合用于在北黄海地区生物多样性丰富的海域进行相关防污涂料的应用。
开展对吲哚类化合物抗紫贻贝附着的生物活性研究,吲哚类化合物能够明显抑制紫贻贝幼体附着,其 EC50 值介于 7.69 ~ 67.17 mg/L。吲哚(67.17 mg/L) >吲哚-3-甲醛(114.49 mg/L) > 芦竹碱(259.5 mg/L),提示吲哚母环可能是吲哚类化合物活性中心。5-氯吲哚(9.47 mg/L) > 5–氰基吲哚(9.85 mg/L) > 5-溴吲哚(15.67 mg/L) > 5-甲氧基吲哚(32.91 mg/L) > 吲哚(67.17 mg/L)、6-氯吲哚 (8.44 mg/L)> 6-溴吲哚(14.9 mg/L) > 6–氰基吲哚(17.17 mg/L)> 6–氨基吲哚(35.36 mg/L)> 吲哚(67.17 mg/L),说明吲哚类化合物结构存在取代基-活性的关系,同时,卤代吲哚类化合物存在取代位置-活性的关系,即 6 位 >
摘要iv5 位 > 7 位,且氯原子在吲哚类化合物的结构中有着重要的作用,是良好的抗紫贻贝附着的活性基团;海上挂板实验,证明 6 位取代的卤代吲哚类化合物的抗污活性,其防污效果与环境友好型海洋防污剂辣椒碱、Sea-Nine 211 相近,进一步验证了 6 位取代的卤代吲哚类化合物作为海洋防污剂开发的可能。
以藤壶、草苔虫、紫贻贝、卤虫四种模式生物对几种吲哚类化合物活性研究,卤虫对吲哚类化合物的敏感性实验的结果和污损生物藤壶、草苔虫、紫贻贝附着抑制实验结果基本上可互相验证,且与海上挂板结果最接近,证明了卤虫敏感性用于筛选海洋防污剂的可靠性。因此,建立以卤虫为模型生物的活性物质筛选对新型海洋防污剂的研发将有非常重要的意义。
其他摘要Marine biofouling is one of the major challenges for the marine activities. How to effectively solve the marine biofouling problem is a problem for human to develop marine resources. In many marine antifouling control methods, antifouling coating was the most convenient and economical. After TBT banned, low toxicity, high efficiency, green, safe and environment friendly marine antifouling coating would be care about marine fouling control.
The investigation of marine fouling organisms in Yantai Coastal had been developed in different seasons to understand seasonal variation characteristics. Based on the laboratory assessment, several kinds of common marine antifouling agents (capsaicin and Sea-Nine 211) had been used to screen antifouling activity. The activity of indole compounds had been conducted to illustrate the relationship between structure-activity, and screen a simple structure, high activity, antifouling lead compound. At the same time, it had been found that laboratory evaluation were should to be unified for the method and standard to screen antifouling agents. The main conclusions were as follows:
From the field test, 34 species of marine biofouling organisms were identified,and among which Hiatella orientalis, Bugula neritina, Mytilus edulis, Balanus
amphitrite, Membranipora grandicella, Crassostrea gigas, Caprella sp. Hydroides elegans, Tubularia mesembryanthemum,et al. were dominant species in Yantai
coastal. All of biofouling organisms referred to in Yantai coastal were observed all the year around in the monthly panel test, and the biomass were from 2.8 to 1500 g / m2 . By the analysis of community development, it would be concluded that the period of attachment peak for biofouling was from May to November, and the 
Abstract number of fouling organisms in summer and autumn raised to the most (5984.3 g/m2, 23 species; 10231.5 g/m2 , 22 species). 
Six compounds were used to evaluate the antifouling activities. It was showed that the compound of TCPM, Sea-Nine 211and Pyridine thioketone would be applied in antifouling coating in Yantai coastal.
Based on the results of the above studies, the antifouling activity of indoles against M. edulis was studied. It was shown that indoles inhibited the attachment of M. edulis, and they range in EC50 from 7.69 mg/L to 67.17 mg/L. The acticity of indoles substituted in 3 position were decreased in the order of indole (67.17 mg/L) >indole-3-carboxaldehyde (114.49 mg/L) > gramine (259.5 mg/L), the results indicated that the ring would be active center. At the same time, it was concluded that they were the relationship between substituent activity of the compound, with the order of 5-Chloroindole (9.47 mg/L) > 5-Cyanoindole (9.85 mg/L) > 5-Bromoindole (15.67 mg/L) > 5-Methoxyindole (32.91 mg/L) > Indole (67.17 mg/L)、6-Chloroindole (8.44mg/L) > 6-Bromoindole (14.9 mg/L) > 6-Cyanoindole (17.17 mg/L) > 6-Aminoindole(35.36 mg/L) > Indole (67.17 mg/L). Compared with the activity of the halogen substituted compounds, the relationship between the position and activity of the substituted group was found, 6 position > 5 position > 7 position, and the chlorine atom play an important role in the structure of indoles. Compared to Sea-Nine 211 and capsaicin, 6 substrituted indoles would be developed to marine antifouling agents.
Several test organisms were used to evaluate the activity of indoles. The sensitivity of brine shrimp against indoles was similar to the antifouling activity of B.amphitrite, M. edulis, B. neritina, against to indoles, and nearly to the result of field test. It was proved that the sensitivity of brine shrimp would be used to screen the marine antifouling agents. Therefore, it was very important to establish a new type of screening antifouling agents with the suitable model organism.
语种中文
文献类型学位论文
条目标识符http://ir.yic.ac.cn/handle/133337/17532
专题中国科学院烟台海岸带研究所知识产出_学位论文
作者单位中国科学院烟台海岸带研究所
第一作者单位中国科学院烟台海岸带研究所
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刘苏静. 烟台近海海域典型污损生物调查及其防除研究[D]. 北京. 中国科学院大学,2016.
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