南海软海绵Halichondria sp.化学成分研究

为了寻找有生物活性的次生代谢产物,对从采集自中国南海的软海绵(Halichondria sp.)进行了化学成分研究,从中共分离得到了9个化合物,并对部分化合物进行了抗菌活性测试。根据现代波谱技术并结合文献数据,鉴定化合物的结构为:1,2,3,4-四氢-3-羧基-2-卡波林(1),色氨酸(2),环(异亮氨酸-脯氨酸)(3),开环(脯氨酸-缬氨酸)(4),环(丙氨酸-脯氨酸)(5),胆甾醇(6),二-(2-乙基己基)邻苯二甲酸酯(7),邻苯二甲酸正丁异丁酯(8)和邻苯二甲酸二异丁酯(9)。     

美花石斛化学成分及其护肤活性研究

本文研究美花石斛(Dendrobium loddigesii)的化学成分及其护肤活性。采用色谱法从美花石斛粗提物中分离得到12个化合物,利用波谱学方法分别鉴定为拖鞋状石斛素(1)、2,4,7-三羟基-9,10-二氢菲(2)、3,6,9-三羟基-3,4-二氢蒽-1(2H)-酮(3)、3,5′-二甲氧基-3′,4,9′-三羟基-7′,9-环氧-8,8′-木酚素(4)、5-(4-羟基-3-甲氧基苯乙基)-2-(4-羟基-3-甲氧基苯基)苯并二氢呋喃-3,7-二醇(5)、5-(4′′-羟基-3′′-甲氧基苯乙基)-2-(4′-羟基-5′-甲氧基苯基)-7-甲氧基苯并二氢吡喃-3-醇(6)、丁香脂素(7)、异香草醛(8)、松柏醛(9)、2-甲氧基-5-羟甲基苯酚(10)、二氢松柏醇(11)、4-羟基-3-甲氧基苯乙醇(12)。其中化合物3～5、7～12为首次从美花石斛中分离得到;化合物1、2、6(100μg/mL)有一定的自由基清除活性(>80%);化合物2(10μg/mL)有一定促胶原蛋白分泌活性(>20%)。结果显示从美花石斛的茎中分离得到了12个化合物,3个表现出良好的护肤活性。     

海南国产沉香的化学成分研究

从国产沉香(Aquilaria sinensis)的95%乙醇提取物中分离得到6个化合物,经波谱数据分析,分别鉴定为3,3'-(3-hydroxypropane-1,2-diyl)diphenol(1)、guaiacy lacetone(2)、6-羟基-2-(4'-羟基-2-苯乙基)色酮(3)、6-羟基-2-(2-羟基-2-苯乙基)色酮(4)、6-羟基-2-(2-苯乙基)色酮(5)和5α,6β,7α,8β-四羟基-2-(4'-甲氧基-2-苯乙基)-5,6,7,8-四氢色酮(6)。其中化合物1为新化合物,化合物3为首次从国产沉香中分离得到。     

两种柳珊瑚Anthogorgia caerulea和Menella kanisa的化学成分及其抗海洋污损生物附着活性研究北大核心CSCD

采用多种色谱分离技术,从北部湾的两种柳珊瑚Anthogorgia caerulea和Menella kanisa分离出7种次级代谢产物,运用MS、1H NMR和13C NMR等波谱方法并结合文献对照分别鉴定为N-(1-羟甲基-2-羟基)3,6-二烯-十七烷基-十六脂肪酸酰胺(1),邻苯二甲酸二丙酯(2),3-(2-苯乙基)苯酚(3),对甲氧基苯甲酸甲酯(4),邻苯二甲酸二己酯(5),梾木甙(6),次黄嘌呤核苷(7),其中化合物1为新化合物,其他化合物均首次从小月柳珊瑚(Menella kanisa)和花柳珊瑚(Anthogorgia caerulea)中分别分离得到。除化合物3,7外均显示出抗海洋污损生物藤壶幼虫附着能力,其中以化合物6的活性最好,化合物1的活性次之,其抗藤壶幼虫附着EC50分别为6. 89,8. 72μg/m L。     

虫类中药蛴螬中含氮化合物研究

从虫类中药蛴螬Holotrichia diomphalia Bates的乙醇提取物中分离得到13个化合物,其结构经谱学数据和与已知化合物比较,分别鉴定为N-[2-(4-羟苯基)-乙基]乙酰胺(1)、环(酪氨酸-脯氨酸)(2)、吡啶-3-甲酰胺(3)、胸苷(4)、戊内酰胺(5)、5-(羟甲基)-1H-吡咯-2-醛(6)、环(脯氨酸-缬氨酸)(7)、环(脯氨酸-丙氨酸)(8)、羟吲哚(9)、1,2,3,4-四氢-1,3,4-三氧-β-咔啉(10)、吲哚-3-醛(11)、黄苷(12)和苯基丙氨酸(13)。化合物1～13均为首次从该种动物药中分离得到。     

两种柳珊瑚Anthogorgia caerulea和Menella kanisa的化学成分及其抗海洋污损生物附着活性研究

采用多种色谱分离技术,从北部湾的两种柳珊瑚Anthogorgia caerulea和Menella kanisa分离出7种次级代谢产物,运用MS、1H NMR和13C NMR等波谱方法并结合文献对照分别鉴定为N-(1-羟甲基-2-羟基)3,6-二烯-十七烷基-十六脂肪酸酰胺(1),邻苯二甲酸二丙酯(2),3-(2-苯乙基)苯酚(3),对甲氧基苯甲酸甲酯(4),邻苯二甲酸二己酯(5),梾木甙(6),次黄嘌呤核苷(7),其中化合物1为新化合物,其他化合物均首次从小月柳珊瑚(Menella kanisa)和花柳珊瑚(Anthogorgia caerulea)中分别分离得到。除化合物3,7外均显示出抗海洋污损生物藤壶幼虫附着能力,其中以化合物6的活性最好,化合物1的活性次之,其抗藤壶幼虫附着EC50分别为6. 89,8. 72μg/m L。     

南海半红树植物黄槿内源真菌GT20036029代谢产物研究

应用多种色谱技术从半红树药用植物黄槿内生真菌GT20036029中分离得到9个化合物,通过波谱学方法并与已知化合物数据作比较,鉴定它们分别为N-(2-羟基苯乙基)乙酰胺(1)、环(L-脯氨酸-D-异亮氨酸)(2)、环(L-亮氨酸-L-脯氨酸)(3)、环(D-亮氨酸-L-脯氨酸)(4)、环(亮氨酸-酪氨酸)(5)、环(苯丙氨酸-丝氨酸)(6)、脑苷脂B(7)、(25S)-纽替皂苷元-3-O-α-L-鼠李糖-(1→2)-β-D-葡萄糖苷(8)和(25S)-异纽替皂苷元-3-O-α-L-鼠李糖-(1→2)-β-D-葡萄糖苷(9)。化合物1为首次从海洋真菌代谢产物中分离得到。化合物8显示了较好的肿瘤细胞生长抑制活性。     

南海深海细菌Bacillus amyloliquefaciens GAS 00152抗菌代谢产物研究

采用多种色谱分离技术,从南海深海细菌Bacillus amyloliquefaciens GAS 00152发酵液中分离得到12个化合物,经波谱数据分析分别鉴定为4-苯基-3-丁烯酰胺(1)、苯乙酰胺(2)、苯乙酸-2-(4-羟苯基)乙酯(3)、对羟基苯乙醇(4)、环(甘氨酸-2-氨基丁酸)(5)、环(甘氨酸-亮氨酸)(6)、环(甘氨酸-L-脯氨酸)(7)、环(D-脯氨酸-L-缬氨酸)(8)、环(4-羟基脯氨酸-亮氨酸)(9)、环(N-甲基甘氨酸-苯丙氨酸)(10)、环(L-2-羟基脯氨酸-苯丙氨酸)(11)、环(2-哌啶酸-苯丙氨酸)(12)。其中,化合物1为新天然产物。测试化合物1~12对番木瓜炭疽菌和香蕉黑星菌的抑制活性,发现化合物9对两种热带水果致病菌显示出中等抗菌活性。     

美洲大蠊愈创活性成分研究北大核心CSCD

采用色谱分离手段从美洲大蠊中分离得到17个化合物,利用波谱解析鉴定了它们的结构,分别命名为环(酪氨酸-酪氨酸)(1)、环(酪氨酸-脯氨酸)(2)、环(缬氨酸-酪氨酸)(3)、环(甘氨酸-苯丙氨酸)(4)、环(甘氨酸-色氨酸)(5)、环(色氨酸-丝氨酸)(6)、环(色氨酸-天冬酰胺)(7)、ginsenine(8)、6-羟基香豆素(9)、6-羟基色满-2-酮(10)、1-(3-乙基苯基)-1,2-乙二醇(11)、1-(4-乙基苯基)-1,2-乙二醇(12)、(E)-3,4-二羟基苯亚甲基丙酮(13)、2-羟基-3',4'-二羟基苯乙酮(14)、原儿茶酸(15)、对羟基苯甲酸甲酯(16)和丁香酸(17)。其中,化合物1~14均为首次从美洲大蠊中分离得到。此外,对化合物促进创面愈合作用进行了观察,化合物13显示较强的抑制NO生成活性。     

美洲大蠊愈创活性成分研究

采用色谱分离手段从美洲大蠊中分离得到17个化合物,利用波谱解析鉴定了它们的结构,分别命名为环(酪氨酸-酪氨酸)(1)、环(酪氨酸-脯氨酸)(2)、环(缬氨酸-酪氨酸)(3)、环(甘氨酸-苯丙氨酸)(4)、环(甘氨酸-色氨酸)(5)、环(色氨酸-丝氨酸)(6)、环(色氨酸-天冬酰胺)(7)、ginsenine(8)、6-羟基香豆素(9)、6-羟基色满-2-酮(10)、1-(3-乙基苯基)-1,2-乙二醇(11)、1-(4-乙基苯基)-1,2-乙二醇(12)、(E)-3,4-二羟基苯亚甲基丙酮(13)、2-羟基-3',4'-二羟基苯乙酮(14)、原儿茶酸(15)、对羟基苯甲酸甲酯(16)和丁香酸(17)。其中,化合物1~14均为首次从美洲大蠊中分离得到。此外,对化合物促进创面愈合作用进行了观察,化合物13显示较强的抑制NO生成活性。     

Chemical defence in mussels: antifouling effect of crude extracts of the periostracum of the blue mussel Mytilus edulis

Shells of the blue mussel Mytilus edulis remain free of fouling organisms as long as they possess an intact periostracum, and a multiple antifouling defence that comprises a ripple-like microtopography and the production of chemical antifouling compounds has been suggested previously. This study investigates the chemical defence strategy of blue mussels for the first time. Six crude extracts of the periostracum of intact shells were made using solvents of increasing polarity. These extracts were tested against common fouling organisms in laboratory based bioassays. Non-polar and moderately polar fractions showed the highest activities: the diethyl ether fraction strongly inhibited attachment of Balanus amphitrite cyprids and the marine bacteria Cobetia marina and Marinobacter hydrocarbonoclasticus. Attachment of the benthic diatom Amphora coffeaeformis was significantly reduced by the dichloromethane extract, whereas both ethyl acetate and diethyl ether fractions slowed diatom growth. These results provide the first evidence of surface bound compounds that may moderate surface colonisation.     

Butenolide inhibits marine fouling by altering the primary metabolism of three target organisms

Butenolide is a very promising antifouling compound that inhibits ship hull fouling by a variety of marine organisms, but its antifouling mechanism was previously unknown. Here we report the first study of butenolide's molecular targets in three representative fouling organisms. In the barnacle Balanus (=Amphibalanus) amphitrite, butenolide bound to acetyl-CoA acetyltransferase 1 (ACAT1), which is involved in ketone body metabolism. Both the substrate and the product of ACAT1 increased larval settlement under butenolide treatment, suggesting its functional involvement. In the bryozoan Bugula neritina, butenolide bound to very long chain acyl-CoA dehydrogenase (ACADVL), actin, and glutathione S-transferases (GSTs). ACADVL is the first enzyme in the very long chain fatty acid β-oxidation pathway. The inhibition of this primary pathway for energy production in larvae by butenolide was supported by the finding that alternative energy sources (acetoacetate and pyruvate) increased larval attachment under butenolide treatment. In marine bacterium Vibrio sp. UST020129-010, butenolide bound to succinyl-CoA synthetase β subunit (SCSβ) and inhibited bacterial growth. ACAT1, ACADVL, and SCSβ are all involved in primary metabolism for energy production. These findings suggest that butenolide inhibits fouling by influencing the primary metabolism of target organisms.     

The influence of natural surface microtopographies on fouling

Multiple antifouling strategies of marine organisms may consist of combinations of physical, chemical and mechanical mechanisms. In this study, the role of surface microtopography (< 500 microns) of different marine organisms, such as Cancer pagurus, Mytilus edulis, Ophiura texturata and the eggcase of Scyliorhinus canicula, has been investigated as a possible component of their defence systems. High resolution resin replicates of these natural surface structures were exposed to natural fouling in field experiments. Abundances of recruits were determined and compared to those on untextured, but otherwise identical, control surfaces to quantify the influence of the different microtopographies on fouling rates. Antifouling effects of microtopographies varied with type of microtopography and coloniser species. The surface microtopography of C. pagurus significantly rejected macrofoulers. The surface structures of the eggcase and O. texturata had repellent effects on microfoulers. Barnacle settlement was temporarily reduced on surface microtopographies of M. edulis and the eggcase. These results emphasise the promising nontoxic antifouling properties of microtextured surfaces.     

Antifouling and antibacterial compounds from a marine fungus <Emphasis Type="Italic">Cladosporium</Emphasis> sp. F14

To investigate the antifouling secondary metabolites from marine-derived fungi, we used bioassay-guided column chromatography techniques, such as HPLC, to separate and purify compounds from Cladosporium sp. F14. Extensive spectral analyses including 1D NMR spectra and MS were employed for structure elucidation of the compounds. Antilarval activity of the compounds was evaluated in settlement inhibition assays with laboratory-reared Balanus amphitrite and Bugula neritina larvae, while antibacterial activity was assessed with disc diffusion bioassay on growth inhibition of six marine bacterial species. In total, nine compounds were obtained. Among them, 3-phenyl-2-propenoic acid, cyclo-(Phe-Pro) and cyclo-(Val-Pro) had various antibacterial activities against three fouling bacteria, furthermore, 3-phenyl-2-propenoic acid and bis(2-ethylhexyl)phthalate effectively inhibited larval settlement of B. neritina and B. amphitrite larvae, respectively, indicating that the two compounds are potential natural antifouling agents.     

Design and Biological Evaluation of Antifouling Dihydrostilbene Oxime Hybrids

By combining the recently reported repelling natural dihydrostilbene scaffold with an oxime moiety found in many marine antifoulants, a library of nine antifouling hybrid compounds was developed and biologically evaluated. The prepared compounds were shown to display a low antifouling effect against marine bacteria but a high potency against the attachment and growth of microalgae down to MIC values of 0.01 μg/mL for the most potent hybrid. The mode of action can be characterized as repelling via a reversible non-toxic biostatic mechanism. Barnacle cyprid larval settlement was also inhibited at low μg/mL concentrations with low levels or no toxicity observed. Several of the prepared compounds performed better than many reported antifouling marine natural products. While several of the prepared compounds are highly active as antifoulants, no apparent synergy is observed by incorporating the oxime functionality into the dihydrostilbene scaffold. This observation is discussed in light of recently reported literature data on related marine natural antifoulants and antifouling hybrids as a potentially general strategy for generation of improved antifoulants.     

Antifouling enzymes and the biochemistry of marine settlement

Antifouling coatings are used extensively on marine vessels and constructions, but unfortunately they are found to pose a threat to the marine environment, notably due to content of metal-based biocides. Enzymes have repeatedly been proposed as an alternative to traditional antifouling compounds. In this review, the enzymes claimed to hold antifouling activity are classified according to catalytic functions. The enzyme functions are juxtaposed with the current knowledge about the chemistry of settlement and adhesion of fouling organisms. Specific focus will be on bacteria, microalgae, invertebrate larvae and macroalgae zoospores. Two main concepts in enzyme-based antifouling are identified: breakdown of adhesive components and catalytic production of repellent compounds in-situ. The validity of the various modes of action is evaluated and the groups of enzymes with the highest potential are highlighted.     

Screening of Marine Algal Extracts for Anti-settlement Activities against Microalgae and Macroalgae

The ban on the use of TBT-based antifouling paints for boats under 25 m in length has lead to a search for new non-toxic antifoulants. One of the most promising alternative technologies to heavy metal based antifouling paint is the development of antifouling coatings whose active ingredients are naturally occurring compounds from marine organisms. This is based on the principle that marine organisms also face the problem of the presence of epibionts on their own surfaces. In this study, the antifouling activity of a series of aqueous, ethanolic and dichloromethane extracts from thirty algae from the North East Atlantic coast was investigated. The extracts were tested in laboratory assays against species representative of two major groups of fouling organisms, viz . macroalgae and microalgae. The activity of several extracts was comparable to that of heavy metals and biocides (such as TBTO and CuSO 4 ) currently used in antifouling paints and their lack of toxicity with respect to the larvae of oysters and sea urchins suggests a potential for novel active ingredients.     

Antifouling potential of the marine microalga Dunaliella salina

Marine organisms have usually been viewed as sources of environmentally friendly compounds with antifouling activity. We performed a series of operations to investigate the antifouling potential of the marine microalga Dunaliella salina. For the ethyl acetate crude extract, the antialgal activity was significant, and the EC₅₀ value against Skeletonema costatum was 58.9 μg ml^?1. The isolated purified extract was tested for antifouling activity, the EC ₅₀ value against S. costatum was 21.2 μg ml^?1, and the LC₅₀ against Balanus amphitrite larvae was 18.8 μg ml^?1. Subsequently, both UHR–TOF–MS and GC–MS were used for the structural elucidation of the compounds, and a series of unsaturated and saturated 16- and 18-carbon fatty acids were detected. The data suggested that the fatty acid extracts from D. salina possess high antifouling activity, and could be used as substitutes for potent, toxic antifouling compounds.     

Marine microbial natural products in antifouling coatings

Ecological problems associated with current antifouling technologies have increased interest in the natural strategies that marine organisms use to keep their surfaces clean and free from fouling. Bacteria isolated from living surfaces in the marine environment have been shown to produce chemicals that are potential antifoulants. Active compounds from the cells and culture supernatant of two bacterial strains, FS‐55 and NudMB50–11, isolated from surface of the seaweed, Fucus serratus, and the nudibranch, Archidoris pseudoargus, respectively, were extracted using solid phase extraction. The extracts were combined with acrylic base paint resin and assayed for antifouling activity by measuring their ability to inhibit the growth of fouling bacteria. These formulations were found to be active against fouling bacteria isolated from marine surfaces. The formulation of antifouling paints that incorporate marine microbial natural products is reported here for the first time. This is a significant advance towards the production of an environmentally friendly antifouling paint that utilises a sustainable supply of natural biodegradable compounds.