CN104356730B - 一类丁烯酸内酯化合物在制备抗海洋生物污损涂料中的应用 - Google Patents
一类丁烯酸内酯化合物在制备抗海洋生物污损涂料中的应用 Download PDFInfo
- Publication number
- CN104356730B CN104356730B CN201410583640.XA CN201410583640A CN104356730B CN 104356730 B CN104356730 B CN 104356730B CN 201410583640 A CN201410583640 A CN 201410583640A CN 104356730 B CN104356730 B CN 104356730B
- Authority
- CN
- China
- Prior art keywords
- formula
- coating material
- marine
- biofouling prevention
- marine biofouling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 13
- 238000000576 coating method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 title claims abstract description 9
- 230000002265 prevention Effects 0.000 title claims abstract description 9
- SQEBMLCQNJOCBG-HVHJFMEUSA-N (5s)-3-(hydroxymethyl)-5-methoxy-4-methyl-5-[(e)-2-phenylethenyl]furan-2-one Chemical class C=1C=CC=CC=1/C=C/[C@]1(OC)OC(=O)C(CO)=C1C SQEBMLCQNJOCBG-HVHJFMEUSA-N 0.000 title claims abstract description 5
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- -1 polyethylene ethyl acetate copolymer Polymers 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 241000251557 Ascidiacea Species 0.000 claims description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 15
- 230000003373 anti-fouling effect Effects 0.000 abstract description 15
- XMLBVCBGTUQJHY-UHFFFAOYSA-N 5-hydroxy-4-methoxy-5-propan-2-ylfuran-2-one Chemical compound COC1=CC(=O)OC1(O)C(C)C XMLBVCBGTUQJHY-UHFFFAOYSA-N 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002519 antifouling agent Substances 0.000 abstract description 9
- AEKPZNDJHWFONI-LJQANCHMSA-N C([C@]1(C(=O)OC)C(=C(O)C(=O)O1)C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 Chemical compound C([C@]1(C(=O)OC)C(=C(O)C(=O)O1)C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 AEKPZNDJHWFONI-LJQANCHMSA-N 0.000 abstract description 7
- YCHNFUWRXHTAFK-UHFFFAOYSA-N aspernolide A Natural products C=1C=C2OC(C)(C)CCC2=CC=1CC1(C(=O)OC)OC(=O)C(O)=C1C1=CC=C(O)C=C1 YCHNFUWRXHTAFK-UHFFFAOYSA-N 0.000 abstract description 7
- MJCHJLWNXODVGT-UHFFFAOYSA-N aspernolide B Natural products O1C(=O)C(O)=C(C=2C=CC(O)=CC=2)C1(C(=O)OC)CC1=CC=C(O)C(CCC(C)(C)O)=C1 MJCHJLWNXODVGT-UHFFFAOYSA-N 0.000 abstract description 7
- AEKPZNDJHWFONI-UHFFFAOYSA-N butyrolactone II Natural products O1C(=O)C(O)=C(C=2C=CC(O)=CC=2)C1(C(=O)OC)CC1=CC=C(O)C=C1 AEKPZNDJHWFONI-UHFFFAOYSA-N 0.000 abstract description 7
- DXVJWCRTDUCRKF-UHFFFAOYSA-N butyrolactone IV Natural products COC(=O)C1(Cc2ccc3CC(Oc3c2)C(C)(C)O)OC(=O)C(=C1c4ccc(O)cc4)O DXVJWCRTDUCRKF-UHFFFAOYSA-N 0.000 abstract description 7
- NSXYYYUKWBLFQH-UHFFFAOYSA-N butyrolactone V Natural products C=1C=C2OC(C)(C)C(O)CC2=CC=1CC1(C(=O)OC)OC(=O)C(O)=C1C1=CC=C(O)C=C1 NSXYYYUKWBLFQH-UHFFFAOYSA-N 0.000 abstract description 7
- YCHNFUWRXHTAFK-XMMPIXPASA-N methyl (2R)-2-[(2,2-dimethyl-3,4-dihydrochromen-6-yl)methyl]-4-hydroxy-3-(4-hydroxyphenyl)-5-oxofuran-2-carboxylate Chemical compound O([C@@]1(CC=2C=C3CCC(C)(C)OC3=CC=2)C(=O)OC)C(=O)C(O)=C1C1=CC=C(O)C=C1 YCHNFUWRXHTAFK-XMMPIXPASA-N 0.000 abstract description 7
- NSXYYYUKWBLFQH-MHECFPHRSA-N methyl (2r)-4-hydroxy-2-[[(3s)-3-hydroxy-2,2-dimethyl-3,4-dihydrochromen-6-yl]methyl]-3-(4-hydroxyphenyl)-5-oxofuran-2-carboxylate Chemical compound O([C@@]1(CC=2C=C3C[C@H](O)C(C)(C)OC3=CC=2)C(=O)OC)C(=O)C(O)=C1C1=CC=C(O)C=C1 NSXYYYUKWBLFQH-MHECFPHRSA-N 0.000 abstract description 7
- MJCHJLWNXODVGT-XMMPIXPASA-N methyl (2r)-4-hydroxy-2-[[4-hydroxy-3-(3-hydroxy-3-methylbutyl)phenyl]methyl]-3-(4-hydroxyphenyl)-5-oxofuran-2-carboxylate Chemical compound C([C@]1(C(=O)OC)C(=C(O)C(=O)O1)C=1C=CC(O)=CC=1)C1=CC=C(O)C(CCC(C)(C)O)=C1 MJCHJLWNXODVGT-XMMPIXPASA-N 0.000 abstract description 7
- NVAIFFOQCAKMAH-HOYKHHGWSA-N methyl (2r)-4-hydroxy-3-(4-hydroxyphenyl)-2-[[(2r)-2-(2-hydroxypropan-2-yl)-2,3-dihydro-1-benzofuran-5-yl]methyl]-5-oxofuran-2-carboxylate Chemical compound O([C@@]1(CC=2C=C3C[C@@H](OC3=CC=2)C(C)(C)O)C(=O)OC)C(=O)C(O)=C1C1=CC=C(O)C=C1 NVAIFFOQCAKMAH-HOYKHHGWSA-N 0.000 abstract description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000025 natural resin Substances 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 2
- 239000004480 active ingredient Substances 0.000 abstract 1
- 239000012466 permeate Substances 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 11
- 241000238586 Cirripedia Species 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 241001465318 Aspergillus terreus Species 0.000 description 7
- 229930188620 butyrolactone Natural products 0.000 description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical class O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- FBMORZZOJSDNRQ-UHFFFAOYSA-N Demethoxy,B,HCl-Adriamycin Natural products C1C2C(=C)CCCC2(C)CC2(O)C1=C(C)C(=O)O2 FBMORZZOJSDNRQ-UHFFFAOYSA-N 0.000 description 4
- JUTMAMXOAOYKHT-UHFFFAOYSA-N karrikinolide Natural products C1=COC=C2OC(=O)C(C)=C21 JUTMAMXOAOYKHT-UHFFFAOYSA-N 0.000 description 4
- 230000003000 nontoxic effect Effects 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229930014626 natural product Natural products 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 229930000044 secondary metabolite Natural products 0.000 description 3
- YMHOBZXQZVXHBM-UHFFFAOYSA-N 2,5-dimethoxy-4-bromophenethylamine Chemical compound COC1=CC(CCN)=C(OC)C=C1Br YMHOBZXQZVXHBM-UHFFFAOYSA-N 0.000 description 2
- 241000058445 Celina Species 0.000 description 2
- 241001086210 Chaetoceros gracilis Species 0.000 description 2
- 241000050051 Chelone glabra Species 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 241000545067 Venus Species 0.000 description 2
- 229930194009 aspernolide Natural products 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- RCAULRNMJFUWRP-UHFFFAOYSA-N Acacetin-7-beta-D-glucurono-(1->2)-beta-D-glucuronid Natural products CC1OC1C1=CC(O)C(C)OC1=O RCAULRNMJFUWRP-UHFFFAOYSA-N 0.000 description 1
- 241000228212 Aspergillus Species 0.000 description 1
- 241000134991 Aspergillus flavipes Species 0.000 description 1
- 241000981399 Aspergillus melleus Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000252233 Cyprinus carpio Species 0.000 description 1
- 241001195836 Cypris Species 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000371997 Eriocheir sinensis Species 0.000 description 1
- 241000243251 Hydra Species 0.000 description 1
- 240000001427 Mallotus nudiflorus Species 0.000 description 1
- 241000021181 Nagia Species 0.000 description 1
- 241000133262 Nauplius Species 0.000 description 1
- 208000031481 Pathologic Constriction Diseases 0.000 description 1
- 241000237509 Patinopecten sp. Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241000195474 Sargassum Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- RCAULRNMJFUWRP-HETMPLHPSA-N aspyrone Chemical compound C[C@@H]1O[C@H]1C1=C[C@H](O)[C@@H](C)OC1=O RCAULRNMJFUWRP-HETMPLHPSA-N 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 210000003677 hemocyte Anatomy 0.000 description 1
- 229940000351 hemocyte Drugs 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 1
- 230000000366 juvenile effect Effects 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000001069 nematicidal effect Effects 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 150000002960 penicillins Chemical class 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 235000020637 scallop Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 210000001215 vagina Anatomy 0.000 description 1
Classifications
-
- 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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1535—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Paints Or Removers (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明公开了一类丁烯酸内酯在制备抗海洋生物污损涂料中的应用。本发明的butyrol actone V，aspernolide A，butyrolactone IV，aspernolide B，butyrolactone II，4‑(4‑Hydrox yphenyl)‑5‑(4‑hydroxyphenylmethyl)‑2‑hydroxyfurane‑2‑one，5,6‑dihydropenicillic acid，5,6‑dihydro‑6‑hydroxy‑penicillic acid具有抗海洋生物污损活性，能用于制备抗海洋生物污损涂料，如将其单独或组合渗入或扩散于成膜天然树脂，聚乙烯乙酸乙酯共聚物以及其它可水解，可溶或不溶性树脂等聚合物中，制成抗污损涂料，抗污损涂料能释放出足够量的有效成分至表面达到防污作用，并且这些化合物是天然活性成分，而且均不易溶于水，极易溶于氯仿、乙酸乙酯、甲醇等有机溶剂，具有良好的亲油性，因此可单独或组合应用于制备海洋防污剂中，具有良好的应用前景。
Description
技术领域：
本发明属于生物领域，具体涉及一类丁烯酸内酯化合物在制备抗海洋生物污损涂料中的应用。
背景技术：
在开发海洋、利用海洋的历史进程中，人类一直面临着防除海洋附着生物的问题。海洋污损生物(marine fouling organism)是海洋生物种栖息或附着在船舶和各种水下人工设施上，对人类经济活动产生不利影响的各种动物、植物和微生物的总称。全世界海洋污损生物共4000余种，我国沿海记录614种，其中最主要的类群是藤壶、藻类、水螅、尤介虫(石灰虫)、双壳类和海鞘等。海洋污损生物在船体、水管、渔箱、油井等各种物体表面附着、生长以至形成群落，造成海洋生物污损，严重影响和阻碍了人们对海洋资源的探索与利用。
20世纪70年代以后由于汞、砷等防污剂的禁用，大部分船体的防污一直都基于防污漆释放廉价且持续时间长的有机锡。20世纪80年代，人们发现有机锡在鱼类、贝类体内会积累，导致遗传变异甚至还有可能进入食物链，于是到80年代末，各国纷纷立法，禁用或限用有机锡防污涂料。国际海事组织(IMO)于2001年10月通过了国际协定即控制船体防污中有害防污剂的应用，到2008年全面禁止在防污涂料中使用有机锡。随后在市场占主导地位的防污涂料是低释放率的含铜防污涂料，然而，重金属元素会在海洋中，特别是在海港中大量聚集，导致海藻的大量死亡，影响鲤鱼、虾、蟹及各种软体、背囊动物的胚胎生长，破坏其血细胞，从而破坏其生态平衡，因此也最终将会被禁用。开发无毒防污剂已经成为国际上急需解决的重要课题，这方面的研究突破将具有全球性的影响，同时将会占有全球市场。海洋天然产物防污剂属于无毒防污剂，是海洋生物自身产生的具有防污活性的次级代谢产物，这些天然化合物能很快降解，且不危害海洋生物的生命，有利于保持生态平衡，因此，研制开发海洋天然产物防污剂已成为获得高效无毒防污剂的重要途径之一。
式(1)-式(8)所示的化合物是一类丁烯酸内酯类化合物。其中式(1)所示的化合物，其为butyrolactone V，公开于文献[1].Lin,Ting；Lu,Chunhua；Shen,Yuemao.Secondary metabolites of Aspergillus sp F1,a commensal fungal strainof Trewia nudiflora.Natural Product Research,2009,23(1):77-85；[2].Nagia,Mohamed Ms；El-Metwally,Mohammad Magdy；Shaaban,Mohamed；El-Zalabani,Soheir M；Hanna,Atef G.Four butyrolactones and diverse bioactive secondary metabolitesfromterrestrial Aspergillus flavipes MM2:isolation and structuredetermination.Organic and medicinal chemistry letters,2012,2(1):2-9.[3].Haritakun,Rachada；Rachtawee,Pranee；Chanthaket,Rungtiwa；Boonyuen,Nattawut；Isaka,Masahiko.Butyrolactones from the Fungus Aspergillus terreus BCC4651.Chemical&Pharmaceutical Bulletin,2010,58(11):1545-1548中。式(2)所示的化合物，其为aspernolide A，公开于文献Parvatkar,Rajesh R.；D'Souza,Celina；Tripathi,Ashootosh；Naik,Chandrakant G.Aspernolides A and B,butenolides from a marine-derived fungus Aspergillus terreus,Phytochemistry,2009,70(1):128-132中。式(3)所示的化合物，其为butyrolactone IV，公开于文献Rao,K.V.；Sadhukhan,A.K.；Veerender,M.；Ravikumar,V.；Mohan,E.V.S.；Dhanvantri,S.D.；Sitaramkumar,M.；Babu,J.M.；Vyas,K.；Reddy,G.O.Butyrolactones from Aspergillus terreus.Chemical&Pharmaceutical Bulletin,2000,48(4):559-562中。式(4)所示的化合物，其为aspernolide B，公开于文献Parvatkar,Rajesh R.；D'Souza,Celina；Tripathi,Ashootosh；Naik,Chandrakant G.Aspernolides A and B,butenolides from a marine-derived fungus Aspergillus terreus,Phytochemistry,2009,70(1):128-132中。式(5)所示的化合物，其为butyrolactone II，公开于文献[1].Nitta,K；Fujita,N；Yoshimura,T；Arai,K；Yamamoto,Y.Metabolic Products of Aspergillus terreus.IX.Biosynthesisof Butyrolactone Derivatives isolated from Strains IFO 8835and 4100.Chemical&Pharmaceutical Bulletin,1983,31(5):1528-1533；[2].Rao,K.V.；Sadhukhan,A.K.；Veerender,M.；Ravikumar,V.；Mohan,E.V.S.；Dhanvantri,S.D.；Sitaramkumar,M.；Babu,J.M.；Vyas,K.；Reddy,G.O.Butyrolactones from Aspergillus terreus.Chemical&Pharmaceutical Bulletin,2000,48(4):559-562；[3].Haritakun,Rachada；Rachtawee,Pranee；Chanthaket,Rungtiwa；Boonyuen,Nattawut；Isaka,Masahiko.Butyrolactonesfrom the Fungus Aspergillus terreus BCC 4651.Chemical&PharmaceuticalBulletin,2010,58(11):1545-1548中。式(6)所示的化合物，其为4-(4-Hydroxyphenyl)-5-(4-hydroxyphenylmethyl)-2-hydroxyfurane-2-one，公开于文献Cotelle,P.；Cotelle,N.；Teissier,E；Vezin,H.Synthesis and antioxidant properties of a new lipophilic ascorbic acidanalogue.Bioorganic&Medicinal Chemistry,2003,11(6):1087-1093中。式(7)所示的化合物，其为5,6-dihydropenicillic acid，公开于文献Kimura,Y；Nakahara,S；Fujioka,S.Aspyrone,a nematicidal compound isolated from thefungus,Aspergillus melleus.Bioscience Biotechnology and Biochemistry,1996,60(8):1375-1376中。(8)所示的化合物，其为5,6-dihydro-6-hydroxy-penicillic acid，公开于专利Maruhashi M,Ito M,Hanada K.Penicillin analog.Japan:03-184968,1991-12-08中。
发明内容：
本发明的目的是提供如式(1)-式(8)所示的任一丁烯酸内酯类化合物在制备抗海洋生物污损涂料中的应用。
本发明通过抗海洋大型污损生物藤壶幼虫附着活性测试发现，本发明的式(1)-式(8)所示的丁内酯类化合物butyrolactone V(式1)，aspernolide A(式2)，butyrolactoneIV(式3)，aspernolide B(式4)，butyrolactone II(式5)，4-(4-Hydroxyphenyl)-5-(4-hydroxyphenylmethyl)-2-hydroxyfurane-2-one(式6)，5,6-dihydropenicillic acid(式7)，5,6-dihydro-6-hydroxy-penicillic acid(式8)抑制藤壶幼虫附着的EC50值分别为22.13μg/mL，7.37μg/mL，7.37μg/mL，16.07μg/mL，20.27μg/mL，11.32μg/mL，19.29μg/mL，10.08μg/mL；除了式(7)的EC50/LC50值为36外，其它化合物的EC50/LC50值均大于100，具有良好的无毒性的抗海洋生物污损活性。
因此本发明提供式(1)-式(8)所示的任一丁烯酸内酯类化合物在制备抗海洋生物污损涂料中的应用。
优选，式(1)-式(8)所示的任一丁烯酸内酯类化合物在制备抗藤壶幼虫附着涂料中的应用。
优选，式(8)所示的丁烯酸内酯类化合物在制备抗石灰虫、管虫、海鞘和牡蛎附着涂料中的应用。
将本发明丁内酯化合物butyrolactone V(式1)，aspernolide A(式2)，butyrolactone IV(式3)，aspernolide B(式4)，butyrolactone II(式5)，4-(4-Hydroxyphenyl)-5-(4-hydroxyphenylmethyl)-2-hydroxyfurane-2-one(式6)，5,6-dihydropenicillic acid(式7)，5,6-dihydro-6-hydroxy-penicillic acid(式8)单独或组合渗入或扩散于成膜天然树脂，聚乙烯乙酸乙酯共聚物以及其它可水解、可溶或不溶性树脂等聚合物中，制成抗污损涂料，抗污损涂料能释放出足够量的有效成分至表面达到防污作用。
本发明的丁烯酸内酯化合物butyrolactone V(式1)，aspernolide A(式2)，butyrolactone IV(式3)，aspernolide B(式4)，butyrolactone II(式5)，4-(4-Hydroxyphenyl)-5-(4-hydroxyphenylmethyl)-2-hydroxyfurane-2-one(式6)，5,6-dihydropenicillic acid(式7)，5,6-dihydro-6-hydroxy-penicillic acid(式8)都是从真菌中分离得到的，属于天然活性成分，而且均不易溶于水，极易溶于氯仿、乙酸乙酯、甲醇等有机溶剂，具有良好的亲油性，因此可单独或组合应用于制备海洋防污剂等。
本发明的丁烯酸内酯化合物butyrolactone V(式1)，aspernolide A(式2)，butyrolactone IV(式3)，aspernolide B(式4)，butyrolactone II(式5)，4-(4-Hydroxyphenyl)-5-(4-hydroxyphenylmethyl)-2-hydroxyfurane-2-one(式6)，5,6-dihydropenicillic acid(式7)，5,6-dihydro-6-hydroxy-penicillic acid(式8)具有抗海洋生物污损活性，能用于制备抗海洋生物污损药物，如将其单独或组合渗入或扩散于成膜天然树脂，聚乙烯乙酸乙酯共聚物以及其它可水解，可溶或不溶性树脂等聚合物中，制成抗污损涂料，抗污损涂料能释放出足够量的有效成分至表面达到防污作用，并且这些化合物是天然活性成分，而且均不易溶于水，极易溶于氯仿、乙酸乙酯、甲醇等有机溶剂，具有良好的亲油性，因此可单独或组合应用于制备海洋防污剂中，具有良好的应用前景。
附图说明
图1是实施例2的实验结果图。
具体实施方式：
以下实施例是对本发明的进一步说明，而不是对本发明的限制。
实施例1：式(1)-式(8)所示的丁烯酸内酯类化合物的抗海洋大型污损生物藤壶幼虫附着活性测试
活性测试模型是采用目前实验室最常用的海洋污损生物模型之一纹藤壶虫金星幼虫(Barnacles larvae)的附着抑制试验。藤壶成虫以纤细角毛藻(Chaetocerosgracilis Schutt)为食物，在0.22μm过滤海水中将藤壶的无节幼体培养到金星幼体阶段，每毫升2个幼虫，培养温度28℃。用产生的金星阶段幼体进行活性试验。采用24孔聚苯乙烯板测定化合物的抗幼虫附着活性。将化合物butyrolactone V(式1)溶于DMSO，用无菌过滤海水稀释成不同的浓度溶液(60–140μg/mL)作为测试液。每个孔中加入1mL测试液和20±2个成熟的藤壶幼虫，每个浓度设5个重复样，无菌过滤海水做空白对照。将24孔细胞培养板置于30℃培养箱中放置24小时。在显微镜下统计附着的幼虫数，用spss 11.0软件进行统计分析，计算EC50值。
其它单体化合物aspernolide A(式2)，butyrolactone IV(式3)，aspernolide B(式4)，butyrolactone II(式5)，4-(4-Hydroxyphenyl)-5-(4-hydroxyphenylmethyl)-2-hydroxyfurane-2-one(式6)，5,6-dihydropenicillic acid(式7)，5,6-dihydro-6-hydroxy-penicillic acid(式8)参照上述方法进行抗海洋大型污损生物藤壶幼虫附着活性测试。
实验结果显示，式(1)～式(8)所示的丁烯酸内酯类化合物抑制藤壶幼虫附着的EC50值为分别为22.13μg/mL，7.37μg/mL，7.37μg/mL，16.07μg/mL，20.27μg/mL，11.32μg/mL，19.29μg/mL，10.08μg/mL；除了式(7)的EC50/LC50值为36外，其它化合物的EC50/LC50值均大于100，由此说明式(1)～式(8)所示的丁烯酸内酯类化合物具有抗藤壶幼虫附着活性且无毒性，能用于制备抗海洋生物污损涂料中。
实施例2：式(8)所示的丁烯酸内酯类化合物的野外海上挂板活性测试
野外海上挂板试验采用传统的抗污损生物野外海上挂板试验方法。分别将0.2g和0.4g含式(8)所示的丁烯酸内酯类化合物用1mL的甲醇完全溶解，然后与10mL含45％polyurethane的树脂充分混合后平铺于干燥的PVC(10×10×0.3cm)板上，风干后悬挂于深圳大亚湾扇贝养殖海区(东经114°32’59,北纬22°40’37)。把含0.2g式(8)所示的丁烯酸内酯类化合物的PVC作为处理组1，含0.4g式(8)所示的丁烯酸内酯类化合物的PVC作为处理组2。每个处理设三个平行。取1mL甲醇10mL含45％polyurethane的树脂充分混合后涂板作为对照。挂板于第2个月取出，检查污损生物的种类并测量污损生物所占整块PVC板的面积百分比。用SPSS 11.0软件进行统计分析对照板上与处理板上污损生物所占面积百分比大小的差异性(t检验)。
实验结果如图1显示：挂板2个月后，对照板上已经附着了大量的污损生物藤壶、石灰虫、管虫、海鞘和牡蛎等污损生物(污损生物占整块板的面积百分比为87.43)，而处理组1(处理1)板上只有少量的藤壶和石灰虫等污损生物(污损生物占整块板的面积百分比为43.41)，而处理组2(处理2)板上有更少量的藤壶和石灰虫等污损生物(污损生物占整块板的面积百分比为21.65)。由此说明式(8)所示的丁烯酸内酯类化合物具有抗藤壶、石灰虫、管虫、海鞘和牡蛎等海洋污损生物的附着活性，能用于制备抗海洋污损涂料中。
Claims (3)
1.式(7)-式(8)所示的任一丁烯酸内酯类化合物在制备抗海洋生物污损涂料中的应用；
2.根据权利要求1所述的应用，其特征在于，式(7)-式(8)所示的任一丁烯酸内酯类化合物在制备抗藤壶幼虫附着涂料中的应用。
3.根据权利要求1所述的应用，其特征在于，式(8)所示的丁烯酸内酯类化合物在制备抗石灰虫、管虫、海鞘和牡蛎附着涂料中的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410583640.XA CN104356730B (zh) | 2014-10-27 | 2014-10-27 | 一类丁烯酸内酯化合物在制备抗海洋生物污损涂料中的应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410583640.XA CN104356730B (zh) | 2014-10-27 | 2014-10-27 | 一类丁烯酸内酯化合物在制备抗海洋生物污损涂料中的应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104356730A CN104356730A (zh) | 2015-02-18 |
| CN104356730B true CN104356730B (zh) | 2017-02-01 |
Family
ID=52524052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410583640.XA Expired - Fee Related CN104356730B (zh) | 2014-10-27 | 2014-10-27 | 一类丁烯酸内酯化合物在制备抗海洋生物污损涂料中的应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104356730B (zh) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106700787A (zh) * | 2015-11-12 | 2017-05-24 | 香港科技大学 | 一种基于自抛光聚合物/丁烯酸内酯及其衍生物的环境友好海洋防污涂料 |
| JP7244821B2 (ja) * | 2018-12-11 | 2023-03-23 | 学校法人北里研究所 | 骨代謝阻害活性を有する新規化合物及びその製造方法 |
| CN112042655B (zh) * | 2020-08-07 | 2021-05-04 | 中国科学院南海海洋研究所 | 丁烯酸吡咯二酮化合物在制备海洋污损生物防除剂中的应用 |
| US12082584B2 (en) * | 2021-03-18 | 2024-09-10 | The Hong Kong University Of Science And Technology | BOC-butenolide, an antifouling compound that has potent ability to inhibit the settlement of marine invertebrate larvae |
| CN115772256B (zh) * | 2022-12-07 | 2023-09-29 | 珠海市耕海科技有限公司 | 环保防污乳状液及其制备方法和应用 |
| CN116240728B (zh) * | 2022-12-30 | 2024-01-16 | 佛山港科涂工技术有限公司 | 水性仿生环保防污涂料及其制备方法和应用 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1156471A (zh) * | 1994-07-06 | 1997-08-06 | 单一检索有限公司 | 防污组合物 |
| CN1270616A (zh) * | 1997-07-24 | 2000-10-18 | 水产养殖Crc有限公司 | 甲壳类动物和水产养殖设备的防生物附着 |
| CN102105542A (zh) * | 2008-07-24 | 2011-06-22 | 香港科技大学 | 防污的呋喃-2-酮衍生物 |
| CN103351369A (zh) * | 2013-04-19 | 2013-10-16 | 中国海洋大学 | 一种木脂素化合物及其制备方法与作为天然海洋生物防污剂的应用 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0733741A (ja) * | 1993-07-22 | 1995-02-03 | Mitsui Toatsu Chem Inc | 脂溶性ビタミンｃ−ニコチン酸アミドコンプレックス及び防汚剤 |
-
2014
- 2014-10-27 CN CN201410583640.XA patent/CN104356730B/zh not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1156471A (zh) * | 1994-07-06 | 1997-08-06 | 单一检索有限公司 | 防污组合物 |
| CN1270616A (zh) * | 1997-07-24 | 2000-10-18 | 水产养殖Crc有限公司 | 甲壳类动物和水产养殖设备的防生物附着 |
| CN102105542A (zh) * | 2008-07-24 | 2011-06-22 | 香港科技大学 | 防污的呋喃-2-酮衍生物 |
| CN103351369A (zh) * | 2013-04-19 | 2013-10-16 | 中国海洋大学 | 一种木脂素化合物及其制备方法与作为天然海洋生物防污剂的应用 |
Non-Patent Citations (1)
| Title |
|---|
| Antifouling activity of synthetic γ-hydroxybutenolides;Michael Stewart等;《International Biodeterioration & Biodegradation》;20140331;第88卷;第176-184页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104356730A (zh) | 2015-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104356730B (zh) | 一类丁烯酸内酯化合物在制备抗海洋生物污损涂料中的应用 | |
| Xu et al. | Potent antifouling compounds produced by marine Streptomyces | |
| CN101715770B (zh) | 环（脯氨酸-苏氨酸）在海洋污损生物防除中的应用 | |
| Targett et al. | Antifouling agents against the benthic marine diatom, Navicula salinicola Homarine from the gorgonians Leptogorgia virgulata and L. setacea and analogs | |
| ES2392142T3 (es) | Composiciones antiincrustantes de espinosina, procedimientos de uso de las mismas y artículos protegidos de la adhesión de organismos bioincrustantes | |
| Krug | Defense of benthic invertebrates against surface colonization by larvae: a chemical arms race | |
| Feng et al. | The plant alkaloid camptothecin as a novel antifouling compound for marine paints: Laboratory bioassays and field trials | |
| Mooney et al. | Ichthyotoxicity of four species of gymnodinioid dinoflagellates (Kareniaceae, Dinophyta) and purified karlotoxins to larval sheepshead minnow | |
| CN102757677B (zh) | 一类吲哚生物碱在制备抗海洋生物污损涂料中的应用 | |
| Fusetani et al. | Antifouling compounds | |
| Fu et al. | Controlling the main source of green tides in the Yellow Sea through the method of biological competition | |
| Prakash et al. | Antimicrofouling properties of chosen marine plants: An eco-friendly approach to restrain marine microfoulers | |
| Mallin et al. | Response of two zooptankton grazers to an ichthyotoxic estuarine dinoflagellate | |
| CN104592798B (zh) | 乙酸橙酰胺在海洋污损生物防除中的应用 | |
| CN101724305B (zh) | 环(脯氨酸-丙氨酸)在海洋污损生物防除中的应用 | |
| Dahms et al. | Laboratory bioassays for screening marine antifouling compounds | |
| Bryan et al. | A comparative study of the non-acidic chemically mediated antifoulant properties of three sympatric species of ascidians associated with seagrass habitats | |
| CN111269603B (zh) | 一种吡嗪喹唑啉二酮生物碱化合物在制备海洋污损生物防除剂中的应用 | |
| CN111234586B (zh) | 一种吡嗪喹唑啉三酮生物碱化合物在制备海洋污损生物防除剂中的应用 | |
| CN103642299A (zh) | 一类苯并杂环生物碱在制备抗海洋生物污损涂料中的应用 | |
| CN101485321A (zh) | 齐墩果酸在制备海洋环保防污剂中的应用 | |
| CN103484409B (zh) | 一种源于海洋细菌抑藻活性物质棕榈油酸及其制备方法 | |
| CN102321089A (zh) | 一种螺环生物碱化合物及其制备方法和抗海洋生物污损方面的应用 | |
| CN101717594B (zh) | 环脯氨酸-亮氨酸在海洋污损生物防除中的应用 | |
| JP5103425B2 (ja) | 水中有害付着生物に対する防汚剤 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170201 |