Φσζικά προϊόνηα από Ιωάννου Ευςταθίου θαλάζζιοσς οργανιζμούς: Ροφςςησ Βαςίλειοσ μια οικολογική προςέγγιςη για την αντιμετώπιςη τησ βιοεπίςτρωςησ Τομέασ Φαρμοκογνωςίασ και Χημείασ Φυςικών Προϊόντων Τμήμα Φαρμακευτικήσ, ΕΚΠΑ Άδεια Χρήζης Το παρόν εκπαιδεσηικό σλικό σπόκειηαι ζε άδειες τρήζης Creative Commons. Για εκπαιδεσηικό σλικό, όπως εικόνες, ποσ σπόκειηαι ζε άδεια τρήζης άλλοσ ηύποσ, ασηή πρέπει να αναθέρεηαι ρηηώς.
Τομέας Φαρμακογνωσίας και Χημείας Φυσικών Προϊόντων, Τμήμα Φαρμακευτικής, Εθνικό και Καποδιστριακό Πανεπιστήμιο Αθηνών Marine Biofouling
Marine Biofouling
Marine Biofouling Unprotected vessel hulls may gather 50 kg of fouling per m in less than six months of being at sea. On a large ship with 40,000 m of underwater area would add up to 6,000 tones of fouling. A ship with heavily fouled hulls may roughly require 70% additional propulsion power in comparison to a ship with clean hulls. Fuel consumption increases of about 40% have been observed due to biofouling and the cost of a voyage can be increased by about 77%. ull maintenance is more expensive and time-consuming because drydocking operations need to be more frequent and longer. The repair costs the maritime industries over 6.5 billion USD per year. A 5% increase in biofouling causes a 4% increase in emission of CO, NO x and SO gases. 3
Shipping accounts for approximately 90% of world trade and seaborne trade has quadrupled over the past three decades. The world fleet is consuming approximately 300 million tons of oil annually (-5% of the total oil consumption). Biofouling on vessels hulls increases frictional drag which reduces speed or requires increased power and fuel consumption to maintain speed. It is estimated that the value of the antifouling market worldwide is approximately 50 billion USD per year, a market in which most products include organotin paints that have been prohibited from use since 008. The economic costs of fouling have been a driving force behind the development of antifouling technologies, a global industry that is now worth approximately 4 billion USD annually and is expected to grow to 5 billion USD in 05. An efficient antifouling protection will be saving globally over 50 billion USD per year. 4
Off shore oil platforms Aquaculture 5
Common organotin biocides Anti-fouling systems timeline Anti-fouling systems Resin or pitch used on ship hulls. 900 Copper-based paints containing mercury oxide, arsenic halogen compounds. Introduction of free association TBT-based antifouling paints. 960s 970s Environmental impacts /measures taken Long-life anti-fouling paints provide protection to hulls for up to 4 months. Self-polishing anti-fouling paints containing TBT hailed by shipping industry. Anti-fouling toxin is partly released by a reaction with seawater and paint polishes away layer by layer, continuously exposing new layer to seawater. Biocide delivery rate is more or less constant. Ships can now drydock just once every five years. Introduction of self -polishing co-polymer TBT based anti-fouling paints. Introduction of non-stick coating for small vessels. Various tin-free alternatives developed. 980s Early 990s 003 008 Worrying side-effects of TBT on oysters (deformities) identified in France. Various countries ban TBT on boats less than 5 meters long. IMO Resolution recommends Governments ban TBT on vessels less than 5 meters in length; TBT leaching from paint should be less than 4 μg/ cm / day. Prohibition of application of organotin compounds acting as biocide in anti-fouling systems Complete prohibition on organotin compounds acting as biocides in anti-fouling systems 6
Marine organisms Tetrahedron, 008, 64, 584-590. J. Nat. Prod., 008, 7, 386-39. Mar. Drugs, 009, 7, 84-95. Chemistry & Biodiversity, 00, 7, 86-95. Bioorg. Med. Chem. 00, 8, 3 330. Chemistry & Biodiversity, 00, 7, 666-676. 7
omoditerpenes from the red alga Sphaerococcus coronopifolius R 0 3 5 4 6 7 8 9 0 R 9 8 7 3 4 5 R : R= R= : R= OO R = O 3: R= OO R = O 5: R= O 6: R= O 7: R= 4: R= O R= O O 3 O 8 9 4 R 3 R 3 9 4 8 0 5 5 7 4 6 O O O R 9 7 OR 8 0 R O 3 : R 9 4 : R = O R = O = 8 = 0 : R 5 3 5 7 : = OO R = OO 4 6 = α-o = α-o 7 3: R = R = OO O R = 3: : R = OO R = β-o 8 = β-o 9 0 : R = OO R = α- O MICs 3 ( g/ml) R = against R = β- MDR and methicillin resistant Staphylococcus aureus : OO SA99B O RN40 EMRSA-5 ATCC 5943 XU (TetK)/ EMRSA- Compounds (NorA) (MsrA) (meca) (meca) (meca) 4 4 4 5: R= O 5: R= O 6: R= 6: R=,, 3 4 5 6 Nor -3 0.5 3-3 3 0.5 8 0.5 3 3 0.5 3 0.5 3-64 8 0.5 64-8 8
9 5 4 8 0 5 7 0 9 8 3 (A) (B) (C) 0 9 8 7 5 4 3 9 7 5 3 (A) (B) (C)
Determination of antifouling activity omosphaerol Effects of bromosphaerol on settlement (grey area) and mortality (black area) of B. amphitrite cyprids EC 50 = 0.3 mg/l Therapeutic Ratio (LC 50 /EC 50 ) of bromosphaerol = 434.78 Mar. Biotechnol., 0, 3, 764-77 Balanus amphitrite only small molecules with a TR>50 and an EC 50 <5 mg/l against both hard and soft foulers should be considered for applications 0
PROJECT MARIPAINTS Novel Self-ealing Eco-friendly Coatings with Antifouling and Anticorrosion Properties for Maritime Applications GSRT: ΣΥΝ_5_74 natural antifoulant natural antifoulant Fig.. The concept of antifouling and anticorrosion technology Development of self-healing marine paints with anticorrosion and antifouling properties incorporating copper oxide nanocontainers loaded with natural antifoulants in topcoat formulations
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Acknowledgements PROJECT MARIPAINTS NCSR Demokritos (G. Kordas) NKUA Dept artment of Biology (G. Verroiopoulos) NTUA School of Chemical Engineering (C. Charitidis) Kefalonia Fisheries Wilckens Petrocoll Institute of Biology, Medicinal Chemistry and Biotechnology, National ellenic Research (T. Calogeropoulou, K. Proussis) Institute of Marine Sciences (ISMAR), CNR Genoa (M. Faimali, V. Piazza) Funding: GSRT Project SYNERGASIA 0 MARIPAINTS ΕΥΡΩΠΑΪΚΗ ΕΝΩΣΗ ΕΥΡΩΠΑΪΚΟ ΤΑΜΕΙΟ ΠΕΡΙΦΕΡΕΙΑΚΗΣ ΑΝΑΠΤΥΞΗΣ Υπουργείο Παιδείας, Δια Βίου Μάθησης και Θρησκευμάτων ΓΓΕΤ ΕΥΔΕ-ΕΤΑΚ 4
Χρηματοδότηση Το παρόν εκπαιδεσηικό σλικό έτει αναπηστθεί ζηα πλαίζια ηοσ εκπαιδεσηικού έργοσ ηοσ διδάζκονηα. Το έργο «Ανοικτά Ακαδημαϊκά Μαθήματα Ε.Μ.Π.» έτει τρημαηοδοηήζει μόνο ηη αναδιαμόρθωζη ηοσ εκπαιδεσηικού σλικού. Το έργο σλοποιείηαι ζηο πλαίζιο ηοσ Επιτειρηζιακού Προγράμμαηος «Εκπαίδεσζη και Δια Βίοσ Μάθηζη» και ζσγτρημαηοδοηείηαι από ηην Εσρωπαϊκή Ένωζη (Εσρωπαϊκό Κοινωνικό Ταμείο) και από εθνικούς πόροσς.