PT115055B

PT115055B - USE OF NAPIRADIOMYCINES WITH ANTI-SCALING ACTIVITY AND ITS COMPOSITIONS.

Info

Publication number: PT115055B
Application number: PT115055A
Authority: PT
Inventors: Manuel De Oliveira E Vasconcelos Vitor; Maria Pereira Gaudêncio De Matos Susana; Gonçalves Sobral De Almeida Rita; Florbela Bento Martinho De Sá Pereira Maria; Maria Barros Dos Santos Gomes Sanches Ilda; Paula Dos Santos Carvalho Piçarra Susana; Cristina Oliveira González Cunha Isabel; Reis De Almeida Joana
Original assignee: Ciimar - Centro Interdisciplinar De Investigação Marinha E Ambiental
Priority date: 2018-10-04
Filing date: 2018-10-04
Publication date: 2021-04-13
Also published as: PT115055A

Abstract

O PRESENTE PEDIDO DESCREVE A UTILIZAÇÃO DE COMPOSTOS PERTENCENTES À FAMÍLIA NAPIRADIOMICINA NA INIBIÇÃO DA INCRUSTAÇÃO DE MICRORGANISMOS E MACRORGANISMOS MARINHOS A SUPERFÍCIES EM CONTACTO COM A ÁGUA, SEM COMPROMETER VIABILIDADE DOS ORGANISMOS. ESTES COMPOSTOS IMPEDEM A INCRUSTAÇÃO DE DIFERENTES ORGANISMOS MARINHOS, APRESENTANDO AINDA BAIXO EFEITO NOCIVO PARA OS ECOSSISTEMAS MARINHOS. DESTA FORMA, ESTES COMPOSTOS PODEM SER USADOS EM COMPOSIÇÕES DE TINTAS, VERNIZES, PRIMÁRIOS E SELANTES, PARA SUPERFÍCIES EM CONTACTO COM ÁGUA, COMO AGENTES ANTI-INCRUSTANTES, E COMO UMA ALTERNATIVA VANTAJOSA À UTILIZAÇÃO DE BIOCIDAS INCLUINDO COMPOSTOS DE COBRE.THIS REQUEST DESCRIBES THE USE OF COMPOUNDS BELONGING TO THE NAPIRADIOMYCIN FAMILY IN THE INHIBITION OF THE INCRUSTATION OF MARINE MICRO-ORGANISMS AND MACRORGANISMS TO SURFACES IN CONTACT WITH THE WATER, WITHOUT COMMITTING THE ORGANISM VIABILITY. THESE COMPOUNDS PREVENT THE INCRUSTATION OF DIFFERENT MARINE ORGANISMS, HAVING STILL LOW HARMFUL EFFECTS FOR MARINE ECOSYSTEMS. THEREFORE, THESE COMPOUNDS CAN BE USED IN COMPOSITIONS OF PAINTS, VARNISHES, PRIMALS AND SEALANTS, FOR SURFACES IN CONTACT WITH WATER, AS ANTI-SCARING AGENTS, AND AS AN ADVANTAGE ALTERNATIVE TO THE USE OF INCLUDED COMPOUNDS.

Description

DESCRIÇÃODESCRIPTION

Utilização de napiradiomicinas com atividade anti-incrustante e suas composiçõesUse of napiradiomycins with anti-fouling activity and their compositions

Área Técnica presente pedido refere-se à inibição da incrustação de organismos marinhos a superfícies em contacto com a água às quais os organismos marinhos se fixam, mais especificamente, ao uso de compostos naturais enquanto agentes inibidores da bioincrustação marinha em superfícies presentes em ambiente marinho. 0 uso de compostos naturais anti-incrustantes apresenta-se como uma alternativa à utilização de biocidas contendo cobre, possuindo baixo impacto ecológico.Technical Area of this application refers to the inhibition of the incrustation of marine organisms to surfaces in contact with water to which marine organisms attach, more specifically, to the use of natural compounds as inhibitors of marine bio-encrustation on surfaces present in the marine environment. The use of natural antifouling compounds presents itself as an alternative to the use of biocides containing copper, having low ecological impact.

presente pedido refere-se à utilização de compostos pertencentes à família napiradiomicina com atividade micro e macro antiincrustante na preparação de composições eficazes na proteção de superfícies em ambiente marinho contra a colonização e crescimento de microrganismos e macrorganismos marinhos bioincrustantes. As napiradiomicinas apresentam-se com baixo impacto ambiental e podem ser vistas como alternativa à utilização de biocidas, incluindo compostos de cobre.The present application relates to the use of compounds belonging to the napiradiomycin family with micro and macro anti-fouling activity in the preparation of compositions effective in protecting surfaces in the marine environment against the colonization and growth of bio-fouling microorganisms and macroorganisms. Napiradiomycans have a low environmental impact and can be seen as an alternative to the use of biocides, including copper compounds.

ANTECEDENTES DA INVENÇÃOBACKGROUND OF THE INVENTION

A incrustação biológica consiste na colonização de superfícies submersas por organismos de diferentes grupos taxonómicos, tais como bactérias, diatomáceas, algas, crustáceos, moluscos, bivalves, e outros microrganismos e macrorganismos, num processo dinâmico que começa nos primeiros minutos de submersão e se desenvolve ao longo do tempo. 0 processo de incrustação biológica ocorre em quatro fases: 1) formação de uma camada de matéria orgânica proteica sobre a superfície em contacto com a água; 2) colonização por microrganismos(por exemplo por bactérias Marinobacter hydrocarbonoclastícus, este tipo de colonização 1 designa-se também por biofilme ou microincrustação); 3) colonização por esporos de algas e larvas de invertebrados (por exemplo larva de mexilhão Mytílus galloprovíncíalís, macroincrustação) e 4) fixação de macrorganismos (Salta et al. , 2013, Yang et al. 2017).Biological encrustation consists of the colonization of submerged surfaces by organisms of different taxonomic groups, such as bacteria, diatoms, algae, crustaceans, molluscs, bivalves, and other microorganisms and macrorganisms, in a dynamic process that begins in the first minutes of submersion and develops when over time. The biological encrustation process occurs in four stages: 1) formation of a layer of organic protein matter on the surface in contact with water; 2) colonization by microorganisms (for example by bacteria Marinobacter hydrocarbonoclastícus, this type of colonization 1 is also known as biofilm or micro-encrustation); 3) colonization by algae spores and invertebrate larvae (for example mussel larva Mytílus galloprovincíalís, macro-encrustation) and 4) fixation of macrorganisms (Salta et al., 2013, Yang et al. 2017).

A incrustação biológica, também conhecida como bioincrustação ou incrustação, que ocorre por exemplo em navios e infraestruturas marítimas, constitui um problema significativo para a indústria naval e outras indústrias com dependências marítimas ou aquáticas. Um casco de navio não tratado irá acumular rapidamente incrustações de macrorganismos marinhos, aumentando consideravelmente o seu atrito na água, e consequentemente, o consumo de combustível e a emissão de gases poluentes (CO2 e SO2). Outras indústrias marinhas, como por exemplo, mas sem limitação, a aquacultura, plataformas de petróleo e de gás, outras infraestruturas de produção de energia localizadas no mar, infraestruturas portuárias, estuarinas e marítimas, também apresentam problemas significativos com organismos marinhos bioincrustantes.Biological fouling, also known as bio-fouling or fouling, which occurs, for example, in ships and marine infrastructures, constitutes a significant problem for the naval industry and other industries with maritime or aquatic dependencies. An untreated ship's hull will quickly accumulate incrustations of marine macroorganisms, considerably increasing its friction in the water, and consequently, fuel consumption and the emission of polluting gases (CO2 and SO2). Other marine industries, such as, but not limited to, aquaculture, oil and gas platforms, other energy production infrastructures located at sea, port, estuarine and maritime infrastructures, also present significant problems with bio-encrusting marine organisms.

Estima-se que os métodos anti-incrustação atualmente em uso poupem à indústria naval cerca de € 60 mil milhões/ano em combustível (Schultz et al., 2011) . Além disso, a incrustação em cascos de embarcações e a transferência de água de lastro são as principais causas da introdução e propagação de espécies marinhas nãoindígenas nos ecossistemas em todo o mundo, podendo conduzir a desequilíbrios ecológicos (Ashton et al., 2016) .The antifouling methods currently in use are estimated to save the naval industry around € 60 billion / year in fuel (Schultz et al., 2011). In addition, fouling on vessel hulls and the transfer of ballast water are the main causes of the introduction and propagation of non-indigenous marine species in ecosystems worldwide, which can lead to ecological imbalances (Ashton et al., 2016).

Até à data, a forma mais eficaz de prevenir bioincrustações marinhas tem consistido na aplicação de tintas com princípios ativos tóxicos, como por exemplo, tributilestanho (TBT) ou cobre. Foi comprovado que o TBT causa danos significativos ao ecossistema incluindo plantas, espécies animais e seres humanos (Ruiz et al., 1996) . A Organização Marítima Internacional (OMI) exigiu a proibição da aplicação de TBT a partir de 1 de Janeiro de 2003, e a proibição total da sua presença em cascos desde 1 de Janeiro de 2008, implicando a sua remoção total.To date, the most effective way to prevent marine bio-fouling has been to apply paints with toxic active ingredients, such as, for example, tributyltin (TBT) or copper. TBT has been shown to cause significant damage to the ecosystem including plants, animal species and humans (Ruiz et al., 1996). The International Maritime Organization (IMO) has demanded a ban on the application of TBT from 1 January 2003, and a total ban on its presence in hulls since 1 January 2008, implying its total removal.

A limpeza mecânica, por jato de água ou raspagem, de superfícies marinhas foi introduzida como uma alternativa aos produtos biocidas que podem ser muitas vezes tóxicos para o ambiente, como por exemplo compostos de cobre. Contudo, a maioria destes métodos requer mão-de-obra intensiva e frequente, originando custos elevados.Mechanical cleaning, by water jet or scraping, of marine surfaces has been introduced as an alternative to biocidal products that can often be toxic to the environment, such as copper compounds. However, most of these methods require labor intensive and frequent, resulting in high costs.

Os compostos biocidas atualmente em uso são cobre metálico, óxido de cobre ou outras formulações à base de cobre. Quando, por razões ecológicas, os compostos de cobre são usados em concentrações reduzidas, as tintas utilizadas em superfícies aquáticas perdem eficácia, tornando-se necessário acrescentar outros compostos biocidas de reforço contra os macrorganismos mais resistentes para alcançar um desempenho aceitável.The biocidal compounds currently in use are metallic copper, copper oxide or other copper-based formulations. When, for ecological reasons, copper compounds are used in low concentrations, the paints used on aquatic surfaces lose their effectiveness, making it necessary to add other biocidal reinforcing compounds against the most resistant macrorganisms to achieve acceptable performance.

Desta forma, surgiu a necessidade de encontrar novas soluções para prevenir a incrustação de organismos marinhos, com o objetivo de substituir os metais e óxidos metálicos em tintas. Adicionalmente, existem tintas com compostos anti-incrustantes específicos contra cracas, tais como um derivado de imidazol, a medetomidina (Catemina 1), e o macrólido de 16-membros isolado de uma espécie de Streptomyces, a ivermictina, descrito emEP2723821Al. Os documentos EP1154688 e WO201074802 descrevem o uso de medetomidina em conjunto com outras substâncias na prevenção da bioincrustração. 0 documento EP1910477 descreve o uso de spiroimidazolina (Catemina 3) para o mesmo fim. A Catemina 1 tem uma ação específica sobre cracas mas não tem qualquer efeito contra o crescimento de algas (Dahlstrom et al., 2000) .Thus, the need arose to find new solutions to prevent the fouling of marine organisms, with the aim of replacing metals and metallic oxides in paints. In addition, there are paints with specific antifouling compounds against barnacles, such as an imidazole derivative, medetomidine (Catemina 1), and the 16-member macrolide isolated from a species of Streptomyces, ivermictine, described in EP2723821Al. EP1154688 and WO201074802 describe the use of medetomidine in conjunction with other substances in preventing bioincrustration. EP1910477 describes the use of spiroimidazoline (Catemina 3) for the same purpose. Catemina 1 has a specific action on barnacles but has no effect against algae growth (Dahlstrom et al., 2000).

Frequentemente, os algicidas são herbicidas e inibidores da fotossíntese tais como Diuron® (um derivado de ureia) da DuPont Agricultural Products por Wilmington, Del., EUA; e Irgarol 1051® (um derivado de 1,3,5-triazina) da Ciba Inc., Tarrytown, NY, EUA.Algicides are often herbicides and photosynthesis inhibitors such as Diuron® (a urea derivative) from DuPont Agricultural Products by Wilmington, Del., USA; and Irgarol 1051® (a 1,3,5-triazine derivative) from Ciba Inc., Tarrytown, NY, USA.

A estratégia mais comum é a utilização de fungicidas, tais como piritionato de zinco (complexo de coordenação de zinco (II)) por Arc Chemicals Inc.; e piritionato de cobre (complexo de coordenação de cobre (II)) por Arc Chemicals Inc.; tolilfluanida (um derivado de N-dimetilsulfamoil-anilina) pela Bayer Chemicals, Pittsburgh, Pa., EUA; diclofluanida (um derivado de N-dimetilsulfamoilanilina) pela Bayer Chemicals; zinebe (etileno-bisditiocarbamato de zinco (II)) da EMC Corp.; ZINRAM™ (bis (dimetiltiocarbamato)de zinco(II)) por Taminco; ou compostos de amónio quaternário. Uma outra estratégia é a utilização de compostos tóxicos, mas com tempo de meia-vida curto, tais como SeaNine™ 211N (um derivado de isotiazolinona solução a 30% (p/p) de 4,5-dicloro-2-n-octil-4isotiazolin-3-ona em xilenos) da Rohm and Haas Company, Filadélfia, Pa., EUA; e compostos afins (Jacobson and Willingham, 2000) . Uma abordagem que tem recebido atenção crescente consiste em identificar produtos naturais que podem atuar como antiincrustantes (Satheesh et al. , 2016) . No entanto, entre os produtos naturais marinhos, apenas o composto ivermictina é utilizado em tintas como agente anti-incrustante.The most common strategy is to use fungicides, such as zinc pyrithione (zinc (II) coordination complex) by Arc Chemicals Inc .; and copper pyrithionate (copper (II) coordination complex) by Arc Chemicals Inc .; tolylfluanide (a derivative of N-dimethylsulfamoyl-aniline) by Bayer Chemicals, Pittsburgh, Pa., USA; diclofluanide (a derivative of N-dimethylsulfamoylaniline) by Bayer Chemicals; zineb (ethylene-zinc (II) bisditiocarbamate) from EMC Corp .; ZINRAM ™ (zinc (II) bis (dimethylthiocarbamate)) by Taminco; or quaternary ammonium compounds. Another strategy is to use toxic compounds, but with a short half-life, such as SeaNine ™ 211N (an isothiazolinone derivative 30% (w / w) solution of 4,5-dichloro-2-n-octyl -4isothiazolin-3-one in xylenes) from Rohm and Haas Company, Philadelphia, Pa., USA; and related compounds (Jacobson and Willingham, 2000). An approach that has received increasing attention is to identify natural products that can act as antifouling (Satheesh et al., 2016). However, among natural marine products, only the ivermictine compound is used in paints as an antifouling agent.

Apesar dos esforços recentes na descoberta de produtos naturais marinhos com atividade anti-incrustante, esta área encontra-se a dar os primeiros passos e existe a necessidade de encontrar compostos anti-incrustantes ou uma combinação de vários compostos, para aplicação em tintas e outros revestimentos de forma a constituírem uma solução eficaz contra vários tipos de organismos e fases iniciais da incrustação (biofilme), sem os muitos efeitos ecológicos negativos da presença de níveis elevados de compostos metálicos.Despite recent efforts in the discovery of natural marine products with anti-fouling activity, this area is taking its first steps and there is a need to find anti-fouling compounds or a combination of various compounds, for application in paints and other coatings in order to constitute an effective solution against various types of organisms and initial stages of fouling (biofilm), without the many negative ecological effects of the presence of high levels of metallic compounds.

A invenção aqui descrita resolve o identificado no estado da técnica no que refere à utilização de produtos naturais marinhos pertencentes à família napiradiomicina, para inibição eficaz da incrustação de organismos marinhos, quer microrganismos quer macrorganismos, a superfícies em contacto com água do mar sem comprometer a viabilidade dos organismos.The invention described here solves what was identified in the state of the art with regard to the use of natural marine products belonging to the napiradiomycin family, for effective inhibition of the encrustation of marine organisms, whether microorganisms or macrorganisms, to surfaces in contact with sea water without compromising the viability of organisms.

SUMÁRIO DA INVENÇÃOSUMMARY OF THE INVENTION

O presente pedido refere-se à utilização de napiradiomicinas, com fórmula geral I, na inibição da incrustação de organismos marinhos a superfícies em contacto com água do mar, sem induzir efeitos tóxicos nos organismos.The present application relates to the use of napiradiomycins, with general formula I, in inhibiting the fouling of marine organisms on surfaces in contact with sea water, without inducing toxic effects on the organisms.

Estes compostos inibem a incrustação de microrganismos selecionados de diatomáceas e bactérias, como por exemplo, mas sem limitação, bactérias selecionadas dos géneros Marínobacter, Cobetia, Víbrío, Flavobacteráum, Alcalígenes e Aeromonas.These compounds inhibit the incrustation of microorganisms selected from diatoms and bacteria, such as, but without limitation, bacteria selected from the genera Marínobacter, Cobetia, Vibrío, Flavobacteráum, Alkalígenes and Aeromonas.

Estes compostos inibem a incrustação de macrorganismos marinhos a superfícies em contacto com a água, como por exemplo, mas sem limitação, cracas, mexilhões, algas, hidróides, briozoários, esponjas, tunicados, moluscos, ascídias e vermes tubulares.These compounds inhibit the incrustation of marine macroorganisms on surfaces in contact with water, such as, but without limitation, barnacles, mussels, algae, hydroids, bryozoans, sponges, tunicates, mollusks, ascidians and tubular worms.

A incrustação de micro e macrorganismos pode ocorrer em várias superfícies em contacto com a água, nomeadamente sem limitar, um um barco, um navio, uma embarcação, um equipamento de aquacultura, um equipamento de pesca, uma plataforma de petróleo, uma plataforma de gás, uma infraestrutura para produção de energia e infraestruturas portuárias, estuarinas e marítimas.The incrustation of micro and macrorganisms can occur on various surfaces in contact with water, namely without limiting, a boat, a ship, a vessel, an aquaculture equipment, a fishing equipment, an oil platform, a gas platform , an infrastructure for energy production and port, estuarine and maritime infrastructures.

Estes compostos são incorporados em composições utilizadas para tratar superfícies em contacto com água onde a referida incrustação de organismos marinhos ocorre.These compounds are incorporated into compositions used to treat surfaces in contact with water where the said encrustation of marine organisms occurs.

Tais composições podem ser, sem limitação, uma tinta, um verniz, um primário e um selante, podendo compreender pelo menos um composto de fórmula geral I, pelo menos um aditivo, e pelo menos um ingrediente ativo adicional.Such compositions can be, without limitation, a paint, a varnish, a primer and a sealant, which may comprise at least one compound of general formula I, at least one additive, and at least one additional active ingredient.

Nestas composições, pelo menos um composto de fórmula geral I é incorporado numa percentagem 0,001% a 90% (p/p), mais especificamente 0,001% a 10% (p/p).In these compositions, at least one compound of general formula I is incorporated in a percentage from 0.001% to 90% (w / w), more specifically 0.001% to 10% (w / w).

DESCRIÇÃO GERAL DA INVENÇÃOGENERAL DESCRIPTION OF THE INVENTION

O presente pedido refere-se a uma solução ecologicamente aceitável para evitar o estabelecimento de incrustações de organismos marinhos em superfícies em contacto com a água (quer parcialmente, quer totalmente) em ambientes marinhos. As tintas antiincrustantes incluem tradicionalmente altas concentrações de metais, que são ativos contra cracas e algas, mas que apresentam vários efeitos ambientais negativos. Compostos mais ecológicos foram recentemente usados ou propostos para utilização em tintas anti-incrustantes, demonstrando ser eficazes apenas contra um grupo de macroorganismos incrustantes, as cracas. A utilização de napiradiomicinas em composições para a inibição de incrustação de microrganismos e macrorganismos, que podem ser, sem limitar, tintas, vernizes, primários e selantes, com baixo teor ou desprovidas de cobre, irá tornar as referidas composições eficazes contra a micro e macro bioincrustação.The present application refers to an ecologically acceptable solution to prevent the establishment of incrustations of marine organisms on surfaces in contact with water (either partially or totally) in marine environments. Antifouling paints traditionally include high concentrations of metals, which are active against barnacles and algae, but which have several negative environmental effects. More environmentally friendly compounds have recently been used or proposed for use in antifouling paints, proving to be effective only against a group of fouling macroorganisms, barnacles. The use of napiradiomycins in compositions to inhibit the fouling of microorganisms and macrorganisms, which can be, without limitation, paints, varnishes, primers and sealants, with low content or devoid of copper, will make these compositions effective against micro and macro bio-encrustation.

presente pedido apresenta uma solução para resolver o problema da bioincrustação, ao incorporar compostos anti-incrustantes para uma gama alargada de organismos alvo (micro e macro), sem induzir efeitos tóxicos nos organismos e com reduzida toxicidade ambiental.The present application presents a solution to solve the problem of bio-encrustation, by incorporating antifouling compounds for a wide range of target organisms (micro and macro), without inducing toxic effects on the organisms and with reduced environmental toxicity.

presente pedido divulga a utilização de napiradiomicinas, que inibem a incrustação de microrganismos como por exemplo, sem limitar, bactérias e diatomáceas marinhas incrustantes, e macrorganismos marinhos incrustantes, na produção de composições que sejam revestimentos, tais como tintas, vernizes, primários e selantes, para a proteção de superfícies aquáticas contra a bioincrustação, por aplicação das composições às referidas superfícies.The present application discloses the use of napiradiomycins, which inhibit the fouling of microorganisms such as, without limiting, fouling marine bacteria and diatoms, and fouling marine macrorganisms, in the production of compositions that are coatings, such as paints, varnishes, primers and sealants, for the protection of aquatic surfaces against bio-encrustation, by applying the compositions to said surfaces.

Os termos incrustação, bioincrustação e incrustação biológica referem-se ao crescimento de organismos marinhos em superfícies em contacto com a água (total ou parcialmente) às quais os organismos marinhos se fixam. Os organismos marinhos incrustantes são microrganismos e macrorganismos. No caso de a incrustação ocorrer exclusivamente com microrganismos, dá-se a designação de biofilme ou micro-incrustação, e no caso de a incrustação ocorrer exclusivamente com macrorganismos, dá-se o nome de macroincrustação, ou incrustação. 0 termo incrustação é também utilizado para se referir à incrustação de microrganismos e de macrorganismos indiscriminadamente.The terms fouling, bio-fouling and biological fouling refer to the growth of marine organisms on surfaces in contact with the water (in whole or in part) to which marine organisms are attached. The fouling marine organisms are microorganisms and macrorganisms. In case the encrustation occurs exclusively with microorganisms, it is called biofilm or micro-incrustation, and in the case of incrustation occurring exclusively with macrorganisms, it is called macro-encrustation, or incrustation. The term inlay is also used to refer to the inlay of microorganisms and macroorganisms indiscriminately.

Microrganismos marinhos, como por exemplo diatomáceas e bactérias do género Marínobacter, Cobetia, Víbrío, Flavobacteráum, Alcalágenes, Aeromonas, entre outros provocam microincrustações. Organismos invertebrados marinhos de diferentes grupos taxonómicos e em diferentes fases de crescimento, como por exemplo algas, crustáceos, moluscos, bivalves, cracas, mexilhões, hidróides, briozoários, esponjas, tunicados, ascidias, vermes tubulares, entre outros, provocam macroincrustações.Marine microorganisms, such as diatoms and bacteria of the genus Marínobacter, Cobetia, Vibrio, Flavobacteráum, Alcalágenes, Aeromonas, among others, cause micro-incrustations. Marine invertebrate organisms from different taxonomic groups and in different stages of growth, such as algae, crustaceans, molluscs, bivalves, barnacles, mussels, hydroids, bryozoans, sponges, tunicates, ascidias, tubular worms, among others, cause macro-incrustations.

Napiradiomicinas são produtos de fermentação derivados de actinobactérias do género Streptomyces conhecidos por apresentarem atividade antimicrobiana e anticancerigena. A família destes compostos e seus derivados é geralmente conhecida como napiradiomicina(Shiomi et al. , 1986) .Napiradiomycins are fermentation products derived from actinobacteria of the genus Streptomyces known to have antimicrobial and anticancer activity. The family of these compounds and their derivatives is generally known as napiradiomycin (Shiomi et al., 1986).

As napiradiomicinas com atividade anti-incrustante referidas nesta invenção possuem o esqueleto base I, em que RI e R2 são selecionados independentemente um do outro; RI é selecionado entre hidrogénio H e metilo CH₃; R2 é selecionado das subestruturas a, b, c, d, e, f, ou g; Z é selecionado de uma ligação simples, em que R3 é cloro Cl e R4 é hidrogénio H, e de uma ligação dupla, em que R3 e R4 não possuem substituinte.The napiradiomycins with antifouling activity referred to in this invention have the base I skeleton, in which RI and R2 are selected independently of each other; RI is selected from hydrogen H and methyl CH ₃ ; R2 is selected from substructures a, b, c, d, e, f, or g; Z is selected from a single bond, where R3 is chlorine Cl and R4 is hydrogen H, and from a double bond, where R3 and R4 have no substituent.

Fórmula IFormula I

Subestruturas de R2 R2 substructures a The b B c ç d d e and f f g g

As napiradiomicinas podem ser adicionadas a material de construção de tintas e revestimentos, tais como vernizes, primários e selantes, para tratamento das superfícies em contacto com água para inibir a micro e macroincrustação, incluindo na sua constituição pelo menos uma matriz e um aditivo, podendo ainda conter pelo menos um ingrediente ativo adicional. De acordo com uma forma de composição, as napiradiomicinas estão presentes na composição numa quantidade de 0,001% a 90% (p/p). De acordo com outra forma de composição as napiradiomicinas estão presentes na composição numa quantidade de 0,001% a 10% (p/p).Napiradiomycins can be added to the construction material of paints and coatings, such as varnishes, primers and sealants, to treat surfaces in contact with water to inhibit micro and macro encrustation, including at least one matrix and one additive in its constitution, and may still contain at least one additional active ingredient. According to a form of composition, napiradiomycins are present in the composition in an amount of 0.001% to 90% (w / w). According to another form of composition, napiradiomycins are present in the composition in an amount of 0.001% to 10% (w / w).

A matriz pode ser constituída por diversos tipos de materiais por exemplo, mas sem limitação, agentes aglutinantes, agentes poliméricos formadores de películas, materiais de cimento, materiais termoplásticos, fibra de vidro, materiais elastómicos, silicone, e borracha vulcanizada.The matrix can consist of several types of materials for example, but without limitation, binding agents, polymeric film-forming agents, cement materials, thermoplastic materials, fiberglass, elastomeric materials, silicone, and vulcanized rubber.

Os aditivos podem ser constituídos, entre outros, por exemplo, sem limitação, por pigmentos, diluentes orgânicos, enchimentos, diluentes, agentes de dilatação, agentes molhantes, anticongelantes, promotores de aderência, estabilizadores UV, aplanadores, conservantes e combinações destes.Additives can be made up, among others, for example, without limitation, of pigments, organic thinners, fillers, thinners, swelling agents, wetting agents, antifreeze, adhesion promoters, UV stabilizers, planers, preservatives and combinations thereof.

As napiradiomicinas, com fórmula geral I, podem ser incluídas numa composição de tinta ou revestimento como agente anti-incrustante únicos, ou adicionadas em combinação com outros ingredientes ativos ou biocidas, isto é, compostos com atividade biológica, podendo estes ser anti-incrustantes, microbiocidas, antibiofilmes de origem natural, anti-incrustantes de origem natural, antibiofilmes de origem sintética, anti-incrustantes de origem sintética, sais metálicos anti-incrustantes, bactericidas, fungicidas, algicidas, herbicidas, inseticidas, antibióticos, 8 antibacterianos, anti-incrustantes não tóxicos e produtos ou extratos naturais, para produzir um efeito aditivo ou sinérgico, de inibição de incrustação de organismos.Napiradiomycins, with general formula I, can be included in a paint or coating composition as a unique antifouling agent, or added in combination with other active ingredients or biocides, that is, compounds with biological activity, which may be antifouling, microbiocides, antibiofilms of natural origin, antifouling of natural origin, antibiofilms of synthetic origin, antifouling of synthetic origin, metal salts antifouling, bactericides, fungicides, algicides, herbicides, insecticides, antibiotics, 8 antibacterials, antifouling non-toxic and natural products or extracts, to produce an additive or synergistic effect, inhibiting the fouling of organisms.

São exemplos específicos de biocidas, sem limitação, medetomidina; ivermictina; spinosina; SeaNine™ 211N; cateminas; isotiazolona; etilenobisditiocarbamato de manganês; ditiocarbamato de dimetilo e zinco; 2-metil-4-t-butilamino no-6-ciclopropilamino-s-triazina;Specific examples of biocides, without limitation, medetomidine; ivermictine; spinosyn; SeaNine ™ 211N; catemins; isothiazolone; manganese ethylenebisditiocarbamate; dimethyl and zinc dithiocarbamate; 2-methyl-4-t-butylamino no-6-cyclopropylamino-s-triazine;

2,4,5,6-tetracloroisoftalonitrilo; N, N-dimetil diclorofenilureia; zinco etilenobisditiocarbamato; tiocianato de cobre; 4,5-dicloro-2-n-octil-3-isotiazolona; N(fluorodichlorometh- iltio)-ftalimida; N, N-dimetil-Ν'-fenil-N' fluorodiclorometiltio-sulfamida; zinco 2-piridinotiol-l-oxido; dissulfureto de tetrametiltiuram; 2,4,6-triclorofenilmaleimida;2,4,5,6-tetrachloroisophthalonitrile; N, N-dimethyl dichlorophenylurea; ethylenebisditiocarbamate zinc; copper thiocyanate; 4,5-dichloro-2-n-octyl-3-isothiazolone; N (fluorodichloromethylthio) -phthalimide; N, N-dimethyl-Ν'-phenyl-N 'fluorodichloromethylthio-sulfamide; 2-pyridinethiol-1-oxide zinc; tetramethylthiuram disulfide; 2,4,6-trichlorophenylmaleimide;

2,3,5,6-tetracloro-4- (metilsulfonil)-piridina; carbamato de 3iodo-2-propinil butilo; di-iodometilo p-tolil-sulfona; bis dimetil ditiocarbamoil zinco etil-enebisditiocarbamato; dicloreto de fenil (bispiridil) bismuto; 2- (4-tiazolil)-benzimidazole; piridina trifenilborano; fenilamidas; compostos halopropargicos; 2haloalcoxiaril-3-isotiazolonas, como 2- (4-trifluor-etoxifenil)3-isotiazolona, 2-(4-trifluorometoxifenil)-5-cloro-3isotiazolona e 2- (4-trifluor-etoxifenil)-4,5-dicloro-3isotiazolona, anti-incrustantes organometálicos, tais como tributilestanho ou trifenil-estanho, e anti-incrustantes inorgânicos, tais como óxido de zinco, cobre, óxido de cobre ou óxido de dicobre e dióxido de enxofre; e combinações destes.2,3,5,6-tetrachlor-4- (methylsulfonyl) -pyridine; 3iodine-2-propynyl butyl carbamate; di-iodomethyl p-tolyl sulfone; bis dimethyl dithiocarbamoyl zinc ethylenebisditiocarbamate; phenyl (bispyridyl) bismuth dichloride; 2- (4-thiazolyl) -benzimidazole; triphenylborane pyridine; phenylamides; halopropargic compounds; 2haloalkoxyaryl-3-isothiazolones, such as 2- (4-trifluor-ethoxyphenyl) 3-isothiazolone, 2- (4-trifluoromethoxyphenyl) -5-chloro-3isothiazolone and 2- (4-trifluor-ethoxyphenyl) -4,5-dichloro- 3 isothiazolone, organometallic antifouling, such as tributyltin or triphenyltin, and inorganic antifouling, such as zinc oxide, copper, copper oxide or dicobre oxide and sulfur dioxide; and combinations of these.

A bioincrustação marinha causa prejuízos e estragos afetando negativamente diversas indústrias marinhas, como por exemplo, mas sem limitação, a aquacultura, plataformas de petróleo ou de gás e outras infraestruturas de produção de energia localizadas no mar. São exemplos de superfícies marinhas ou superfícies aquáticas, um barco, um navio, uma embarcação, um equipamento de aquacultura, um equipamento de pesca, uma plataforma de petróleo, uma plataforma de gás, uma infraestrutura para produção de energia e infraestruturas portuárias, estuarinas e marítimas, entre outras.Marine bio-encrustation causes damage and damage, negatively affecting several marine industries, such as, but not limited to, aquaculture, oil or gas platforms and other energy production infrastructures located at sea. Examples of marine or aquatic surfaces are a boat, a ship, a vessel, aquaculture equipment, fishing equipment, an oil platform, a gas platform, an energy production infrastructure and port, estuarine and maritime, among others.

APLICAÇÃO PREFERENCIALPREFERENTIAL APPLICATION

Uma importante aplicação prática e industrial do presente pedido consiste em utilizar os compostos de fórmula geral I, de uma forma livre ou encapsulada, em composições como por exemplo, sem limitar, uma tinta ou um revestimento, como por exemplo, um verniz, um primário ou um selante, sem cobre ou com uma baixa percentagem de cobre. A tinta ou revestimento é consequentemente aplicada(o) a superfícies em ambiente marinho. A incrustação de microrganismos marinhos e macrorganismos irá consequentemente ser inibida. A aplicação preferencial da invenção consiste em adicionar napiradiomicínas aos ingredientes de uma composição para inibição da micro e macroincrustação, que posteriormente serão aplicados, por exemplo, sobre cascos de navios.An important practical and industrial application of the present application is to use the compounds of general formula I, in a free or encapsulated form, in compositions such as, for example, without limiting, a paint or a coating, such as a varnish, a primer or a sealant, without copper or with a low percentage of copper. The paint or coating is consequently applied (o) to surfaces in a marine environment. The encrustation of marine microorganisms and macrorganisms will consequently be inhibited. The preferred application of the invention is to add napyradiomycin to the ingredients of a composition for inhibiting micro and macro encrustation, which will later be applied, for example, on ship hulls.

EXEMPLOS:EXAMPLES:

Tabela 1. Atividade anti-incrustante de compostos da família napiradiomicina, com fórmula geral I.Table 1. Anti-fouling activity of compounds from the napiradiomycin family, with general formula I.

Composto Compound 1 1 2 two 3 3 A THE B B Estrutura Química Chemical Structure Esqueleto base Base skeleton I I I I I I I I R¹ R ¹ -H -H -H -H -H -H R² R ² OH OH Z Z simples simple simples simple dupla pair simples simple

R³ R ³ Cl Cl Cl Cl N.E . HUH . Cl Cl R⁴ R ⁴ H H H H N.E . HUH . H H Actividade Antimicroincrustante Antimicro-fouling activity Inibição de crescimento Marinobacter hydrocarbonoc lasticus(%) Growth inhibition Marinobacter hydrocarbonoc lasticus (%) N. I . N. I. N. I . N. I. N. I . N. I. Inibição de formação de biofilme Marinobacter hydrocarbonoc lasticus(%) Inhibition of biofilm formation Marinobacter hydrocarbonoc lasticus (%) 84,4 ± 4, 0 84.4 ± 4.0 61,9 ± 8,6 61.9 ± 8.6 70,9 ± 3,9 70.9 ± 3.9 Actividade Antimacroincrustante Antimacro-fouling activity Inibição da fixação Mytilus galloprovinci alis (%) Inhibition of fixation Mytilus galloprovinci alis (%) 90 90 100 100 100 100 Taxa mo r ta1idade Mytilus galloprovinci alis (%) Mo rity rate Mytilus galloprovinci alis (%) 0, 0 0, 0 0, 0 0, 0 0, 0 0, 0 N.E. - não existe. N. I. - não inibe. N.E. - does not exist. N. I. - does not inhibit.

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Claims

1. Use of napiradiomycins with general formula I ⁰

I 11 JI OH OR ⁴

I in that,

RI and R2 are selected independently of each other

RI is selected between H and CH ₃

R2 is selected from

Z is selected from a single bond, where R3 is Cl and R4 is H, and from a double bond, where R3 and R4 have no substituent, characterized by inhibiting the fouling of marine organisms on surfaces in contact with water, without compromising the viability of organisms.

2. Use of napiradiomycins, according to claim 1, characterized by inhibiting the incrustation of marine microorganisms and macrorganisms on surfaces in contact with water.

3. Use of napiradiomycins, according to the claim

2, characterized by inhibiting the encrustation of at least one type of microorganisms selected from bacteria and diatoms.

4. Use of napiradiomycins, according to claim 3, characterized by inhibiting the fouling of at least one species of marine microorganisms in the genera Marínobacter, Cobetia, Vibrío, Flavobacteráum, Alkalígenes and Aeromonas.

5. Use of napiradiomycins, according to claim 2, characterized by inhibiting the fouling of at least one type of marine fouling macrorganism selected from barnacles, mussels, algae, hydroids, bryozoans, sponges, tunicates, mollusks, ascidias and tubular worms.

6. Use of napiradiomycins, according to claim 1, characterized in that the surface in contact with the water is selected from a boat, a ship, a vessel, an aquaculture equipment, a fishing equipment, an oil platform, a gas platform, an infrastructure for energy production and port, estuarine and maritime infrastructures.

7. Use of napiradiomycins, according to the preceding claims, characterized in that at least one napiradiomycin is incorporated into compositions for inhibiting the fouling of marine organisms on surfaces in contact with water.

Use of napiradiomycins, according to claim 7, characterized in that compositions for inhibiting the fouling of marine organisms on surfaces in contact with water, are selected from a paint, a varnish, a primer and a sealant.

Composition for inhibiting the fouling of marine organisms on surfaces in contact with water, according to claims 7 and 8, characterized in that it comprises at least one compound of general formula I, at least one matrix, at least one additive and at least least one additional active ingredient.

10. Use of napiradiomycins, according to claims 7-9, characterized in that at least one napiradiomycin is incorporated in a percentage of 0.001% to 90% (ρ / ρ), more specifically 0.001% to 10% (w / w), in compositions to inhibit the fouling of marine organisms on surfaces in contact with water.