SE524377C2 - Method and surface treatment agent to prevent growth on surfaces under water - Google Patents

Abstract

An ecofriendly method of inhibiting biofouling on surfaces under water by using nicotine and selenium in the form of Se(0), or such a substance that can be converted into them. Both of the substances are necessary to oxygen dependent organisms and will be used after conversion, but are toxic in high doses. By adding the substances to paint or other surface treatment agent that marine surfaces are treated with, organisms that are trying to establish themselves on the surfaces will be exposed to so high doses, that reactions on which the settling is based are disturbed. When the substances leak out into the seas, they will act as environment protectors, as they promote the development of organisms.

Description

20 25 30 35 524 377 h) 3. Nyberg-Swenson B E, Are acetylcholine-induced acetylgroups driving fuel cells in the systems of transducin, t and G proteins? With. Hypothesis 2002, Vol. 58, No.5, pages 388-394.

WO 00/42851 (= SE 513 474 C2, Elwing, H and Mårtensson, L) proposes the use of medetomidine or a structural or biological analogue thereof, eg clonidine (catemins) to prevent the growth of crustaceans, especially barnacles. The catechemes probably take the place of another substance in the transport of electrons to oxygen, but without the ability of this sleeve to conduct electrons, which prevents the formation of energy. Catemines contain an imidazole ring and may bind to the same receptors as electron-conducting substances with the same ring (adenine, guanine, (hypo) xanthine, etc.). It is typer your types of receptors that activate adenylate cyclase and protein kinases and previous trials with catechins have shown a gi fi effect in sea brush worms and fish. If so, catemins are toxic to all oxygen-dependent organisms.

WO 00/42851 states that "the cyprid larvae (which form barnacles) react unexpectedly to the catechins that are normally active in vertebrates". As it is inevitable that the substances of boat bottom paints will eventually spread in the oceans, and just as PCBs, DDTs and their substances are enriched in organisms, catemins do not appear to be a praiseworthy alternative to other tested substances. Catamines are stable substances. If they were to be oxidized quickly, they would lose their toxic property, but thus also their functionality.

DISCLOSURE OF THE INVENTION The object of the present invention is to provide a process and a surface treatment agent which are highly effective against marine growth but are nevertheless environmentally friendly.

This is achieved by designing the method and the surface treatment agent of the type mentioned in the introduction with the features stated in the characterizing parts of claims 1 and 6, respectively.

By using substances that are toxic in higher doses but that in lower doses are converted into substances necessary for an organism, growth is counteracted without adversely affecting the environment. The establishment of crustaceans and other organisms on solid surfaces is prevented at the same time as the marine environment is supplied with useful substances for oxygen-dependent organisms. The invention involves the use of at least one substance which is toxic upon exposure in higher doses but essential in lower doses as organisms may convert it into an important necessary molecule for energy generation. This means that a toxic substance covered by the present invention prevents biofouling but is not toxic to marine organisms when it leaks. The problem of finding a surface treatment agent that is highly effective against marine growth but is nevertheless environmentally friendly is solved in a corresponding manner in that the initially mentioned surface treatment agent for preventing biofouling includes the features stated in the characterizing part of claim 6.

By designing the method and the surface treatment agent of the kind mentioned in the introduction with the features stated at the end of the characterizing parts of claims 1 and 6, respectively, a 35 m ro -fi- (Jxl -a w. B »method and a surface treatment agent that is highly effective against marine growth but is nevertheless environmentally friendly.

It is suitable that the method or the surface treatment agent of the type mentioned in the introduction is designed with the features stated in the characterizing parts of claims 2-5 and 7-9, respectively.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The establishment of crustaceans and other organisms on boat keels is a serious problem for shipping in many countries. So far, only toxic substances in paints or other surface treatment agents have been shown to be able to prevent biofouling. But these substances are just as toxic to marine organisms when they leak out. They do not decompose but accumulate in the oceans. Therefore, it is very important to find alternatives that are gentle on the environment.

The invention comprises the use of the substances specified in the characterizing parts of claims 1-2 and 6-7, respectively. In the search among substances that are toxic upon exposure in higher doses but essential in lower doses as organisms can convert them into important molecules necessary for energy generation, nicotine and selenium in atomic form, See (0), appear to be very commendable.

Diluted nicotine solutions have previously been used as a pesticide but have been banned due to their high validity. When they were handled by people who were not sufficiently aware of how dangerous the disease is, (fatal) accidents occurred among both children and adults.

But nicotinamide, or the formation of nicotinamide dinucleutide (NAD1), is an extremely important substance in connection with the transport of hydrogen (electrons and protons) to oxygen, which is the condition for the cells' energy formation and thus the existence of life. Nicotine is converted to nicotinamide by organisms and binds to the same receptors as acetylcholine (3. Nyberg-Swenson B. E., Are acetylcholine-induced ..., loco cit.). The reactions of these substances control the activity between muscle and nerve cells or between nerve cells. If the nicotine supply is too high or too fast, which can lead to the death of an organism, the nicotine probably does not have time to be converted to nicotinamide but binds directly to the receptors. But nicotine lacks the important ability to transport charges. The resulting inactivity, the lack of energy, is devastating to an organism. NAD * can also promote fermentation processes that provide energy but not enough to sustain the life of a higher-ranking organism.

Fermentation processes can also be favored when the transport of electrons to oxygen is disturbed or insufficient. An example of this is the formation of lactic acid in connection with strenuous physical exertion. But at the same time, the amount of NADH is increasing. The hydrogen and an electron in it are used later when the normal transport of hydrogen and electrons to oxygen has started properly again. An important link among many in the chain of hydrogen conveyors is the selenium link. It contains two selenium particles with different valences (-II and 0), of which the first selenium particle replaces sulfur in cysteine bound to a protein (1. Nyberg-Swenson, B. E., The selenium link, loco cit.). Until 1952, when selenium l0 15 20 25 30 35 524 377 .En proved to be an essential substance for animals and could prevent muscular dystrophy fi, the substance was considered only a gi fl. If Se (0) or a selenium salt (selenite, selenate, etc.) is added to an organism in high doses, this leads to an excretion of Se (0) together with the other Se form (1. Nyberg-Swenson, BE, The selenium link, loco cit.). The Se (-II) content can be so low that the organism is damaged or even dies. Therefore, Se (0) and Se salts are classified as strong toxins.

Because both nicotinamide and the Se link are necessary substances in the transport of hydrogen (or electrons and protons) in the same chain, a too high supply of nicotine and Se (0) or a selenium salt, has synergistic toxic effects.

The development of many organisms takes place to a very large extent to solid surfaces. Organisms utilize substances in the fastening material that are necessary for their development. Without chemical reactions and bonds with these substances, the organisms would not be able to stick or live on the surfaces. This has been done for bacteria that develop in connection with minerals (PEDERSEN, K., “Diversity and activity of microorganisms in deep igneous rock aquifers of the Fennoscandian shield”, In: Subsurface Microgeobiology and Biogeochemistry. Edited by Fredrickson JK and Fletcher M. , 2001, ISBN 0-471-3 1577-X) and higher organisms such as barnacles are certainly no exception. No organism can therefore use a basis for its development that results in exposure to high doses of toxins such as nicotine and / or Se (0).

In practice, such a substrate is achieved by using a surface treatment agent according to claim 8 and suitably with any of the features stated in the characterizing parts of claims 11 and 12.

With at least one of nicotine and Se (0) or substances that can be converted to these substances (nomicotine, myoamine, anabasine, selenite, selenate, etc.) in surface treatment agents (eg boat bottom paints) that are intended to protect against growth on surfaces in a marine environment, growth is counteracted thanks to the toxic effects of the substances. It is inconceivable that an organism can avoid the substances if they are included in surface treatment agents (paints) on treated (painted) surfaces, eg boat keels, which they try to adhere to, as the substances can bind to receptors in the organism. This is why a nicotine ck cover on a garment may be enough to injure the wearer.

The antifouling agents applied to a polymer contained in paints or other marine surface treatment agents prevent them from leaking to the environment too quickly.

But a leak is inevitable. However, the content of the substances in the sea becomes very low due to the additional dilution effect. At such low doses, nicotine and selenium have only positive effects. The risk is insignificant that any organism in the sea will be exposed to toxic doses in an armored manner other than by contact with the treated surfaces on which it is desired to avoid them. Instead, the substances act as environmental protection as they promote the development of organisms.

Paints suitable for admixture with the antifouling agents may be completely conventional standard dyes, for example acrylate-based paints, the polymer being polyacrylate. 10 15 20 524 577 Um Compared to all existing or proposed substances, nicotine and Se (0) are not only non-toxic but also valuable substances for all oxygen-dependent organisms in the content that they may occur in the oceans in connection with a use to avoid growth in marine environments.

Selenium has an extremely important importance and is very vulnerable due to the fact that only a very small amount is required for good function. But many of the Earth's selenium resources are today inactivated by the substance's strong bond to fl your metals (Hg, Cd, Pb, etc), DDT, PCBs, freons and other halogeno-organic compounds - the only cause of the substances' toxicity (2. Nyberg- Swenson BE , ”Is molecular oxygen..., Loco cit.). In Finland, selenite has been successfully added to the soil over large areas. The oceans would certainly feel good about the same measure, which can be done via boat bottom colors. The positive environmental effect will be twofold.

A further development of the innovation is facilitated by the knowledge of how the above-mentioned substances react in organisms, something that is not used for other substances used.

Nicotine and Se (0) are stable substances well suited for incorporation in polymer paint intended for coating marine structures.

As a complement, the substances in question can be applied on the outside or inside pipes and other marine structures by (high-pressure) flushing, although it is inevitable that spray liquid will spread in the surroundings. This does not cause any inconvenience from an environmental point of view if only protective measures are taken against exposure risks for the individuals involved.

Claims (9)

A method for preventing marine organisms, such as sea urchins, from establishing (settling) on a solid surface by applying to said surface at least one overgrowth preventing active substance, characterized by that, as mentioned, at least one active substance is chosen which has a toxic effect in higher doses, but which substance is converted into a substance necessary for said organism which is functional in lower doses and that in order to prevent the growth of an oxygen-dependent organism selects as mentioned at least one substance which partly inhibits the transport of hydrogen (electrons and protons) to oxygen, (which is a condition for the energy formation of nerve and muscle cells and thus their activity, which is a condition for an establishment) and partly used after conversion of the oxygen-dependent organism. Process according to Claim 1, characterized in that at least one hydrogen transport-inhibiting substance is selected as said, at least one of nicotine and selenium in atomic form, Se (0), or substances which can be converted into them (nomicotin, myoamine, anabasine, selenite, selenate etc). A method according to any one of claims 1-2, wherein said solid surface is a marine structure. The method of claim 3, wherein said solid surface is a ship's hull. The method of claim 3, wherein said solid surface is a seawater pipeline. Surface treatment agent for application to a solid surface for preventing the establishment of marine organisms, such as barnacles, on the surface, which surface treatment agent comprises a mixture of at least one active substance which prevents growth and a carrier for the active substance, characterized by that as said at least one active substance is selected one which has a gi fi effect in higher doses, but which substance is converted into a substance necessary for said organism which is functional in lower doses and that it partly slows down the transport of hydrogen (electrons and protons) to oxygen, (which is a condition for the energy formation of nerve and muscle cells and thus their activity, which is a condition for an establishment) and is partly used after transformation of the oxygen-dependent organism. Surface treatment agent according to Claim 6, characterized in that at least one of the nicotine and selenium in atomic form, Se (0), or substances which can be converted into them (nomicotine, myoamine, anabasine, selenite) is selected as said at least one hydrogen transport inhibiting substance. , selenate etc). Surface treatment agent according to one of Claims 6 to 7, characterized in that the carrier is a polymer which prevents the active substance from leaking out rapidly. \IN Surface treatment agent according to Claim 8, characterized in that the polymer is a paint for painting surfaces which are exposed to marine growth, for example ship hulls and pipelines in seawater.