ES2387518T5 - Metal complexes of siderophores used as bleaching catalysts - Google Patents

Description

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DESCRIPTION

Metal complexes of siderophores used as bleaching catalysts

The present invention relates to metal complexes of siderophores as well as their use as bleaching catalysts, in particular in washing and cleaning means.

For effective bleaching with hydrogen peroxide it must be transformed into a species that activates bleaching. One possibility to manufacture peroxide compounds consists in the use of peracid precursors, the so-called bleaching activators, such as TAED, which are transformed into active species through perhydrolysis.

Another possibility for manufacturing active species is the enzymatic catalyzed perhydrolysis of carboxylic acid esters or nitrile compounds using perhydrolases.

Finally, the use of bleaching catalysts to produce active species is also known, where bleaching catalyst is understood as a substance that can improve the bleaching power of hydrogen peroxide in a bleachable substance, without having to stoichiometrically intervene in the reaction .

The use of bleaching catalysts has the advantage over other bleaching activation methods that sub-stoichiometric amounts of the compound are achieved, so that space and weight savings can be achieved in the formula of the product containing the bleach. In addition to weight reduction, in particular in washing and cleaning applications, there is also the advantage that the contribution of substances to the environment decreases, which for ecological reasons is preferable. Transportation and packaging costs can also be saved.

It should also be borne in mind that using bleach activators such as nitriles or TAED in the presence of water can cause premature hydrolysis, while this problem can be avoided if bleaching catalysts are used. Furthermore, in the activation of non-catalyzed bleaching, the formation of acids carried out from peracids produces a deviation from the pH value, which can adversely influence the bleaching power. In addition, the bleaching power of most bleaching activators at low temperatures is usually insufficient.

For the reasons mentioned above, the use of bleaching catalysts has a special interest compared to other bleaching activation techniques, so that there is a need for new bleaching catalysts.

As bleaching catalysts, in particular, the metal complexes of organic ligands such as salt, saldimines, tris (salicylicidenaminoethyl) amines, monocyclic polyazaalkanes, polycyclic polyazaalkanes that make cross bridge, terpiridines and tetra amido ligands have been described. A drawback of the described metal complexes is that they do not have sufficient bleaching power, in particular at low temperature, but in case they possess sufficient bleaching power, they lead to an unwanted injury to the colors and fibers of the tissues. .

The manufacture of complex ligands of an organic nature is also carried out in a conventional manner based on non-renewable raw materials such as oil and coal. These production methods have the disadvantage that the unrecoverable resources are reduced, so that they are no longer available for subsequent generations. There is in general the need to manufacture predominantly complex ligands

or preferably entirely from renewable raw materials. This is done, for example, on a large scale for citric acid, which is manufactured from a biotechnical point of view with the help of fungal cultures. Citric acid may form complexes based on metal ions such as chelates, but such citric acid complexes, in particular for washing and cleaning applications, do not have great importance.

The present invention therefore had the task of preparing new bleaching catalysts, preferably those that could be manufactured from renewable raw materials. Ideally, in the case of ligands, natural products or derivatives that can be manufactured from them in a simple way. In addition, the new bleaching catalysts should facilitate efficient cleaning of hard surfaces as well as tissues, preferably without damaging the latter or their color. In addition, the new bleaching catalysts should have sufficient storage stability to be used in washing and cleaning media.

This task is solved by the use of metal complexes of siderophores as bleaching catalysts.

Siderophores are complex ligands that are secreted by organisms (especially microbes), to firmly bind iron (III) ions and transport the charged complex to cells, to get important iron. The functional groups that serve for the formation of the iron complex as the groups of

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catecholate, salicylate, hydroxamate, oxazole rings, thiazole rings, citrate-hydroxamate groups, alfaceto-carboxylate groups, alpha-hydroxy carboxylate groups or carboxylic acid amide groups, of which generally at least two, There are mainly at least three in the molecule. Because the siderophores are natural products, they can be easily and economically produced from renewable raw materials, for example, by growing the appropriate microorganisms in the relevant media and separating the siderophores secreted by them. The truth is that siderophores can be eagerly imported by countless microorganisms and can be used because they have a good biological degradation, which is an important advantage for bleaching catalysts, particularly for washing and cleaning means, since in They will definitely end up in the environment.

Due to their ability to form complexes with iron ions, siderophores also have antibacterial properties, so that in terms of literature, the possibilities of using siderophores as preservative and disinfection media for different types have been described application purposes (for example, DE 19642127, DE 4433376, EP641275 and EP682091). In addition, desferrioxamine B can be used in the medical field thanks to its ability to form complexes with iron ions.

It is also known that siderophores can be used for bleaching pulp in papermaking or they can participate in the natural pulp bleaching process. In this context, hydroxyate siderophores, desferrioxamine B and nocardamine are mentioned in particular. First, there is talk about a mediator role in terms of the breakdown of lignin by laccases (Niku-Paavola et al. (2003) American Chemical Society Symp Ser 855, 176-190; Milagres et al. ( 2002) Enzyme and Microbial Technology 30, 562-565). Here in general it is mentioned that iron siderophores catalyze redox reactions and can activate oxygen. However, the use of siderophores in the washing and cleaning means has not been described.

In older publications the manufacture of a manganese siderophore complex has also been described. Beyer et al. (1968, Archives of Biochemistry and Biophysics 271, 149-156) describe the manufacture of manganese complexes of desferrioxamine B. They have proven that these complexes possess the activity of superoxide dismutase, that is, they catalyze the reaction of O2-in H2O2 and O2. As possibilities of application of these complexes, their use as antioxidants and pharmaceutical agents is generally mentioned and the use of siderophores in washing and cleaning means is not taken into account.

Faulkner et al. (1994, Archives of Biochemistry and Biophysics 310, 341-346) describe the manufacture of Mn (III) complexes of desferrioxamine B and E. Here we also discuss the possibility of their use as antioxidants and in particular in the medical field .

In WO93 / 03045, various metal complexes of Desferrioxamine B are published, as well as their use as contrast media.

EP0325559 reveals the existence of a method for the manufacture of different metal complexes of desferrioxamine B and E as well as desferritiocin in pure form.

Duckworth et al. (2006, Abstracts of Papers, 232nd ACS National Meeting, San Francisco, CA, United States, Sept. 10-14, 2006, American Chemical Society) publish theoretical studies on different metal complexes of desferrioxamine B.

Joshi et al. (1994, Proceedings Indian Academy of Sciences, Chemical Sciences 106 (5), 1089-1108) publish research on the interaction of nucleic acids with desferrioxamine B complexes with copper, cobalt and nickel ions.

Abergel et al. (2006, Abstracts of Papers, 232nd ACS National Meeting, San Francisco, CA, United States, Sept. 10-14, 2006, American Chemical Society) publish enterobactin complexes with iron, gallium, aluminum, indium and vanadium ions, for investigate the interaction of these complexes with the Siderocalin protein.

Yoder et al. (2006, Journal of Environmental Science and Health, Part A: Toxic / Hazardous Substances & Environmental Engineering 41 (3), 369-380) report on complexes of a Pioverdine with aluminum, calcium, copper, iron, manganese, magnesium and zinc as well as studies on its fluorescence.

US5371234 publishes the existence of pioverdine complexes PF244 with metal ions of iron, aluminum, chromium, gallium and actinides as well as the use of pioverdine PF244 to form complexes with these metal ions. Choi et al. (2006, Journal of Inorganic Biochemistry 100 (12), 2150-2161) talk about different metal complexes of methanobactin as well as thermodynamic research regarding these complexes.

The use of metal complexes based on siderophores as bleaching agents in washing and cleaning means and / or their use for cleaning fabrics or dishes has not yet been described in the prior art and is therefore something new. It was also surprising that metal complexes with siderophores allowed efficient cleaning of

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tissues, without damaging them excessively and at the same time their behavior was very correct against the colored fabrics.

A first objective of the present invention is therefore the washing and cleaning means that at least contain a siderophore, preferably at least one metal-siderophore complex. Because they alter colors and fabrics minimally, they are considered preferred washing and cleaning agents. The siderophores as well as the metal-siderophore complexes can be used in their free form as well as in the form of any of their salts.

Another objective of the present invention is therefore the use of siderophores, in particular metal-phosphorus complexes, in the washing and cleaning means, in particular in the washing and cleaning means for cleaning hard surfaces and fabrics.

Another object of the present invention is also the use of siderophores, in particular siderophoresometal complexes, as auxiliary means for cleaning hard surfaces and as auxiliary means for cleaning tissues.

The object of the present invention is also the use of siderophores, in particular siderophoresometal complexes, for cleaning and / or removal of impurities, in particular tea, coffee, blood, soot, egg, milk, butter, ink, makeup stains. , bar, lips, chocolate, chocolate cream, olive oil, blackberries, blueberries, apple juice, red wine, peanut oil as well as mixtures thereof.

It is also possible to catalyze other redox reactions as only bleaching reactions with this type of new catalysts. The objective of the present invention is therefore the use of siderophores, in particular siderophore-metal complexes, for bleaches cellulose and / or raw cotton.

Because its antiseptic properties according to the invention have been established, another objective of the present invention is the use of siderophore-metal complexes, in particular in washing and cleaning means, to kill germs, in particular to kill bacteria and / or fungi. .

The objective of the present invention is also a method for cleaning fabrics or hard surfaces, characterized in that the cleaning is carried out using a siderophore-metal complex, so that due to the especially good properties for the fiber and The color of the siderophore-metal complexes is preferably a good method for color and / or fiber.

The siderophores are used in a particularly preferred configuration according to the invention directly in the form of a catalytically active siderophore-metal complex. However, it is also possible to create the catalytically active siderophore-metal complex in situ. For this, the siderophore and the metal ion, if necessary in the form of any salt, must be spatially separated from one another and / or applied one after the other. The union of siderophore and metal ion and therefore the formation of the bleaching catalyst can be carried out right in the application. The spatial separation of the siderophore and the metal ion can be carried out so that a multi-compartment system is used, where the siderophore and the metal ion are in different compartments. By mixing the components of the various compartments of the multi-compartment system, a siderophore-metal complex can be produced in situ. Alternatively, the siderophore and the metal ion can be contained in different compartments of a powder detergent, that is to say in different granules or in different layers of a multilayer granulate. By dissolving the granules during application the siderophore and the metal ion can bind and thereby form the catalytically active complex.

The special objective of the present invention is also to achieve a method for cleaning tissues or hard surfaces, characterized in that the cleaning is carried out using a metal siderophore-ion complex, where the metal siderophore-metal complex has been created in situ.

In addition, the siderophores and siderophore-metal complexes have been used in a preferred configuration together with an oxygen source, such as a bleaching medium (or a bleach activator), which we will describe later. Surprisingly, it has been found that the siderophore-metal complexes even without adding an oxygen source create a relatively strong cleaning and bleaching effect.

A special objective of the present invention is also a method for cleaning tissues or hard surfaces that is characterized in that the cleaning is carried out using a metal sideophore-ion complex, where no bleaching means or bleaching activator is added, so that preferably only oxygen from the air is used as the source of oxygen.

In the case of siderophores, these are compounds, which according to their true definition are only produced by the organism under conditions of lack of iron. This limitation is not valid for the present invention, since also complex ligands, which are produced in case of sufficient presence of iron, could fulfill the objective of the present invention. Therefore, within the scope of the present invention, the term "natural siderophore" is understood as a naturally occurring complex ligand that has the same properties to form complexes as well as a structure and function similar to that of a siderophore . So

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Under the concept of "siderophore" according to the invention, so-called "calcoforos" are also understood to have the same structure as the siderophores. In a special configuration in the case of the naturally occurring siderophore it is a siderophore in a more limited sense according to the aforementioned definition.

By a siderophore it is understood in a broad sense according to the invention that compound having at least two, preferably at least three, in particular two or three, especially exactly three radicals chosen from the group consisting of hydroxamate, catecholate, alpha-hydroxy carboxylate, alpha-ketocarboxylate, carboxylic acid amide, citrahydroxamate as well as, partially or fully hydrogenated oxazol or thiazole, so that those compounds are preferred, which have at least three, preferably just three radicals chosen from the catecholate, hydroxamate as well as the oxazol or thiazole, partially or totally hydrogenated.

By "catecholate" is meant the twice deprotonated form of brenzocatechin. The catecholate radicals can be totally or partially protonated, in particular in the presence of the uncomplexed free form of the corresponding siderophore. These protonated forms of the catecholate are encompassed in the concept of "catecholate." Also other radicals mentioned, in particular the non-complex form of the siderophore, can be presented in a protonated or deprotonated state. In this sense, the hydroxamic acid radicals are included under the term "hydroxamate" and under the concept of "carboxylate" the carboxylic acid radicals. In a complex where the metal is the cation, the aforementioned radicals are preferably deprotonated.

In a particularly preferred configuration, the siderophore is a compound that has at least two, preferably just two groups of hydroxamate and at least one other group that forms a complex, which can be a catecholate, carboxylate, alpha-hydroxycarboxylate, alpha-keto- carboxylate, carboxylic acid amide, phenolate as well as partially or fully hydrogenated oxazol or thiazole, so that the other group that forms a complex is preferably chosen from the catecholate, and if necessary the oxazole or thiazole, partially or totally hydrogenated.

In a particularly preferred configuration according to the invention, the siderophore is a compound that has at least three, preferably just three hydroxamate groups.

In another particularly preferred configuration, the siderophore is a compound that has at least two, preferably just two catecholate groups and at least one other complex forming group, selected from hydroxamate, carboxylate, alpha-hydroxy carboxylate, alpha-keto carboxylate, phenolate, carboxylic acid amide, and if necessary the imidazole, oxazole or thiazole, partially or totally hydrogenated, so that the other complex forming group is preferably chosen from the hydroxamates, and if necessary the oxazole or thiazole, partially or totally hydrogenated .

In another especially preferred configuration, the siderophore is a compound that has at least three, preferably just three catecholate groups.

In another particularly preferred configuration, the siderophore is a compound that has at least two, preferably just two oxazole groups, if partially or totally hydrogenated, and at least one other complex forming group, chosen from hydroxamate, carboxylate, alpha-hydroxycarboxylate , alpha-keto-carboxylate, phenolate, carboxylic acid amide, and if necessary the imidazole or thiazole, partially or totally hydrogenated, so that the other group that forms complexes is preferably chosen from hydroxamates, catecholates and if necessary thiazole, partially or totally hydrogenated.

In another especially preferred configuration, the siderophore is a compound that has at least three, preferably just three groups of partially or totally hydrogenated oxazole.

In another particularly preferred configuration the siderophore is a compound that has at least two, preferably just two thiazole groups, if partially or totally hydrogenated, and at least one other complex forming group, chosen from hydroxamate, carboxylate, alpha-hydroxycarboxylate , alpha-keto-carboxylate, phenolate, carboxylic acid amide, and if necessary the imidazole or oxazole, partially or totally hydrogenated, so that the other group that forms complexes is preferably chosen from hydroxamates, catecholates and if necessary oxazole, partially or totally hydrogenated.

In another especially preferred configuration, the siderophore is a compound that has at least three, preferably just three thiazole groups.

In another particularly preferred configuration, the siderophore is a compound that has at least two, preferably just two alpha-hydroxycarboxylate groups, and at least one other complex forming group, selected from hydroxamate, catecholate, carboxylate, alpha-keto carboxylate, phenolate. , carboxylic acid amide, and if necessary the imidazole, oxazole or thiazole, partially or totally hydrogenated, so that the other group that forms complexes is preferably chosen from the hydroxamates, catecholates and if necessary from the oxazole or thiazole, partial or fully hydrogenated.

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In another especially preferred configuration, the siderophore is a compound that has at least three, preferably just three alpha-hydroxycarboxylate groups.

A "siderophore" means within the scope of the present invention that compound that appears naturally

or it does not appear naturally, which have the aforementioned combination of functional groups, regardless of how they were obtained.

In a preferred configuration, the siderophore consists of a siderophore of natural origin or a derivative thereof, so that by a derivative of a siderophore of natural origin it is understood, in particular, a compound obtained from a siderophore of natural origin , for example by halogenation, alkylation, sulfonation, nitration, hydroxylation, decarboxylation or similar modification reactions, without the base structure of the naturally occurring siderophore being destroyed. The modification can be carried out in vitro biotechnically, that is, during production in a microorganism, or chemically. The modification can be used so that the properties of the siderophore significantly improve in its use as a bleaching catalyst ligand, for example in regard to oxidation stability, solubility or color.

In another preferred configuration the siderophore according to the invention may be a modified oligopeptide preferably comprising 2 to 8 modified peptide bonds if necessary, so that it may be a cyclic oligopeptide, especially a cyclic pentapeptide or a cyclic hexapeptide. . The aforementioned functional groups may be components of the amino acid radicals, but instead, in particular the hydroxamate groups, they may also be components of the cyclic chain of peptides and have been formed by the modification of the peptide bonds.

In another especially preferred configuration, the siderophore is a naturally occurring siderophore.

In the case of naturally occurring siderophores, they may be sideromycins, siderochromes or sideroamines. However, due to its structure, as indicated above, it can be treated in a broader sense of calcóforos such as methanobactin, which are not really known as siderophores but which according to the invention are attributed to the group of siderophores.

In the case of siderophores of unnatural origin, the aforementioned derivatives of siderophores of natural origin can be treated in a preferred configuration. In addition, it can be any compound whenever the aforementioned combination of functional groups occurs. In this case, as in many other naturally occurring siderophores, it is possible in particular to be an oligopeptide, especially a cyclic oligopeptide such as a cyclic hexapeptide.

Some siderophores which are used according to the invention are mentioned below. They are always iron-free siderophores forms even if the term "Desferri" has not been put before them.

As siderophores of natural origin with three hydroxamate groups, in particular according to the invention, deferricromes can be used, especially deferricrome, desferricromo A or desferricromo C, tetraglicidesferricromo, desferricrocina, desferricrisina, desferrirodina, hexahydrodesferrirodina, deferrirubina, deferricoprogen II , Exochelin MS, Fusigen (Fusarinin C), nocardamine, desferrisalmicin, desferrialbomycin, in particular desferrialbomycin δ1, δ2, Ɛ, desferrioxamine, in particular desferrioxamine A, A1, A2, B, C, D1, D2, E, Et1, Et2, Et3, Fm, G, H, I, X1, X2, X3, X4, Te1, Te2 or Te3, as well as deferrimycins, in particular deferrimycin A1. It is preferably desferrioxamine E in the case of the siderophore with three hydroxamate groups.

As siderophores of natural origin with two hydroxamate groups and one catecholate group, in particular according to the invention, the Pioverdins, especially the Pioverdine C, D, E or Pa.

As siderophores of natural origin with two hydroxamate groups and a dihydro-oxazole ring, in particular according to the invention, mycobactins, in particular mycobactin J, P, S, or T.

As siderophores of natural origin with two hydroxamate groups and an alpha-hydroxycarboxylate group, aerobactin, arthrobactin, acinetoferrin, an aquanoqueline, in particular aquariums A, B, C or D, an ornibactin, can be used in particular according to the invention , in particular C4, C6 or C8 ornibactin, a nanoquelin, in particular nanoquelin B or C, or schizoquines.

As a siderophore of natural origin with two hydroxamate groups and an imidazole group, Exoquelina MN can be used in particular according to the invention.

As a siderophore of natural origin with two hydroxamate groups and several carboxylic acid amide groups, rodotorulic acid or a marinabactin can be used according to the invention, especially marinebactin A, B, C, D1, D2 or E.

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As a siderophore of natural origin with a hydroxamate group, a catecholate group and a keto carboxylate group, in particular according to the invention, Azobactin D.

As a siderophore of natural origin with a hydroxamate group, a catecholate group and an alpha-hydroxy carboxylate group, a Pseudobactin, in particular Pseudobactin, Pseudobactin 7NSK2, 7SR1, A, A214, M114 or St3, can be used according to the invention. .

As a siderophore of natural origin with a hydroxamate group, a catecholate group and a partially hydrogenated oxazole ring can be used according to the invention in particular an Acinetobactin.

As a siderophore of natural origin with a hydroxamate group, an alpha-hydroxy carboxylate group and several carboxylic acid amide groups can be used according to the invention in particular Pseudobactin.

As a siderophore of natural origin with a hydroxamate group, and several carboxylic acid amide groups, putrebactin can be used in particular according to the invention.

As a siderophore of natural origin with three alpha-hydroxy carboxylate groups, Acromobactin can be used in particular according to the invention.

As a naturally occurring siderophore with two alpha-hydroxy carboxylate groups, two carboxylic acid amide groups and two other carboxylate groups, Rizoferrin can be used in particular according to the invention.

As natural siderophore with two alpha-hydroxycarboxylate groups and one catecholate group, alterobactins, especially alterobactin A or B, can be used according to the invention.

As the naturally occurring siderophore with three catecholate groups, agrobactin, enterobactin (Enteroquelin), Fluvibactin, Homofluvibactin or Bacillibactin (Corinebactin) can be used according to the invention in particular.

As a siderophore of natural origin with two catecholate groups and an alpha-hydroxy carboxylate group, Petrobactin can be used according to the invention in particular.

As a naturally occurring siderophore with two catecholate groups and several carboxylic acid amide groups, Salmoquelin, azotoquelin or a Mixoquelina, especially Mixoquelina A or B, can be used according to the invention.

As a siderophore of natural origin with a catecholate group and two carboxylic acid amide groups, Chlobabactin can be used according to the invention in particular.

As a siderophore of natural origin with three groups of partially hydrogenated thiazole rings, Yersiniabactin can be used in particular according to the invention.

As a siderophore of natural origin with two groups of partially hydrogenated thiazole rings, Ferritiocin or Pyoquelin A can be used according to the invention in particular.

As a siderophore of natural origin with two partially hydrogenated oxazole groups and a catecholate group, Vulnibactin can be used according to the invention in particular.

Like other naturally occurring siderophores which are used in accordance with the invention, daunorubicin, succinimycin, rifamycin, trencam, pseudomonin, corrugatin, gallichrome, fusygen, a deferristafiloferrin, in particular deferristafiloferrin A or B, deferrimaduraferrin, in particular a fusarin, are known Fusarina C, PN, X or Z or triacetilfusarinina C, dimerumic acid, mugineinic acid, coeliquelina, WCS, methanobactin, gonobactin, amonabactin, in particular the amonabactin P or T, an amphibibactin, in particular amphibibactin, a rhizobactin, in particular rizobactin 1021 or DM4, ruckerbactin, anguibactin, brucebactin, carboximicobactin, erythrobactin, cepabactin, meningobactin, crisobactin, quinolobactin, thioquinolobactin, vibriobactin, vancrobactin, parabactin and balibactin.

The siderophore used according to the invention preferably has a complex-forming constant in relation to iron (III) of less than 10-3 M-1, in particular less than 10-7, especially less than 10 -20M-1.

Siderophores of natural origin are mainly made of microorganisms, particularly bacteria. In addition siderophores of other organisms are produced, in particular of certain plants, which form a life in common with the symbiotic organisms of the roots. According to the invention, all naturally occurring siderophores are suitable for forming siderophore-metal complexes according to the invention. The siderophores of natural origin used according to the invention preferably come from microorganisms, in particular from bacteria,

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Especially from Acinetobacter, Actinomyces, Alcaligenes, Bordetella, Alteromonas, Agrobacterium, Aeromonas, Arthrobacter, Azotobacter, Bacillus, Corynebacterium, Brucella, Burkholderia, Erwinia, Penicillium, Aspergillus, Neurospora, Ustillagobacterium, Acrochlobacterium, Escherichrobacterium, Escherichophacterium , Fusarium, Neisseria, Pseudomonas, Shewanella, Shigella, Rhizobiom, Rhodotorula, Ralstonia, Salmonella, Staphylococcus, Streptomyces, Vibrio or Yersinia.

Siderophores of natural origin can be obtained on the one hand from their natural producer, but alternatively they can also be produced in another organism, so that these organisms are modified by genotechnology by incorporating one or more DNAs that encode the enzymes that they take part in the synthesis of the siderophores. In addition, the chemical synthesis of siderophores must also be taken into account as another alternative.

As production organisms for heterogeneous production, microorganisms, preferably fungi, yeasts and bacteria, in particular of the species Aspergillus, Bacillus, Brevibacillus, Actinomyces, Esherichia, Streptomyces, Corynebacterium, Pseudomonas, Saccharomyces, Hansenuta, Pichia and Lactous are also taken into account .

The genetic alteration of the producing organisms is relatively simple, so multiple genotechnological changes are possible, to manufacture a siderophore of adequate structure, purity, performance or duration of the process. In this way a catalyst based on siderophores can be adapted to the requirements in multiple ways compared to one manufactured by biotechnology. It is also possible to manufacture other biomolecules by means of the corresponding production organisms, which are beneficial for the use or purification of the product, for example, the co-expression of an enzyme that produces hydrogen peroxide such as an oxidase or by catalase, superoxide dismutase and Other enzymes, reduce oxidative stress. This is only possible with biotechnological methods.

With regard to siderophores of natural origin, it is preferable to manufacture them so that the biotechnological productivity of the ligands that form complexes is especially sustainable from renewable raw materials and favors the economic pathways of the process, which are not accessible with the synthesis conventional chemistry

Another advantage of naturally occurring siderophores is that they are biologically disaggregated, since they are absorbed by multiple microorganisms and are clearly natural substances. This is an important advantage when the complexes go to the environment through unwanted processes. Derivatives of naturally occurring siderophores should also readily disintegrate.

As the central atom for the metal-siderophore complex, those metal atoms in any of their oxidation states are taken into account. It is preferably in the case of the central atom of the metal-siderophore complex of an element, which is chosen from Ag, Al, Au, B, Bi, Ce, Co, Cr, Cu, Eu, Fe, Ga, Hg, Mn, Mo, Ni, Pb, Pt, Ru, Ti, U, V, W, Zn and Zr in any oxidation state, in particular Ag (I), Al (III), Au (II), B (III), Bi (III), Ce (III), Ce (IV), Co (II), Co (III), Cr (III), Cu (I), Cu (II), Eu (II), Eu (III), Faith (II), Fe (III), Ga (III), Hg (II), Mn (II), Mn (III), Mo (IV), Ni (II), Pb (II), Pt (II), Ru (II), Ru (III), Ru (IV), U (IV), V (IV), V (V), W (VI), or Zn (II). It is preferably in the central atom of the metal-siderophore complex of an atom of a transition metal, which is preferably chosen from the group consisting of Mn, Fe, W, Co, Cr, Zn, Bi, Mo, V, Ce and Cu , especially of the group consisting of Co, Mn, Ce, Zn, Bi or Fe, in any of its oxidation states. In a particularly preferred configuration the central atom is chosen from Ce (III), Ce (IV), Co (II), Co (III), Fe (III), Mn (II), Mn (III), Zn (II ) and Bi (II).

In accordance with the invention, siderophores complexes with at least three hydroxamate groups, in particular desferrioxamines, deferricromoses and coprogen, in particular desferrioxamine E with metal ions of Mn, Fe, Co, Ce, Cr, Zn, stand out , Cu, Mo, V, W and Bi; siderophores complexes with at least two hydroxamate groups and at least one catecholate group, in particular Pioverdine Pa, with metal ions of Mn, Fe, Co, Ce, Zn, Cu, Mo, V, and Bi; siderophores complexes with at least two hydroxamate groups and at least one alpha hydroxycarboxylate group, in particular ornibactin, arthrobactin and schizookines with metal ions of Mn, Fe, Co, Ce, Zn, Cu, Mo, V, W and Bi; siderophores complexes with at least two hydroxamate groups and at least one carboxylic acid amide group, in particular rodotorúlico acid, with metal ions of Mn, Fe, Co, Ce, Zn, Cu, Mo, V, W and Bi; siderophores complexes with at least three partially hydrogenated thiazole rings, in particular Yersiniabactin, with metal ions of Mn, Fe, Co, Ce, Cr, Zn, Cu, Mo, V, and Bi; siderophores complexes with at least two alpha-hydroxy carboxylate groups and at least two carboxylic acid amide groups and at least two other carboxylate groups, in particular Rizoferrin with metal ions of Mn, Fe, Co, Ce, Zn, Cu, Mo, V, W and Bi; siderophores complexes with at least three catecholate groups, in particular Enterobactin, with metal ions of Mn, Fe, Co, Ce, Cu, V and Bi.

The metal siderophore complex can be presented in the form of any salt and if necessary also comprises other ligands and / or co-ligands. As ligands and / or co-ligands, the anions of salts, phosphonates, amines, polymers, polyols as well as co-builder (support substances) and surfactants, in particular those mentioned below, are taken into account. As counterions, cationic counterions are taken into account depending on the

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metal-siderophore complex charge such as alkali and alkaline earth metal ions or anionic counterions, such as halide ions or organic acid anions.

The fabrication of the metal-siderophore complex can generally be carried out in a simple manner so that a metal salt of the corresponding metal is mixed with the relevant siderophore or with a salt of the corresponding siderophore in an aqueous medium. By setting a suitable redox potential, the formation of a desired oxidation stage can be favored.

Another objective of the present invention are the siderophore-metal complexes, which are characterized in that the central atom is chosen from Ag, Al, Au, B, Bi, Ce, Co, Cr, Cu, Eu, Fe, Ga, Hg , Mn, Mo, Ni, Pb, Pt, Ru, Ti, U, V, W, Zn and Zr in any oxidation state, in particular Ag (I), Al (III), Au (II), B (III ), Bi (III), Ce (III), Ce (IV), Co (II), Co (III), Cr (III), Cu (I), Cu (II), Eu (II), Eu (III ), Fe (II), Fe (III), Ga (III), Hg (II), Mn (II), Mn (III), Mo (IV), Ni (II), Pb (II), Pt (II ), Ru (II), Ru (III), Ru (IV), U (IV), V (IV), V (V), W (VI), or Zn (II) with the exception of desferrioxamine metal complexes B and E, preferably with the exception of the metal complexes of all desferrioxamines, as well as with the exception of the metal complexes of desferritiocin, methanobactin, the Al and Cr complexes, preferably all the metal complexes of Pioverdine Pf244 and complexes of Al, Cu, Mn and Zn, preferably of all the metal complexes of Pioverdine of Pseudo Aeruginous monkeys, in particular with the exception of the metal complexes of all the Pioverdinas. In the case of siderophores it can be any of the siderophores mentioned above.

It is especially that the central atom of the metal-siderophic complex is an atom of a transition metal from the group consisting of Mn, W, Co, Cr, Zn, Bi, Mo, V, Ce and Cu, especially by Co, Mn, Ce, Zn or Bi, in any of the oxidation states. In a particularly preferred configuration the central atom is chosen from Co (II), Co (III), Cr (III), Ce (III), Ce (IV), Mn (II), Mn (III), Zn (II ) and Bi (III).

In a particularly preferred configuration the metal-siderophore complexes are chosen from the group of coprogen complexes with metal ions of Mn, W, Co, Cr, Zn, Bi, Mo, V, Ce, Cr and Cu; siderophores complexes with at least two hydroxamate groups and at least one alpha-hydroxy carboxylate group, in particular ornibactin, arthrobactin and schizoquines, with metal ions of Mn, W, Co, Cr, Zn, Bi, Mo, V , Ce, Cr and Cu; siderophores complexes with at least two hydroxamate groups and at least one carboxylic acid amide group, in particular rodotorúlico acid, with metal ions of Mn, W, Co, Cr, Zn, Bi, Mo, V, Ce, Cr and Cu ; siderophores complexes with at least three partially hydrogenated thiazole rings, in particular Yersiniabactin, with metal ions of Mn, W, Co, Cr, Zn, Bi, Mo, V, Ce, Cr and Cu; siderophores complexes with at least two alpha-hydroxy carboxylate groups, at least two groups of carboxylic acid amides and at least two other carboxylate groups, in particular Rizoferrin, with metal ions of Mn, W, Co, Cr, Zn , Bi, Mo, V, Ce, Cr and Cu; siderophores complexes with at least three groups of catecholate, in particular of enterobactin, with metal ions of Mn, Co, Ce, Cu, V and Bi.

A special objective of the present invention is the use of the aforementioned siderophore-metal complexes with the aforementioned central atoms in detergents or washing means, especially for cleaning fabrics or for cleaning hard surfaces.

Another special objective of the present invention is also the use of the aforementioned siderophore-metal complexes with the central atoms indicated as auxiliary means for cleaning tissues as well as for cleaning hard surfaces.

Another special objective of the present invention is also the use of the aforementioned siderophore-metal complexes with the central atoms indicated for the bleaching of cellulose and / or raw cotton.

Another special objective of the present invention is the washing means and detergents, in particular those having surfactants, which contain a siderophore-metal complex according to the invention.

In the case of washing media and detergents according to the invention, all imaginable detergents, both concentrates and also media that are used undiluted, can be used for commercial use, in the dishwasher or in hand washing . Among them are, for example, detergents for fabrics, carpets or natural fibers, for which the denomination detergent according to the present invention is used. To this group belong dishwashers for machine and hand washing or all types of detergents for hard surfaces such as metal, glass, porcelain, ceramics, bricks, plaster, lacquered surfaces, plastics, wood or leather; The detergent concept according to the invention is used for all of them. In a broader sense, sterilization and disinfection means are also taken into account as washing and cleaning means according to the invention.

The configurations of the present invention comprise all forms of presentation, convenient and / or established according to the state of the art of detergents according to the invention. Among them are solid, powdered, liquid, gel or pasty media, or if necessary in several phases, compressed or uncompressed. Among them are also, for example, extrudates, granules, tablets or "pouches" in both large and portioned packages.

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In a preferred configuration the washing means or detergents according to the invention contain the siderophore-metal complexes according to the invention described above in an amount of up to 5% by weight, in particular from 0.001% by weight to 1% by weight , and preferably from 0.01% by weight to 0.5% by weight, especially from 0.01% by weight to 0.25% by weight, based on the total weight of the detergent or washing medium.

In addition to the siderophore-metal complexes according to the invention, the means according to the invention may contain other bleaching catalysts and / or bleaching means and / or bleach activators. The substances used preferably of this type of substances as well as the amounts used are indicated in WO2008 / 101909.

The active oxygen content of the detergent or of the washing medium, in particular of the dishwashing detergent, with respect to the total weight of the medium, is preferably between 0.4 and 10% by weight, in particular between 0.5 and 8% by weight, and in particular between 0.6 and 5% by weight. Especially preferred media have an active oxygen content of greater than 0.3% by weight, in particular greater than 0.7% by weight, especially above 0.8% by weight and preferably greater than 1.0% by weight .

Alternatively to what happens with the bleaching media, enzymes can be used at the same time to treat hydrogen peroxide, which from other substrates are capable of producing hydrogen peroxide in situ. These are oxidereductases, which can transfer the electrons of a substrate in general organic, such as glucose, to oxygen as an electron receptor and thus facilitate in situ the formation of the desired hydrogen peroxide. Oxide reductase can be used together with the corresponding organic substrate. Since the impurities to be treated can already contain the required substrate, the use of oxidreductases can be carried out without adding the corresponding substrate.

As regards the oxidreductases that produce the hydrogen peroxide preferably used in accordance with the invention and the amounts used, all this is indicated in WO2008 / 101909.

In addition to at least one siderophore and / or at least one siderophore-metal complex and the aforementioned bleaches and other auxiliary bleaching substances contained, a detergent according to the invention contains other substances such as other enzymes, enzyme stabilizers, surfactants, Builder, solvents, thickeners as well as other usual substances, indicated below. The means according to the invention preferably contain non-ionic, anionic, cationic and amphoteric surfactants. As surfactants, nonionic, anionic and / or amphoteric surfactants are preferably used according to the invention. The surfactants are found in the washing media or detergents according to the invention in an amount of preferably 5% to 50%, especially 8% to 30%, with respect to the prepared medium.

As regards support substances, Builder and co-builder, polymers, solvents and thickeners preferably used in accordance with the invention and at their preferred concentrations, all this is indicated in WO2008 / 101909. The washing means and detergents according to the invention may contain, if necessary, similar substances, sequestering media, electrolytes, and other auxiliary substances such as optical brighteners, thickening inhibitors, glass corrosion inhibitors, corrosion inhibitors, color transfer inhibitors, foam inhibitors, substances that facilitate disintegration, abrasive substances, active ingredients that repel soil-release or soil-repellents, colorants and / or flavorings, as well as antimicrobial active substances, UV absorbers. As regards the preferred configurations of these usual substances as well as their preferred amounts, reference is made in patent application WO2008 / 101909.

Especially preferred bleach catalyst granules are those containing a) 0.1 to 30% by weight of the metal-siderophore complex as well as other bleaching catalysts that are needed b) 10 to 99% by weight of a support material, as well as c) 0.1 to 5% by weight of a binder from the group of organic polymers.

The other bleaching catalyst to be used according to a) is preferably chosen from the aforementioned bleaching catalysts.

As a support material b) all detergents and washing means which are used with the substances or mixtures of substances compatible with the rest of the ingredients, in particular the aforementioned structural substances, especially carbonates, which include bicarbonates, are basically suitable. sulfates, chlorides, silicates and phosphates. As the support material, alkali metal carbonates, alkali metal bicarbonates, alkali metal sesquicarbonates, alkali silicates, alkaline metasilicates, alkaline phosphates and mixtures of these substances are suitable, where carbonates are preferred in the sense of the present invention alkalines, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate and / or alkaline phosphates. In a particularly preferred configuration, the pentasodium triphosphate is used as support material,

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Na5P3O10 (sodium tripolyphosphate) or the corresponding potassium salt pentapotassium triphosphate K5P3O10 (potassium tripolyphosphate).

The weight percentage of the support material b) in a total granulation weight of the bleaching catalyst may vary in principle between the established limits, so that in terms of handling and actual bleaching power after mixing with other active substances in washing and cleaning, it has been shown that percentages by weight greater than 20% by weight, preferably greater than 40% by weight and in particular greater than 60% by weight, are preferred. As a consequence, bleach catalyst granules are preferred in the scope of the present invention, in which the weight percentage of the support material b) in a total granulate weight is from 20 to 99% by weight, preferably between 40% and 95% by weight and in particular between 60% and 90% by weight.

As a third substance, the bleach catalyst granules according to the invention contain a binder c) of the group of organic polymers. The polymers can be nonionic, anionic, cationic or amphoteric in nature. Natural polymers and modified polymers of natural origin are used as are synthetic polymers.

The group of non-ionic polymers used as binders c) preferably includes polyvinyl alcohols, acetylated polyvinyl alcohols, polyvinyl pyrrolidone and polyalkylene glycols, in particular polyethylene oxide. Preferred polyvinyl alcohols and acetylated polyvinyl alcohols have a molecular weight of the order of 10,000 to 100,000 gmol-1, preferably 11,000 to 90,000 gmol-1, in particular 12,000 to

80,000 gmol-1 and preferably from 13,000 to 70,000 gmol-1. Preferred polyethylene oxides have molar masses between 200 and 5,000,000 g / mol, and degrees of polymerization n from about 5 to> 100,000.

In the group of anionic polymers used as binders c), homo-or copolymeric polycarboxylates, polyacrylic acids and polymethacrylic acids, in particular those already mentioned above as organic structural substances useful for detergents and washing means, stand out. as well as polymers containing sulfonic acid groups, in particular those that have already been mentioned as conventional hardeners.

As regards the group of cationic and amphoteric polymers used as binders c) the polymers mentioned above are preferably highlighted as active polymers in washing and cleaning.

In the preferred bleach catalyst granules according to the invention the percentage by weight of the binder c) in the total weight of the granulate is between 0.2 and 4.5% by weight, preferably between 0.5 and 4.0% by weight and in particular between 1.0 and 4.0% by weight.

The bleach catalyst granules preferably have an average particle size between 0.1 and 1.0 mm, especially between 0.2 and 0.8 mm and in particular between 0.3 and 0.7 mm, so that the percentage by weight of particles with a particle size below 0.1 mm is at least 4% by weight, especially at least 6% by weight and preferably at least 8% by weight, being at the same time at most 80% by weight, in particular at most 60% by weight and preferably at most 40% by weight. The percentage by weight of the particles with a particle size between 0.2 and 0.8 mm is preferably between 30 and 70% by weight, in particular between 45 and 65% by weight and preferably between 40 and 60% by weight.

In addition to the bleaching catalyst, enzymes or other substances, especially sensitive, can also be mixed in the manner described above.

A detergent according to the invention, in particular a detergent according to the invention for hard surfaces may also contain one or more propellant agents or media (INCI Propellants), usually in an amount of 1 to 80% by weight, preferably 1, 5 to 30% by weight, especially 2 to 10% by weight, in particular 2.5 to 8% by weight, especially 3 to 6% by weight.

A specific object of the invention is the procedures for cleaning hard tissues or surfaces, in which at least one metal-phosphorus complex according to the invention is used in one of the process steps. It is both manual and mechanical procedures. The configurations are equivalent, for example, to manual washing, to the manual removal of stains from fabrics or hard surfaces or to use together with a mechanical procedure, so that mechanical procedures are preferred, in particular for tissue cleaning , due to a more precise handling in terms of the quantities used and the times of action.

A specific objective of the invention is the use of siderophore-metal complexes according to the invention for the cleaning of hard tissues or surfaces.

A powder washing medium according to the invention may preferably contain some components of those mentioned below:

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-Anionic surfactants, such as, for example, alkyl benzolsulfonate, alkyl sulfate, in amounts of preferably 5-30%, in particular 8-15%, especially 15-20%, -Non-ionic surfactants, such as, polyglycol fatty alcohol ether, alkyl polyglucoside, fatty acid glucamide, preferably 0.1-20% by weight, in particular 2-15% by weight, especially 6-11% by weight, -Aromatic substances, such as for example, zeolite, polycarboxylate, sodium citrate, preferably 5-60% by weight, in particular 10-55% by weight, especially 15-40% by weight, -Alcalis, such as sodium carbonate, preferably a 1-30% by weight, in particular 2-25% by weight, especially 5-20% by weight, - Bleaching media, such as sodium perborate, sodium percarbonate, preferably 5-25% by weight, in particularly 10-20% by weight, - Corrosion inhibitors, for example sodium silicate, preferably 1-6% by weight, in particular r 2-5% by weight, especially 3-4%, - Stabilizers, for example phosphonates preferably 0-1% by weight, - Foam inhibitor, for example, soaps, silicone oils, preferably 0.1- 4% by weight, in particular 0.2-2% by weight, especially 1-3% by weight, -Enzymes, for example proteases, amylases, cellulases, lipases, preferably 0.1-2% by weight, in in particular 0.2-1% by weight, especially 0.3-0.8% by weight, - Thickening inhibitor, for example carboxymethyl cellulose, preferably 0-1% by weight, - Coloring inhibitor, for example derivatives of polyvinylpyrrolidone, preferably 0-2% by weight, -Regulatory medium, for example sodium sulfate, preferably 0-20% by weight, -Optical bleacher, for example, stilbene derivative, biphenyl derivative, preferably 0.1-0, 3% by weight, in particular 0.1-0.4% by weight, -Odorous materials, -Water, -Soap, -Bleaching activators -Cellulose derivatives -Dirt repellent -0.01 to 5% by weight pr preferably 0.02 to 4% by weight and in particular 0.05 to 3% by weight of siderophores and / or siderophore-metal complexes as bleaching catalysts.

A liquid washing medium according to the invention may preferably contain the following components, which are chosen from the following: -Anionic surfactants, such as, for example, alkyl benzolsulfonate, alkyl sulfate, in amounts of preferably 5-40%, in particular 8-30%, especially 15-25%, -Non-ionic surfactants, such as, for example, polyglycol fatty alcohol ether, alkyl polyglucoside, fatty acid glucamide, preferably 0.1-25% by weight, in particular 5-20% by weight, especially 10-15% by weight, -Aromatic substances, such as, for example, zeolite, polycarboxylate, sodium citrate, preferably 0-15% by weight, in particular 0.01- 10% by weight, especially 0.1-5% by weight, - Foam inhibitor, for example, soaps, silicone oils, paraffins, preferably> 1% by weight, in particular 0.2-2% by weight , especially 1-3% by weight, -Enzymes, for example proteases, amylases, cellulases, lipases, preferably a 0 , 1-2% by weight, in particular 0.2-1% by weight, especially 0.3-0.8% by weight, -Optical bleacher, for example, stilbene derivative, biphenyl derivative, preferably 0, 1-0.3% by weight, in particular 0.1-0.4% by weight, -Odorous materials, -Stabilizers -Water, -Sapon, preferably 1-20% by weight, preferably 2-15% by weight, in particular 5-10% by weight, -Alcohols / solvents, preferably 0-25% by weight, preferably 1-20% by weight, in particular 2-15% by weight, -2 to 20% by weight, preferably 4 to 15% by weight and in particular 6 to 12% by weight of bleaches; as well as -0.01 to 5% by weight, preferably 0.02 to 4% by weight and in particular 0.05 to 3% by weight of siderophores and / or siderophore-metal complexes as bleaching catalysts.

Another object of the present invention is also a product containing a composition according to the invention or a washing or cleaning means according to the invention, in particular a cleaner according to the invention of hard surfaces, and a dispenser or dispenser. In the case of the product, it may be a single compartment or multi-compartment container, in particular two compartments. The manually operated dispenser, belonging to the group of sprayers (compressed gas container; also known as a sprayer), sprayers that create their own pressure, pump sprayer and plunger sprayer, in particular the pumping sprayer and the spraying spray is preferred. Plunger with a transparent polyethylene container or polyethylene terephthalate. The sprayers are described in detail in WO 96/04940 (Procter & Gamble) and in the cited American patents, to which reference is also made herein. Piston sprayers and washed bottles or pump diffusers have the advantage over containers

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of compressed gas, that no propellant means should be used. Using the appropriate accessories for particles and nozzles, etc ... (called "nozzle-valves") that are placed in the sprayer can be dosed the enzyme that is in this configuration optionally, even in an immobilized form of particles , that is as cleaning foam.

According to the invention, preferred dishwashing detergents comprise -5 to 70% by weight, preferably 10 to 60% by weight and in particular 20 to 50% of structural substances, with the exception of polymers active in washing and cleaning; -2 to 28%, preferably 4 to 20% by weight, and in particular 6 to 15% by weight of active polymers in washing and cleaning; -0.5 to 10% by weight, preferably 1 to 8% by weight and in particular 2 to 6% by weight of surfactants, preferably non-ionic and / or amphoteric surfactants; -0.5 to 8% by weight, preferably 1 to 7% by weight and in particular 2 to 6% by weight of enzymes; -2 to 20% by weight, preferably 4 to 15% by weight and in particular 6 to 12% by weight of bleaching media; -0.01 to 5% by weight, preferably 0.02 to 4% by weight and in particular 0.05 to 3% by weight of siderophores and / or siderophore-metal complexes as bleaching catalysts.

The presentation of dishwashing detergents according to the invention can be carried out differently. The means according to the invention can be presented in liquid or solid form as well as in combination. As solid forms of presentation, powders, granules, extrudates or compacts are especially suitable, in particular the tablets. Liquid forms of presentation based on water and / or organic solvents may be somewhat thickened, in the form of gels.

The means according to the invention can be presented in the form of single-phase or multi-phase products. Particularly preferred are dishwasher detergents with one, two, three or four phases. Dishwashing detergents are characterized in that they are presented in the form of a unit or dose already prepared with two or several phases. Each phase of the multiphase medium can have the same or different aggregate states. Dishwashing detergents that have at least two distinct phases and / or at least two liquid phases and / or at least one solid phase are preferred. The following examples clarify the invention, without being limited thereto.

Sample Settings

Example 1: Manufacture of metal complexes of desferrioxamine E and study of its action or effect of bleaching on tea a) Manufacture of a tea solution 1 liter of distilled boiling water is poured onto 1.6 g of black tea, not scented and Let the mixture stand for 5 minutes. The undissolved compounds are then filtered through a folded filter and after allowing to cool to room temperature the pH value is adjusted to 10.0 with a solution of sodium hydroxide. The solution can be used for 1-2 days.

b) Manufacture of 0.025 mmol siderophore-metal complexes (with respect to the metal atom) of the analyzed metal salt is stirred in 25 ml of deionized water with 0.050 mmol of desferrioxamine E (DFE) for 24 hours at room temperature in an open container. The pH is then adjusted to 10 and the mixture is allowed to stand for 48 hours at room temperature and then by sterile filtration with the help of a supplementary syringe filter the undissolved components are removed. At the same time, a solution without desferrioxamine E metals is prepared that does not mix with the metal salt.

c) Bleaching power measurement A solution of hydrogen peroxide based on 1050 µL 30% by weight of perhydrol in 100 ml of borate buffer is prepared. The metal complexes will be diluted with 50 mM borate buffer at pH 10.0 5.88 mg of metal per liter. For comparison, the bleaching power of a conventional bleaching catalyst is determined. To this end, a solution of Mn-TACN (manganese and triazacyclononane ion complex) with 5.88 mg per liter is prepared.

Table 1: Pipetting scheme:

Null value

Uncatalyzed bleaching Catalyzed by the complex

Tea solution

400 µl 400 µl 400 µl

Borate buffer

100 µl 100 µl 100 µl

Deionized water

500 µl 400 µl 300 µl

H2O2 solution

0 µl 100 µl 100 µl

Siderophore-metal complex solution

0 µl 0 µl 100 µl

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The hydrogen peroxide solution is added at the end, before closing the containers and incubation at 40 ° C for one hour. The extinction measurement is then carried out at 400 nm in a water spectrophotometer. The reduction in extinction ΔΕ minus that of uncatalyzed bleaching is a measure of the bleaching power and shows how intensely the hydrogen peroxide bleach can favor the analyzed metal complex.

Table 2: Bleaching power of DFE metal complexes compared to Mn-TACN

Sample / metal salt used

ΔΕ -ΔΕ of the null value Improvement /%) vs. uncatalyzed Improvement (%) compared to Mn-TACN

Without metal complex (not catalyzed)

0.305 0.0

Mn-TACN

0.565 85.2 0.0

Desferrioxamine E without metal salt

0.258 -15.4 -54.3

FeCl3 + 7 H2O with desferrioxamine E

0.277 -9.2 -51.0

MnCl2 with desferrioxamine E

0,332 8.9 -41.2

CoCl2 with desferrioxamine E

0.681 123.3 20.5

It has been shown that with the manganese-cobalt metal siderophore-metal complexes the bleaching power of hydrogen peroxide can be improved. With the cobalt complex, a greater bleaching power was also obtained than with Mn-TACN, which was used as an example of the current state of the art.

Example 2: Manufacture of other siderophore-metal complexes and study of the bleaching effect on tea

15 The manufacture of siderophore-metal complexes as well as the performance of the test were carried out as described in example 1. The washing tests were not carried out in water but in the formula of a liquid detergent, conventional in The market as a parent.

The bleaching power of different metal complexes of the following siderophores were manufactured and studied:

20 a) Siderophore with three hydroxamate groups: Ferricrome, Coprogen b) Siderophore with two hydroxamate groups and one catecholate group: Pioverdine Pa c) Siderophore with two hydroxamate groups and one alpha-hydroxycarboxylate group: Ornibactin, Arthrobactin, schizookines d) Siderophore with two hydroxamate groups and several carboxylic acid amide groups: rodotoruic acid

E) Siderophore with three partially hydrogenated thiazole rings: Yersiniabactin f) Siderophore with two alpha-hydroxy carboxylate groups, two carboxylic acid amide groups and two other carboxylate groups: Rhizoferrin g) Siderophore with three catecholate groups: Enterobactin

30 To evaluate the bleaching power, the bleaching power of the hydrogen peroxide solution without catalyst was used, so that values greater than 100 were equivalent to a better bleaching power and values less than 100 were equivalent to bleaching power worse than hydrogen peroxide detergent without catalyst.

35 Table 3: Bleaching power of different siderophore-metal complexes

EC

Eu You VOSO4 Na3VO4 Cr Mo W Mn (II) Mn (III)

Ac. rodotorúlico

150 115 116 138 133 133 140 134 145 145

Ornibactin

149 99 109 136 122 130 137 144 138 148

Pioverdina Pa

161 103 95 122 152 119 142 117 134 144

Rhizoferrin

153 104 85 106 133 116 129 117 119 107

Arthrobactin

138 89 93 115 137 119 124 126 117 125

Coprogen

154 93 92 117 141 111 129 122 125 134

Enterobactin

121 92 66 96 112 91 93 87 128 131

Ferricrome

141 98 91 111 131 96 130 130 137 124

Yersiniabactin

138 88 83 115 142 120 123 116 136 139

Schizoquins

163 121 115 168 146 155 170 151 173 152

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Table 4: Bleaching power of different siderophore-metal complexes

Faith (II)

Faith (III) Co Neither Cu Zn To the Ga Bi

Ac. rodotorúlico

136 99 333 108 119 132 100 114 131

Ornibactin

130 88 342 110 135 146 107 107 128

Pioverdina Pa

126 94 349 92 148 128 92 106 137

Rhizoferrin

128 85 288 95 131 142 93 99 134

Arthrobactin

109 101 340 97 137 122 95 91 125

Coprogen

113 83 313 97 131 114 91 85 137

Enterobactin

99 68 362 76 115 104 79 79 112

Ferricrome

114 108 337 94 122 117 95 92 134

Yersiniabactin

123 107 347 94 133 121 85 94 134

Schizoquins

138 149 290 98 131 152 119 114 144

As can be seen from the table, a clear improvement in bleaching power can be achieved by

5 numerous siderophore-metal complexes. Especially striking is the strong increase in bleaching power due to siderophores complexes with cerium, vanadium, manganese and cobalt ions. In addition, the strong bleaching power of schizokinen metal complexes, rodotorúlico acid and ornibactin stands out.

Example 3: Bleaching of impurities due to tea and blueberry stains on tissues using Mn-DFE and Mn10 schizoquines

With the Mn-desferrioxamine complex according to example 1, the action or effect of bleaching on tea and blueberry stains on cotton fabrics was analyzed and compared with an Mn-schizoquine complex. Here, washing mini-tests were carried out and then a quantitative digital optical evaluation was carried out.

15 Solutions: -1050 µL hydrogen peroxide solution 30% by weight of perhydrol in 100 ml of borate buffer (see example 1). -Mn-desferrioxamine complex (see example 1) is diluted with 50 mM borate buffer at pH 10.0 on 5.88 mg of metal per liter,

20-Mn-schizoquine complex, manufactured analogously to the desferrioxamine complex, -Synthetic running water consisting of deionized water with defined hardness -Defined glycine / NaOH-150 mM buffer, pH 10

Table 5: Pipetting scheme

Null value

Uncatalyzed bleaching Catalyzed complex

Synthetic running water

2.7 ml 2.4 ml 2.1 ml

Glycine / NaOH buffer

0.3 ml 0.3 ml 0.3 ml

H2O2 solution

0.0 ml 0.3 ml 0.3 ml

Solution of the siderophore-metal complex

0.0 ml 0.0 ml 0.3 ml

25

Dirt due to tea spots and blueberries in the cotton fabric was trimmed with a diameter of 1 cm and covered with 3 ml of bleach according to the pipetting scheme and removed for 30 minutes at temperatures of 30 ° C 40 times by minute with 180º turns relative to the horizontal. The tissues were then washed under running water and air dried overnight. The edges or edges of the fabric were then fixed on a standard surface, to measure the reflection of the light: for this the degree of whiteness L * of the washed tissue was measured compared to a standard target (d / 8, 8 mm, SCI / SCE), which had been regularized to L * = 100. The measurement was performed on a color measuring device (Minolta Cm508d) with a light type setting of 10 * / D65. The L * value minus that of the uncatalyzed white is a measure of the bleaching power and indicates how strongly it favors the bleaching of hydrogen peroxide to the metal complex sample. The results are indicated to

35 continued.

Table 6: Results of the mini blueberry stain wash test

Sample

L * ΔΕ versus the null value ΔΕ uncatalyzed bleaching

Null value

75.35 0.00

Without metal complex (not catalyzed)

84.73 9.38 0

MnCl2 with desferrioxamine E

86.57 11.22 1.84

MnCl2 with schizokinen

87.11 11.75 2.37

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Table 7: Results of the mini wash test for tea stains

Sample

L * ΔΕ versus the null value ΔΕ uncatalyzed bleaching

Null value

72.99 0.00

Without metal complex (not catalyzed)

78.42 5.43 0.00

MnCl2 with desferrioxamine E

80.66 80.66 2.24

MnCl2 with schizokinen

80.98 80.98 2.56

It can be detected that the schizoquine-manganese complex as well as the desferrioxamine-Emanganese complex improves the bleaching power of hydrogen peroxide both in terms of blueberry stains as well as in tea stains, although at 30 ° C a very low temperature has been chosen.

While in the case of desferrioxamine E it is a tris-hydroxamate siderophore, schizoquine represents a hydroxamate-alpha-hydroxycarboxylate siderophore.

10 Example 4: Exploration of the washing power of the Mn-DFE compared to the TAED. To compare the washing power of the Mn-DFE against that of the TAED, the catalyst was incorporated into a conventional washing powder form with dissolved builder (support) (sodium percarbonate). As catalyst, 2.7% by weight of TAED were used, respectively, compared to Mn-DFE complexes with 5 mg respectively,

10 mg or 20 mg of Mn ions. The washing tests were performed in a Miele W 918 dishwasher at 20 ° C as well as at 30 ° C, 16 ° dH (German hardness), pH 10.5. The important washing process lasted 60 minutes and the washing process was repeated five times.

As fabrics, cotton (Co) fabrics were used as well as mixed fabrics of 35% cotton and 65% of

20 polyester (PE / Co). The following soils were used: C-02 (Olive oil / soot on cotton), C-10 (pigment / peanut oil / high concentration of milk on cotton), BC-2 (coffee on cotton), BC-3 ( tea on cotton), CS-1 (blood aged on cotton), CS-3 (red wine aged on cotton), CS-10 (butter fat with dye on cotton), CS-12 (black currants on cotton), CS -13 (apple juice on cotton), CS-44 (chocolate soda on cotton), CS-103 (red wine not aged on cotton), E

25 117 (blood / milk / ink on mixed cotton fabric), E-160 (chocolate cream in cotton), PCS-17 (makeup on mixed polyester / cotton fabric).

Table 8: Results of washing at 30 ° C

Dirt

Tissue TAED Mn-DFE (10 mg Mn) Mn-DFE (20 mg Mn) LSD

C-02 Olive oil / soot

Co 31.2 33.3 34.3 1.9

BC-2 Coffee

Co 63.3 64.5 64.7 0.9

BC-3 Tea

Co 62.7 66.3 67.2 2.2

CS-12 Blackcurrants

Co 65.9 70.6 70.5 2.2

CS-13 Apple Juice

Co 84.4 85.6 85.7 0.7

CS-44 Red wine, not aged

Co 70.8 74.2 73.1 2.2

CS-44 Chocolate soft drink

Co 48.5 53.4 55.4 3.1

C-10 Pigment and peanut oil / raised conc. in milk

Co 55.8 56.8 56.8 0.9

E-160 Chocolate Cream

Co 61.8 64.9 66.7 2.2

CS-1 Aged blood

Co 47.2 48.5 49.2 5.4

Table 9: Washing results at 20ºC

Dirt

Tissue TAED Mn-DFE (5 mg Mn) Mn-DFE (10 mg Mn) Mn-DFE (20 mg Mn) LSD

CS-10 Fat butter with coloring

Co 72.7 72.6 73.3 74.8 0.7

BC-2 Coffee

Co 62.1 63.1 63.0 63.7 1.4

BC-3 Tea

Co 59.7 60.6 61.2 63.4 2.6

CS-12 black currants

Co 66.4 68.5 69.6 70.9 2.9

CS-13 apple juice

Co 83.7 84.8 85.4 85.4 1.1

CS-44 Red wine, not aged

Co 61.5 62.9 64.0 65.6 2.0

CS-44 Chocolate soft drink

Co 47.3 48.7 50.1 52.3 2.5

E08716923

10-29-2015

E-117 Blood / milk / ink

PE / Co 16.9 17.9 17.2 17.5 1.1

E-160 Chocolate Cream

Co 60.7 61.8 63.1 64.0 2.6

PCS-17 Makeup

PE / Co 77.6 77.0 78.0 78.8 1.4

It can be seen that the Mn-DFE in all the stains analyzed both at 20 ° C and also at 30 ° C has a cleaning power at least somewhat better, in some spots, even much better than TAED, which minimally damages the fiber as well as the Mn-DFE. The cleaning power is as expected

5 below 20 ° C than at 30 ° C, so that the decrease in cleaning power is relatively minimal.

Example 5: Bleaching with oxygen from the air

To explore the bleaching power without adding oxidizing media, that is, with the oxygen in the air as unique

In the oxidation medium, tests were carried out with Mn-desferrioxamine to compare with the Mn complexes of triazacyclononane (TACN) and tetraazacyclododecane, with the Mn complex of a terpiridine as well as with cobaltopentamine on the edges of a cotton fabric . The test was carried out as described in example 3 with the difference that no hydrogen peroxide had been added and the pH was adjusted to 11.0. In addition, incubation was carried out for 60 minutes instead of 30 minutes. As in

In Example 3, the commercially used liquid detergent formula was used as a matrix, where a 150 mM glycine / NaOH solution was used as standard. Tea (EMPA 167-13-07) and blueberries (CFT CS-15 025 0) were used as dirt. The average value was finally calculated from the values obtained.

Table 10: Results of bleaching with air oxygen

Sample

Bleaching achieved ΔL

Liquid detergent (Matrix)

0.00

Matrix, pH11

1.09

Matrix + Mn (III) DFE (10µM Mn), pH11

1.61

Matrix + Mn-terpyridine (10µM Mn), pH11

0.92

Matrix + Mn-TACN (10µM Mn), pH11

0.78

Matrix + Mn-tetraazacyclododecane (10µM Mn), pH11

1.11

Matrix + Cobaltopentamine (10µM Mn), pH11

1.25

It can be seen that Mn-DFE even with oxygen in the air as the only source of oxygen produces a significant bleaching effect against catalysts containing Mn known and used in the state of the art. Example 6: Determination of color alteration

25 To find out the color alteration, tests were carried out with different colored tissues differently, as described by Luijkx et al (Tenside Surf. Det. 41 (2004) 4). For this, the tissues were washed 20 times at 40 ° C with a detergent containing Mn-DFE (10 mg Mn). The same stoichiometric amount of Mn-TACN was used to make the comparison. It was deduced that Mn-DFE produces a much weaker color modification in

30 the numerous colored tissues that Mn-TACN. Thus, in the use of Mn-DFE in particular in Direct Yellow on cotton as well as in Reactive Blue 33 on cotton, a color modification was observed ten times weaker than when using Mn-TACN.

Example 7: Determination of bactericidal efficacy

35 In a commercial detergent powder formula containing percarbonate as a bleaching medium as well as Mn-DFE as a bleaching catalyst, bactericidal efficacy was studied in quantitative suspension tests. For this purpose, 5.88 g of detergent formula were dissolved with 7 mg of Mn-DFE in 900 ml of distilled water and 9 ml of the solution thus obtained was mixed and mixed with a suspension of test germs.

40 (see below). After 40 minutes of action at 30 ° C, the bleaching that remained with the sodium thiosulfate solution had been completely deactivated and then the number of live germs was determined. The suspension test was carried out based on DIN EN 1040 (dilution neutralization method). The value of efficacy in terms of the reduction of live bacteria is indicated as a reduction rate in powers of ten.

45 For Staphylococcus aureus DSM 799, a reduction factor of 2.12 * 10 ^ 2 and for Pseudomonas aeruginosa DSM 939 for a number could be detected for a number of starting germs N = 4.75 * 10 ^ 8 / ml of starting germs N = 4.2 * 10 ^ 8 / ml a reduction factor <2.8 * 10 ^ 5. The formula therefore has a detectable bactericidal action.

fifty

Claims (10)

1. Washing medium or detergent, characterized in that it contains a siderophore. 2. Washing medium or detergent according to claim 1, characterized in that the siderophore is in the form of a siderophore-metal complex. 3. Washing medium or detergent according to claim 1 or 2, characterized in that in the case of the siderophore it is a compound, which contains at least two radicals from the group consisting of 10 hydroxamate, catecholate, alpha-hydroxy carboxylate, alpha-keto carboxylate, phenolate, carboxylic acid amide, citrahydroxamate as well as if necessary, partially or fully hydrogenated oxazole or thiazole. 4. Washing medium or detergent according to one of claims 1 to 3, characterized in that in the The siderophore case is a naturally occurring siderophore chosen from the group consisting of sideromycins, siderochromes and sideramines. 5. Washing medium or detergent according to claim 4, characterized in that the naturally occurring siderophore is chosen from the group consisting of deferricromes, tetraglycidesferricromes, deferricrocin, deferricrisine, deferrirodine, hexahydroferrheodine, deferrirubin, deferricoprogen, deferricoprogen II, deferric acid , 20 Exochelins, Fusigen (Fusarinin C), nocardamine, desferrisalmicin, desferrialbomicinas, desferrioxaminas, desferrimicinas, Pioverdinas, mycobactins, aerobactin, arthrobactin, acinetoferrina, aququelquelins, ornibactina, acinoferctin, azinophobabacinins, phanobabacinins, acne Pseudobactin, Putrebactin, Acromobactin, Rhizoferrin, alterobactins, agrobactin, enterobactin (Enteroquelina), fluvibactina, homofluvibactina, bacillibactina (corinebactina), petrobactina, salmoquelina, 25 azotoquelina, mioxoctinine, feribactin, Pibabazine daunorubicin, succinimycin, rifamycin, trencam, pseudomonin, corrugatin, gallichrome, fusygen, deferristafiloferrin, deferrivibrioferrin, desferrimaduraferrine, Fusarines, dimerumic acid, mugineinic acid, coeliqueline, WCS, methabactin, rhinobactin carboximicobactin, erythrobactin, cepabactin, meningobactin, crisobactin, quinolobactin, thioquinolobactin, 30 vibriobactin, vancrobactin, parabactin and balibactin. 6. Washing medium or detergent according to one of claims 1 to 5, characterized in that in the metal of the siderophore-metal complex it is an element chosen from the group consisting of Ag, Al, Au, B, Bi, Ce, Co, Cr, Cu, Eu, Fe, Ga, Hg, Mn, Mo, Ni, Pb, Pt, Ru, Ti, U, V, W, Zn and Zr in any oxidation state. 35 7. Washing medium or detergent according to one of claims 1 to 6, characterized in that the siderophore-metal complex is selected from the siderophores complexes with at least three hydroxamate groups, in particular the deferrioxamines, deferricromes and coprogen, especially desferrioxamine E with metal ions of Mn, Fe, Co, Ce, Cr, Zn, Cu, Mo, V, W and Bi; siderophores complexes with at least two hydroxamate groups and at least one catecholate group, in particular Pioverdine Pa, with metal ions of Mn, Fe, Co, Ce, Zn, Cu, Mo, V, and Bi; siderophores complexes with at least two hydroxamate groups and at least one alpha-hydroxy carboxylate group, in particular ornibactin, arthrobactin and schizoquine with metal ions of Mn, Fe, Co, Ce, Zn, Cu, Mo, V, W and Bi; siderophores complexes with at least two hydroxamate groups and at least one carboxylic acid amide group, in particular rodotorúlico acid, with metal ions of Mn, Fe, Co, Ce, Zn, Cu, Mo, V, W and Bi; complexes of 45 siderophores with at least three partially hydrogenated thiazole rings, in particular Yersiniabactin, with metal ions of Mn, Fe, Co, Ce, Cr, Zn, Cu, Mo, V, and Bi; siderophores complexes with at least two alpha-hydroxy carboxylate groups and at least two carboxylic acid amide groups and at least two other carboxylate groups, in particular Rizoferrin with metal ions of Mn, Fe, Co, Ce, Zn, Cu, Mo, V, W and Bi; siderophores complexes with at least three catecholate groups, in particular Enterobactin, with metal ions of Mn, Fe, Co, Ce, Cu, V and Bi. fifty

8.

 Use of washing means or detergents according to one of claims 1 to 7 to clean fabrics.

9.

 Use of washing means or detergents according to one of claims 1 to 7 to clean hard surfaces.

55

10.

 Use of siderophores in washing media or detergents, which contain surfactants.

eleven.

Use according to claim 10, characterized in that the siderophore is in the form of a siderophore-metal complex.

60 18