DE19520743A1 - Oligo-galacturonate and poly-galacturonate mixed complexes - Google Patents

Abstract

Oligo- or polygalacturonate mixed complexes of formula (I) are new: Me = alkaline earth and/or transition metal; Ps<-> = galacturonation; X = organic or inorganic acid anion with charge n; M = alkali metal; Ps = carboxyl free neutral saccharide unit; z = average bond number in the Me contg. complex (2-3); q is related to the stoichiometric factors a,b,c and m by the expression (A) and has a value 0.0001-(z-1); term (B) is the sum of the bonds of the complex contg. X; a-c = \-0 so that the largest value of a+b+2c is z-1.000; n = 1-10; m = 0.0001-2; x = 0-56; y = 0-35; and N' = an average polymerisation (N) factor (2-300). Also claimed are compsns. contg. (I).

Description

The invention relates to oligo- or polygalacturonate mixed complexes and drug containing these compounds tel and food compositions. The invention relates a process for the preparation of these compounds.

It is known that in the treatment of the under different macro, meso and micro element deficiencies and the Deficiency states caused by vitamin deficiency not only one deficiency, but several essentials at the same time Nutrients, elements or ions, vitamins, eat tial amino acids are required as the effects these substances often reinforce each other synergistically. First was the synergistic effect of magnesium and vitamin B₆ recognized [J. Durlach: J. Med. Besancon, 5, 349-359 (1969); P. Fr. M. 8058 (CI. A 61k); C.A. 77. 39245y). In order to achieve a better effect, the Mag nesium-vitamin B₆ complex by amino acids (glycine, gluta minic acid) added [D. L. Leussing and N. Hug: Anal. Chem. 38, 1388-1392 (1966); R. Kristen et al .: Eur. J. Clin. Phar macol. 34, 133-137 (1988)).

In US Pat. No. 2,871,326 there are mixed complexes xe metal-polygalacturonate complexes described in which a certain part of the carboxylate ions of polygalactu ronic acid not metal ions, but the cations organi bases (active pharmaceutical ingredients) are bound. The "ge mixed "character of these mixed complexes is accordingly here due to the carboxylate anions of the galacturonate unit bound cations of different types (metal catio nen and cations of amine bases).

From those according to Hungarian Patent No. 203 365 produced basic metal complexes acidic oligo- and Under biological conditions, polysaccharides become the Me metal ions released at greater speed, and the Metal complexes give their total metal ion content in biologically usable form on the living organism.

In the interest of optimal treatment the difference  deficiencies there is a need for resources which is the effective submission of several under various substances essential for the organism (Ele elements, vitamins, amino acids and. guarantee. Wu It is also worthwhile that as a carrier the drug tel and food substances are available that the Active ingredients or nutrients with improved effectiveness give away.

The object of the invention was therefore to provide Mixed complexes other than those important to the organism Metal cations which are essential building materials, substances present in anionic form, such as vitamins, Amino acids or pharmaceutical active ingredients in contain chemically bound form and are capable of this Dispensing substances highly effectively.

The invention is based on the knowledge that in the new mixed complexes of the general formula (I) both anio niche as well as cationic components chemically bound can be and then in the metabolic process with high effi ciency become accessible to the organism. This will make the Problem solved with the means according to the invention. The invention accordingly relates to oligo- or poly mixed galacturonate complexes of the general formula (I)

HO - [{Me ^{Z +} (Ps ^- ) _zq (OH ^- ) _a (HCO₃ ^- ) _b (CO₃² ^- ) _c (X ^n- ) _m } (M⁺Ps ^- ) _x (Ps) _y ] _{N ′} -H ( I)

wherein
Me stands for alkaline earth metal atom and / or transition metal atom,
Ps⁻ galacturonation means
X ^n- are identical or different anions of organic and / or inorganic acids is,
M represents alkali metal atom,
Ps denotes a carboxyl-free neutral saccharide unit,
z represents the (average) charge number of the Me atoms contained in the molecule of the mixed complex, and their value is a real number ranging from 2 to 3,
q an expression formed from the stoichiometric factors a, b, c and m

represents with the Be  condition that its value ranges from 0.0001 to (z-1) real number, where

is the sum of the charges of the anions X ^n- contained in the molecule of the mixed complex,
a, b and c independently of one another have the value 0 or a real number greater than 0 on the condition that the value of a + b + 2c can be at most z-1,0001,
n is an integer from 1 to 10,
in a real number from 0.0001 to 2,
x a real number from 0 to 56,
y is a real number from 0 to 35 and
N 'is a factor indicating the average degree of polymerization (N), which can assume the values 2N300.

The mixed complexes according to the invention are accordingly Me tall oligo and metal polygalacturonate complexes that little contain at least two different anions. Unlike the ones from U.S. Patent 2,871,326 mixed complexes the mixed character of the mixed complexes according to the invention by the to the galacturonate anions of the oligo or wise polygalacturonic acid bound one, two and / or trivalent metal ions as well as through the over two and trivalent metal ions bound anions of organic and / or given inorganic acids.

In the formula of the mixed complexes according to the invention, Me ^{z + can be used,} inter alia, for Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Cr ³⁺ , Mn ²⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , Cu ^{2 +} , Zn ²⁺ , Ni ²⁺ , Ga ³⁺ . Me ^{z +} can also stand for a cation formed from a transition metal and oxygen atoms, such as the vanadyl cation VO ²⁺ .

In these mixed complexes, the oligo- or polygalacturonic acid, in the chemical and in the physical sense, is the carrier of the metal cations bonded directly to the carboxylate groups and of the metal ions bonded via divalent or trivalent metal ions which can be derived from the acids of the general formula H _n X of the general formula X ^n- , therefore the oligo- or polygalacturonic acid is referred to below as the carrier. In mixed complexes of this type, the carrier can be any acidic oligosaccharide or polysaccharide, for example alginic acid, carboxycellulose and carragen. From the point of view of the mixed complexes according to the invention, those acidic polysaccharides which are relatively inexpensive and of constant quality are of the greatest practical importance. Of the acidic polysaccharides, the natural pectin found in plants, which is a partially methyl-esterified polygalacturonic acid [ML Fishman and JJ Jen: Chemistry and Function of Pectins, Am. Chem. Soc. Symposyum Series 310, Washington, DC, 1986], the greatest practical importance.

The object of the invention was accordingly by oligo- and Mixed polygalacturonate complexes. The oligo and Polygalacturonic acid shows namely for Ca ions, compared with other acidic polysaccharides, a very high one Selectivity, it can strongly affect the brush border membranes calcium ions bound to the intestinal cells and villi bind and against the metal ions to be introduced replace and in this way the membrane for an effective Absorption of the ions introduced with the mixed complex öff nen [T. Fazekas, B. Selmeczi, P. Stefanovits (editors): Magnesium in biological systems; Environmental and biomedi cal aspects, Akademiai Kiadö, Budapest, 291-300, 1992).

In the complexes according to the invention, the carrier can be an acidic polysaccharide consisting of galacturonic acid units, which in the following - without specifying the degree of polymerization and the carboxylate group - is designated by the formula HPs (C₆H₈O₆), which contain 1 mol of carboxylate groups or oligo- Polygalacturonic acid or a galacturonic acid unit thereof means. In these mixed complexes, the anions X ^n- of inorganic and / or organic acids are bonded to the galacturonate ions of the support via divalent and / or trivalent metal ions, ie the anions X ^n- are derived from structural units of the general formula Ps⁻Me ²⁺ , Ps⁻Me ³⁺ or (Ps⁻) ₂Me ³⁺ worn. The methyl esterified portion of galacturonic acid is illustrated by the formula CH₃Ps, the quantitative meaning is the same as that of the previous formula. Repeated galacturonic acid units are therefore present in the polymer molecule of the carrier.

The lies in the mixed complexes according to the invention average degree of polymerization (N) of the support between 2 and 300. The polymeric molecules of the pectic acids also contain carboxylate as a natural "impurity" free (neutral) saccharide units, such as L-Ramnose, D-Galac tose, L-arabinose, D-xylose, D-glucose and D-mannose [Fish man and Jen: Chemistry and Function of Pectins, Am. Chem. Soc. Symposyum Series 310, Washington, DC, 1986, pp. 4 and 18]. (In the exemplary embodiments, the empirical formulas the mixed complexes the content of neutral saccharides Always better than glucose for the sake of clarity [C₆H₁₀O₅) specified).

The invention also relates to pharmaceutical preparations. The pharmaceutical preparations according to the invention contain the compound of the general formula (I) - where the meaning of Me, Ps⁻, X ^n- , M, Ps, z, q, N ', a, b, c, n, m, x and y is the same as above - in addition to the usual pharmaceutical carriers, extenders and other auxiliaries, at least one active ingredient.

The invention also relates to food compositions which, based on their total mass, contain at least one mixed complex of the general formula (I) in an amount of 0.001-10% by mass, the meaning of Me, Ps⁻, X ^n- , M, Ps, z, q, N ′, a, b, c, n, m, x and y is the same as above.

The food compositions are made by in a suitable step of food production mixed complexes in the form of a dried product or a suspension or a solution to the food be given to the total mass of the composition based on the dry matter content 0.001-10 mass%.

The invention also relates to the production of mixed complexes of the general formula (I), in which the meaning of Me, Ps⁻, X ^n- , M, Ps, z, q, N ', a, b, c, n, m, x and y is the same as above. It is characteristic of the process that one

• a) basic metal oligo- or metal-polygalacturonates of the general formula (II) HO - [{Me ^{Z +} (Ps ^- ) _{zq ′} (OH ^- ) _a (HCO₃ ^- ) _b (CO₃² ^- ) _c } (M⁺Ps ^- ) ^x (Ps) ^y ] ^{N ′} -H (II) where the meaning of Me, Ps⁻, M, Ps, z, N ′, a, b, c, x and y is the same as above, and
  q ′ stands for an expression a + b + 2c formed from the stoichiometric factors a, b and c on the condition that its value is a real number ranging from 0.001 to (z-1),
  with acids of the general formula (H⁺) _n X ^n- , in which the meaning of X ^n- and n is the same as above, or sets
• b) acids of the general formula (H⁺) _n X ^n- , in which the meaning of X ^n- and n is the same as above, with an excess of metals Me or Me compounds, the meaning of Me being the same as above is and Me compounds the oxides, hydroxides, car bonate, hydrogen carbonates or basic carbonates are to be understood, implemented and the compound (s) obtained with oligo- or polygalacturonic acid or pectin to react or
• c) a mixture of oligo- or polygalacturonic acid or pectin and acids (H⁺) _n X ^n- with metals Me or their compounds and

if desired, the resulting mixed complex of the general formula (I) with an acid (H⁺) _n X ^n- , in which the meaning of X ^n- and n is the same as above, but the acid is different from that in variants a), b) or c) used.

The starting materials for process a) are those according to of Hungarian Patent No. 203 365 ba Use metal oligo or metal polygalacturonates det. In these basic metal complexes, they can be linked to the divalent or trivalent metal ions bound, the basi OH Charakter ions representing character in any Ratio through carbonate and / or bicarbonate ions be exchanged. Based on the total carboxyl groups content of the carrier is also new in an amount of 0-95%  trale structural units of the general formula Me (Ps) ₂ and Me (Ps) ₃ permitted, where the meaning of Me and Ps the same as above.

The basic metal complexes are reacted with acids of the general formula H _n X. This process can be illustrated by the acid-base reaction according to the following reaction scheme 1, in which, for the sake of simplicity, n = 1 and Me = magnesium, ie the starting compounds are basic magnesium polygalacturonate and a monovalent acid.

Reaction scheme 1

2 HO-Mg-Ps + HX → (X-Mg-Ps · HO-Mg-Ps) + H₂O

According to process variant b) according to the invention, the acids of the general formula H _n X are first reacted with metals Me or their compounds. The metals or metal compounds are used in excess. The reaction mixture obtained, in which the acids of the general formula H _n X, their salts and / or basic salts and the metals or metal compounds present in excess, are reacted with the carrier (pectin or pectic acid). This process variant is illustrated by reaction scheme 2 (here, too, for the sake of simplicity, n = 1 and Me = Mg).

Reaction scheme 2

HX + 2 Mgo + H₂O → HO-Mg-X + Mg (OH) ₂ and
HO-Mg-X + Mg (OH) ₂ + 2 HPs → (X-Mg-Ps · HO-Mg-Ps) + 2 H₂O

The nature of the formation of the mixed complex regarding analogous reactions take place when polyvalent acids H _n X or a mixture of such acids with the metals or metal compounds and then the compounds obtained are reacted with the carrier. In the first section of the reaction, the neutral salts of the acid H _n X with magnesium or the other metals can also be formed, as illustrated in reaction scheme 3.

Reaction scheme 3

2 HX + 4 MgO + 2 H₂O → MgX₂ + 3 Mg (OH) ₂, then
MgX₂ + 3 Mg (OH) ₂ + 4 HPs → (2 X-Mg-Ps.2 HO-Mg-Ps) + 4 H₂O

The use of process variant b) is always particularly advantageous when the reactivity of the acid (s) H _n X used for the preparation of the mixed complex, for example flavonoids or individual amino acids, is low.

In process variant c) for the preparation of the mixing complexes, a mixture of acids of the general formula H _n X and the carrier is reacted with metals or metal compounds. This process variant is illustrated (while maintaining the simplifications made above, ie using magnesium oxide as the metal component and a monohydric acid) by the reaction scheme 4.

Reaction scheme 4

2 HPs + HX + 2 MgO → (X-Mg-Ps · HO-Mg-Ps) + H₂O

It can be seen that the three different ver driving variants in the case of the same stoichiometric Ver result in identical end products.

In addition to the previously described process variants a) -c), there are numerous other possibilities for the preparation of the complexes according to the invention by, if desired, mixing complexes prepared according to one of variants a) -c) with an acid of the general formula H _n X belonging acid H _n X ', which, however, is a different one than that originally used for the production.

This combined reaction path is always particularly expedient if several acids of the general formula H _n X are to be incorporated into the molecule of the mixed complex and one of these is unstable in more basic media or at higher temperatures. Such a combined method variant is shown in Reaction Scheme 5, in which the simplifications made above are retained, but Me stands for Ca. In the illustrative case, the mixed complex prepared according to process variant b) is reacted with a decomposable acid of the general formula HX '.

Reaction scheme 5

HX + 4 CaO + 3 H₂O → HO-Ca-X + 3 Ca (OH) ₂
HO-Ca-X + 3 Ca (OH) ₂ + 4 HPs → (X-Ca-Ps.3 HO-Ca-Ps) + 4H₂O
(X-Ca-Ps.3 HO-Ca-Ps) + Hx ′ → (X-Ca-Ps · X′-Ca-Ps. 2 HO-Ca-Ps) + H₂O

These decomposable acids include, among others L-ascorbic acid and acetylsalicylic acid. That's why if, in this example, HX ′ stands for L-ascorbic acid, the reaction described in the first equation for a higher temperature (up to the boiling point of the reaction mixture sches) while the third equation appropriate reaction at a lower temperature temperature (at room temperature).

The product according to reaction scheme 5 can alternatively can also be obtained by one from a Process variant c) of the mixed complex produced, as in Reaction Scheme 6 with the usual simplifications is shown.

Reaction scheme 6

4 HPs + HX + 4 CaO → (X-Ca-Ps.3 HO-Ca-Ps) + H₂O, and
(X-Ca-Ps.3 HO-Ca-Ps) + HX '→ (X-Ca-Ps.X'-Ca-Ps.2 HO-Ca-Ps) + H₂O

In this case too, the first implementation will be useful at higher, the second at lower temperature taken.

In the process according to the invention, the metals Me in Form of elemental metal powder, metal oxides, metal hydr oxides, metal (hydrogen) carbonates, basic metal car bonaten, basic metal oligo or metal polygalacturo naten implemented.

If metal carbonates and / or hydrogen carbonates are also used in the preparation of the mixed complexes, the (residual) basic OH ions bound to the metal (in part) can be replaced by carbonate and / or hydrogen carbonate ions in the end product. The carbonates of the di- or trivalent metals can be used as a reaction component when the acid of the general formula H _n X is a stronger acid than carbonic acid. However, this condition is generally met.

The basic metal polygalacturonate, pectin or polygalacturonic acid used as the starting material in the process according to the invention forms a colloidal system which is poorly soluble in water. The metals and metal compounds used to prepare the mixed complexes, as well as, in some cases, the acid (s) of the general formula H _n X, are likewise insoluble or only slightly soluble in water, which is why the mixed complexes are prepared in practically any case by at the interfaces of the different materials phase heterogeneous reactions. The starting materials, the intermediaries and the mixed complex end products are at most only slightly soluble in organic solvents, so that the process proceeds via heterogeneous reactions even when using organic solvents. It is obvious to the person skilled in the art that the taking of heterogeneous reactions with a speed that is also acceptable for practical use requires appropriately selected reaction conditions. The reaction rate can be advantageously influenced by contacting large surfaces, by appropriate concentrations and stoichiometric ratios, by intensive stirring, adequate reaction time and appropriate temperatures.

The acids used to introduce the anions X ^{n- of} the general formula H _n X are generally non-polymeric, inorganic acids such as HJ, HF, H₂SeO₃, H₂SeO₄ and H₃PO₄, or organic acids, regardless of whether their acid character is characterized by Groups -COOH, -SO₃H, = HPO₄, guaranteed by phenolic -OH or by other groups. However, polymeric acids, for example polyphosphoric acid, can also be used. In the case of polyvalent acids, their acid salts formed with different (inorganic or organic) bases and the partial esters of the polyvalent acids, for example with other KHF₂, riboflavin-5'-phosphate-Na, pyridoxal-5-phosphate, menadione sulfite , be used.

With regard to their origin, these can be organic Acids equally natural, semi-synthetic or syn be theoretical connections based on their biological effect, their chemical structure and their own  can be assigned to the following main groups NEN:

• - vitamins,
• - flavonoids,
• - active pharmaceutical ingredients,
• - amino acids, oligopeptides,
• - other, biologically active and advantageously effective organic acids.

The most important representatives of the healing effects organic acids of natural origin are the acids components of different medicinal plants or medicinal plants zen extracts.

The temperature can vary over a wide range (from Room temperature to the boiling point of the solvent) free can be selected, however their value influences the process time required for the reaction. In some cases, for Example when heat-decomposing reagents including vitamins, but determines this Point of view the upper limit of the still applicable tempera door.

The end point of the reaction can be determined by detecting the Consumption of a reaction component, conveniently on the we most reactive component. The to prove the different connections and for loading analytical methods that serve their quantity known to the person skilled in the art or in the chemical literature Find.

The solution used in the process according to the invention medium is generally water, but it can also be Ge mix water and an organic solvent, such as Ethanol or ethyl acetate can be used. The amount of water required to carry out the reaction depends primarily on the performance of the mixer and the applied temperature. Generally the amount is of the solvent ten to fifty times the amount of registered carrier.

It is also known to those skilled in the art that some compounds, for example vitamins, also through the action of air  suffer oxygen and / or light decomposition. Should com plexes are produced with such components, so must these harmful effects by using an internal ten gas and / or eliminated by excluding the light will. Contain for drying of decomposable components mixed complexes, it is also on an industrial scale more convenient, instead of spray drying lyophilisia application.

In certain cases, for example in the case of Enrich products of the food industry the mixed complexes that are used immediately can be used without drying, the means the entire reaction mixture (suspension or colloid de solution) is incorporated into the respective food product works (among other things in soft drinks).

In the process according to the invention, it is essential that the corresponding stoichiometric ratios of the reaction partners are observed. To explain this using the example of the reaction scheme 1: in the sense of the law of mass action, the equilibrium of the reaction can be shifted in the direction of the formation of the mixed complex if the basic metal complex is used in excess. If the proportions of the reacting components are unfavorable, undesirable side reactions can occur to a not negligible extent. Through such undesirable side reactions, the excess of the acid (s) H _n X can partially dissolve out the metal content of the support to form a salt of the general formula X-Me-X. The possibility of such side reactions taking place is greater if the acid H _n X forms a high stability constant with the metal complex in question - compared to the stability constant of the metal complex or basic metal complex of the support. The stability constants of the metal compounds under various organic and inorganic acids can be found in the specialist literature [Douglas D. Perrin: Stability Constants of Metal-Ion Complexes, Part B, organic Ligands, IUPAC Chemical Data Series No. 22, Pergamon Press, 1979] or using known methods.

For the sake of simplicity, reactions with divalent metals were shown in reaction schemes 1-6. The formation reactions of the mixed complexes proceed in a similar manner if the basic metal polygalacturonate used as the starting material contains a trivalent metal or at the same time several divalent and trivalent metals, or if the acid H _n X is not monovalent. In these cases, different -Me-X structures are bound to the galacturonate units of the mixed complex. The exact structure of these variable groups can be determined, for example, by infrared spectroscopy (FT-IR), electron spin resonance (ESR), mass spectroscopy (MS) and analytical electron spectroscopy (ESCA). Their infrared spectra, the most characteristic absorption bands of which are summarized in Table 2, are well suited for identifying the mixed complexes.

It can be seen from the general formula (I) of the mixed complexes according to the invention that they can contain alkali metals (such as Li, K and Na). No anions X ^{n- are} bonded to these alkali metal galactonate structural units. However, the presence of the alkali metals is surprisingly important for the physical properties of the mixed complexes, primarily for the change in water solubility, because in the case of a sufficiently high alkali metal content the mixed complex becomes water-soluble. In these mixed complexes, alkali metal cations are bound to at most 95% of the galacturonate units. The change in the physical properties also changes the chemical - and thus biological - properties of the mixed complexes more or less, since the greater solubility can promote the rate of absorption and the biological utilization.

The alkali metals can be used as hydroxide, carbonate or bicarbonate in the preparation of the mixed complexes. In the case of process variant a), the alkali metal compound is added before and / or after the reaction with the acid H _n X, while in process variants b) and c) it is advantageous to add it to the reaction mixture as the last reagent.

At what alkali metal content the respective mixed comm plex becomes water-soluble can be determined experimentally because water solubility is dependent on several factors ren, such as the degree of polymerization of the carrier, the type of in Complex contained divalent and trivalent ions, in the case of several metal components of their relationship to each other, the type and amount of the acid component (s) of the mixed complex influenced.

The amount of the reactive components required for the preparation of the mixed complexes according to the invention is determined by stoichiometric calculations, the amount of the other components being based on the amount of the reactive (if pectin is used as the starting material, esterified carboxylate groups also containing) carboxylate groups of the support. Anions X ^{n- can be} bound to 0.01-100% of the divalent and / or trivalent metal ions contained in these mixed complexes. In the case of process variant a), the amount of the reactive OH groups (which come into contact with metals) of the basic metal complex serving as starting material for calculating the amount of acid (s) H _n X can also be considered as a reference basis.

It is a very advantageous circumstance that the mixed complexes according to the invention can be produced with three different process variants and, if desired, also with their combination. This makes it possible to produce the various mixed complexes with knowledge of the properties of the reacting components, primarily the acid (s) H _n X, by the most favorable reaction route under the most advantageous conditions. The selection of the cheapest reaction path and the most advantageous reaction conditions are evident to the person skilled in the art.

Arise in the course of the method according to the invention no by-products by means of a cleaning process should be removed. It is both economical and also very advantageous from the point of view of environmental protection.

In the following, the invention is illustrated by examples but is not limited to the examples.  

The Mg, Fe (II / III) -, Mn (II) and Cu (II) polygalacturonates are according to Ver variant b) of Hungarian Patent No. 203 365 among the Be given in Examples 5, 3, 10 and 1 conditions, the Zn polygalacturonate in an analogous manner manufactured.

Contained in the formula of the medicinal plant active ingredients tendency mixed complexes are all as monovalent anion X⁻ che acid components of the respective medicinal plants indicated their extracts. In these examples, the total acidity of the drug in question or Extract as acid equivalent number in mmol / g or mmol / cm³ specified. In addition, the quantity is 1-2 characteristic flavonoid components of these extracts, which described with those in the German drug book (DAB 8) methods have been determined.

Unless otherwise stated, the reactions are given in aqueous medium.

The final product, the mixed complex, is in the case of one Laboratory procedure by lyophilization, in the case of a large one technical process expedient by spray drying tion by drying the reaction mixture immediately won.

example 1 Production of a magnesium-polygalacturonate-iodide mixed complex

The aqueous suspension of 5.00 g (7.72 mass% Mg containing) freshly prepared basic magnesium polygalac turonate is reacted with 1.885 cm³ 57 mass% hydrogen iodide solution (density 1.701 g / cm³) with intensive stirring. After the reaction has ended, the suspension obtained is dried by lyophilization. 6.87 g of the title product are obtained. Elemental analysis for
HO- [Mg ²⁺ (C₆H₇O₆⁻) (OH⁻) _0.1 (I⁻) _0.9 (C₆H₁₀O₅) _0.608 ) _{N ′} -H:
calculated, mass%: C 27.98, H 3.19, Mg 5.88, I 27.58;
found, mass%: C 21.76, H 4.61, Mg 5.62, I 26.35.

Example 2 Production of a magnesium-polygalacturonate-fluoride mixed complex

From 5.00 g of polygalacturonic acid and 0.957 g of MgO freshly prepared basic magnesium polygalacturonate is reacted in an aqueous medium with vigorous stirring with 0.84 cm 3 of 40% by weight hydrogen fluoride solution. The suspension obtained is dried by lyophilization. 5.5 g of the title product are obtained. Elemental analysis for
HO- [Mg ²⁺ (C₆H₇O₆⁻) (OH⁻) _0.2 (F⁻) _0.8 (C₆H₁₀O₅) _0.214 ] _{N ′} äH:
calculated, mass%: C 34.6, H 3.70, Mg 9.62, F 6.02;
found, mass%: C 28.66, H 4.91, Mg 9.5, F 5.6.

Example 3 Production of a magnesium polygalacturonate dihydro gene phosphate mixed complex

Freshly produced, basic magnesium polygalacturonate containing 1.39 g of magnesium is reacted in an aqueous medium with intensive stirring with 3.1 ml of 85% by mass phosphoric acid. The reaction mixture is dried by lyophilization. 19.6 g of the title product are obtained. Elementary analysis for
HO- [Mg ²⁺ (C₆H₇O₆⁻) (OH⁻) _0.2 (H₂PO₄⁻) _0.8 (C₆H₁₀O₅) _0.214 ] _{N ′} -H:
calculated, mass%: C 27.75, H 3.47, Mg 7.71, P 7.87;
found, mass%: C 23.16, H 4.51, Mg 7.53, P 7.82.

Example 4 Production of a magnesium-polygalacturonate-selenate complex

3.74 g of freshly prepared, basic 288.7 mg Mg containing Mg polygalacturonate is reacted in aqueous suspension with vigorous stirring with 0.763 g (0.005 mol) of 95% by mass selenic acid (H₂SeO₄). The reaction mixture is dried by lyophilization. 4.35 g of the titanium product are obtained.
Elemental analysis for
HO- [Mg ²⁺ (C₆H₇O₆⁻) (OH⁻) _0.158 (SeO₄ ^2- ) _0.421 (C₆H₁₀O₅) _0.477 ] _{N ′} -H:
calculated, mass%: C 31.33, H 3.51, Mg 7.16, Se 9.79;
found, mass%: C 15.77, H 4.45, Mg 6.64, Se 9.07.

Example 5 Production of a magnesium polygalacturonate (Fruoto se) -borate mixed complex

Freshly prepared, containing 474 mg magnesium, basic Mg polygalacturonate is reacted in an aqueous medium with vigorous stirring with 965 mg boric acid (H₃BO₃) and then with 2.81 g fructose. The reaction mixture is dried by lyophilization. 8.94 g of the title product are obtained.
Elemental analysis for
HO- [Mg ²⁺ (C₆H₇O₆⁻) (OH⁻) _0.2 (C₆H₁₀O₄BO₃⁻) _0.8 (C₆H₁₀O₅) _0.497 ] _{N ′} -H:
calculated, mass%: C 36.99, H 4.57, Mg 5.44, B 1.93;
found, mass%: C 31.34, H 5.57, Mg 5.28, B 1.73.

Example 6 Production of a magnesium polygalacturonate L-Ascor bat mixed complex

Basic magnesium polygalacturonate freshly prepared from 20 g of polygalacturonic acid and containing 2.31 g of magnesium is reacted with 13.39 g of L-ascorbic acid in an aqueous medium with vigorous stirring. The suspension obtained is dried by lyophilization. 42.2 g of the titanium product are obtained, which contains 85.6% by mass of dry substance. Elemental analysis for
HO- [Mg ²⁺ (C₆H₇O₆⁻) (OH⁻) _0.2 (C₆H₇O₆⁻) _0.8 (C₆H₁₀O₅) _0.214 ] _{N ′} -H ascorbate:
calculated, mass%: C 38.4, H 3.96, Mg 6.44, vitamin C: 36.0;
found, mass%: C 32.99, H 4.87, Mg 5.42, vitamin C: 28.0.

Example 7 Production of a magnesium polygalacturonate vitamin P- (rutin) mixed complex

1.013 g of freshly prepared, 78.2 mg magnesium containing the basic Mg polygalacturonate are reacted in an aqueous medium with vigorous stirring with 1.817 g rutin trihydrate (C₂₇H₃₀O₁₆ · 3 H₂O). After the reaction has ended, the mixture is dried by lyophilization. 2.8 g of the title product are obtained.
Elemental analysis for
HO- [Mg ²⁺ (C₆H₇O₆⁻) (OH⁻) _0.15 (C₂₇H₂₉O₁₆⁻) _0.85 (C₆H₁₀O₅) _0.608 ] _{N ′} -H:
calculated, mass%: C 47.8, H 4.63, Mg 2.97, rutin: 63.3;
found, mass%: C 42.5, H 5.59, Mg 2.75, rutin: 58.3.

Example 8 Production of a magnesium-polygalacturonate-rutin-ascorbate mixed complex

From 3 g of polygalacturonic acid freshly prepared, 346.4 mg of magnesium-containing basic Mg polygalacturonate is reacted in 40 vol .-% aqueous ethanol first with 7.71 g of rutin hydrate, then with 1.93 g of L-ascorbic acid with vigorous stirring. The reaction mixture is dried by lyophilization. 6.1 g of the title compound are obtained.
Elemental analysis for ascorbate
HO- [Mg ²⁺ (C₆H₇O₆⁻) (OH⁻) _0.15 (C₂₇H₂₉O₁₆⁻) _0.082 (C₆H₇O₆⁻) _0.768 · (C₆H₁₀O₅) _0.608 ] _{N ′} -H

Example 9 Production of a magnesium polygalacturonate vitamin A mixed complex

654.8 mg of vitamin A (retinoic acid: C₂₀H₂₈O₂) are added to the aqueous suspension of freshly made basic Mg polygalacturonate from 1 g of polygalacturonic acid (acid equivalent number 4.75 mol / kg) and 191.5 mg of magnesium oxide, in an aqueous medium with intensive stirring. given. The reaction mixture is dried by lyophilization. 1.69 g of the title compound are obtained. Elemental analysis for
HO- [Mg ²⁺ (C₆H₇O₆⁻) (OH⁻) _0.6 (C₂₀H₂₇O₂⁻) _0.4 (C₆H₁₀O₅) _0.214 ] _{N ′} -H:
calculated, mass%: C 50.43, H 5.65, Mg 6.68, vitamin A: 32.9;
found, mass%: C 44.53, H 6.35, Mg 6.38, vitamin A: 30.2.

Example 10 Production of a magnesium polygalacturonate adenosine triphosphate disodium salt mixed complex

6.2835 g of adenosine-5'-triphosphoric disodium salt (C₁₀H₁₄N₅O₁₃P₃Na₂) are added to the suspension of basic Mg polygalacturonate freshly prepared from 5 g of polygalacturonic acid and containing 346.4 mg of magnesium. The reaction mixture is dried by lyophilization. 9.8 g of the title compound are obtained. Elemental analysis for
HO- [Mg ²⁺ (C₆H₇O₆⁻) (OH⁻) _0.2 (C₁₀H₁₃N₅O₁₃P₃Na₂⁻) _0.8 · (C₆H₁₀O₅) _0.214 ] _{N ′} -H:

Example 11 Production of a magnesium polygalacturonate pyridoxal 5-phosphate mixed complex

10 g of freshly prepared, basic magnesium polygalacturonate containing 921.3 mg of magnesium is reacted in an aqueous medium with vigorous stirring with 8.0355 g of pyridoxal-5-phosphate (vitamin B₆; C₈H₁₂NO₇P). The reaction mixture is dried by lyophilization. 17.25 g of the titanium product are obtained. Elemental analysis for
HO- [Mg ²⁺ (C₆H₇O₆⁻) (OH⁻) _0.2 (C₈H₁₁NO₇P⁻) _0.8 · (C₆H₁₀O₅) _0.214 ] _{N ′} -H:

Example 12 Production of a magnesium polygalacturonate bis (pyride oxin hydrochloride borate) mixed complex

Freshly prepared, 1385.45 mg magnesium-containing basic magnesium polygalacturonate is in an aqueous medium with intensive stirring with the complex acid prepared from 6580.48 mg vitamin B₆ (pyridoxine hydrochloride, C₈H₁₁NO₃ · HCl) and 989.28 mg boric acid (H₃BO₃) bis (pyridoxine hydrochloride borate) implemented. The suspension obtained is lyophilized. 23.89 g of the title product are obtained. Elementary analysis for
HO- [Mg ²⁺ (C₆H₇O₆⁻) (OH⁻) _0.16 (C₁₆H₂₀O₇N₂B⁻) _0.28 (Cl ^- ) _0.56 · (C₆H₁₀O₅) _0.214 ] _{N ′} -H:

Example 13 Preparation of a Magnesium Polygalacturonate Glycine Mixed complex

From 4 g of polygalacturonic acid (acid equivalent number: 4.75 mol / kg) and 765.9 mg of magnesium oxide, freshly prepared basic Mg polygalacturonate is reacted in an aqueous medium with vigorous stirring with 998.4 mg of glycine (C₂H₅NO₂). The reaction mixture is dried by lyophilization. 5.5 g of title product, elemental analysis for
HO- [Mg ²⁺ (C₆H₇O₆⁻) (OH⁻) _0.3 (C₂H₄NO₂⁻) _0.7 (C₆H₁₀) O₅) _0.214 ] _{N ′} -H:

Example 14 Preparation of a Magnesium Polygalacturonate Salicylate Mixed complex

Using 4 g pectin (acid equivalent number 4.2 mol / kg), 677.21 mg (16.8 mmol) of magnesium oxide and 1160.21 mg (8.4 mmol) salicylic acid (C₇H₆O₃) after all three Process variants of the Mg-polygalacturonate-salicylate mixture complex manufactured.

Process variant a): first the pectin with the  Magnesium oxide reacted and then the resulting basic Mg polygalacturonate with the salicylic acid for reaction brings.

Process variant b): The salicylic acid is mixed with the Magnesium oxide implemented and the product obtained with the Reacted pectin.

Process variant c): an aqueous mixture containing the salicylic acid and the pectin, with the magnesium oxide implemented.

After each of the three variants, 6.4 g of the title product are finally obtained after lyophilizing the reaction mixture. Elemental analysis for
HO- (Mg ²⁺ (C₆H₇O₆⁻) (OH⁻) _0.5 (C₇H₅O₃⁻) _0.5 (C₆H₁₀) O₅) _0.353 ] _{N ′} -H:
calculated, mass%: C 41.78, H 4.056, Mg 7.28;
found, mass%: C 39.6, H 4.85, Mg 7.1.

The identity of the three products was verified by the IR spectrum. Table 1 shows the antisymmetric and symmetrical vibration bands of the carboxy lat groups of the mixed complexes ν _as (COO⁻) and ν _s (COO⁻) in cm ^-1 .

Table 1

Example 15 Production of a magnesium polygalacturonate acetyl mixed salicylate complex

The aqueous suspension of basic Mg polygalacturonate freshly prepared from 4 g polygalacturonic acid and 0.766 g magnesium oxide is reacted with 3.08 g acetylsalicylic acid (C₉H₈O₄) with vigorous stirring. The reaction mixture is dried by lyophilization. 7.5 g of the title product are obtained. Elemental analysis for
HO- [Mg ²⁺ (C₆H₇O₆⁻) (OH⁻) _0.1 (C₉H₇O₆⁻) _0.9 (C₆H₁₀O₅) _0.214 ] _{N ′} -H:

Example 16 Preparation of a magnesium polygalacturonate (5,5-Di ethyl barbiturate) mixed complex

Basic Mg polygalacturonate freshly prepared from 2 g of pectin (acid equivalent number 4.2 mol / kg) and 338.6 g (8.4 mmol) of magnesium oxide becomes 5,5-diethyl-barbituric acid with 154.72 mg (0.84 mmol) (C₈H₁₂O₃N₂) implemented. The reaction mixture is dried by lyophilization. 2.682 g of the title product are obtained. Elemental analysis for
HO- [Mg ²⁺ (C₆H₇O₆⁻) (OH⁻) _0.9 (C₈H₁₁O₃N₂⁻) _0.1 (C₆H₁₀O₅) _0.214 ] _{N ′} -H:

Example 17 Production of a magnesium polygalacturonate coffee acid re-mixed complex

From 162.5 mg of polygalacturonic acid (acid equivalent number 4.75 mol / kg) and 28 mg of magnesium oxide, freshly prepared basic Mg polygalacturonate is reacted with 100 mg of caffeic acid (C₉H₈O₄) in aqueous suspension with vigorous stirring. The reaction mixture is dried by lyophilization. 0.27 g of the title product is obtained. Elementary analysis for
HO- [Mg ²⁺ (C₆H₇O₆⁻) _1.11 (OH⁻) _0.09 (C₉H₇O₄⁻) _0.8 · (C₆H₁₀O₅) _0.237 ] _{N ′} -H:

Example 18 Production of a magnesium polygalacturonate query tin mixed complex

From 162.5 mg of polygalacturonic acid (acid equivalent number 4.75 mol / kg) 28 mg of magnesium oxide freshly prepared basic Mg polygalacturonate is reacted in an aqueous suspension with vigorous stirring with 158.5 mg of quercetin (C₁₅H₁₀O₇). The reaction mixture is dried by lyophilization. 0.33 g of the title product is obtained. Elementary analysis for
HO- [Mg ²⁺ (C₆H₇O₆⁻) _1.111 (OH⁻) _0.133 (C₁₅H₉O₇⁻) _0.756 · (C₆H₁₀O₅) _0.237 ] _{N ′} -H:

Example 19 Production of a magnesium polygalacturonate Eicosapentaenoic acid-docosahexaenoic acid mixed complex

From 162.5 mg of polygalacturonic acid (acid equivalent number 4.75 mol / kg) 28 mg of magnesium oxide freshly prepared basic Mg polygalacturonate is in aqueous suspension with vigorous stirring with 97.2 mg of a 1: 1 molar mixture of eicosapentaenoic acid (C₂₀H₃₀O₂) and Dokosahexaenoic acid (C₂₂H₃₂O₂) implemented. The reaction mixture is dried by lyophilization. 0.26 g of the title product is obtained. Elemental analysis for
HO- [Mg ²⁺ (C₆H₇O₆⁻) _1.111 (OH⁻) _0.445 (C₂₀H₂₉O₂⁻) _0.222 · (C₂₂H₃₁O₂⁻) _0.222 (C₆H₁₀O₅) _0.237 ] _{N ′} -H:

Example 20 Preparation of a zinc polygalacturonate pyridoxal-5  mixed phosphate complex

From 10 g of polygalacturonic acid (acid equivalent number 4.75 mol / kg) and 2.329 g of zinc dust, freshly prepared basic zinc polygalacturonate is distilled in aqueous suspension with vigorous stirring with the solution of 4.725 g of pyridoxal-5-phosphate (phosphate of vitamin B₆; C₈H₁₂NO₇P) water implemented. The reaction mixture is dried by lyophilization. 14.2 g of the title product are obtained. Elemental analysis for
HO- [Zn ²⁺ (C₆H₇O₆⁻) _1.333 (OH⁻) _0.166 (C₈H₁₁NO₇P⁻) _0.501 · (C₆H₁₀O₅) _0.283 ] _{N ′} -H:

Example 21 Production of an iron (II / III) polygalacturonate Ascorbate-folate mixed complex

Freshly made, containing 4.422 g of iron basic iron (II / III) polygalacturonate is in aqueous Suspension with intensive stirring first with 393 g Folsäu right (vitamin B₉; C₁₉H₁₉N₇O₆), then with 4.03 g L-ascorbic acid implemented. The mixed complex suspension obtained is obtained by Lyophilize dried. 31.3 g of the title pro are obtained duktes.

Example 22 Production of an iron (II / III) polygalacturonate Riboflavin-5'-phosphate-Na mixed complex

Freshly prepared, 787 mg of iron containing basic iron (II / III) polygalacturonate is reacted in aqueous suspension with vigorous stirring with 2174 mg of riboflavin-5'-phosphate sodium dihydrate (vitamin B₂; C₁₇H₂₀N₄NaO₉P · H₂O). The resulting mixed complex suspension is lyophilized. 6.91 g of the title compound are obtained. Elemental analysis for
HO- [Fe ^2.7+ (C₆H₇O₆⁻) _1.2 (OH⁻) _1.2 (C₁₇H₁₉N₄NaO₉P⁻) _0.3 (C₆H₁₀O₅) _0.255 ] _{N ′} -H:

Example 23 Preparation of a Manganese (II) Polygalacturonate Thiamine-pyrophosphate mixed complex

Freshly prepared, 439.5 mg manganese-containing basic manganese (II) polygalacturonate is reacted in an aqueous suspension with vigorous stirring with 1894 mg thiamine pyrophosphate (vitamin B₁; C₁₂H₁₈N₄O₇P₂S · 4 H₂O). The reaction mixture is dried by lyophilization. 2.6 g of the title product are obtained.
Elemental analysis for
HO- [Mn ²⁺ (C₆H₇O₆⁻) _1.2 (OH⁻) _0.3 (C₁₂H₁₇N₄O₇P₂S⁻) _0.5 · (C₆H₁₀O₅) _0.256 ] _{N ′} -H:

Example 24 Production of a manganese (II) polygalacturonate panto thenat mixed complex

From 29.45 g of polygalacturonic acid (acid equivalent number 4.75 mol / kg) freshly prepared basic manganese (II) poly galacturonate is reacted in aqueous suspension with vigorous stirring with pantothenic acid (C₉H₁₇NO₅), which was previously released from 10 g of Ca pantothenate. The reaction mixture is dried by lyophilization. 45.9 g of the title compound are obtained.
Elemental analysis for
HO- [Mn ²⁺ (C₆H₇O₆⁻) _1.333 (OH⁻) _0.267 (C₉H₁₆NO₅⁻) · (C₆H₁₀O₅) _{0.283] N '-H:}

Example 25 Production of a manganese (II) polygalacturonate-ascorbate-menadione sulfite mixed complex

Basic manganese (II) polygalacturonate containing 265.47 mg of manganese is mixed in an aqueous medium with intensive stirring first with 130.65 mg L-ascorbic acid, then with an ion exchanger (Varion KS in the H⁺ cycle, manufacturer: NITROKÉMIA, Fzf) desalted solution of 2004 mg Mena dione sodium bisulfite (vitamin K₃; C₁₁H₉O₂SO₃Na) converted. The reaction mixture is dried by lyophilization. 21.1 g of the title compound are obtained.
Elemental analysis for

Example 26 Preparation of a copper (II) polygalacturonate Nicotinate mixed complex

Freshly prepared, basic copper (II) polygalacturonate containing 969.6 mg of copper is reacted in an aqueous suspension with intensive stirring with 757.7 mg of nicotinic acid (vitamin B₃; C₆H₅NO₂). The reaction mixture is dried by lyophilization. 5.4 g of the title product are obtained.
Elemental analysis for
HO- [Cu ²⁺ (C₆H₇O₆⁻) _1.335 (OH⁻) _0.318 (C₆H₄NO₂⁻) _0.347 · (C₆H₁₀O₅) _0.285 ] _{N ′} -H:

Example 27 Manufacture of a magnesium polygalacturonate feeder mixed extract complex

20 g air-dried, ground Wegwarte (cichorium intybus) are in 250 cm³ 96 vol .-% boiling ethanol extracted and then filtered. The filtrate is with 96 vol .-% Add ethanol to 250 cm³. The extract has one Dry matter content of 1.61 g / 100 cm³, an acid equiva lent number of 5.26 µmol / cm³, a rod content of 14.2 mg / 100 cm³ and a quercetin content of 11.5 mg / 100 cm³.

50 cm³ of this extract are reacted with 78.5 mg of magnesium-containing, freshly prepared basic Mg-polygalacturate in aqueous suspension at room temperature. The reaction mixture is dried by lyophilization. 1.826 g of the title product are obtained.
Molecular formula of the mixed complex:
HO- [Mg ²⁺ (C₆H₇O₆⁻) (OH⁻) _0.92 (X⁻) _0.08 (C₆H₁₀O₅) _0.61 ] _{N ′} -H

Example 28 Manufacture of a magnesium polygalacturonate feeder root extract mixed complex

In the manner described in Example 27, a Extract from 20 g of dried ground ground waiting root (cichorii radix). The extract is dry substance content of 416 mg / 100 cm³, an acid equivalent number of 3.68 µmol / cm³, a rod content of 41 mg / 100 cm³ and a quercetin content of 29 mg / 100 cm³.

50 cm³ of this extract are reacted with 77.49 mg of magnesium-containing, freshly prepared basic Mg-polygalacturoate in aqueous suspension with vigorous stirring. The reaction mixture is dried by lyophilization. 1.196 g of the title product are obtained. Sum formula of the mixed complex:
HO- [Mg ²⁺ (C₆H₇O₆⁻) (OH⁻) _0.94 (X⁻) _0.06 (C₆H₁₀O₅) _0.61 ] _{N ′} -H

Example 29 Production of a Magnesium-Polygalakturonat-Oder red lead extract complex

In the manner described in Example 27, 25 g dried, ground Odermennig (Agrimonia eupatoria, herba) prepares an extract. The extract is dry substance content of 1.838 g / 100 cm³, an acid equivalent number of 37.72 µmol / cm³, a rod content of 120.5 mg / 100 cm³ and a quercetin content of 297 mg / 100 cm³.

25 cm³ of this extract are reacted in an aqueous medium with intensive stirring with 1.5 g of freshly prepared magnesium polygalacturonate, which contains 7.72% by mass of magnesium. The reaction mixture is dried by lyophilization. 1.902 g of the title product are obtained. Sum formula of the mixed complex:
HO- [Mg ²⁺ (C₆H₇O₆⁻) (OH⁻) _0.8 (X⁻) _0.2 (C₆H₁₀O₅) _0.61 ] _{N ′} -H

Example 30 Production of a magnesium polygalacturonate sand straw flower extract mixed complex

In the manner described in Example 27, 10 g dried, ground sand straw flower (Helichrysum arena rium) prepares an extract. The extract is dry  substance content of 796 mg / 100 cm³, an acid equivalent number of 16.31 µmol / cm³, a ruting content of 186 mg / 100 cm³ and a quercetin content of 93.8 mg / 100 cm³.

40 cm³ of this extract are reacted in an aqueous medium with vigorous stirring with 1.5478 g of freshly prepared magnesium polygalacturonate, which contains 7.72% by mass of magnesium. The reaction mixture is dried by lyophilization. 1.8 g of the title product are obtained.
Molecular formula of the mixed complex:
HO- [Mg ²⁺ (C₆H₇O₆⁻) (OH⁻) _0.867 (X⁻) _0.133 (C₆H₁₀O₅) _0.61 ] _{N ′} -H

Example 31 Production of a magnesium polygalacturonate dandelion root extract mixed complex

In the manner described in Example 27, 10 g dried, ground dandelion root (Taraxacum offi cinale, radix) prepares an extract. The extract has one Dry matter content of 655 mg / 100 cm³, an acid equiva lent number of 16.83 µmol / cm³, a ruting content of 19.9 mg / 100 cm³ and a quercetin content of 11.6 mg / 100 cm³.

50 cm³ of the dandelion root extract are reacted in an aqueous medium with intensive stirring with 1 g of freshly prepared basic magnesium polygalacturonate, which contains 7.72% by weight of magnesium. The reaction mixture is dried by lyophilization. 1.28 g of the title product are obtained.
Molecular formula of the mixed complex:
HO- [Mg ²⁺ (C₆H₇O₆⁻) (OH⁻) _0.736 (X⁻) _0.264 (C₆H₁₀O₅) _0.61 ] _{N ′} -H

Example 32 Manufacture of a Magnesium Polygalacturonate Houseleek and Milk thistle extract mixed complex

281.9 mg of lyophilized ground houseleek (Sempervi vum hirtum) (acid equivalent number 1.49 mmol / g) and 338.6 mg (to the aqueous colloid solution of 2 g pectin (acid equivalent number 4.2 mol / kg) 8.4 mmol) of magnesium oxide. After the reaction has ended, stirring is continued in a known manner from 142.4 mg of milk thistle (Silybum inarianum) (acid equivalent number 2.95 mmol / g) [H. Wagner et al .: Drug Research (Drug Res.) 18, 688-696 (1968)) extract was added to the reaction mixture. After the reaction, the mixed complex suspension is dried by lyophilization. 2.916 g of the title product are obtained.
Molecular formula of the mixed complex:
HO- [Mg ²⁺ (C₆H₇O₆⁻) (OH⁻) _0.9 (X⁻) _0.05 (X′⁻) _0.05 (C₆H₁₀O₅) _0.35 ) _{N ′} -H
(In this empirical formula, X ^- stands for the anions originating from the acidic components of the houseleek, X ′ ^- for the anions originating from the acidic components of the milk thistle.)

Example 33 Production of a magnesium polygalacturonate poplar bud extract mixed complex

2 g of freshly prepared basic polygalacturonate, the Contains 7.33 mass% magnesium, is in an aqueous medium intensive stirring with 86.22 cm³ of an alcoholic Black poplar leaf buds (Populus nigra, gemma) berei extracted extract (acid equivalent number 2,798 mmol / 100 ml) set.

The poplar bud extract is prepared as follows: 50 g ground, dried poplar buds are in 200 cm³ de still water at 35 ° C for 24 hours and then filtered off. The solid is dried and then in a Soxlet extractor for 5 hours with petroleum ether ex trahed. After drying again with 200 cm³ 65 vol .-% Extracted ethanol for 3 hours. The ex received tract is made up to 250 cm³ with 65 vol .-% ethanol.

The reaction mixture is dried by lyophilization. 5.02 g of the title product are obtained.
Molecular formula of the mixed complex:
HO- (Mg ²⁺ (C₆H₇O₆⁻) (OH⁻) _0.6 (X⁻) _0.4 (C₆H₁₀O₅) _0.51 ] _{N ′} -H

Example 34 Manufacture of perrocomp tablets

According to process variant a), a metal polyga lacturonate-folate mixed complex produced and by Zer dust drying isolated. 133 mg of the ferro obtained Comp powders contain: 5 mg iron, 1.5 mg zinc, 0.5 mg man gan, 0.5 mg copper, 0.03 mg cobalt, 13 mg potassium and 0.1 mg Folic acid (C₁₉H₁₉N₇O₆). From 133 or 266 mg of this active ingredient  fes and the usual tableting aids such as magne sium stearate, talc, poly (vinyl butyral) and on a tablet te related 20-40 mg L-ascorbic acid as an antioxidant Prepares tablets of 280 or 420 mg mass and then on cover the usual way. The Ferrocomp Tablets can be taken in a dose of 1-3 × 2 tablets a day Use to prevent and cure anemia be det.

Example 35 Production of magnesium polygalacturonate houseleek and Wheat Containing Milk Thistle Extract Complex Flour

3 g of the dried product prepared according to Example 32 and finely ground mixed complex with 6 kg Wei Homogenized zen flour. The flour made in this way has an increased biological value, it contains 0.05% by mass Mixed complex.  

Table 2

Claims (5)

1. Oligo- or polygalacturonate mixed complexes of the general formula (I) HO - [{Me ^{Z +} (Ps ^- ) _zq (OH ^- ) _a (HCO₃ ^- ) _b (CO₃² ^- ) _c (X ^n- ) _m } (M⁺ Ps ^- ) _x (Ps) _y ] _{N ′} -H (I) where
Me stands for alkaline earth metal atom and / or transition metal atom,
Ps⁻ galacturonation means
X ^n- are identical or different anions of organic and / or inorganic acids is,
M represents alkali metal atom,
Ps denotes a carboxyl-free neutral saccharide unit,
z represents the (average) charge number of the Me atoms contained in the molecule of the mixed complex, and their value is a real number ranging from 2 to 3,
q an expression formed from the stoichiometric factors a, b, c and m represents with the condition that its value is a real number ranging from 0.0001 to (z-1), wherein is the sum of the charges of the anions X ^n- contained in the molecule of the mixed complex,
a, b and c independently of one another have the value 0 or a real number greater than 0 on the condition that the value of a + b + 2c can be at most z-1,0001,
n is an integer from 1 to 10,
m is a real number from 0.0001 to 2,
x a real number from 0 to 56,
y is a real number from 0 to 35 and
N 'is a factor indicating the average degree of polymerization (N), which can assume the values 2 N 300. 2. Pharmaceutical preparation, characterized in that it is in addition to the usual pharmacological carriers, extenders and / or other auxiliaries in a compound of the general formula (I) - wherein the meaning of Me, Ps⁻, X ^n- , M, Ps , z, q and N 'and a, b, c, n, m, x and y is the same as in claim 1 - bound contains at least one active ingredient. 3. Food composition, characterized in that it is based on its total mass in an amount of 0.001-10% by mass at least one mixed complex of the general formula (I) - in which the meaning of Me, Ps⁻, X ^n- , M, Ps, z, q and N 'and a, b, c, n, m, x and y is the same as in claim 1 - contains. 4. A process for the preparation of mixed complexes of the general formula (I) - wherein the meaning of Me, Ps⁻, X ^n- , M, Ps, z, q and N 'and a, b, c, n, m, x and y is the same as in claim 1 - characterized in that one

• a) basic metal oligo- or metal-polygalacturonates of the general formula (II) HO - [{Me ^{z +} (Ps⁻) _{zq ′} (OH⁻) _a (HCO₃⁻) _b (CO₃ ^2- ) _c } (M⁺Ps ⁻) _X (Ps) _y ) _{N ′} -H (II) where the meaning of Me, Ps⁻, M, Ps, z, N ′, a, b, c, x and y is the same as above, and
  q ′ stands for an expression a + b + 2c formed from the stoichiometric factors a, b and c on the condition that its value is a real number ranging from 0.001 to (z-1),
  with acids of the general formula (H⁺) _n X ^n- , in which the meaning of X ^n- and n is the same as above, or sets
• b) acids of the general formula (H⁺) _n X ^n- , in which the meaning of X ^n- and n is the same as above, with an excess of metals Me or Me compounds, the meaning of Me being the same as above is and Me compounds the oxides, hydroxides, car bonate, hydrogen carbonates or basic carbonates are to be understood, implemented and the compound (s) obtained with oligo- or polygalacturonic acid or pectin to react or
• c) a mixture of oligo- or polygalacturonic acid or pectin and acids (H⁺) _n X ^n- with metals Me or their compounds and

if desired, the resulting mixed complex of the general formula (I) with an acid (H⁺) _n X ^n- , in which the meaning of X ^n- and n is the same as above, but the acid is different from that in variants a), b) or c) used.