CARBOXYLIC ACID LOADED SALT CARRIER AND THE METHOD FOR PRODUCING THEREOF

Abstract

A solid compound prepared as a powder that exhibits good flowability and having a specific structure is provided. The solid compound contains a carrier carboxylic acid salt and a loaded carboxylic acid, wherein the pKa of the corresponding carboxylic acid of the carrier carboxylic acid is lower than or equal to the pKa of the loaded carboxylic. The loaded carboxylic acid is physisorbed within the structure of the carrier carboxylic acid salt, and wherein the water content of the solid compound is less than 2 equivalents of water relative to the carrier carboxylic acid. Processes and pharmaceutical compositions containing the solid compound are also provided.

Claims

1-19. (canceled)

20. A solid compound prepared as a powder that exhibits good flowability, the solid compound comprising a following structure, ##STR00045## a carrier carboxylic acid salt (M.sup.2+).sub.1+m(R.sup.1COO).sub.2.sup.(m+1)? in which M.sup.2+ is an alkaline earth metal ion or a divalent metal ion selected from the group consisting of iron (Fe), copper (Cu), zinc (Zn), manganese (Mn), tin (Sn), lead (Pb), and nickel (Ni), or a mixture of thereof, R.sup.1 is an optionally substituted C.sub.1-C.sub.10-alkyl group, an optionally substituted mono- or polyunsaturated C.sub.1-C.sub.10-alkyl group, or an optionally substituted aryl group, wherein the substituents are selected from the group consisting of carbonyl group (?O), carboxylic acid group (COOH), amino group (NH.sub.2), hydroxy group (OH), halogen, cyano group (CN), and a mixture thereof, and wherein m is 0 to 2, a loaded carboxylic acid R.sup.2COOH, wherein R.sup.2 is an optionally substituted C.sub.1-C.sub.10-alkyl group or an optionally substituted mono- or polyunsaturated C.sub.1-C.sub.10-alkyl group, wherein the substituents, if present, are selected from the group consisting of carbonyl group (?O), carboxylic acid group (COOH), amino group (NH), hydroxy group (OH), halogen group, cyano group (CN), and a mixture thereof, and wherein 2?n?10; wherein a pK.sub.a1 of a corresponding carboxylic acid of the carrier carboxylic acid (R.sup.1COO).sup.(m+1)??pK.sub.a1 of the loaded carboxylic acid(s) R.sup.2COOH, wherein the loaded carboxylic acid(s) R.sup.2COOH is physisorbed within a structure of the carrier carboxylic acid salt (M.sup.2+).sub.1+m(R.sup.1COO).sub.2.sup.(m+1)?, wherein a water content of the solid compound is less than 2 equivalents of water relative to the carrier carboxylic acid salt.

21. The solid compound according to claim 20, wherein the structure of the solid compound further comprises o R.sup.4COOH of a second loaded carboxylic acid R.sup.4COOH, wherein R.sup.2 and R.sup.4 are independently selected from the group consisting of an optionally substituted C.sub.1-C.sub.10-alkyl group and an optionally substituted mono- or polyunsaturated C.sub.1-C.sub.10-alkyl group, wherein substituents, if present, are selected from the group consisting of carbonyl group (?O), carboxylic acid group (COOH), amino group (NH.sub.2), hydroxy group (OH), halogen, cyano group (CN), and a mixture thereof, and wherein 0.1<o?10.

22. The solid compound according to claim 20, wherein R.sup.2COOH.sup.4 is a short-chain carboxylic acid or a mixture of formic, acetic, glycolic, propionic, lactic and/or butyric acid(s), and/or wherein the solid compound further comprises, as a second loaded carboxylic acid R.sup.4COOH, a short-chain carboxylic acid or a mixture of formic, acetic, glycolic, propionic, lactic and/or butyric acid(s).

23. The solid compound according to claim 20, wherein M.sup.2+ is calcium (Ca) or magnesium (Mg).

24. The solid compound according to claim 20, wherein (R.sup.1COO).sup.(m+1)? comprises a carrier carboxylic acid selected from the group consisting of formate, acetate, glycolate, propionate, lactate, butyrate, succinate, fumarate, maleicate, adipate, malate, malonate, citrate, tartrate, aspartate, glutamate, benzoate, salicylate, and ascorbate.

25. The solid compound according to claim 20, wherein a mean particle diameter of the solid compound is in a range from 10 to 500 ?m.

26. The solid compound according to claim 20, wherein the solid compound comprises water by less than 10.0 wt %.

27. A process for preparing the solid compound according to claim 20, the process comprising: propounding the carrier structure by a) premixing the (R.sup.1COO).sup.(m+1)? and R.sup.2COOH carboxylic acids, wherein a liquid acid concentration is above 70%, b) adding an alkaline earth metal base comprising the M.sup.2+ cation to (a), thereby obtaining a mixture, c) stirring the mixture of (b) below the boiling point of the most volatile acid present, thereby obtaining a second mixture, d) drying the second mixture obtained in (c).

28. A process for preparing the solid compound according to claim 20, the process comprising: propounding the carrier structure by a) premixing an alkaline earth metal base comprising M.sup.2+ cation with the (R.sup.1COO).sup.(m+1)? acid, wherein a liquid acid concentration is above 70%, thereby obtaining a mixture, b) stirring the mixture of (a) below the boiling point of the acid present, thereby creating a (M.sup.2+).sub.1+m(R.sup.1COO).sub.2.sup.(m+1)? salt, c) adding the R.sup.2COOH acids to the (M.sup.2+).sub.1+m(R.sup.1COO).sub.2.sup.(m+1)? salt created in (b), d) stirring the mixture of (c) below the boiling point of the most volatile acid present, e) drying the mixture obtained in (d).

29. The process for preparing the solid compounds according to claim 27, wherein the solid compound is stirred at temperatures below the boiling point of any components for less than 50 minutes.

30. The process for preparing the solid compounds according to claim 27, wherein the reaction mixture is cooled to a temperature below 60? C. for packing a final product without further purification.

31. A process comprising: utilizing the solid compound according to claim 20 as an acidity regulation and/or as a buffering agent in at least one application selected from the group consisting of cosmetic, pharmaceutical, food, and feed applications.

32. A process comprising: utilizing the solid compound according to claim 20 as an anti-microbial preservative in at least one application selected from the group consisting of cosmetic, pharmaceutical, food, and feed applications.

33. A process comprising: utilizing the solid compound according to claim 20 as a flavoring and palatability agent in at least one application selected from the group consisting of pharmaceutical, food, and feed applications.

34. A process comprising: utilizing the solid compound according to claim 20 as a color retention agent in at least one application selected from the group consisting of food and feed applications.

35. The A process comprising: utilizing the solid compound according to claim 20 as a zootechnical additive in animal nutrition.

36. The A process comprising: utilizing the solid compound according to claim 20 as a nutraceutical additive in human and animal nutrition supplementation.

37. A pharmaceutical composition comprising the solid compound according to claim 20.

38. A process comprising: utilizing the solid compound according to claim 20 as an active ingredient in a cosmetic.

Description

HEREIN SHOWS

[0160] FIG. 1: the schematic representation of the ex-post process for manufacturing the inventive carboxylic acid loaded carboxylic acid salt carrier from the components of the carrier carboxylic acid (R.sup.1COO).sub.2?m.sup.(m+1)? or (R.sup.1COO).sub.2.sup.(m+1)?, the loaded carboxylic acid(s) R.sup.2COOH, and earth metal base, comprising M.sup.2+.

[0161] FIG. 2: the schematic representation of the in-situ process for manufacturing the inventive carboxylic acid loaded carboxylic acid salt carrier from the components of the carrier carboxylic acid (R.sub.1COO).sub.2?m.sup.(m+1)? or (R.sup.1COO).sub.2.sup.(m+1)?, the loaded carboxylic acid(s) R.sup.2COOH, and earth metal base, comprising M.sup.2+.

[0162] FIG. 3: the distribution curve of the particle diameter by cumulative volume (cum. volume) of the sample magnesium glutamate with loaded lactic acid MgGlu-HLac [2] in FIG. 4(A), calcium acetate with loaded acetic acid CaAcHAc [2] in FIG. 4(B) and calcium tartrate with loaded acetic acid and propionic acid CaT-HAcHProp [1,1] in FIG. 4(C).

[0163] FIG. 4(A): the graph of the thermogravimetric analysis (TGA) of the dry sample MgFo-HProp [2], by the loss of weight as a function of increasing temperature (whilst exposed to a constant heating rate).

[0164] FIG. 4(B): the graph of the differential thermal analysis (DTA) of the dry sample MgFo-HProp [2] showing the caloric phenomena as a function of increasing temperature (whilst exposed to a constant heating rate).

[0165] FIG. 5(A): the graph of the thermogravimetric analysis (TGA) of the partially hydrated sample CaAcHAc [2], which was not dried after the synthesis, displaying the loss of weight as a function of increasing temperature (whilst exposed to a constant heating rate) and two second-order phase transitions of dehydration and desorption of the loaded carboxylic acid.

[0166] FIG. 5(B): the graph of the differential thermal analysis (DTA) of the partially hydrated sample CaAcHAc [2], which was not dried after the synthesis, displaying the caloric phenomena as a function of increasing temperature (whilst exposed to a constant heating rate) and two distinct endothermic physicochemical phenomena in agreement to the trends observed for TGA analysis of CaAcHAc [2].

[0167] FIG. 6: pH values of several representative compounds of invention compared to the pH values of the corresponding isolated components thereof, which are the loaded carboxylic acid(s) R.sup.2COOH and the carrier carboxylic acids (R.sup.1COO).sub.2?m.sup.(m+1)?, constituting a pair of measurements along the vertical axis. Each of the 73 pairs is assigned with a number 1-73, referencing to the according number explained in the table 5. All measurements were performed at 0.1 molar (M) concentration (c) of the samples, which is 0.1 mol per liter (mol/L). The pH difference of the compounds of invention compared to the pH of the corresponding carrier carboxylic acid and/or the loaded carboxylic acid(s) indicates the acid efficacy of the inventive compounds. The reader is referred to the table 5 for the listed values, which are the base of this figure.

[0168] FIG. 7(A): volume comparison of french style bread (FSB) in liters, proofing the applicability the compound of invention for the use as a preservative in bakery goods (example 12). The bread samples were exposed to the dosing of the compounds of invention according to the description at the x-axis.

[0169] FIG. 7(B): comparison of the areal cross sections of the samples of FIG. 7(A) and related to example 12.

[0170] FIG. 8: color development of a beef chuck steak blank sample (crosses) and a beef chuck steak sample calcium acetate with loaded acetic acid (CaAsc-Hac [2], raute) in dependency of the time as described in example 13. The colors of the RGB:R were transformed to black/white color.

[0171] FIG. 9(A): total bacteria count of the samples described in example 14, showing the usability of compounds of invention as preservative in meat products.

[0172] FIG. 9(B): total yeast count of the samples described in example 14, showing the usability of compounds of invention as preservative in meat products.

[0173] FIG. 10(A): the results of the test proofing the preservation effectiveness by testing for the total bacteria count (TBC, see example 15).

[0174] FIG. 10(B): the results of the test proofing the preservation effectiveness by testing for the total yeast/fungi count (see example 15).

[0175] FIG. 10(C): the results of the test proofing the preservation effectiveness by testing for the Enterobacteria/?-Glucoronidase-positive-Enterobacteria (E/?) count (see example 15).

LIST OF REFERENCE SYMBOLS USED IN THE FIGURES

[0176] (T1.2) tank [0177] (PM1.1) premixer [0178] (M1.1) mixer [0179] (P1.1) packaging device [0180] (S1.1) sieve [0181] (SM1.1) sieve mill [0182] (VS1.1) vacuum drying system [0183] (C1.1) mill/nibbler

List of Abbreviations for the Carboxylic Acids and Salts

[0184] The following table 3 lists examples of starting materials of the preferred embodiment of the compound of invention next to their pK.sub.a's and some relevant boiling points (T.sub.b,acid) for acidic forms, which are preferably used as loaded carboxylic acids. The abbreviations are used for the compound names as described in the nomenclature below.

TABLE-US-00005 TABLE 3 Abbreviations (first column) of components used for the names of preferred compounds according to the invention, next to the names for the salt- and acidic forms of the components and the acidic strength of the acidic form of the components (pK.sub.a1). abbreviation salt form acidic form pK.sub.a1 T.sub.b, acid Asp aspartate aspartic acid 1.99 Glu glutamate glutamic acid 2.16 Mal malonate malonic acid 2.83 T tartrate tartaric acid 2.98 Sal salicylate salicylic acid 2.75 Fum fumarate (trans) fumaric acid 3.00 Cit citrate citric acid 3.09 Ma malate malic acid 3.40 Fo formate formic acid 3.77 101 Gly glycolate glycolic acid 3.83 75 Lac lactate lactic acid 3.86 122 Asc ascorbate ascorbic acid 4.25 Suc succinate succinic acid 4.19 Ben benzoate benzoic acid 4.20 Ad adipate adipic acid 4.43 Ac acetate acetic acid 4.76 118 Bu butyrate butyric acid 4.82 163 Prop propionate propionic acid 4.88 141

Nomenclature:

[0185] If not indicated elsewise, the name of the carrier salt M.sup.2+(R.sup.1COO).sub.2?m.sup.(m+1)? is separated by the loaded, functional acid(s) (R.sup.2COOH) by a minus (?), wherein the carrier is always named in front of the loaded carboxylic acid component. Brackets [ . . . ] indicate the molar equivalents of loaded acid(s) with respect to the carrier salt and correspond to n as outlined in the claims.

List of Compound Names

[0186]

TABLE-US-00006 TABLE 4 Exemplary names used for several preferred compounds according to the invention, based on the abbreviations of the compounds given in table 3, next to the explanations of the names and the molar ratio of the loaded carboxylic acid to the carrier carboxylic acid salt carrier:loaded acid(s). compound name explanation carrier:loaded acid(s) MgFo-HAc [2] magnesium formate with loaded acetic acid 1:2 MgFo-HProp [2] magnesium formate with loaded propionic acid 1:2 MgAsp-Sal [2] magnesium aspartate with loaded salicylic acid 1:2 CaAsc-HAc [2] calcium ascorbate with loaded acetic acid 1:2 CaAsc-HAc [3] calcium ascorbate with loaded acetic acid 1:3 CaAsc-HProp [2] calcium ascorbate with loaded propionic acid 1:2 MgGlu-HLac [2] magnesium glutamate with loaded lactic acid 1:2 CaAc-HAc [2] calcium acetate with loaded acetic acid 1:2 CaSal-HLac [2] calcium salicylate with loaded lactic acid 1:2 CaT-HAc-HProp [1,1] calcium tartrate with loaded acetic acid and 1:1:1 propionic acid CaT-HAc [2] calcium tartrate with loaded acetic acid 1:2 CaT-HLac [2] calcium tartrate with loaded lactic acid 1:2 CaT-HProp [2] calcium tartrate with loaded propionic acid 1:2 CaCit-HAc [2] calcium citrate with loaded acetic acid 1:2 CaCit-HFo [2] calcium citrate with loaded formic acid 1:2 CaGlu-HAc [4] calcium glutamate with loaded acetic acid 1:4 CaCit-HAc [6] calcium citrate with loaded acetic acid 1:6 CaCit-HAc [2] calcium citrate with loaded acetic acid 1:2

Example 1the General Ex-Post Process

[0187] A typical process according to the preferred ex-Post process is schemed in FIG. 1.

[0188] In the ex-post process, the alkaline earth metal base, which is present in tank T1.1, and the carrier carboxylic acid, which is present in tank T1.2, are added to the reactor (R1) whilst gently mixing. After the reaction is finished, the formed carrier carboxylic acid salt is pre-dried by using for instance a vacuum drying system (VS1.1) whilst still mixing. The product (carrier salt) in the reactor (R1) is pre-sieved (SM1.1) and directed to an intermediary tank T1.3.

[0189] The sieved carrier salt from tank T1.3 and the to be loaded carboxylic acid from tank T1.4 are released to a mixer (M1.1) whilst gently mixing. Alternatively, an externally acquired carrier salt from tank T1.5 and the to be loaded carboxylic acid from tank T1.4 are released to a mixer (M1.1) whilst gently mixing. The obtained carboxylic acid loaded carboxylic acid salt carrier product from the mixer (M1.1) is further dried whilst still mixing for instance by hyphenation to the same vacuum drying system (VS1.1) used in the previous step. The dried product from M1.1 is subsequently grinded by a mill/nibbler (C1.1) to ensure adequate particle size. After passing a sieve (S1.1) the product is packaged (P1.1).

[0190] In an embodiment of the preferred process of the invention, the carrier carboxylic acid (R.sup.1COO).sub.2?m.sup.(m+1)? is purchased as a starting material to be loaded with the carboxylic acid R.sup.2COOH. It has for example been shown, that purchased anhydrous calcium citrate is suitable to generate the salt carrier structure, whilst being blended with acetic acid to create calcium citrate with loaded acetic acid (CaCit-HAc). However, in this embodiment the essential character of the invention lacks and hence does not show as optimal results as the onward continued or simultaneous process according to the invention, the ex-post or in-situ process, respectively.

Example 2the General In-Situ Process

[0191] A typical process according to the more preferred in-situ process is schemed in FIG. 2.

[0192] In the in-situ process, the alkaline earth metal base is present in tank T1.1. The ligand acid and the loading/free acid are released from tank T1.2 and from tank T1.3 respectively to be premixed in vessel (PM1.1) until a homogeneous premixture of the components is obtained. The acid premixture from PM1.1 is released to the reactor (R1). Subsequently the alkaline earth metal base from tank T1.1 is gently added to R1 whilst mixing.

[0193] After the reaction is finished, the obtained product is dried by using for instance a vacuum drying system (VS1.1). The drying is conducted in such a manner that the loaded carboxylic acid is not released, e.g. via evaporation, from the carboxylic acid loaded carboxylic acid salt carrier. The obtained carboxylic acid loaded carboxylic acid salt carrier is subsequently grinded by a mill/nibbler (C1.1) to ensure adequate particle size. After passing the sieve (S1.1), the product is packaged (P1.1).

[0194] Examples for compounds of invention successfully processed via the in-situ process are comprising different most preferred compounds of invention of a loaded carboxylic acid(s) and a carrier carboxylic acid salt, like calcium citrate with loaded formic acid with the molar ratio of n=2 (CaCit-HFo [2]), calcium tartrate with loaded lactic acid with n=2 (CaT-HLac [2]), magnesium aspartate with loaded salicylic acid with n=2 (MgAsp-Sal [2]), whereas higher acids loads are exemplary given by calcium glutamate with loaded acetic acid with n=4 (CaGlu-HAc [4]) or calcium citrate with loaded acetic acid with n=6 (CaCit-HAc [6]).

Example 3In-Situ Synthesis MgFo-HAc

[0195] This example represents the laboratory synthesis of magnesium formate with loaded acetic acid, MgFo-HAc [2], via the most preferred in-situ process according to the invention.

[0196] As starting materials for MgFo-HAc [2], magnesium oxide (MgO) with a purity of >97% and particle size of <0.03 mm, glacial acetic acid (CH.sub.3COOH) with a purity of 99-100% and formic acid (CH.sub.2O.sub.2) with a purity of >96% were used.

[0197] The chemical equation describes the synthesis of MgFo-HAc [2]:

##STR00040##

[0198] A solution of 41.55 g MgO, 120.10 g CH.sub.3COOH and 95.90 g CH.sub.2O.sub.2 was stirred for 30 minutes at ambient temperature (23? C.) in a sealed 5 dl thermo-glass beaker.

[0199] A white paste was obtained and dried at 95? C. for 45 min to obtain a white, solid, free-flowing and dust-free product.

[0200] PH measurements are suitable to determine the acidity of the obtained carboxylic acid loaded carboxylic acid salt carrier MgFo-HAc [2], which is characteristic for the loaded, physisorbed loaded acetic acid. The acidic efficiency of the loaded acetic acid within the magnesium formate carrier structure was evidenced by the comparison of the obtained pH values to the isolated magnesium formate as reference material. The pH value of MgFo-HAc [2] (pH 5.10 at 0.1 M and at r.t.) was evidently lower than the pH value of the reference material magnesium formate (pH 7.90 at 0.1 M and at r.t.) and hence, it is concluded that magnesium formate as a carboxylic acid salt carrier was successfully generated according to the process of invention, beneficially providing a repository function for excess free acetic acid.

Example 4In-Situ Synthesis CaT-HAcHProp [1,1]

[0201] This example represents the laboratory synthesis of calcium tartrate with loaded acetic acid and propionic acid, CaT-HAcHProp [1,1], via the most preferred in-situ process according to the invention.

[0202] For the production of calcium tartrate with 2 molar equivalence of free loaded acetic acid and propionic acid 1:1 (CaT-HAcHProp [1,1]), calcium hydroxide (Ca(OH).sub.2) with a purity of >98% and particle size of <0.02 mm, glacial acetic acid (CH.sub.3COOH) with a purity of 99-100%, tartaric acid (C.sub.4H.sub.6O.sub.6) with a purity of >99% and propionic acid (C.sub.2H.sub.5COOH) with a purity>99.5% were used.

[0203] The chemical equation describes the synthesis of CaT-HAcHProp [1,1]:

##STR00041##

[0204] For this, 23.29 g of Ca(OH).sub.2, 18.5 g of CH.sub.3COOH, 46.46 g of C.sub.4H.sub.6O.sub.6 and 22.93 g of C.sub.2H.sub.5COOH were mixed for 30 minutes at ambient temperature (23? C.) in a sealed 5 dl thermo-glass beaker. A white, hydrated paste was obtained, and the water side-product was evaporated at 95? C. for 5 min to obtain a grey, solid, free-flowing and dust-free product.

[0205] Evidence of the successful loading of propionic acid and acetic acid and the acidic efficiency of the compound of invention was evidenced by comparison of CaT-HAcHProp [1,1] to the acidity to isolated calcium tartrate. The pH value of CaT-HAcHProp [1,1] (pH 3.63 at 0.1 M and at r.t.) was evidently lower than the pH value of the reference material calcium tartrate (pH 7.33 at 0.1 M and at r.t.) and hence, it is concluded that calcium tartrate with loaded acetic acid and propionic acid was successfully generated according to the process of invention, beneficially providing a repository function for excess free acetic acid.

Example 5Comparison Between In-Situ Process and Ex-Post Process

[0206] This example demonstrates the comparison between the in-situ process and the ex-post process for the generation of calcium tartrate with loaded acetic acid with 2 molar equivalence of loaded acid (CaT-HAc [2]) as an exemplary the compound of invention.

[0207] In-situ process: This example showcases the laboratory synthesis of a carboxylic acid loaded carboxylic acid salt carrier CaT-HAc [2] according to the more preferred in-situ process of invention as opposed to the preferred ex-post process of this invention.

[0208] For the production of CaT-HAc [2], calcium hydroxide (Ca(OH).sub.2) with a purity of >98% and a particle size of <0.02 mm, glacial acetic acid (CH.sub.3COOH) with a purity of 99-100% and tartaric acid (C.sub.4H.sub.6O.sub.6) with a purity of >99% were used.

[0209] The following equation describes the synthesis of CaT-HAc [2]:

##STR00042##

[0210] For the in-situ synthesis, 24.37 g of Ca(OH).sub.2, 38.71 g of CH.sub.3COOH and 48.62 g of C.sub.4H.sub.6O.sub.6 were mixed for 30 minutes at ambient temperature (23? C.) in a sealed 5 dl thermo-glass beaker to avert the evaporation of reaction water and acid. The lower pK.sub.a of tartaric acid (C.sub.4H.sub.6O.sub.6) at 2.89 in comparison to acetic acid's pK.sub.a of 4.76 enabled the simultaneous addition of all three substances whilst assuring the formation of the C.sub.4H.sub.4CaO.sub.6 carrier structure with inbound free acetic acid.

[0211] A white, hydrated paste was obtained, and the water side-product was evaporated at 95? C. for 5 min to evaporate the water side product whilst avoiding the evaporation of acetic acid. After drying, a white, solid, free-flowing and dust-free product was obtained.

[0212] To evidence that excess acetic acid was loaded inside the calcium tartrate carrier structure and the compound of invention possess acidic features as expected for the compound of the invention, the pH of calcium tartrate acetic acid CaT-HAc [2] was compared to the pH of isolated calcium tartrate.

[0213] As a result, the pH value of CaT-HAc [2] (pH 3.56 at 0.1 M and at r.t.) was evidently lower than the pH value of the reference material calcium tartrate (pH 7.33 at 0.1 M and at r.t.) and hence, it is concluded that calcium tartrate with loaded acetic acid was successfully generated according to the process of invention, beneficially providing a repository function for excess free acetic acid.

[0214] Ex-post process: This example showcases the laboratory synthesis of a carboxylic acid loaded carboxylic acid salt carrier CaT-HAc [2] according to the preferred ex-post process of invention as opposed to the more preferred in-situ process of this invention.

[0215] For the synthesis of CaT-HAc [2] via ex-post process, calcium hydroxide [Ca(OH).sub.2] with a purity of >98% and particle size of <0.02 mm, glacial acetic acid (CH.sub.3COOH) with a purity of 99-100% and tartaric acid (C.sub.4H.sub.6O.sub.6) with a purity of >99% were used.

[0216] The following chemical equations describe the synthesis of CaT-HAc [2] via ex-post process as a two-step approach:

##STR00043##

[0217] For the ex-post synthesis of CaT-HAc [2], 24.37 g of Ca(OH).sub.2 and 48.62 g of C.sub.4H.sub.6O.sub.6 were first stirred for 30 minutes at ambient temperature (23? C.) in a sealed 5 dl thermo-glass beaker. A white hydrated powder was obtained and 38.71 g of CH.sub.3COOH were subsequently added. The mixture of the three components was subsequently stirred for 10 minutes at ambient temperature (23? C.) in a sealed 5 dl thermo-glass beaker.

[0218] A white, hydrated paste was obtained, and the water side-product was evaporated at 95? C. for 10 min to evaporate the water side product whilst avoiding the evaporation of acetic acid. After drying, a white, solid, free-flowing and dust-free product was obtained.

[0219] As a result, the pH value of CaT-HAc [2] (pH 2.89 at 0.1 M and at r.t.) was evidently lower than the pH value of the reference material calcium tartrate (pH 7.33 at 0.1 M and at r.t.) and hence, it is concluded that calcium tartrate with loaded acetic acid was successfully generated according to the process of invention, beneficially providing a repository function for excess free acetic acid.

[0220] The compounds CaT-HAc [2], processed via in-situ and ex-post process, were compared. Both the in-situ process and the ex-post process facilitate the manufacturing of CaT-HAc [2] with a repository function for excess free acid. The pH value of CaT-HAc [2] via ex-post process (pH 2.89 at 0.1 M and at r.t.) and via in-situ process (pH 3.56 at 0.1 M and at r.t.) are comparable. However, for sake of economy it can be concluded that the in-situ process is most preferable due to the substantial reduction of both reaction and drying times.

Example 6Acid Holding Capacity of the Compound of Invention

[0221] This example shows the acid holding capacity for very high carboxylic acid loading (n=4), representatively demonstrated for calcium tartrate with loaded acetic acid with 4 molar equivalence of loaded acid (CaT-HAc [4]).

[0222] The skilled person of the art knows that when providing at least two starting materials in the first step of the process according to the invention, the starting materials can be chosen one to another in stoichiometric or sub-stoichiometric ratios. To illustrate acid capacity performance of a featured carrier calcium tartrate with loaded 4 molar equivalent acetic acid, CaT-HAc [4], was synthesized according to the in-situ process of invention and analyzed with respect to the acidic strengths of the compound of the invention.

[0223] For the synthesis of calcium tartrate with loaded acetic acid CaT-HAc [4], calcium hydroxide (Ca(OH).sub.2) with a purity of >98% and particle size of <0.02 mm, glacial acetic acid (CH.sub.3COOH) with a purity of 99-100% and tartaric acid (C.sub.4H.sub.6O.sub.6) with a purity of >99% were used. The following chemical equation describes the synthesis of CaT-HAc [4]:

##STR00044##

[0224] For the in-situ process of CaT-HAc [4], 17.57 g of Ca(OH).sub.2, 55.81 g of CH.sub.3COOH and 35.05 g of C.sub.4H.sub.6O.sub.6 were blended for 30 minutes at ambient temperature (23? C.) in a sealed 5 dl thermo-glass beaker. A grey paste was obtained and dried at 95? C. for 6 min to obtain a white, solid, free-flowing and dust-free product.

[0225] The pH value of CaT-HAc [4], (pH 3.33 at 0.1 M and at r.t.) was evidently lower than the pH value of the reference material calcium tartrate (pH 7.33 at 0.1 M and at r.t.) and hence, the high acidic efficiency is demonstrated, which is directly correlated to a very high loading capacity of the compound of invention CaT-HAc [4]. The successful generation of very high carboxylic acid(s) loaded compounds via most preferred in-situ process of invention is verified, beneficially providing a high-dose repository function for excess of liquid acids.

Example 7Acidity of the Compound of Invention

[0226] This example demonstrates the acidic strength of several representative compounds of invention, which is quantified via pH measurements.

[0227] For the pH measurements, a Seven2Go portable pH meter S2 (pH measuring-range: ?2 to 20; resolution: 0.01) with an InLab Ultra Micro-ISM electrode (measuring range: pH ?1 to pH 11; low temperature membrane glass type; ceramic diaphragm; reference system with Ag.sup.+ ion trap by argenthal) as well as with an in-lab routine pH electrode (measuring range: pH 0 to pH 14; ceramic diaphragm; reference system with Ag.sup.+ ion trap by argenthal) from Mettler-Toledo AG (Analytical, Switzerland) was used.

[0228] The acidity of several representative compounds of invention is demonstrated by the comparison of the pH values of the compound of invention to the non-loaded carboxylic acid R.sup.2COOH and/or to the carrier carboxylic acid salt M.sup.2+(R.sup.1COO).sub.2?m.sup.(m?1)? under comparable conditions like the solvent, the concentration, the temperature for all samples.

[0229] For sake of comparability, compounds of the same loading ratio n=2, which is 2:1 of the loaded carboxylic acid with respect to the carrier carboxylic acid, were selected for this analysis. Further examples of other loading ratios are given in table 5. The components used for this pH-characterization were dry, solid, free-flowing and exhibited complete solubility as the reference salts themselves exhibited. The analytes were dissolved in millipore water, stirred for 5 minutes in an airtight vial to perform the pH measurements thereafter at r.t. All measurements were performed at 0.1 molar (M) concentration of the samples, which is 0.1 mol per liter (mol/L).

[0230] For sake of reliability, every result stated is the average of at least three single measurements. The following table 5 summarizes the results of the pH analysis for the compound of invention (third row), the corresponding carrier carboxylic acid (fourth row) and the loaded carboxylic acid (fifth row), related to the corresponding abbreviations (second row) and numbers (first row). The numbers 1-73 (nr., first row) are used as an assignment for the 73 pairs, comprising the compound of invention (third row), the corresponding carrier carboxylic acid (fourth row) and the loaded carboxylic acid (fifth row), as used in the FIG. 6.

TABLE-US-00007 TABLE 5 Summarized experimental pH values of exemplary compounds of invention named (third column), next to their row wise corresponding carrier carboxylic acid (fourth column) and the loaded carboxylic acid (fifth column). The enumeration (nr.) of the corresponding pairs is consistent with the FIG. 6. pH values carrier loaded abbreviation carboxylic carboxylic nr. (compound) compound acid acid 1 CaAc-HAc [2] 5.05 8.57 2.88 2 CaAc-HAc [3.5] 4.59 8.57 2.88 3 CaAc-HAc [3] 4.62 8.57 2.88 4 CaAc-HProp [2] 5.16 8.57 2.94 5 CaAsc-HAc [2] 4.42 8.28 2.88 6 CaAsc-HAc [3] 4.22 8.28 2.88 7 CaAsc-HAc [4] 4.22 8.28 2.88 8 CaAsc-HAc [5] 4.15 8.28 2.88 9 CaAsc-HAc [6] 4.12 8.28 2.88 10 CaAsc-HProp [2] 4.88 8.28 2.94 11 CaAsp-HAc [2] 4.42 8.15 2.88 12 CaAsp-HGly [2] 3.88 8.15 2.41 13 CaBen-HAc [2] 4.46 8.29 2.88 14 CaBen-HProp [2] 4.64 8.29 2.94 15 CaCit-HAc [2] 4.77 7.76 2.88 16 CaCit-HAc [5] 4.31 7.76 2.88 17 CaCit-HAc [6] 4.15 7.76 2.88 18 CaCit-HFo [2] 3.77 7.76 2.38 19 CaCit-HLac [2] 4.27 7.76 2.44 20 CaCit-HLac [4] 4.16 7.76 2.44 21 CaCit-HProp [2] 4.50 7.76 2.94 22 CaFo-HAc [2] 4.74 8.24 2.88 23 CaFo-HFo [2] 5.19 8.24 2.38 24 CaFo-HProp [2] 5.79 8.24 2.94 25 CaFum-HAc [2] 4.17 8.11 2.88 26 CaFum-HFo [2] 3.58 8.11 2.38 27 CaFum-HLac [2] 3.68 8.11 2.44 28 CaFum-HProp [2] 4.27 8.11 2.94 29 CaGlu-HAc [2] 4.52 7.24 2.88 30 CaGlu-HAc [4] 4.35 7.24 2.88 31 CaGlu-HLac [4] 3.60 7.24 2.44 32 CaGly-HProp [2] 4.63 7.24 2.94 33 CaLac-HAc [2] 4.58 8.28 2.88 34 CaLac-HLac [2] 3.45 8.28 2.44 35 CaLac-HLac [3] 3.38 8.28 2.44 36 CaLac-HLac [4] 3.30 8.28 2.44 37 CaMa-HAc [2] 4.53 7.45 2.88 38 CaM-HAc-HProp [1,1] 4.47 7.45 2.91 39 CaMa-HAc-HProp- 4.97 7.45 2.75 HLac [1,1,1] 40 CaM-HProp [2] 4.45 7.45 2.94 41 CaSal-HLac [2] 3.43 7.59 2.44 42 CaSuc-HAc [2] 4.69 7.95 2.88 43 CaSuc-HProp [2] 5.01 7.95 2.94 44 CaT-HAc [2] 3.52 7.33 2.88 45 CaT-HAc [4] 3.33 7.33 2.88 46 CaT-HAc [5] 3.84 7.33 2.88 47 CaT-HAc-HProp [1,1] 3.63 7.33 2.91 48 CaT-HAc-HPro-HLac 3.33 7.33 2.75 [1,1,1] 49 CaT-HLac [2] 3.27 7.33 2.44 50 CaT-HProp [2] 3.71 7.33 2.94 51 MgAc-HAc [2] 5.06 8.57 2.88 52 MgAc-HProp [2] 5.51 8.57 2.94 53 MgAsc-HAc [2] 4.34 8.28 2.88 54 MgAsp-Sal [2] 3.79 8.15 2.11 55 MgCit-HAc [2] 4.19 7.76 2.88 56 MgCit-HFo [2] 3.82 7.76 2.38 57 MgCit-HLac [2] 3.96 7.76 2.44 58 MgCit-HProp [2] 4.48 7.76 2.94 59 MgFo-HAc [2] 5.10 7.90 2.88 60 MgFo-HFo [2] 6.54 7.90 2.38 61 MgFo-HLac [2] 3.72 7.90 2.44 62 MgFo-HProp [2] 4.84 7.90 2.94 63 MgFum-HAc [2] 4.13 8.11 2.88 64 MgFum-HFo [2] 3.76 8.11 2.38 65 MgFum-HLac [2] 3.69 8.11 2.44 66 MgFum-HProp [2] 4.24 8.11 2.94 67 MgGlu-HLac [2] 4.00 7.24 2.44 68 MgLac-HAc [2] 4.43 7.94 2.88 69 MgLac-HAc-HProp 4.48 7.94 2.63 [1,1] 70 MgLac-HLac [2] 3.31 7.94 2.44 71 MgLac-HProp [2] 4.45 7.94 2.94 72 MgSuc-HAc [2] 4.69 7.95 2.88 73 MgSuc-HProp [2] 5.18 7.95 2.94

[0231] The results given in table 5 are schemed in FIG. 6, were the pH values of the compounds of invention are compared with the paring components along the vertical axis.

[0232] The significant differences of the pH values between the compounds of invention compared to the pH of the corresponding carrier carboxylic acid salt M.sup.2+(R.sup.1COO).sub.2?m.sup.(m+1)? and/or the corresponding non-loaded carboxylic acid R.sup.2COOH indicate the acid efficacy of the inventive compounds as well as the stability of the carrier components.

[0233] First, the stability of the carrier carboxylic acid salt M.sup.2+(R.sup.1COO).sub.2?m.sup.(m+1)? is validated for all samples, as they exhibit pH values in the range 7,2<pH<8,6 (FIG. 6, crosses). This lack of acidic activity further evidences the completeness of the resalting reaction, which is the synthesis of the latter according to the process of invention. Therefore, the carrier beneficially acts as a non-reactive carrier compound as intended and facilitate to tune the acidity exclusively via the loaded carboxylic acid R.sup.2COOH.

[0234] In contrast to the carrier carboxylic acid salt, the compounds of invention exhibit a significant acidity (3,3<pH<6,5, rectangles), comparable to the acidity of the corresponding isolated carboxylic acid R.sup.2COOH(FIG. 6, circles). This observation shows the acidic efficiency of the physiosorbed carboxylic acid R.sup.2COOH. The acid strength upon solvation of the compounds of invention demonstrates the controlled acid release in solution, whereas the compounds of invention proofed to be beneficially stable against alternative release e.g. via thermal desorption of the loaded acids (the reader is referred to the examples 8 and 9).

[0235] As a representative example for a high loaded compound of invention, calcium tartrate with loaded lactic acid CaT-HLac [2] showed the pH 3,27 (c=0,1M), which was evidently lower than the pH value of calcium tartrate with pH 7,33 (c=0,1M) and hence, the repository function even for a molar excess compound of loaded free acetic acid (n=2) is clearly shown, further validating the technical eligibility of the process of invention.

[0236] However, all solutions containing the invention compound in water are characterized by a significant acidic pH when compared to the neutral to slightly alkaline character of the non-loaded corresponding carrier carboxylic salts.

Example 8Thermal Analysis of a Dry Compound

[0237] This example demonstrates the thermal analysis, comprising thermogravimetry (TGA) and differential thermal analysis (DTA) for a representative compound of the invention MgFo-HProp [2] in the dry state, giving information about the release of the loaded acid(s) and the stability of the carrier structure.

[0238] Thermal analysis was carried out with a Linseis STA 1600 simultaneous thermal analyzer to determine simultaneous changes of weight (TGA signal) and caloric measurable transformations (DTA signal) in a temperature range between r.t. and 300? C. The compound of invention (100 mg) was placed on a sample holder of the measuring device and heated to 300? C. in a gas flow of 50 ml/min nitrogen upon exposure to a heating rate of 2 Kelvin per minute.

[0239] The results of the thermal characterization of sample MgFo-HProp [2] in the dry state are given in FIG. 4.

[0240] The FIG. 4(A) shows the curve obtained from the thermogravimetric analysis (TGA) of the dried sample MgFo-HProp [2] by the change of weight as a function of increasing temperature whilst exposed to a constant heating rate. A single second-order phase transition around the turning point T.sub.x is obtained. Sample MgFo-HProp [2] shows total loss of 24.4% weight upon heating in the range of 125? C. to 200? C. The loss of weight is correlated to the desorption of the physiosorbed loaded carboxylic acid, as the temperature of weight loss around T.sub.x coincides with the boiling point of the loaded propionic acid (boiling point T.sub.b=141).

[0241] On one hand the anhydrous character of the sample is evidenced as no other change of weight is observed, especially not in the range of the boiling point of water (100? C.), validating the efficiency of the drying step in the course of the manufacturing process invention. On the other hand, the thermal stability of the carrier carboxylic acid salt MgFo-H Prop [2] is clearly validated in a temperature range r.t. and 300? C., as no further loss of weight is observed at accelerated temperatures in the range of 200? C. >T>300? C.,

[0242] The position of the turning point T.sub.x gives evidence for the strength of the physisorption of the inclusion compound of invention, as more energy is required for the evaporation of loaded propionic acid if compared to the evaporation of propionic acid (Ts=141? C.), thus validating the stability of the compound of invention.

[0243] Furthermore, the flat shape of the weight-loss curve around the T.sub.x in the range from 125? C. to 200? C. indicates a gentle release of the loaded carboxylic acid compound, indicating the desired control of the acid-release. Such a controlled release is beneficially preventing an undesired burst release of the loaded carboxylic acid. The loss of weight, when attributed to the desorption of the loaded acid only, can be beneficially exploited for quantitative information about the loading capacity of compound of invention.

[0244] The FIG. 4(B) shows the DTA-signal obtained of the differential thermal analysis (DTA) of the dried sample MgFo-HProp [2] showing the caloric phenomena as a function of increasing temperature (whilst being exposed to a constant heating rate). A single significant caloric change of the sample MgFo-HProp [2] is detected between 125? C. and 200? C. In agreement with the temperature range of the major loss of weight recorded by the TGA signal, the DTA signal shows an endothermic reaction within this temperature range, indicating the desorption of the physiosorbed loaded carboxylic acid from the carboxylic carrier inclusion. The position of the absolute minimum T.sub.x gives evidence for the strength of the physisorption of the inclusion compound of invention, as more energy is required for the evaporation of loaded propionic acid if compared to the evaporation of propionic acid (Ts=141? C.), thus validating the stability of the compound of invention.

[0245] The coincidence of TGA and DTA curves in FIG. 4 demonstrates semi-quantitatively the release of propionic acid and the purity of the product of invention, and the thermal stability of the carrier carboxylic acid salt MgFo-HProp [2] up to 300? C.

Example 9Thermal Analysis Prior Drying

[0246] This example demonstrates the thermal analysis, comprising thermogravimetry (TGA) and differential thermal analysis (DTA) for CaAcHAc [2] prior the drying step according to the process of invention, giving information about the water content prior drying, the efficiency of thermal purification upon drying, the release of the loaded acid and the stability of the carrier structure.

[0247] Thermal analysis was carried out according to example 8.

[0248] The FIG. 5(A) shows the graph of the thermogravimetric analysis (TGA) of the partially hydrated sample CaAcHAc [2] prior drying in the course of the process of invention and represents the loss of weight as a function of increasing temperature whilst being exposed to a constant heating rate. The result graph shows two distinct steps of weight-loss. The first significant loss of weight (?7.0 wt % of total weight) takes place between 25-135? C. and in the second stage of weight-loss (11.7 wt % of the total weight) can be observed in a range from 135-300? C. The overall loss of weight of the partially hydrated sample CaAcHAc [2] upon a constant heating rate between r.t. and 300? C. is 18.74%.

[0249] Two distinct second-order phase transitions indicate the expected physical phenomena of evaporation of the side product water upon drying and the desorption of the loaded carboxylic acid. The evaporation of water is indicated by the first turning point T.sub.1 of the TGA curve, as it coincides with boiling point of water (100? C.), whereas the desorption of the loaded carboxylic acid is related to the second turning point of the TGA curve T.sub.x, as T.sub.x can be related to the boiling point of the loaded acetic acid (118? C.).

[0250] The evaporation of water takes place around T.sub.1 and is complete at a significantly lower temperature compared to the temperature range, where the evaporation of the loaded acetic acid takes place (around T.sub.x). Hence, these exemplary results of the representative sample of the compound of invention, CaAcHAc [2], for the TGA analysis demonstrate the successful drying of the compound of invention.

[0251] Even if the TGA analysis does not provide absolute qualitative information, information about the released material is possible when referred to the caloric information of the DTA curves as shown in FIG. 5(B).

[0252] The FIG. 5(B) shows the graph of the differential thermal analysis (DTA) of the partially hydrated sample CaAcHAc [2] prior drying in the course of the process of invention and demonstrates the caloric phenomena as a function of increasing temperature whilst exposed to a constant heating rate. The DTA signals show two distinct endothermic physicochemical phenomena by two minima of the DTA signal, validating the drying of the sample from water (T.sub.1) and the desorption of the physiosorbed loaded carboxylic acid from the carboxylic carrier inclusion (T.sub.x).

[0253] However, the position of the absolute minimum T.sub.x gives evidence for the strength of the physisorption of the inclusion compound of invention, as more energy is required for the evaporation of loaded acetic acid if compared to the evaporation of acetic acid (boiling point T.sub.b=118? C.), thus validating the stability of the compound of invention. The comparably increased thermal energy required to release the loaded carboxylic acid from the carrier structure indicates an overlay of the energy required for evaporation, which is generally required for the isolated carboxylic acid, and the energy required to overcome the attractive forces of physisorption from the loaded carboxylic acid on the inclusion compound according to the invention.

[0254] As no further changes of TGA and DTA signal are observed, the purity of the compound of invention with respect to low molecular weight impurities is verified. Furthermore, the thermal stability of the carrier carboxylic acid salt sample CaAcHAc [2] in a temperature range between r.t. and 300? C. is validated.

[0255] The drying according to the process of invention facilitates beneficially thermal purification of the carboxylic acid loaded carboxylic acid salt carrier from the main side product water, as the boiling point of and the loaded acids(s) differs from the boiling point of the side product.

Example 10Particle Size and Particle Size Distributions

[0256] This example demonstrates the powder quality, e.g. flowability and non-aerosol properties, of representative compounds of the invention as evidenced via diffraction granulometry.

[0257] The powder particle size and size distributions were determined by a Cilas 920 laser diffraction granulometer manufactured from Quantachrome (wavelength of the incident laser beam: 830 nm), which measures particle size distributions in the 0.2 to 500 ?m size range of wet dispersions or dry powders. All optical components are permanently mounted on a cast iron base plate, which means the analyzer is always in alignment, sample recirculation was achieved by two peristaltic pumps. The data analysis of the acquired diffraction pattern was performed based on the Fraunhofer Mie diffraction theories.

[0258] The results of the representative samples are given by the distribution curves in FIG. 3, showing the cumulative volume (cum. volume) plotted vs. the particle diameter. The distribution curve of the sample magnesium glutamate with loaded lactic acid MgGlu-HLac [2] is shown in FIG. 4(A), whereas the results of calcium acetate with loaded acetic acid CaAcHAc [2] are shown in FIG. 4(B) and the results of calcium tartrate with loaded acetic acid and propionic acid CaT-HAcHProp [1,1] are given in FIG. 4(C).

[0259] The analysis of the shape of the distribution curves facilitate to evaluate the mean particle diameters (d.sub.av d.sub.50 d.sub.90 as introduced above). The characteristic mean particle diameters (d.sub.av d.sub.50 d.sub.90) of the particle size distribution are given in the following table 6.

TABLE-US-00008 TABLE 6 The characteristic mean particle diameters (d.sub.av d.sub.50 d.sub.90) of exemplary compounds of invention, based on the analysis of the particle size distribution curve in FIG. 4. compound name d.sub.av/?m d.sub.50/?m d.sub.90/?m MgGlu-HLac [2] 99 68 233 CaAc-HAc [2] 221 208 400 CaT-HAc-HProp [1,1] 220 209 400

[0260] The particle size distributions of the samples CaAcHAc [2] and CaT-HAcHProp [1,1] show comparable mean particle diameter d.sub.av of approximately 220 ?m, which is in the preferred particle size range according to the invention, beneficially supporting flowability. Furthermore, the shape of the distribution curves of the samples CaAcHAc [2] and CaT-HAcHProp [1,1](see FIG. 4(B) and FIG. 4(C)) are similar, indicating that the process of invention is suitable to be used for a variety of samples with possibly differing granulation properties. The mean particle diameters (d.sub.50 d.sub.90) validate the uniform and/or homogeneous character of particle sizes of CaAcHAc [2] and CaT-HAcHProp [1,1]. Herein, the size distribution curves of these representative samples demonstrate the suitability of the compound of invention for any powder-processing manufacturing processes, e.g. for precise weight bottling, gravity feeding, and smooth and precise powder dosing for commercial scale.

[0261] In contrast, the sample MgGlu-HLac [2] shown in FIG. 4(A) comprises smaller particles with an average particle size d.sub.av of approximately 99 ?m (see Table 6). The broader distribution of the MgGlu-HLac [2] sample is visible by the flattened shape of the distribution curve of FIG. 4(A) and the difference in the mean particle diameters d.sub.ay and doo. Even if the unity of the particle size-distribution and the particulate size for sample MgGlu-HLac [2] is smaller than obtained for the samples CaAcHAc [2] and CaT-HAcHProp [1,1], beneficially no aerosol features are indicated. By the preferred size-ranges true for the compound of invention, no inhalation through the lungs or any harmful respiration of the particles is expected. Therefore, the contact with living creatures during processing and handling does not necessarily need to be strictly avoided, which is advantageously for a save handling purpose.

Example 11Use as a Preservative in Bakery Goods

[0262] This example demonstrates the applicability the compound of invention for the use as a preservative in bakery goods.

[0263] A variety of compounds of invention were applied as preservative for bakery goods as test objects, French style bread (FSB) and Mexican style tortilla (MST). The compounds used in this test were selected as they are approved as GRAS food additives with regards to the FDA and EFSA (Food Additives Database and Substances Added to Food Database, 2021), and therefore applicable for bakery goods application.

[0264] The preparation of the French style bread was performed according to the ingredients of table 7. The baking process was conducted using the Princess Bread Machine 152006 (Setting: P1; 1.5 lb loaf size; medium color) with a total baking time of 2:53 hours. Subsequently, the bread was cooled down to 21? C. and cut into 20 mm thick slices.

[0265] All ingredients were mixed to a dough and flat tortilla shaped samples were formed. All samples were baked for a total of 3 minutes each side on a stove-top pan at approximately 300? C. Subsequently, the tortilla samples were cooled down to 21? C.

TABLE-US-00009 TABLE 7 Recipes of French style bread (FSB) and Mexican Style Tortilla (MST). ingredients FSB/g MST/g flour 350 320 water 190 6 canola oil 15 2 sugar 15 63.8 salt 5 237 dry yeast 7 320

[0266] The samples were exposed to the compounds of invention according to the dosing respective the flour weight as shown in table 7, except for the blanks without exposition of to the compound of invention. Then, single samples were each airtight sealed in a polyethylene zip-lock bag and kept under comparable conditions (r.t., in the dark) for 30 days. It is recognized that defining the shelf life of a food is a difficult task and is an area of intense research for food product development scientists, including food technologists, microbiologists, packaging experts like Gabric et al., therefore preservation efficacy was established by visual and olfactory detection of initial mold infestation. The results of the preservative test are summarized in the table 8.

TABLE-US-00010 TABLE 8 Results of the preservation capability of additives in bakery goods. preservation/days additive dosing object <7 7-14 15-21 22-30 >30 none (blank) MST x CaAc-HProp [2] 0.3% MST x none (blank) FSB x CaAc-HProp [2] 0.2% FSB x CaAc-HAc [2] 0.3% FSB x CaT-HAc [3] 0.3% FSB x

[0267] The chemical kinetic principles of the compound of the invention allows for a significant increase preservation of at least 7 days for all samples without a loss of the food quality. An increase from 0.2 wt of the compound of invention is effective to increase the preservation time up to 30 days. An increased shelf life upon exposure to even small doses of the compound of invention opens pathway for new food packaging. Therein, the preservation capabilities of the inventive compound outperform conventional preservatives in comparative industries due to their low cost and health benefits. Especially for products for immediate consumption like for fresh bakery goods, where packaging requirements are often minimal, the compound according to the invention effectively prevents food quality loss.

Example 12Use for Volume Enhancing and Dough Conditioning in Bakery Goods

[0268] The following tests demonstrate the bread improving and dough conditioning effects of a several exemplary compounds according to the invention. French style bread (FSB) was used as a test object.

[0269] All additives were dosed that way, that each sample contained 200 ppm of ascorbate, which is typically used as the active ingredient in industry standard bread improvers. One sample was not exposed to any additive (blank), one reference was exposed to ascorbic acid (200 ppm) and another reference was exposed to calcium ascorbate (220 ppm), and two samples were exposed to compounds according to the invention, comprising calcium ascorbate with loaded acetic acid (CaAsc-HAc [2], 280 ppm) and calcium ascorbate with loaded acetic acid (CaAsc-HProp [2], 300 ppm).

[0270] The volume improving effect was established by volumetric measurements. The results of the conducted tests can be found in the FIG. 7(A), showing that the additives lead to volume expansion of the bread with respect to the blank sample. The volume enhancing effect of the compounds of invention are outperform the industry standard bread improver additive at equal dosing of the active ingredient ascorbic acid and/or ascorbate, evidencing the suitability of the inventions compound as volume enhancing additive for doughs of bakery goods. FIG. 7(B) presents the cross section of different samples, beneficially showing even volume expansion according to the optical requirements in the baking industry.

Example 13Use for Color Retention in Meat Products

[0271] The following tests outlines the color retention function of the compound according to the invention for the exemplary sample calcium ascorbate with loaded acetic acid (CaAsc-HAc [2]). Samples of grass-fed, grass-finished beef chuck steak were used as test objects. All tests were conducted under equal conditions at 20? C. The inventive compound CaAsc-HAc [2] fulfills the requirements of GRAS food additives with regards to the regulations of the FDA and EFSA. The additive was dosed at 0.2 wt % and was applied topically to the sample.

[0272] The color retention effectiveness was established by the method of k-means clustering and an ex-post analysis of the mean RGB:R shift. The colors give an indication of the state of myoglobin in the meat, weather it is deoxygenated, oxygenated, methionated or present in the state of carboxy-myoglobin. The FIG. 8 shows a clear change in color for the blank sample (dashed line) compared to the sample treated with CaAsc-HAc [2] (solid line).

[0273] The method of k-means clustering and the ex-post analysis of mean RGB:R shift revealed a more quantitative view on the before mentioned color shift. The time-trace of the color change shows a significant difference already after 24 h for the blank sample compared to the sample treated with CaAsc-HAc [2] as shown in FIG. 8(B).

[0274] indicating that the blank sample loses its signature red color earlier than the treated sample over the time frame of 72 hours (see FIG. 8(B)). It can be concluded that CaAsc-HAc [2] facilitates an effective color retention of meat products.

Example 14Use as Preservative in Meat Products

[0275] The following test series outlines the preservation functions of calcium ascorbate with loaded acetic acid (CaAsc-HAc [2]) as a representative sample of the inventive compounds. Samples of grass-fed, grass-finished beef chuck steak were used as test objects. All tests were conducted under equal conditions. The inventive compound CaAsc-HAc [2] fulfills the requirements of GRAS food additives with regards to the regulations of the FDA and EFSA. The additive was dosed at 0.2 wt % and was applied topically to the sample. Tests were conducted at 4? C. and 20? C. The preservation effectiveness was established by testing for total bacteria count and yeast/fungi count. The test for total bacteria count (see FIG. 9(A)) indicates that the treated samples at both 4? C. and 20? C. showed less bacterial infestation in comparison to their blank counter trials. The test for yeast count (see FIG. 9(B)) reveals that the treated samples slightly outperform their blank counter trials.

[0276] The application of the inventive compound facilitates an effective reduction of the total bacteria count and yeast formation in the first 164 hours after incubation. Therefore, the inventive compound CaAsc-HAc [2] is beneficially applicable as preservative application in meat products.

Example 15Use as Preservative Application in Silage

[0277] The following test series outlines the silage preservation functions of calcium formate with loaded formic acid (CaFo-HFo [2]), calcium formate with loaded propionic acid (CaFo-HProp [2]) as representative compounds according to the invention. Samples of forage comprising of approximately 90% pasture grass and 10% green rye with a DM-content of 30.75% were used as test objects. All tests were conducted under equal conditions. The inventive compounds CaFo-HProp [2] and CaFo-HFo [2] fulfill the requirements of GRAS food additives based on the regulations of the FDA and EFSA. The additives were dosed at 0.5 wt % and were applied topically to the samples. Tests were conducted under r.t. in a time frame of 31 days. The preservation effectiveness was established by testing for total bacteria count (TBC), yeast/fungi count and Enterobacteria/?-Glucoronidase-positive-Enterobacteria (E/?). The test results indicate that both CaFo-HProp [2] and -CaFo-HFo [2] at 0.5 wt % dosing was able to dramatically reduce TBC (see FIG. 10(A)), yeast count (see FIG. 10(B)) and E/? count (see FIG. 10(C)). Especially CaFo-HProp [2] was able to completely inhibit the growth of yeasts and ?-Glucoronidase-positive-Enterobacteria (especially E. coli) which are especially undesirable in silage fermentation (FIG. 10).

[0278] It can be concluded that the inventive compounds are able to outperform the blank trial in reducing total bacteria count, yeast formation and Enterobacteria formation in the first 744 hours after incubation.

Example 16Use for Cosmetic Application

[0279] This example demonstrates the use of the compound of invention for cosmetic application, here shown by the applicability as additive for a shaving soap.

[0280] Liquid shaving soaps were manufactured comprising no additives (blank), with 1 wt % malic acid, 1 wt % calcium citrate, 2 wt % calcium salicylate with loaded lactic acid (CaSal-HLac [2]) and 1% calcium citrate with loaded acetic acid (CaCit-HAc [2]) being added. An overview of the samples is given in Table 9.

TABLE-US-00011 TABLE 9 Samples and results of application in shaving soap. nr. additive % wt thickening stability (>24 h) 1 blank 0 ? no 2 malic acid 1 + no 3 calcium citrate 1 ? yes 4 CaSal-HLac [2] 2 ++ yes 5 CaCit-HAc [2] 1 +++ yes

[0281] Each sample of Aleppo-style Arabic soap, consisting of 16% sodium hydroxide, 71.4% olive oil and 12.6% laurel oil, was cut into 22 g sample-sizes and was placed into a bowl to which 22 g of water was added. The mix was stirred with hard soap pieces remaining undissolved and placed for 50 seconds at 600 W in a microwave oven. Afterwards, the respective additives were added in their before mentioned dosing with 44 g of water which resulted in the dissolving of the remaining hard soap pieces. additionally, a change in color and consistency could be observed as the mixture turned into a white and creamy substance. The mixture was placed for 80 seconds in a microwave at 600 W. Thereafter the resulting mixture was hand-blended and filled into a jar for testing and storage. Table 9 outlines the thickening and stability results.

[0282] All in all, the mix of the acid-loaded carrier substances with the hard Aleppo-style Arabic soap and water yielded a thick-foamy, yet liquid soap which turned out to be stable. This results in a product suitable as a shaving soap as the flow properties display a gliding effect when shaving, enabling a smoother and closer shave whilst employing acids with the potential to clean out the skin's impurities whilst simultaneously disinfecting razor burns.