Cocrystal of citric acid and glycine and uses thereof

Abstract

The present invention relates to a co-crystal of citric acid and glycine, the co-crystal containing citric acid and glycine in a molar ratio of 1:3. The inventors have unexpectedly discovered that this co-crystal of citric acid and glycine can be suitably produced in the form of a powder that exhibits extremely low hygroscopicity and can impart a sour taste that is very similar to that of citric acid. The present invention also provides a process that allows the preparation of this co-crystal in high yield.

Description

Detailed Description of the Invention

[0001] [Technical field] The present invention relates to a co-crystal of citric acid and glycine and a process for preparing such a co-crystal. The co-crystal of the present invention contains citric acid and glycine in a molar ratio of 1:3.

[0002] The present invention further relates to granular compositions comprising particles containing at least 5 wt.% of said co-crystals, and the application of such compositions in edible products, e.g. as food ingredients for granule-dusting candies. [Background technology]

[0003] It is well known to coat sugar confectionery with a blend of sugar and acid powder (called "acid dusting"). The use of powdered citric acid in acid dusting is fraught with stability problems arising from the fact that citric acid is hygroscopic. Citric acid powder attracts significant moisture from the surroundings. This process adversely affects not only the appearance but also the taste and texture of the coated confectionery product.

[0004] US Patent No. 3,558,325 describes a method for improving the taste, smoothness, richness and flavor of an alcoholic beverage by incorporating therein 0.01% to 6.0% of a non-toxic, palatable and acceptable salt formed by reacting alpha-alanine or alpha-glycine with an acid selected from the group consisting of ascorbic acid, malic acid, gluconic acid, citric acid, tartaric acid and cyclamic acid. Example I describes the preparation of glycine-citrate by dissolving 1.9 grams of citric acid in 3 cc of hot water and then gradually adding 0.75 grams of glycine until all components are dissolved. A small amount of activated charcoal was added and the solution was filtered under suction. The filtrate was clarified and then small amounts of methanol and isopropanol were added until turbidity was produced. The salt was crystallized by cooling. The salt was recrystallized in water. The glycine citrate thus obtained melts at 168-169°C and has the empirical formula CH 13NO9 was obtained.

[0005] Losev et al. (Selective Effect of Carboxylic Acids on Glycine Polymorphisms and Cocrystal Formation, Doklady Physical Chemistry, 2011, Vol. 439, Part 2, pp. 153-156) described a study investigating the effect of the addition of carboxylic acids on the crystallization of alpha-glycine in experiments involving cocrystallization and subsequent mechanical treatment. Upon mechanical treatment, the formation of 1:1 cocrystals of stoichiometric amounts of the acids was not observed during crystallization from aqueous solutions of the crystals.

[0006] US Patent Application Publication No. 2018 / 0228753 describes co-crystals of substituted glycine compounds with coformers such as tartaric acid or fumaric acid.

[0007] WO 2020 / 260194 describes granular compositions containing at least 1 wt.% malate particles having a diameter of 50-1000 μm and containing at least 70 wt.% co-crystals of malic acid and alkali metal hydrogen malate. These granular compositions can be used for sour coating of confectionery. [Summary of the Invention] [Means for solving the problem]

[0008] The present inventors have unexpectedly discovered a co-crystal of citric acid and glycine that exhibits extremely low hygroscopicity and can be conveniently produced in the form of a powder that can impart a sour taste that is very similar to that of citric acid.

[0009] Thus, a first aspect of the present invention relates to a co-crystal of citric acid and glycine, said co-crystal containing citric acid and glycine in a molar ratio of 1:3.

[0010] Although the inventors do not wish to be bound by theory, it is believed that when particles of the co-crystal of the present invention come into contact with saliva, the co-crystal instantly dissociates into citric acid and glycine, and therefore, when an edible product coated with particles of this co-crystal is ingested, the taste of citric acid is instantly released in the mouth.

[0011] A second aspect of the present invention relates to a granular composition comprising citric acid / glycine cocrystal particles containing at least 5 wt.% of the cocrystal described above.

[0012] A third aspect of the present invention is providing seed particles containing at least 50 wt.% crystalline material comprising an organic acid; preparing an aqueous solution containing citric acid and glycine in a molar ratio of 0.25 to 0.40; spraying the aqueous solution onto the seed particles to produce loaded particles; removing water from the load particles; The present invention relates to a process for preparing co-crystal particles comprising a co-crystal of citric acid and glycine, comprising:

[0013] A fourth aspect of the present invention is preparing an aqueous mixture containing citric acid and glycine in a molar ratio of 0.25 to 0.40 and containing 1 to 40 wt.% water; - crystallizing a co-crystal of citric acid and glycine; drying the crystallized cocrystal; The present invention relates to another process for preparing co-crystal particles comprising a co-crystal of citric acid and glycine, comprising:

[0014] The process for preparing the co-crystal particles described above offers the advantage that the co-crystals can be produced in high yields. When citric acid and glycine are applied in a molar ratio of 1:3, a yield approaching 100% can be achieved.

[0015] A fifth aspect of the present invention relates to the use of particles containing at least 5 wt.% of a co-crystal of the present invention as a food ingredient.

[0016] A sixth aspect of the invention relates to a method of preparing an edible product comprising combining a granular composition of the invention with one or more other food ingredients.

[0017] A seventh aspect of the invention relates to an edible product containing at least 0.05 wt.% co-crystal particles containing at least 5 wt.% of a co-crystal of the invention. [Brief description of the drawings]

[0018] [Figure 1A] The DSC curve is shown. [Figure 1B] A DVS graph is shown. [Diagram 2] The powder samples were analyzed by differential scanning calorimetry (Q2000, TA Instruments). The samples were heated from -10°C to 200°C at a rate of 10°C / min. The DSC curves so obtained are shown. [Diagram 3] A scanning electron microscope image (50x) of the granules is shown. [Figure 4] A sample of the granules was analysed by DSC as in Example 2. The DSC so obtained is shown.

[0019] [Mode for carrying out the invention] One aspect of the present invention relates to a co-crystal of citric acid and glycine, containing citric acid and glycine in a molar ratio of 1:3.

[0020] The term "co-crystal," as used herein, refers to a crystalline single-phase material composed of two or more different molecular or ionic compounds in a stoichiometric ratio that are not solvates or simple salts.

[0021] According to a preferred embodiment, the cocrystal of the present invention exhibits an endothermic peak at a temperature between 130 and 200° C., more preferably between 140 and 190° C., with an enthalpy of at least 110 J / g, more preferably at least 110 J / g, even more preferably at least 120 J / g, and most preferably at least 140 J / g, as determined by differential scanning calorimetry. Preferably, the enthalpy of the endothermic peak does not exceed 195 J / g, more preferably does not exceed 190 J / g. Even more preferably, the cocrystal exhibits an endothermic peak at a temperature between 150 and 180° C., most preferably between 155 and 170° C., with an enthalpy of at least 120 J / g, more preferably at least 130 J / g, and most preferably at least 150 J / g, as determined by differential scanning calorimetry. Preferably, the enthalpy of the endothermic peak in the recited temperature range does not exceed 190 J / g, more preferably does not exceed 180 J / g.

[0022] Another aspect of the invention relates to a granular composition comprising citric acid / glycine cocrystal particles containing at least 5 wt.% of the cocrystal of the invention. The cocrystal particles preferably contain at least 40 wt.%, more preferably at least 70 wt.%, and most preferably at least 80 wt.% of the cocrystal.

[0023] In addition to the citric acid / glycine cocrystal particles, the granular composition of the present invention may contain other granular components such as sugar, salt or acid powders. Preferred acid powders are malic acid-based powders, such as PURAC® Powder MA or PURAC® Powder MAX. The term "malic acid" as used herein also encompasses edible salts of malic acid, unless otherwise specified.

[0024] According to a preferred embodiment, the co-crystal particles in the granular composition contain at least 50 wt.%, more preferably at least 70 wt.%, more preferably at least 85 wt.%, and most preferably at least 90 wt.% of a co-crystal of citric acid and glycine.

[0025] The granular composition preferably contains at least 1 wt.% co-crystalline particles.

[0026] In one embodiment of the invention, the co-crystal particles comprise a majority of the granular composition, such that the granular composition preferably comprises at least 50 wt.%, more preferably at least 75 wt.%, and most preferably at least 90 wt.% of the co-crystal particles.

[0027] In another embodiment, the granular composition contains a combination of co-crystal particles and sugar particles. Such a blend can be suitably used in the sour coating of confectionery. Thus, such a granular composition preferably comprises 1-95 wt.% co-crystal particles and 5-99 wt.% sugar particles, more preferably 2-50 wt.% co-crystal particles and 50-98 wt.% sugar particles. Even more preferably, the granular composition comprises 3-30 wt.% co-crystal particles and 60-97 wt.% sugar particles. Preferably, the combination of co-crystal particles and sugar constitutes at least 40 wt.%, more preferably at least 60 wt.%, most preferably at least 80 wt.% of the granular composition.

[0028] In yet another embodiment, the granular composition contains a combination of co-crystal particles and particles containing malic acid. Such a blend can be suitably used in sour coating of confectionery. Thus, such a granular composition preferably contains 10-90 wt.% of co-crystal particles and 10-90 wt.% of particles containing at least 20 wt.% of malic acid, more preferably 20-80 wt.% of co-crystal particles and 20-80 wt.% of particles containing at least 20 wt.% of malic acid. Even more preferably, the granular composition contains 30-70 wt.% of co-crystal particles and 30-70 wt.% of particles containing at least 20 wt.% of malic acid.

[0029] The water content of the co-crystal particles typically does not exceed 5 wt.%, more preferably the water content does not exceed 3 wt.%.

[0030] The granular composition of the present invention has a volume-weighted mean diameter D of preferably 50 to 1,200 μm, more preferably 300 to 1,100 μm. 4,3 has.

[0031] According to another preferred embodiment, the particles of the granular composition have the following particle size distribution: D 10 ≧10μm, 50μm≦D 50 ≦1,000μm, D 90 ≦1,600μm, %, where the vol.% of particles having a diameter smaller than Dx is equal to x vol.% and the vol.% of particles having a diameter larger than Dx is equal to (100-x) vol.%.

[0032] The particle size distribution of a granular composition may suitably be determined by laser diffraction using a Mastersizer 3000 from Malvern Panalytical, as described in the Examples.

[0033] Another aspect of the present invention is a method for producing a providing seed particles containing at least 50 wt.% of a crystalline material comprising an organic acid preferably selected from citric acid, malic acid, lactic acid, acetic acid, fumaric acid, adipic acid, tartaric acid, and combinations thereof; preparing an aqueous solution containing citric acid and glycine in a molar ratio of 0.25 to 0.40; spraying the aqueous solution onto the seed particles to produce loaded particles; removing water from the load particles; The present invention relates to a process for preparing co-crystal particles comprising a co-crystal of citric acid and glycine, comprising:

[0034] Preferably, the seed particles contain at least 30 wt.% of an organic acid selected from citric acid, malic acid, lactic acid, acetic acid, fumaric acid, adipic acid, tartaric acid, and combinations thereof.

[0035] According to a particularly preferred embodiment, the seed particles contain at least 50 wt.%, more preferably at least 70 wt.%, and most preferably at least 90 wt.%, of a co-crystal of citric acid and glycine as described herein above.

[0036] The aqueous solution used in the present process contains citric acid and glycine preferably in a molar ratio of 0.28 to 0.37, more preferably in a molar ratio of 0.30 to 0.35, and most preferably in a molar ratio of 0.32 to 0.34.

[0037] The aqueous solution containing citric acid and glycine used in the present process preferably contains no more than 30 wt.%, more preferably no more than 15 wt.%, even more preferably no more than 5 wt.%, of an organic solvent (e.g., methanol, ethanol or isopropanol), and most preferably no organic solvent at all.

[0038] The aqueous solution containing citric acid and glycine preferably contains at least 30 wt. %, more preferably 35 to 55 wt. %, and most preferably 40 to 50 wt. % of the combination of citric acid and glycine.

[0039] Preferably, the water is removed from the loaded particles before the water contacts the loaded particles by exposing the particles to a gas stream having a temperature of at least 50° C., more preferably a temperature of between 60 and 150° C. The gas stream preferably contains at least 90 vol.% air.

[0040] Water may be suitably removed from the particle load in a fluidized bed dryer. The bed temperature of the fluidized particle load is preferably maintained at 40-98° C. The inlet temperature of the gas used to remove water from the particle load fluidized in the fluidized bed dryer is preferably in the range of 70-180° C.

[0041] The process can advantageously be carried out in a fluidized bed granulator or in a spray dryer, in which case the seed particles and the aqueous solution are introduced simultaneously into the spray dryer. The seed particles can be obtained from the fines of the dried product (recycle).

[0042] In a fluidized bed granulator, a fluidized bed of seed particles is first formed. An aqueous solution is then sprayed onto the seed particles to produce loaded particles, and simultaneously a gas stream is passed through the fluidized bed to remove water from the loaded particles.

[0043] According to a particularly preferred embodiment, the process results in citric acid / glycine cocrystal particles as defined herein above.

[0044] Yet another aspect of the present invention is a method for producing a medicament for use in a method for the preparation of a medicament for use in a pharmaceutical composition comprising the steps of: preparing an aqueous mixture containing citric acid and glycine in a molar ratio of 0.25 to 0.40 and containing 1 to 40 wt.% water; - crystallizing a co-crystal of citric acid and glycine; drying the crystallized cocrystal; The present invention relates to another process for preparing co-crystal particles comprising a co-crystal of citric acid and glycine, comprising:

[0045] The water content of the aqueous mixtures described herein refers to the total water content, including any water contained in hydrates, such as citric acid monohydrate.

[0046] The aqueous mixture used in this process may be an aqueous solution containing sufficiently dissolved citric acid and sufficiently dissolved glycine prior to the precipitation step. Precipitation of the co-crystals from this solution may be induced, for example, by the addition of seed crystals, cooling and / or dehydration.

[0047] According to another embodiment, the aqueous mixture comprises undissolved glycine and / or undissolved citric acid.The inventors have unexpectedly discovered that if water is added to a mixture containing citric acid and glycine in a molar ratio of 0.25 to 0.40, co-crystals of citric acid and glycine are formed.

[0048] The amount of water present in the aqueous mixture is preferably in the range of 1 to 40 wt.%, more preferably 2 to 25 wt.%, even more preferably 3 to 15 wt.%, and most preferably 5 to 10 wt.%.

[0049] Preferably, the precipitation of the co-crystal of citric acid and glycine is carried out at a temperature in the range of 10-95°C, more preferably 20-90°C, and most preferably 30-80°C.

[0050] The aqueous mixture used in the present process preferably contains citric acid and glycine in a molar ratio of 0.28 to 0.37, more preferably in a molar ratio of 0.30 to 0.35, and most preferably in a molar ratio of 0.32 to 0.34.

[0051] The aqueous mixture containing citric acid and glycine used in the present process preferably contains no more than 15 wt.%, more preferably no more than 5 wt.%, even more preferably no more than 2 wt.%, of an organic solvent (e.g. methanol, ethanol or isopropanol), and most preferably no organic solvent at all.

[0052] The aqueous mixture containing citric acid and glycine preferably contains at least 60 wt.%, more preferably 75 to 98 wt.%, and most preferably 90 to 95 wt.%, of a combination of citric acid and glycine.

[0053] In a preferred embodiment, the recovered co-crystals are subjected to a drying step to reduce the water content to less than 5 wt.%, more preferably less than 2 wt.%, and most preferably less than 1 wt.%.

[0054] According to a further preferred embodiment, the recovered co-crystals or the recovered and dried co-crystals are subjected to a size reduction step, such as grinding or milling. Classification of the size-reduced co-crystal particles, for example by sieving, can be used to achieve a more uniform particle size.

[0055] According to a particularly preferred embodiment, the process results in citric acid / glycine cocrystal particles as defined herein above.

[0056] A further aspect of the present invention relates to the use of particles containing at least 5 wt.%, more preferably at least 50 wt.%, most preferably at least 80 wt.% of a co-crystal of citric acid and glycine as defined herein above, as a food ingredient.

[0057] Preferably, the use involves the application of co-crystal particles in or on an edible product having a moisture content of less than 30 wt.%, more preferably less than 15 wt.%, most preferably less than 15 wt.%.

[0058] According to a preferred embodiment, the use comprises the application of a co-crystal in or on a confectionery product.

[0059] According to a particularly preferred embodiment, the use comprises the application of the co-crystal particles as a coating to the surface of an edible product, such as a confectionery product.

[0060] Another aspect of the invention relates to a method of preparing an edible product comprising combining a granular composition as described herein above with one or more other food ingredients. Preferably, combining the granular composition with one or more other food ingredients does not involve decomposition of the co-crystal.

[0061] In one embodiment, the method includes combining the granular composition with sugar. In this embodiment, the granular composition preferably contains at least 20 wt.%, more preferably at least 30 wt.%, and most preferably at least 50 wt.% of co-crystal particles. By mixing the granular composition with sugar, a coating composition can be prepared that can be suitably used for sour coating of confectionery products.

[0062] In another embodiment, the method comprises application of a granular composition to a surface of an edible product such as a confectionery product. In this embodiment, the granular composition preferably comprises 1-95 wt.% co-crystal particles and 5-99 wt.% sugar particles, more preferably 2-50 wt.% co-crystal particles and 50-98 wt.% sugar particles.

[0063] In another preferred embodiment, the granular composition comprises 10 to 90 wt.% co-crystal particles and 10 to 90 wt.% particles containing at least 20 wt.% malic acid, more preferably 20 to 80 wt.% co-crystal particles and 20 to 80 wt.% particles containing at least 20 wt.% malic acid.

[0064] Yet another aspect of the present invention relates to an edible product comprising at least 0.05 wt.%, more preferably 0.15-30 wt.%, of co-crystal particles comprising at least 5 wt.% of a co-crystal of citric acid and glycine as described herein above.

[0065] The moisture content of the edible product to which the co-crystal particles of the present invention are applied is preferably less than 30 wt.%, more preferably less than 15 wt.%, and most preferably less than 15 wt.%.

[0066] Preferably, in addition to the co-crystal particles, the edible product contains at least 0.05 wt.%, more preferably 0.15-30 wt.%, of particles comprising at least 20 wt.% malic acid.

[0067] According to a particularly preferred embodiment, the edible product is coated with co-crystal particles. More preferably, the edible product is coated with a mixture of co-crystal particles and sugar particles. Even more preferably, the edible product is coated with a granular composition comprising co-crystal particles and sugar particles as described above.

[0068] The edible product of the present invention is preferably a confectionery product, more particularly a soft candy.

[0069] The invention is further illustrated by the following non-limiting examples. [Example]

[0070] Example 1 In a 100 ml glass bottle, 21.11 g of citric acid monohydrate food grade (0.10 mol) and 22.72 g of glycine (0.30 mol) were placed. The powders were mixed by shaking the flask. Water (2.63 g) was added to the bottle and the mixture so obtained was stored at 40° C. After 2 hours, the thick slurry had turned into a white solid mass.

[0071] The next day, a portion of the solid mass (11.02 g) was dried overnight at room temperature under reduced pressure (p<10 mbara). The moisture content of the dried product was 0.4 wt.%. The dried product was analyzed by differential scanning calorimetry (Q2000, TA Instruments) and dynamic vapor sorption (DVS).

[0072] The DSC curve so obtained is shown in Figure 1 A. The DVS graph so obtained is shown in Figure 1 B.

[0073] The enthalpy of 128.1 J / g and the temperature of the endothermic peak at 158.6° C. observed in the DSC curve are somewhat lower than those observed in some of the experiments described below, which may be due to incomplete conversion of the starting material to the 1:3 co-crystal.

[0074] The DVS graphs show that the moisture uptake at 80% RH was about 2-3 wt.%, which is significantly lower than that of citric acid monohydrate at 80% RH (about 20 wt.%).

[0075] Example 2 Approximately 4,255 grams of an aqueous solution containing citric acid and glycine in a 1:3 molar ratio was prepared based on the formulation shown in Table 1.

[0076] [Table 1]

[0077] Demi water was weighed into a 5 L glass beaker equipped with a magnetic stirrer. The powder was added slowly with stirring. The solution was heated to 40° C. to dissolve the powder. Once the powder was dissolved, the solution was cooled to room temperature.

[0078] Then 0.3 g of citric acid and glycine cocrystal (1:3 mol / mol) was added and the solution was left overnight to crystallize. The next day, the solution had turned into a white paste. Solid-liquid separation by centrifugation was performed to remove the mother liquor (Centrifuge: 10 min, 3000 rpm, HERMLE Sieva-2 (X-6449), 25 μm-filter cloth). The collected solid was placed on metal trays and dried in a vacuum oven (at 20° C.) to remove the remaining liquid.

[0079] After 2 days, the moisture content of the crystals was approximately 7.5 wt.%. The solid was further dried in a vacuum oven at 30° C. for 5 hours to reduce the moisture content to 5 wt.%. The resulting cake was converted to a powder using a food processor.

[0080] The powder samples were analyzed by differential scanning calorimetry (Q2000, TA Instruments). The samples were heated from -10°C to 200°C at a rate of 10°C / min. The DSC curves so obtained are shown in Figure 2.

[0081] Example 3 Approximately 7450 grams of an aqueous solution of citric acid and glycine (spray solution) having the same composition as the solution in Example 2 was prepared in the same manner as in Example 2.

[0082] Granulation tests were carried out in a fluid bed granulator (Procell LabSystem) by spraying the spray solution onto the fluidized powder of Example 2. The operating conditions of the granulator are summarized in Table 2.

[0083] [Table 2]

[0084] FIG. 3 shows a scanning electron microscope image (50×) of the granules.

[0085] A sample of the granules was analysed by DSC as in Example 2. The DSC so obtained is shown in Figure 4. The moisture content and DSC profile are shown in Table 3.

[0086] [Table 3]

[0087] The upward shift of the endothermic peak to 164.42° C. (compared to the DSC curve of Example 2) is believed to be due to the decrease in water content and the corresponding increase in crystalline cocrystals.

[0088] The particle size distribution of the granules was determined using a Mastersizer 3000, Malvern. ·Measurement: Dry dispersion Analysis model: General purpose Pressure: 0.5bar Dispersant refractive index: 1 Particle absorption rate: 0 Particle refractive index: 1.53

[0089] The particle size measurements are shown in Table 4.

[0090] [Table 4]

[0091] Example 4 The moisture sorption of the granules of Example 3 was determined at 20° C. and 40° C. At 20° C., the maximum moisture absorption at RH 90% was 0.5 wt.%. At 40° C., the maximum moisture absorption at RH 90% was 1.2 wt.%.

[0092] Example 5 The moisture absorption of the granule samples of Example 3 was compared to that of commercially available coated citric acid (Iwata Chemical Japan). It was found that when stored in an open cup at 30° C. and 75% RH for one month, the granules did not absorb any water, whereas the coated citric acid absorbed up to 8.4 wt.% water.

[0093] Example 6 The sensory properties of the granules of Example 3 and commercial coated citric acid powders (Iwata and Capol) were compared with those of commercial coated citric acid by using them in an acid dusting with a 15:85 (w / w) blend of acid powder and sugar. The actual content of citric acid in the granules was less than that of Capol coated citric acid, but there was no significant difference in acidity intensity (see Table 6).

[0094] Attribute ranking sensory evaluation (scores from 1 to 9) was performed in a session with 18 trained panelists. The results are summarized in Table 5.

[0095] [Table 5]

[0096] Comparative Example In a 100 ml glass bottle, 21.00 g of citric acid monohydrate food grade (0.10 mol) and 7.56 g of glycine (0.10 mol) were placed. The powders were mixed by shaking the flask. Water (2.61 g) was added to the bottle and the mixture was stored at 40° C.

[0097] After 2 hours a clear viscous solution had formed with a small amount of residual solid remaining at the bottom of the flask. The next day a portion of the product (10.35 g) was dried overnight at room temperature under reduced pressure (p<10 mbara).

[0098] A foamy viscous syrup was formed which was difficult to process and analyze.

Claims

1. A co-crystal of citric acid and glycine containing citric acid and glycine in a molar ratio of 1:

3.

2. 2. The co-crystal of claim 1, which exhibits an endothermic peak at a temperature between 130 and 200° C. and has an enthalpy of at least 110 J / g as determined by differential scanning calorimetry.

3. A granular composition comprising citric acid / glycine cocrystal particles containing at least 5 wt. % of the cocrystal according to claim 1 or 2.

4. 4. The granular composition of claim 3, wherein the co-crystal particles contain at least 50 wt. % of the co-crystal of citric acid and glycine.

5. 4. The granular composition of claim 3, containing at least 1 wt. % of said co-crystal particles.

6. 6. The granular composition of claim 5, comprising at least 90 wt.% of said co-crystal particles.

7. 6. The granular composition of claim 5, comprising 1 to 95 wt. % of the co-crystal particles and 5 to 99 wt. % of sugar particles.

8. Volume-weighted mean diameter D of 50 to 1,200 μm ４，３ The granular composition of claim 3, having

9. The particles of the granular composition have the following particle size distribution: ・D １０ ≧10μm、 ・50μ-≦D ５０ ≦1,000μm, ・D ９０ ≦1,600μm、 and D ｘ The vol. % of particles with a smaller diameter is equal to x vol. %, and D ｘ 4. The granular composition of claim 3, wherein the vol. % of particles having a larger diameter is equal to (100-x) vol. %.

10. 4. The granular composition of claim 3, having a moisture content of less than 5 wt.%.

11. providing seed particles containing at least 50 wt. % of a crystalline material comprising an organic acid preferably selected from citric acid, malic acid, lactic acid, acetic acid, fumaric acid, adipic acid, tartaric acid, and combinations thereof; providing an aqueous solution containing citric acid and glycine in a molar ratio of 0.25 to 0.40; spraying the aqueous solution onto the seed particles to produce loaded particles; removing water from the loaded particles; 1. A process for preparing co-crystal particles comprising a co-crystal of citric acid and glycine, comprising:

12. providing an aqueous mixture containing citric acid and glycine in a molar ratio of 0.25 to 0.40 and containing 1 to 40 wt. % water; - crystallizing a co-crystal of citric acid and glycine; drying the crystallized co-crystal; 1. A process for preparing co-crystal particles comprising a co-crystal of citric acid and glycine, comprising:

13. 3. Use of particles containing at least 5 wt. % of the cocrystal of claim 1 or 2 as a food ingredient.

14. 10. A method of preparing an edible product comprising combining the granular composition of claim 3 with one or more other food ingredients.

15. 10. An edible product comprising at least 0.05 wt. % of co-crystal particles containing at least 5 wt. % of the co-crystal of claim 1 or 2.

16. 16. The edible product of claim 15, which is a confectionery product.

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