METHOD OF PREPARATION OF CHEWY CANDIES COMPRISING

CRYSTALLINE ALLULOSE PARTICLES

FIELD OF THE INVENTION

The present invention relates to confectionery products and more specifically pertains to a method of preparation of chewy candies.

BACKGROUND OF THE INVENTION

Preparation of candies

Traditionally, the primary crystallizing ingredient in candy is sugar as sucrose. It is so traditionally made of sucrose, glucose syrup, fat and gelatin. Turning the sugar into candy involves dissolving it in water, concentrating this solution through cooking, and subsequently allowing the mass either to form mutable solid or to recrystallize.

Key elements in the candy making process are in sugar's physical properties. Specifically its solubility with its effect on the water's boiling point. At room temperature, about 2 kilos of sugar will dissolve in 1 kilo of water. At higher temperatures, more sugar can be dissolved in the same amount of water. Once dissolved, however, the sugar will raise the boiling point of the solution. The result of these physical chemistry properties is a specific relationship between the solution's boiling point and the amount of sugar solids contained therein.

The first part of basic candy making, therefore, is cooking a sugar solution to a specific temperature to form a supersaturated solution with known solids content.

When this solution cools, the sugar's solubility decreases and the sugar crystallizes out of solution.

The next part of making a candy is controlling how this recrystallization takes place.

It is also known as graining.

Varying how the supersaturated syrup is physically treated while it cools controls recrystallization. Suspending a length of string into the solution and letting it slowly cool undisturbed will allow the sugar to recrystallize into large crystals on the string to form rock candy.

Cooling that same solution quickly with agitation will cause fine crystals to form and be suspended in saturated sugar syrup to become fondant. Fondant is used in confectionery creme centers. The sugar particle size could be as low as 10 μηι

Other variables can be introduced to control the size of the condense crystals and resulting to the mouthfeel/texture of the candies.

Variables might include seeding the solution with undissolved sugar crystals, changing the temperature at which agitation is begun, and adding invert sugar. The size of the added crystals during seeding serves as a pattern for the crystal size in subsequent graining and allows the confectioners to control the finished particle size.

Undissolved sugar will also seed the solution, leading to undesirable crystal formation.

Allowing condensing steam to dissolve residual sugar can prevent this.

Temperature varying of the syrup when agitation begins allows a great deal of control over grain size.

To obtain larger crystals, agitation should begin at higher temperatures.

Smaller crystals are obtained by agitating at lower temperatures. The two extremes of this range of temperatures are usually avoided to prevent the finished candy being too gritty or lacking body.

Sucrose is a disaccharide consisting of one molecule each of glucose and fructose. Breaking this bond will yield a mixture of glucose and fructose monosaccharide known as invert sugar. When invert sugar is present in a batch of candy, it tends to reduce the grain size. At higher levels, the invert sugar can even prevent crystal formation to yield a mutable sugar glass such as hard candies. Adding invert sugar allows confectioners to include the exact amount needed to control crystallization. The desired amount of invert sugar can be obtained by using invert-containing ingredients such as glucose syrup.

Chewy Candies with chewy texture can be group into two basic types:

- Ungrained candies that are candies in which the sugar isn't crystallized. These include hard candies, as well as chewy candies such as toffee and caramel.

Hard candies start with a basic sugar/ glucose syrup blend cooked down to around 2% moisture and blended with flavors and colors. Varying the ratio of sweeteners produces different textures and different stability. Cooking the basic sugar/glucose syrup blend to a moisture level between 3 to 15% forms the basis of a chewy non-grained candy. Cooking to these higher moisture levels will not favor the production of invert sugar, as is the case with hard candies.

As a result, the addition of glucose syrup is critical to prevent undesired graining in chewy candies. The key is basic sugar / glucose syrup ratio. The more sugar crystals, the softer (initial bite) and grainier the candy is. The more glucose syrup it will be chewier and sticky. Caramels, on the other hand, require milk and more fat in the formula to provide flavor and color. In caramels, the Maillard reaction that goes on with the reducing sugars and milk proteins is important for developing both flavor and color. The higher the amount of reducing sugar (higher DE) Maillard reaction will speed up.

- Grained candies that include products such as after-dinner mints, fondants/creme centers, and fudge. Grained candy formulas are similar to those of chewy candies. To promote crystallization, however, the formula must have a higher level of sugar solids and the process usually includes agitation.

The choice of sugar

Because of their taste and functional properties, the sugar like sucrose, invert sugar, glucose syrup and the like, were largely used for the preparation of such candies,

However, it is known that excess intake of these nutritive sweeteners has long been associated with diet-related health issues, such as obesity, heart disease, metabolic disorders and dental problems.

Accordingly, consumers are increasingly looking for ways to decrease the amount of nutritive sweeteners in their diets.

So, there is a need for seeking to develop replacements for nutritive sweeteners that are better able to mimic the desirable taste and functional properties of the nutritive sweeteners, but which also has low or no calories.

The lower glycemic index of polyols (also named sugar alcohols), as compared to sugars such as sucrose and glucose, makes them suitable in the management of diabetes or in weight management.

Furthermore, the well-established dental benefits of using polyols, such as maltitol, xylitol, instead of conventional sweeteners, such as sucrose (e.g., dramatic reductions in new tooth decay, arrest and, in some instances, reversal of existing dental decay) make polyols desirable for use as alternative sweeteners.

It is for this reason that confectionery manufacturers have been led to develop sugar-free combinations in which polyols are rightly used because of their harmlessness towards the teeth and of their reduced calorific value compared with sucrose.

One of the great difficulties from which formulators of sugar-free confectionery products cannot escape is that of successfully manufacturing products which are in every respect similar to traditional products to the extent that it is difficult to tell them apart, this being without having to substantially alter or complicate the plants and the procedures in place in industries.

This is also true of the confectionery products which are the subject of the present invention.

In document EP 1 .245.579, of which the assignee is proprietor, it was proposed to reduce as much as possible the quantities of polyols to be used in the preparation of such confectionery products.

This was justified for reasons of a technical nature linked to ease of manufacture but also of an economic and metabolic nature, that is to say in particular of digestive tolerance.

Furthermore, it was particularly advantageous to limit as much as possible the incorporation of polyols which indeed contain fewer calories than sugar, but contain more calories than other bulking agents which may also enter into the formulation of such confectionery products, such that, if desired, a substantially higher calorie reduction can thus be obtained.

Such low or zero sweetener should be able to be used in high amounts to provide the bulk, sweetening and functional properties of the nutritive sweeteners being replaced.

It has now been found that allulose can be used in food and beverage products at high levels to provide the required bulk, sweetening and functional properties.

D-allulose, also called D-psicose, has 70% of the relative sweetness of sucrose but a caloric value of 0.2 Kcal/g only.

It is a C-3 epimer of D-fructose, which belongs to "rare sugars". D-allulose can be produced from D-fructose by D-tagatose 3-epimerase (DTEase) family enzymes which have been found in various micro-organisms.

Moreover, D-allulose has been found to have a positive effect on the reduction of the glycemic response induced by the ingestion of maltose and sucrose (Matsuo T. et al., J. Jpn. Soc. Nutr. Food Sci. 2006; 59: 1 19-121 ).

It has already been proposed to use allulose syrup in the manufacture of candies (WO 2015/075473).

However, it remains the difficulty to make a crystallized allulose chew following the normal process established for sugar based chews.

Indeed, the technical problem is that, by using classical recipes and process, the chew becomes soft when hot (difficulty to process on chew lines), sticky and hard when cool (not complying with customer expectation).

It is due to the high solubility of allulose, and its so low speed of crystallization. Besides, the classical process on chew lines even dissolves again the crystals brought through the seeding and there is no new crystal from the cooked saturated mass.

SUMMARY

This invention is thus directed to a method of preparation of chewy candies comprising a ternary composition that comprises:

- rare sugars such as allulose, isomaltulose, tagatose, more specifically allulose,

- soluble dietary fibers such as branched maltodextrin, indigestible dextrins, saccharide oligomers, polydextrose and fructooligosaccharides, more specifically of branched maltodextrins, and

- a poorly soluble compound like:

o polyol such as mannitol erythritol, lactitol, isomalt and xylitol, more specifically mannitol, or o inorganic substances such as talc, carbonate de calcium, clay, or o starches, such as granular starch or any "good for teeth" starches, in such a way to maintain chewiness, to lower sandiness and to avoid stickiness textures.

It also pertains to a process for the manufacture of a chewy candy comprising branched maltodextrins, mannitol and crystalline allulose particles, comprising the step of increasing the quantity of crystalline allulose and/or mannitol seeds, lowering shear rate by using design of mixer limiting the residence time in mixers and lowering the temperature to avoid dissolution of crystals.

DETAILED DESCRIPTION

The present invention relates to confectionery products and more specifically pertains to a method of preparation of chewy candies, comprising a ternary composition that comprises:

- rare sugars such as allulose, isomaltulose, tagatose, more specifically allulose,

- soluble dietary fibers such as branched maltodextrin, indigestible dextrins, saccharide oligomers, polydextrose and fructooligosaccharides, more specifically of branched maltodextrins, and

- a poorly soluble compound like:

o polyol such as mannitol erythritol, lactitol, isomalt and xylitol, more specifically mannitol, or

o inorganic substances such as talc, carbonate de calcium and clay, or o starches, such as granular starch or any "good for teeth" starches, in such a way to maintain chewiness, to lower sandiness and to avoid stickiness textures.

The subject of the invention is therefore a process of preparation of chewy candies comprising a ternary composition of rare suggar, soluble dietary fiber and a poorly soluble compound, comprising:

- preparing a 40/60 to 50/50 ratio by weight of rare sugar and soluble dietary fiber blended,

- optionally, adding a poorly soluble compound in the blend in such a way to obtain a 85/15, 90/10, or 95/5 ratio by weight of rare sugar and soluble dietary fiber on one side, and poorly soluble compound on the other side,

- seeding with a 50/50 or 0/100 ratio of crystalline rare sugar particles having a mean particle size below 100 μηι and crystalline poorly soluble compound, and

- mixing time to 1 to 20 minutes, preferably to 1 to 10 minutes, at a temperature between 20°C to 45°C, preferably to 30°C to 35°C. In the context of this description, "allulose" as rare sugar refers to D-allulose or L- allulose. However D-allulose is preferred in the present invention, because it is easier to obtain.

By mean particle size is intended to refer to mean volume diameter D 4,3. Then, the crystalline allulose according to the invention preferably has mean volume diameter D 4,3 lower than 100 μιτι, preferably greater than 45 μιτι and lower than 100 μιτι.

The mean volume diameter D 4,3 of allulose is determined by means of a laser diffraction analyzer such as that marketed by BECKMAN-COULTER as "LS 230", equipped with its powder dispersion module (dry method), using the instructions for use provided by the supplier. The measurement range of the LASER diffraction granulometer type LS 230 is from 0.04 μιτι to 2000 μιτι. The operating conditions of hopper screw speed and intensity of vibration of the dispersion channel are determined in such a way that the optical concentration is between 4 percent and 12 percent, ideally 8 percent. The results are calculated as volume percent and expressed in μηι.

Crystalline allulose may be prepared as follows.

A D-allulose syrup is first obtained by epimerization of D-fructose at C-3 catalyzed by an enzyme of the D-tagatose 3-epimerase family (DTEase, EC 5.1 .3.-).

The raw material used for the epimerization may be crystalline fructose with a purity about 99%, for instance. It may be diluted with water to about 45% and magnesium chloride may be added thereto before enzymatic epimerization.

To date, at least five DTEases from different organisms have been characterized and employed for D-allulose synthesis. They are commercially available. A putative DTEase from Agrobacterium tumefaciens can also be used, and due to its high substrate specificity towards D-allulose, this enzyme was renamed as D-allulose (D-allulose) 3-epimerase (DPEase, EC 5.1 .3.-). In an embodiment, the D-allulose 3-epimerase is selected from a D- tagatose 3-epimerase from Pseudomonas cichorii, a D-allulose 3-epimerase from Agrobacterium tumefaciens, a D-allulose 3-epimerase from Clostridium sp, a D-allulose 3- epimerase from Clostridium scindens, a D-allulose 3-epimerase from Clostridium bolteae, a D-allulose 3-epimerase from Ruminococcus sp, and a D-allulose 3-epimerase from Clostridium 20 cellulolyticum.

In a preferred embodiment, the parent D-allulose 3-epimerase is a D-allulose 3- epimerase from Clostridium cellulolyticum, more particularly Clostridium cellulolyticum strain H10 (ATCC 35319). According to another embodiment, a variant of a parent D- psicose 3-epimerase is used, as described in WO 2015/032761 .

The resulting allulose syrup may then be passed through microfiltration to remove any insoluble particles, then subjected to carbon filtration to remove its color, and then to a demineralization step on an ion exchange column to further remove minerals and other impurities. The syrup can then be concentrated using a conventional evaporator, for instance. This allulose syrup may further be subjected to an enrichment step by chromatography, for instance by passing it through a chromatographic simulated moving bed (SMB) with a calcium ion exchange resin. This syrup may be further concentrated before being crystallized. Crystallization may be carried out by cooling the concentrated allulose syrup following saturation curve. After crystallization, the crystal cake may be recovered by centrifugation and then washed. The resulting allulose crystals may then be dried.

The crystalline powdered allulose may further subjected to a grinding process in order to reduce its mean particle size to less than 250 μηι, in case there are not enough particles below this mean particle size. Preferably, this grinding process is performed by continuous dry mechanical grinding. Numerous mills are available for such grinding, for instance mills equipped with blades or with rotor/stator, squirrel cage mills, oscillating, conical or cylindrical sieve mills, hammer mills and so on.

In the context of this description, "soluble dietary fibers" is understood to mean, for the purposes of the present inventions branched maltodextrin, indigestible dextrins, saccharide oligomers, polydextrose and fructooligosaccharides, more specifically of branched maltodextrins.

The expression "branched maltodextrins" is understood to mean, for the purposes of the present invention, the maltodextrins described in the document EP-A-1 ,006,128 and in its U.S. counterpart (U.S. Ser. No. 09/455,009), of which the assignee is proprietor. The branched maltodextrine could be technically replaced with any high molecular weight ingredient like glucose syrup, polyols syrup, gum arabic etc., but the goal was to create a good for teeth/polyols free concept. Thus branched maltodextrines were chosen.

For instance, the branched maltodextrins can be a commercially available product such as NUTRIOSE ^® FB06 (Roquette Freres).

The entire content of U.S. Ser. No. 09/455,009 is herein incorporated by reference. These branched maltodextrins have an indigestibility character which has the consequence of reducing their calorific value, by preventing their assimilation in the small intestine.

Their low content of molecules having a low degree of polymerization ("DP") also contributes to their low calorific value.

Their high content of 1 ->6 glucoside linkages has the consequence of reducing their cariogenic power by reducing their assimilation by the microorganisms of the buccal cavity.

This high level of 1 ->6 linkages also confers quite special prebiotic properties on them: it has indeed appeared that the bacteria of the caecum and of the colon in humans and animals, such as butyrogenic, lactic or propionic bacteria, metabolize highly branched compounds.

Moreover, these branched maltodextrins promote the development of bifidogenic bacteria to the detriment of undesirable bacteria.

This results in properties which are quite beneficial to the health of the consumer. According to a preferred variant of the present invention, the said branched maltodextrins have a reducing sugar content of between 2 and 5% and an Mn of between 2000 and 3000 g/mol and may be completely or partially hydrogenated.

In the context of this description, "indigestible dextrins" is understood to mean, for the purposes of the present invention, the indigestible dextrins described in the documents EP 530.1 1 1 or US 5,264,568.

In the context of this description, "saccharide oligomers" is understood to mean, for the purposes of the present invention, the saccharide oligomers described in the document WO 2008/085529 or WO 2009/051977.

In the context of this description, the poorly soluble polyol that means a water solubility of less than 65 g / 100 g of solution at 20°C is a polyol such as mannitol or xylitol.

Preferably, the polyol is mannitol, in a powder form, with two particle sizes:

- in the allulose and soluble dietary fiber blend, it has an average particle size of about 100 μηι (e.g., volume diameter D 4,3),

as seed, it has an average particle size of about 35 μηι (e.g., volume diameter D 4,3).

On the strength of this fact, the applicant understand that the solubility of allulose is so high and the speed of crystallization so low that this process is "re-dissolving" the crystals brought through the seeding and not creating any new crystal from the cooked saturated mass.

To solve this problem, the process of the invention manages, by adding poorly soluble polyol such as mannitol, to bring crystals in the massecuite and to create some new ones by increasing the quantity of seeding, lowering shear rate by using another design of mixer or limiting the residence time in mixers, and lowering the temperature.

This process will allow having an "acceptable for customer" chewy texture, close to the standards on the market. It will help the manufacturing of this type of chew without having to invest in line big modification, keeping process time in standards, and even potentially shortening process times. This could be also used by chew and Chewing gum producers equipped with mixers or pullers.

According to the process of the invention, a 40/60 to 50/50 ratio by weight of allulose and soluble dietary fiber was blended. For instance, the ratio by weight of allulose and soluble dietary fiber can 40/60, 45/55, 50/50 or a combination of these ranges. In a preferred embodiment, the ratio by weight of allulose and soluble dietary fiber can 45/55, or 50/50.

Optionally, a poorly soluble compound, preferably a poorly soluble polyol, more preferably mannitol, can be added in the blend in such a way to obtain a 85/15, 90/10, or 95/5 by weight of the blend of allulose and soluble dietary fiber and of a poorly soluble compound. More specifically, the ratio by weight can be 45/45/10 ratio of allulose, soluble dietary fiber and poorly soluble compound. Alternatively, the ratio by weight can be 40/50/10 ratio of allulose, soluble dietary fiber and poorly soluble compound.

Preferably, before the seeding step, fat and optionally lecithin are added and the mixture is mixed. In particular, fat is present at a percentage of about 3-7 % by weight of the total candy weight, preferably about 5 %. Lecithin can be present at a percentage of about 0.1 % by weight of the total candy weight.

The blend is seeded with a 50/50 or 0/100 ratio of crystalline allulose particles having a mean particle size below 100 μηι and poorly soluble compound, preferably a poorly soluble polyol, more preferably mannitol, and the mixing time to 1 to 20 min, preferably 1 to 10 minutes, at a temperature between 20°C to 45°C, preferably to 30°C to 35°C. More preferably, the mixing time is less than 10 minutes, more preferably less than 5 minutes, still more preferably about 1 minute.

When crystalline allulose particles and poorly soluble compound are used in the seeding step, then the crystalline allulose particles and the poorly soluble compound can be either added in the same step or in two different steps.

In a particular aspect, a gelatin solution is added to the mixture between the two different steps of adding crystalline allulose particles and poorly soluble compound. In another particular aspect, gelatin is a gelatin solution is added to the mixture before adding crystalline allulose particles and/or poorly soluble compound. In particular, the gelatin solution present at a percentage of about 1 % by weight of the total candy weight.

Flavor and/or citric acid can be added at any step. Preferably, the addition is performed after the crystalline allulose addition.

By "about" is intended to refer the value more or less 10 % of the value, preferably more or less 5 %. More instance, about 100 means between 90 and 1 10, preferably between 95 and 105.

EXAMPLES

This invention will be better understood in light of the following example which is given for illustrative purposes only and does not intend to limit the scope of the invention, which is defined by the attached claims. Example 1 :

Four recipes are tested:

- Recipe 1 : blend of branched maltodextrin NUTRIOSE® FB06 and allulose seeded with a mix of allulose and mannitol P35 (SweetPearl® P 35). Single mixing.

Note: DS = Dry solids

TDS = Total Dry Solids

Fp = Finished product

Preparation:

- Add NUTRIOSE ^® FB06 and allulose in the pan with water

- cook up to evaporate the needed water

- add fat (and lecithin), mix strongly till the fat is totally incorporated into the cooked mass

- cool on marble down to 35°C

- add into Zarm (jacketed at 35°C) + Allulose powder

- add the gelatin solution

- add mannitol P35 powder (SweetPearl® P 35)

- run for 15 min with lead on

- add flavor + acid , run for 1 min and empty

- Recipe 2: blend of branched maltodextrin NUTRIOSE® FB06 and allulose seeded with a mix of allulose and mannitol P35 (SweetPearl® P 35). Puller. %DS Ingredient %DS/TDS %DS/Fp

NUTRIOSE ^® FB06 from ROQUETTE

97 FRERES 41 ,89 39,17

99 Allulose 31 ,29 29,26

100 Fat AAK Cebes 20 21 4,50 4,21

100 Lecithin 0,12 0,1 1

40 Gelatin 150BI Gelita 1 ,00 0,94

100 Anhydrous Citric acid 0,71 0,66

100 Flavor 0,49 0,46

99 thin Allulose crystals < 100μηι 10,00 9,35

99 Mannitol P35 (SweetPearl® P 35) 10,00 9,35

Water 0,00 6,5

Total : 100,00 100,00

Preparation:

- Add NUTRIOSE ^® FB06 and allulose in the pan with water

- cook up to evaporate the needed water

- cool down a bit in the pan

- add fat (and lecithin) in a planetary mixer

- add the gelatin solution

- add flavor + acid , run for 1 min

- add all the powders (allulose and mannitol P35)

- empty the mixer and cool on the marble to 35°C

- pull for 1 min on pulling machine

- cool down and form - Recipe 3: blend of branched maltodextrin NUTRIOSE® FB06, allulose and mannitol seeded with 3 % mannitol (SweetPearl® P 35). Puller.

%DS Ingredient %DS/TDS %DS/Fp

97 NUTRIOSE ^® FB06 41 ,89 39,17

99 Allulose 41 ,29 38,61

99 Mannitol powder P100 7,00 6,55

100 Fat AAK Cebes 20 21 4,50 4,21

100 Lecithin 0,12 0,1 1

40 Gelatin 150BI Gelita 1 ,00 0,94

100 Anhydrous Citric acid 0,71 0,66

100 Flavor 0,49 0,46

99 thin Allulose < 100μηι 0,00 0,00

99 Mannitol P35 (SweetPearl® P 35) 3,00 2,81

Water 0,00 6,5

Total : 100,00 100,00 Preparation:

- Add NUTRIOSE ^® FB06, allulose and Mannitol P100 in the pan with water

- cook up to evaporate the needed water

- cool down a bit in the pan

- add fat (and lecithin) in a planetary mixer

- add the gelatin solution

- add flavor + acid , run for 1 min

- add the Mannitol P35 powder

- empty the mixer and cool on the marble to 35°C

- pull for 1 min on pulling machine

- cool down and form

- Recipe 4: blend of branched maltodextrin NUTRIOSE® FB06, allulose and mannitol seeded with 1 % mannitol (SweetPearl® P 35). Puller.

Preparation:

- Add NUTRIOSE ^® FB06, allulose and Mannitol P100 in the pan

with water

- cook up to evaporate the needed water

- cool down a bit in the pan

- add fat (and lecithin) in a planetary mixer

- add the gelatin solution

- add flavor + acid , run for 1 min

- add the Mannitol P35 powder

- empty the mixer and cool on the marble to 35°C

- pull for 1 min on pulling machine

- cool down and form

Each of the four recipes was tested for their stickiness, cold flow, sandiness, chewiness and hardness by a panel of 15 people.

The tests are carried out according to the standard AFNOR V 09-014 (April 1982) on recipes 1 to 3 per group of 5 or 6 samples per test.

The 5 or 6 samples were presented simultaneously, a different order of tasting being stipulated for each member of the panel.

The descriptor stipulated, namely the stick nature in the mouth, is evaluated on a 4-point scale graded in the following way: absence, slight, pronounced, very pronounced.

The analysis of variance (Friedman's ANOVA) distinguishes the samples with regard to their gritty natures (p«0.05). The values obtained are shown in following table.

Conclusion:

- The products of Recipe 1 and 2 are less shiny and sticky but become harder with time, their texture is sandy, they have limited cold flow;

- The texture of the product of Recipe 3 is less sandy. It has no cold flow.

- The product of Recipe 4 has limited sandiness, no cold flow and increased chewiness.

Some more recipes have been tested in comparison to recipe 3 with Xylitol, Erythritol, Isomalt, talc and waxy starch.