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    • 专利摘要:
    The invention relates to a D-allulose syrup comprising, in addition to D-allulose, a mass content of D-allulose dimer expressed in dry mass of less than 1.5%. The invention also relates to a process for the manufacture of this syrup as well as to the use of this syrup for the manufacture of food or pharmaceutical products.
    公开号:FR3061414A1
    申请号:FR1750104
    申请日:2017-01-05
    公开日:2018-07-06
    发明作者:Baptiste Boit；Geoffrey LACROIX
    申请人:Roquette Freres SA；
    IPC主号:
    专利说明:

    © Agent (s): CABINET PLASSERAUD.
    (54) CRYSTALLIZABLE D-ALLULOSE SYRUPS.
    (57) The invention relates to a D-allulose syrup comprising, in addition to D-allulose, a mass content of D-allulose dimer expressed in dry mass less than 1.5%. The invention also relates to a method of manufacturing this syrup as well as to the use of this syrup for the manufacture of food or pharmaceutical products.
    FR 3,061,414 - A1
    i
    Field of the invention
    The invention relates to a D-allulose syrup, one of the advantageous properties of which is that it is more easily crystallizable than the syrups of the prior art. Another subject of the invention relates to the use of this D-allulose syrup for the manufacture of food or pharmaceutical products. Another subject of the invention relates to a process for manufacturing this D-allulose syrup.
    Prior art
    D-allulose (or D-psicose) is a rare sugar with a sweetening power equal to 70% of that of sucrose. Unlike the latter, D-allulose does not cause weight gain because it is not metabolized by humans. It has a very low caloric value (0.2 kcal per gram) and it thus prevents fat gain. In addition, studies have shown that D-allulose is non-cariogenic, even anti-cariogenic. These properties have recently generated considerable interest from the food and pharmaceutical industries.
    D-allulose is generally obtained by the enzymatic route, by reacting an aqueous solution of D-fructose with a D-psicose epimerase as described for example in application WO2015 / 032761 A1 in the name of the Applicant. Whatever the enzyme used, the reaction is not complete and the amount of fructose transformed into D-allulose after epimerization is less than 30%.
    Thus, if it is desired to obtain a composition having a mass content, expressed in dry mass, richer in D-allulose, it is necessary to carry out a step of separation of D-allulose, this in order to isolate it from the other constituents present and in particular fructose. To carry out this separation, a very generally chromatography of the composition resulting from the epimerization reaction, for example by continuous chromatography of simulated moving bed type, which allows to isolate a fraction rich in D-allulose.
    Document JP2001354690 A describes a process for purifying a Dallulose composition starting from a mixture of fructose and D-allulose, said process comprising a separation step consisting of a continuous chromatography step using a particular sequence of samples from the different mix products. A fraction rich in D-allulose (whose richness in D-allulose can reach 98%) and a fraction rich in fructose are recovered. The recovery yield in the fraction rich in D-allulose is 96%.
    At the end of the separation steps cited above, liquid compositions rich in Dallulose are obtained. This is how these liquid compositions, generally called syrups, are used for the manufacture of food or pharmaceutical products. For example, application WO 2015/094342 also in the name of the Applicant describes the manufacture of solid food products comprising a D-allulose syrup, comprising from 50 to 98% D-allulose and a native protein. It is mainly in this form of syrups that various companies have announced the marketing of D-allulose to date.
    Document WO 2016/135458 describes syrups comprising, with respect to its dry mass, at least 80% of allulose and studies their stability over time. No manufacturing protocol for this syrup is described. The composition of the syrups is analyzed by high performance liquid chromatography, which is presented as the standard method used to analyze this type of syrup. The syrups described in this application are presented as having a weakly crystallizable nature.
    However, for certain applications, there may be an advantage in using a D-allulose syrup capable of crystallizing more easily. This is particularly the case for the manufacture of cookies where the use of a crystallizable syrup allows the production of more crisp cookies. Another example relates to the manufacture of short-textured chews where the use of a crystallizable syrup is necessary in order to obtain the short mouth texture characteristic of these chews. A more crystallizable syrup can also increase the hardness of chewing gum and thus improve the texture in the mouth when chewing or increase the hardness of long-textured caramels.
    It is by conducting numerous researches that the Applicant has been able to observe that, in a process for the manufacture of D-allulose syrups, particular impurities are formed during the process. To the best of the Applicant's knowledge, these have never been reported in the literature. They have been identified by the Applicant, using a particular technique of gas phase chromatography, as being dimers of D-allulose. The Applicant has also been able to show that these dimers, unlike other impurities such as glucose or fructose, have a very significant anti-crystallizing effect. However, as these dimers of D-allulose are formed during the process, their presence in the syrup of D-allulose is systematic, and this even if all the precautions have been taken during its manufacture. This makes the syrup weakly crystallizable and thus limits their uses, especially in the above-mentioned applications.
    Going beyond this observation, the Applicant has also continued its efforts to provide new syrups with a crystallizable character which are greater than those of the prior art. To do this, it has developed a special process that allows it to largely remove these impurities from D-allulose syrups.
    Summary of the invention
    The subject of the invention is therefore a D-allulose syrup comprising, in addition to D-allulose, a mass content of D-allulose dimer, determined by gas phase chromatography (GPC), of less than 1.5%.
    This syrup has the advantage of being more crystallizable than the syrups of the prior art with the same dry matter and D-allulose content. This allows advantageous uses, in particular for the manufacture of cookies or chewy dough.
    Another object of the invention on a method for manufacturing the syrup of the invention which comprises:
    • a step of supplying an aqueous composition of D-allulose comprising dimers of D-allulose;
    • a nanofiltration step of said D-allulose composition to provide a retentate and a permeate;
    • a step of recovery of the nanofiltration permeate;
    • a step of concentrating this permeate to provide the D-allulose syrup.
    The use of a nanofiltration step makes it possible to recover a permeate almost free or even free of D-allulose dimer and thus obtain, after the concentration step, the syrup of the invention.
    As mentioned above, the Applicant has noted that, systematically, during the manufacture of D-allulose syrups, particular impurities are formed during the process. To the best of the Applicant's knowledge, these have never been reported in the literature. This is explained by the fact that, by the high performance liquid chromatography technique conventionally used to measure the purity of D-allulose, these impurities are not detected on the chromatograms (see Figures 4 and 5). It is by using a gas chromatography technique that the Applicant has been able to detect their presence (see Figures 6 and 7).
    Another subject of the invention relates to the use of the syrup of the invention for the manufacture of food or pharmaceutical products.
    Brief description of the Figures
    Figure 1: Figure 1 shows the circuit for producing a crystallizable allulose syrup.
    Figure 2: Figure 2 shows a circuit for the production of a crystallizable allulose syrup with recycling loops.
    Figure 3: Figure 3 shows the permeation curve for the nanofiltration step, that is to say the flow rate as a function of the volume concentration factor.
    Figure 4: Figure 4 shows an HPLC chromatogram of a composition rich in Dallulose taken in the process of the invention, before nanofiltration.
    Figure 5: Figure 5 shows an HPLC chromatogram of a permeate taken in the process of the invention, that is to say after nanofiltration.
    Figure 6: Figure 6 shows a GPC chromatogram, in the characteristic area of dimers, of a composition rich in D-allulose taken in the process of the invention, before nanofiltration.
    Figure 7: Figure 7 shows a GPC chromatogram, in the characteristic region of dimers, of a permeate taken in the process of the invention, that is to say after nanofiltration.
    Figure 8: Figure 8 shows the dry matter of the supernatant of a D-allulose syrup after 1 month of storage at 4 and 15 ° C depending on the content of D-allulose dimers.
    Detailed description of the invention
    The D-allulose syrup of the invention is an aqueous solution which is depleted in D-allulose dimers. By "aqueous composition" or "aqueous solution" is generally meant a composition or solution in which the solvent consists essentially of water. By “D-allulose dimer” is meant a compound comprising a D-allulose condensed with at least one second identical or different monosaccharide. These dimers are, for example, dimers of the D-allulose-D-allulose type.
    As described above, the fact that the amount of D-allulose dimers included in the syrup is depleted, ie that its mass content expressed in dry mass is less than 1.5% according to the invention, has made it possible to obtain a syrup more crystallizable.
    These dimers could be detected by CPG and could not be detected during the HPLC analysis, as shown in Figures 4 to 7. It follows that the mass quantities of the various constituents, expressed in dry mass, are in the present request systematically determined by CPG. To determine the amounts of each of the species in the composition, the sample generally undergoes a processing step in order to transform the various species present into methoxime trimethylsilylated derivatives. The mass quantities of each of the species are expressed in this Request, unless otherwise stated, relative to the total dry mass.
    The amounts of glucose, fructose and allulose can be determined in a gas chromatograph equipped with an injector heated to 300 ° C., a flame ionization detector (FID) heated to 300 ° C. and equipped with a DB1 capillary column of 40 meters, having an internal diameter of 0.18 mm and a film thickness of 0.4 μm, the temperature of the column being programmed as follows: from 200 ° C. to 260 ° C. at the right rate from 3 ° C / min, then from 260 ° C to 300 ° C at 15 ° C / min, holding at 300 ° C for 5 min.
    By quantity of dimers of D-allulose means the difference between the total quantity of dimers in a sample, determined by GPC, and the quantity of known dimers possibly present, which are glucose-glucose dimers such as maltose and isomaltose. However, the quantity of these glucose-glucose dimers is generally very low, even non-existent. For example, in the syrup of the invention, the mass amount of glucose-glucose dimers is generally less than 0.2%, often less than 0.1%.
    The possible amount of glucose-glucose dimers can be determined under the same conditions as those described above for glucose, fructose and D-allulose:
    • by carrying out a hydrolysis of the glucose-glucose dimers of the sample;
    • by determining the amount of total glucose in the same chromatograph and under the same conditions, said total glucose comprising the initial so-called free glucose and the glucose resulting from the hydrolysis of the glucose-glucose dimers;
    • by subtracting from this amount of total glucose the amount of initial glucose from the sample.
    The total amount of dimers can be determined in a gas chromatograph under the same conditions as described above, with the difference that the column used is a 30-meter capillary DB1 column, having an internal diameter of 0.32 mm and a film thickness of 0.25 μm and the temperature of the column is programmed as follows: from 200 ° C. to 280 ° C. at a rate of 5 ° C./min, holding at 280 ° C. for 6 min, then from 280 ° C to 320 ° C at 5 ° C / min, holding at 320 ° C for 5 min.
    The method is described in more detail in the Examples section.
    The D-allulose syrup comprises, in addition to the D-allulose, a mass content of D-allulose dimer, determined by gas phase chromatography (GPC), of less than 1.5%. The D-allulose syrup of the invention may have a mass content of D-allulose dimer ranging from 0.1 to 1.4%, advantageously ranging from 0.2 to 1.3%, preferably ranging from 0, 3 to 1.2%.
    D-allulose syrup has an even more crystallizable character when its D-allulose content expressed as dry mass is greater than or equal to 75%. It may have a D-allulose content expressed in dry mass greater than or equal to 80%, for example greater than or equal to 85%, in particular greater than or equal to 90%. The higher the Dallulose content expressed in dry mass, the more the syrup can be crystallized.
    The D-allulose syrup can advantageously comprise, relative to its dry mass:
    • from 75 to 99% of D-allulose;
    • from 0 to 25% of D-fructose;
    • 0 to 10% glucose;
    • from 0 to 1.5% (limit excluded) of D-allulose dimer, for example ranging from 0.1 to 1.4%, advantageously ranging from 0.2 to 1.3%, preferably ranging from 0.3 at 1.2%.
    The D-allulose syrup can have a dry matter greater than 50%, for example ranging from 65 to 85%, in particular ranging from 70 to 83%, for example from 75 to 82%. The greater the dry matter, the more easily the syrup can be crystallized. However, when the dry matter is high, the viscosity of the syrup may increase, which can lead to difficulties in handling it.
    A D-allulose syrup is conventionally obtained by a process comprising:
    • a step of supplying an aqueous composition comprising D-allulose;
    • a step of concentrating said aqueous composition to form the Dallulose syrup.
    The syrup of the invention can be produced according to a process described in detail below, which comprises, before the concentration step, a nanofiltration step.
    This nanofiltration step makes it possible to limit the amount of D-allulose dimers in the syrup of the invention. This nanofiltration step takes place before the concentration step of the composition rich in D-allulose. This step therefore makes it possible to supply a Dallulose syrup, the content of D-allulose dimers of which is lower than that obtained from the same process not using this nanofiltration step.
    In the nanofiltration step, which is essential to the process of the invention, two fractions are formed when a D-allulose composition is subjected to nanofiltration:
    • a permeate, which is depleted in D-allulose dimers;
    • as well as a retentate, which is enriched in D-allulose dimers.
    In Figure 1 which represents a syrup production circuit of the invention, Flux 6 represents the permeate and Flux 9 represents the retentate. For illustrative but non-limiting reasons, unless otherwise indicated, the flows indicated in the following description refer to the flows in the production circuit of this Figure 1.
    The nanofiltration permeate is an intermediate allowing the manufacture of this mother solution.
    The terms “depleted in D-allulose dimers” and “enriched in D-allulose dimers” are obviously relative with respect to the content of D-allulose oligomers in the composition to be nanofiltrated.
    The nanofiltration permeate is an intermediate allowing the manufacture of the Dallulose syrup of the invention.
    An object of the invention therefore relates to a syrup manufacturing process which comprises:
    • a step of supplying an aqueous composition of D-allulose comprising dimers of D-allulose;
    • a nanofiltration step of said D-allulose composition to provide a retentate and a permeate;
    • a step of recovery of the nanofiltration permeate;
    • a step of concentrating this permeate to provide the D-allulose syrup of the invention.
    To carry out the nanofiltration step useful for the invention, the composition to be nanofiltrated is passed over a nanofiltration membrane. It generally has a dry matter ranging from 5 to 15%.
    The temperature of this composition to be nanofiltered can range from 10 to 80 ° C., generally from 15 to 50 ° C., often around 20 ° C.
    Those skilled in the art will know how to choose the membrane useful for this separation. This nanofiltration membrane may have a cutoff threshold of less than 300 Da, preferably ranging from 150 to 250 Da. Ideally, the membrane has a MgSO4 rejection rate of at least 98%. It can in particular be a Dairy DK or Duracon NF1 type membrane manufactured by GE®.
    The pressure applied to the membrane can also vary widely and can range from 1 to 50 bars, preferably from 5 to 40 bars, most preferably from 15 to 35 bars.
    This nanofiltration step can be accompanied by a diafiltration phase.
    Preferably, the volume concentration factor (FCV) of the nanofiltration ranges from 2 to 20. This volume concentration factor is easily adjusted by a person skilled in the art.
    This nanofiltration step can be carried out continuously.
    At the end of this nanofiltration step, the permeate recovered can comprise, relative to its dry mass, from 0 to 1.2% of D-allulose dimers, for example from 0.05 to 1.0%, in particular from 0.1 to 0.5%.
    It goes without saying that the method according to the invention may include other steps, such as the other steps appearing in the conventional method described above and which will be described in detail later. The method according to the invention can also include additional purification steps and also intermediate dilution or concentration steps in order to regulate the dry matter and thus carry out under the best conditions the different steps of the method of the invention. All of these steps can be carried out continuously.
    The syrup of the invention generally has a dry matter greater than or equal to 50%. To increase the dry matter (the permeate has a dry matter lower than 50%), it is necessary to perform a concentration step, during which the content of D-allulose dimers can increase. Since the formation of D-allulose dimers also occurs during this concentration step, it is preferable to select conditions which make it possible to limit the amounts formed in these dimers. The concentration step is thus generally carried out under vacuum, for example at a pressure of 5 to 100 mbar, preferably ranging from 20 to 70 mbar. This vacuum reduces the temperature required for evaporation and reduces the duration of this concentration step. It can be carried out at a temperature ranging from 30 to 80 ° C., advantageously from 34 to 70 ° C., preferably from 37 to 50 ° C. This concentration step can be carried out in a single-stage evaporator, a multiple-stage evaporator, for example a double-stage evaporator. At the end of the concentration step, the D-allulose syrup of the invention can be obtained. It contains a Dallulose dimer content of less than 1.5%. Generally, the syrup of the invention comprises from 0 to 1.2% of D-allulose dimers, for example from 0.1 to 1.2%, in particular from 0.2 to 1.0% or also from 0, 3 to 0.8%.
    The method of the invention further comprises a step of providing an aqueous D-allulose composition comprising dimers of D-allulose. The mass contents of the various constituents of the syrup (and in particular D-allulose, D-fructose and any glucose) are mainly determined by the contents of each of these constituents included in the aqueous composition of D-allulose supplied. For example, if the aqueous composition of D-allulose provided has a high content of D-allulose, the permeate and the syrup obtained from this permeate also have a high content of D-allulose.
    A conventional process for manufacturing a D-allulose composition comprising D-allulose dimers comprises:
    • a step of supplying a D-fructose solution;
    • a step of epimerization of said solution to form a Dallulose composition, comprising D-fructose and D-allulose;
    • optionally a chromatography step to enrich the D-allulose composition with D-allulose;
    • a step of concentrating the composition, possibly enriched, with Dallulose.
    Thus, according to the method of the invention, to provide the composition of D-allulose, a step of chromatography of a composition comprising D-allulose and Dfructose can be carried out. In this case, this composition comprising D-allulose and D-fructose is advantageously obtained by epimerization of a D-fructose solution.
    The D-allulose composition obtained after the chromatography step, which has a higher D-allulose content than that of the composition obtained at the end of the epimerization step, comprises D-allulose dimers. In addition to this Dallulose composition, a composition rich in D-fructose or "raffinate" is also formed during this chromatography step.
    The composition of D-fructose supplied (Flux 1) for carrying out the epimerization step can be a D-fructose syrup, which can be obtained by dissolving D-fructose crystals in water or a glucose syrup / D-fructose. Preferably, this composition comprises a glucose / D-fructose syrup which comprises at least 90% by dry weight of D-fructose, preferably at least 94% of D-fructose.
    In a mode represented in FIG. 2, the composition of D-fructose supplied for carrying out the subsequent epimerization step is a mixture (Flux 1 ′) of this D-fructose syrup with at least one recycled fraction which can be the raffinate (all or part of the raffinate) (Flux 10 or 12), this recycled fraction possibly comprising a higher quantity of Dallulose.
    The composition of D-fructose subjected to the epimerization step can include:
    • from 0 to 10% of D-allulose;
    • from 70 to 100% D-fructose;
    • 0 to 10% glucose;
    • from 0 to 15% of D-allulose dimer.
    The epimerization step is carried out using the D-fructose composition provided previously, possibly after adjusting the dry matter. This step is generally carried out with a dry matter ranging from 30 to 60%, often from 45 to 55%. A D-psicose epimerase type enzyme or a composition comprising this enzyme is introduced into this composition. The composition comprising this enzyme can be a lyophilisate of a host microorganism synthesizing D-psicose epimerase, the latter possibly being Bacillus subtilis, in particular that described in application WO2015 / 032761 A1. The pH is adjusted according to the enzyme used, for example at a pH ranging from 5.5 to 8.5. The reaction can be carried out by heating at a temperature ranging from 40 to 70 ° C, often from 45 to 60 ° C. The reaction can last from 0.1 to 100 hours, for example from 0.2 to 60 hours. This reaction can for example be carried out on an enzymatic column, which has the advantage of also working continuously on this step. It is also possible to operate continuously to work sequentially with several reactors. To carry out this epimerization step, it is possible in particular to use the teaching of document WO 2015/032761 A1.
    At the end of the reaction, a composition is formed comprising D-fructose and Dallulose, generally according to a D-fructose / D-allulose mass ratio ranging from 85/15 to 55/45, often according to a D-fructose mass ratio. / D-allulose ranging from 80/20 to 60/40. This ratio depends on the epimerization parameters used and, of course, on the amount of
    D-allulose and D-fructose in the composition of D-fructose provided in the epimerization step; the amount of D-allulose in this composition can be in particular greater in the event of recycling.
    At the end of this epimerization step, if necessary, a filtration step can be carried out to recover any cellular debris that may be present, especially when a lyophilisate from a host microorganism is used. This step may consist of a microfiltration step. The microfiltered composition corresponds to Flux 3 and the cellular debris is recovered in Flux 8.
    In the process of the invention, additional purification steps can also be carried out. Generally, before the chromatography step, a demineralization step of the composition comprising D-fructose and D-allulose (Flux 3) is carried out which can be carried out by passing over one or more cationic ion exchange resins (by for example a cationic resin of the Dowex 88 type), anionic (for example an anionic resin of the Dowex 66 type) and a cationic-anionic mixture. In Figure 3, this composition corresponds to Flux 4. The composition comprising D-fructose and Dallulose obtained is then demineralized and generally has a resistivity greater than 100 kQ.crri 1 . It is also possible to carry out, before this demineralization step, a step of bleaching the composition comprising D-fructose and D-allulose, for example by passing over a column comprising active carbon.
    The composition comprising D-fructose and D-allulose (Flux 4) can then be subjected to a chromatography step to provide at least one composition rich in D-allulose and one composition rich in D-fructose. In a preferred mode which will be explained in detail later in the description, the composition comprising D-fructose and D-allulose subjected to the chromatography step is a mixture (Flux 4 ′) of the composition resulting from the step epimerization (Flux 4) and at least one recycled fraction, this recycled fraction possibly comprising a higher amount of D-allulose.
    The composition subjected to the chromatography step can comprise, relative to its dry mass:
    • from 22 to 45% of D-allulose, generally from 23 to 37%;
    • from 45 to 75% of D-fructose, generally from 46 to 70%;
    • 0 to 10% glucose;
    • from 2 to 10% of D-allulose dimer.
    To carry out this chromatography step, any type of continuous chromatography can be used, in particular of the simulated moving bed chromatography type.
    SMB), of type Improved Simulated Moving Bed (ISMB), of type Divide Improved Simulated Moving Bed (DISMB), of type Sequential Simulated Moving Bed (SSMB) or of type Nippon Mitsubishi Chromatography Improved (NMCI). Water is generally used as the eluent. The chromatography can be equipped with several columns in series, for example from 4 to 8 columns. The columns include ion exchange resin, for example a cationic calcium ion exchange resin. The dry matter of the composition comprising D-fructose and D-allulose can range from 40 to 70%, generally is about 50%. The temperature of the composition during chromatography generally ranges from 40 to 80 ° C, preferably from 55 to 65 ° C. This chromatography lasts the time to obtain a satisfactory separation and can last several hours.
    At the end of this step, a composition rich in D-allulose (Flux 5) is obtained which can comprise, with respect to its dry matter, at least 80% of D-allulose, advantageously at least 90% of D-allulose. This composition rich in D-allulose can have a dry matter ranging from 5 to 15%. A raffinate (Flux 10) is also obtained at the end of this step, which generally comprises, relative to its dry matter, at least 75% of Dfructose, often at least 80% of D-fructose. This raffinate generally has a dry matter ranging from 15 to 30% approximately.
    The method according to the invention may comprise a step of recycling at least part of the nanofiltration retentate (Flux 9 in FIG. 2) and / or the raffinate (Flux 10 in FIG. 2). These recycling operations are likely to increase the amount of D-allulose dimers in the various compositions prior to the nanofiltration step.
    The composition rich in D-allulose obtained at the end of the chromatography (Flux 5) can thus comprise, relative to its dry mass:
    • from 80 to 98% of D-allulose;
    • from 0 to 20% of D-fructose;
    • 0 to 10% glucose;
    • from 0.5 to 5% of D-allulose dimer.
    The raffinate (Flux 10) can comprise, in relation to its dry mass:
    • from 1 to 10% of D-allulose;
    • from 70 to 99% of D-fructose;
    • 0 to 10% glucose;
    • from 1.3 to 20% of D-allulose dimer.
    The amounts of the various constituents of the D-allulose syrup of the invention can be easily adjusted by a person skilled in the art by choosing the composition of the Dfructose solution used, the parameters of the epimerization step as well as the parameters of the chromatography step. Their choice makes it possible to supply the aqueous Dallulose composition comprising D-allulose dimers useful for the invention and can thus determine the final D-allulose, D-fructose and glucose contents in the syrup of the invention. It is possible to enrich certain constituents for example by adding to the permeate compositions whose purity in these constituents is greater than that of the permeate, in liquid or solid form. For example, D-fructose crystals can be added to increase the D-fructose content in the syrup.
    The syrup of the invention can be advantageously used for the manufacture of food or pharmaceutical products. It can be used in known applications of fallulose and, in general, sweeteners. Among the applications which can advantageously use the more crystallizable nature of the D-allulose syrup according to the present invention, mention may be made of chewing gum in the form of tablets or dragees, long-textured caramels, candies and sucking tablets, cookies, cookies, muffins, cakes, gelatin-based cakes, chews, especially short-textured chews.
    The invention will now be illustrated in the Examples section below. It is specified that these Examples are not limitative of the present invention.
    Examples
    Analytical methods
    Gas chromatography
    The gas chromatograph used is of the Varian 3800 type and is equipped with:
    A split-splitless injector (with or without dividers);
    - A flame ionization detector (FID);
    - A computer system for processing the detector signal;
    An automatic sampler (type 8400).
    The different quantities are determined by gas chromatography in the form of trimethylsilylated methoxime derivatives, then quantified by the method of internal calibration.
    Determination of D-allulose, D-fructose and glucose contents
    The response coefficients applied are 1.25 for D-allulose and D-fructose and 1.23 for glucose. The other monosaccharides were not detected.
    Sample preparation
    In a tare box, weigh 100 to 300 mg of the test sample + 10 ml internal standard solution consisting of methyl o-D-glucopyranoside 0.3 mg / ml in pyridine. In a 2 ml cup, take 0.5 ml from the tare box and evaporate to dryness under a stream of nitrogen. Add 20 mg of methoxylamine hydrochloride and 1 ml of pyridine. Stopper and leave in the Reacti-therm ® type incubation system at 70 ° C for 40 min. Add 0.5 ml of N, O Bis (trimethylsilyl) trifluoroacetamide (BSTFA). Heat 30 min at 70 ° C.
    Chromatographic conditions
    Column: capillary DB1 40 meters, internal diameter 0.18 mm, film thickness 0.4 pm, made of 100% dimethylpolysiloxane, non-polar (J&W Scientific ref.: 121-1043)
    Column temperature: 100 ° C programming up to 260 ° C at a rate of 3 ° C / min, then up to 300 ° C at 15 ° C / min, maintain 5 min at 300 ° C.
    Injector temperature: 300 ° C
    Detector temperature: 300 ° C (Range 10 12 )
    Pressure: 40 psi (constant flow)
    Carrier gas: Helium
    Injection mode: Split (Split flow rate: 100 ml / min)
    Volume injected: 1, ΟμΙ
    D-allulose, D-fructose and glucose were detected in this order. D-allulose, which was unknown, has a retention time under these conditions of between 39.5 and 40 minutes.
    Determination of the contents of dimers of D-allulose and of dimers c / lucose-c / lucose
    The response coefficients applied are 1.15 for the dimers of D-allulose and maltose, and 1.08 for isomaltose. The other glucose dimers were not detected.
    Sample preparation:
    In a tare box, weigh 100 to 300 mg of the sample to be tested + 10 ml internal standard solution consisting of Phenyl beta-D -glucopyranoside at 0.3 mg / ml in pyridine.
    In a 2 ml cup, take 0.5 ml from the tare box and evaporate to dryness under a stream of nitrogen.
    Take up with 0.5 ml of the hydroxylamine hydrochloride solution at 40 g / l in pyridine, stopper, shake and leave for 40 min at 70 ° C.
    Add 0.4 ml of BSTFA and 0.1 ml of N-Trimethylsilylimidazole (TSIM). Heat 30 min at 70 ° C.
    Chromatographic conditions
    Column: capillary DB1 30 meters, internal diameter 0.32 mm, film thickness 0.25 pm (J&W Scientific ref.: 123-1032)
    Column temperature: 200 ° C programming up to 280 ° C at a rate of 5 ° C / min (maintain 6 min), then up to 320 ° C at 5 ° C / min, maintain 5 min at 320 ° C.
    Injector temperature: 300 ° C
    Detector temperature: 300 ° C (Range 10 12 )
    Pressure: 14 psi (constant flow)
    Carrier gas: Helium
    Injection mode: Split (Split flow rate: 80 ml / min)
    Injected volume: 1.2μΙ
    Expression of results:
    The content of the various constituents is expressed in g per 100 g of crude product and is
    given by the following equation:Yes Pe 100 % constituent i = ------ xx ----Se P Ki
    With:
    Si = area of constituent peak (s) i
    Se = area of the internal standard peak
    Pe = Weight of internal standard introduced into the beaker (in mg)
    P = weight of sample weighed (in mg)
    Ki = response coefficient of component i
    If the percentage obtained (expressed here in gross) exceeds 20% for one of the constituents, the sample is diluted and the CPG analysis recommenced in order to obtain a mass quantity of less than 20%.
    The mass quantities expressed in crude are then expressed in dry, dividing for the dry matter of the sample tested.
    The mass amounts of D-allulose, D-fructose and glucose are easily determined, none of the characteristic peaks being co-eluted.
    The maltose peak and D-allulose dimers can be co-eluted. It should be noted, however, that in the syrups of the invention and described in the examples below, maltose is never present.
    If the characteristic maltose peaks are not detected, the surface area of Dallulose dimers is determined by integration of the unknown peaks, between 10 and 17 minutes. If the characteristic peaks of maltose are detected (which may be the case in the syrups of the invention), the amounts of maltose are determined and this amount is subtracted from the total amount of dimers.
    To determine the total amount of glucose-glucose dimers, the following protocol is carried out on a sample:
    • Hydrochloric hydrolysis
    In a 15 ml hydrolysis tube with a Teflon screw cap, weigh approximately 50 to 500 mg of sample approximately (adjust the weighing according to the expected sugar content), add 2 ml with a two-pipette pipette of the solution d internal standard (galactitol 5 mg / ml in RO water), add 3 ml of water and 5 ml of the 4N HCl solution.
    Seal tightly, shake for 1 min with the Vortex shaker. Place the tube in a thermostatically controlled dry bath regulated at 100 ° C for 1 hour, stirring occasionally with a vortex.
    • Demineralisation and concentration
    After cooling, place the entire hydrolysis in a 50 ml beaker. Add 6 to 8 g of a 50/50 mixture of anionic resin AG4 X 4 and AG50 W 8. Leave under magnetic stirring for 5 minutes. Filter on paper. Recover the juice and repeat the demineralization stage until a pH close to water is obtained.
    • Sample preparation
    In a tare box, weigh 100 to 300 mg of the test sample + 10 ml internal standard solution consisting of methyl α-D-glucopyranoside 0.3 mg / ml in pyridine.
    In a 2 ml cup, take 0.5 ml from the tare box and evaporate to dryness under a stream of nitrogen. Add 20 mg of methoxylamine hydrochloride and 1 ml of pyridine. Stopper and leave in Reacti-therm® at 70 ° C for 40 min. Add 0.5 ml of BSTFA. Heat 30 min at 70 ° C.
    The amount of total glucose in the solution (which includes the initial so-called "free" glucose and the glucose resulting from hydrolysis and in particular linked to the presence of maltose and isomaltose) is determined by GPC analysis of the glucose. The amount of maltose is easily deduced therefrom and, by difference with the total amount of dimers attributed to the peaks between 10 and 17 minutes, the amount of D-allulose dimers.
    Example 1: Realization of a continuous industrial process for the manufacture of D-allulose syrup
    Example 1 consists of a method for the continuous production of crystallizable Dallulose syrup. The steps of the process used are detailed in FIG. 1. The composition and the flow rate of the flows of steps 1 to 5 are described in Table 1a.
    Step 1 :
    17.3 tonnes of a Dfructose Fructamyl syrup (Tereos) comprising 95% D-fructose at 50% Dry Matter (DM) (Fluxl) are introduced into a stirred batch reactor of 14 m 3 useful. Flux 1 is maintained at 55 ° C. A lyophilisate of the strain is introduced into the tank
    Bacillus subtilis host of the enzyme D-Psicose 3 Epimerase detailed in patent WO2015032761 in an amount sufficient to have 3.3 * 10 7 units of activity in the reactor. Three reactors are used sequentially so as to provide a syrup essentially composed of fructose and allulose (Flux 2) continuously at a flow rate of 360 kg / h.
    The reaction conditions are as follows:
    • Temperature: 55 ° C • pH = 7 • Reaction time 48h
    At the end of the reaction, Flux 2 is obtained comprising a richness in D-allulose approximately equal to 25% and a richness in D-fructose approximately equal to 75%.
    2nd step :
    Flux 2 passes through a microfiltration membrane during a batch operation. One obtains a Flux 3 free of cellular debris and a microfiltration retentate (Flux 8) comprising the debris from the lyophilisate of Bacillus subtilis which is purged from the circuit. The microfiltration parameters are as follows:
    • Transmembrane pressure: 0-3 bar • Pore size: 0.1 pm • Temperature: 50 ° C • Average flow: 15 L / h / m 2 • Membrane: Sepro PS35 • Volume Concentration Factor: 33
    Step 3:
    Flux 3 is demineralized on the strong cationic resin Dowex 88 followed by a weak anionic resin Dowex 66 at an average flow rate of 2BV / h. The cylinders are maintained at a temperature of 45 ° C. and the resistivity of Flux 4 at the end of demineralization remains greater than 100kQ.cm _1 at the output (Flux 4). Otherwise the regeneration of the resins is carried out.
    Step 4:
    Flux 4 feeds the continuous chromatography (SCC ARI® equipped with 8 columns) of the circuit. The average feed rate is 348 kg / h at 50% DM.
    The chromatography parameters are defined as follows:
    • Volume / column: 2m 3 • Resin: Dowex Monosphere 99Ca / 320 • Temperature: 60 ° C • Water flow / Flow 4 (vol./vol.): 2.4 • Load: 0.09 h -1
    Two fractions are extracted: the raffinate (Flux 10), the fraction rich in D-allulose (Flux 5) which leaves in the direction of step 5. Flux 10 is purged.
    Step 5:
    Flux 5 is passed in batch through a nanofiltration membrane. The parameters are as follows:
    • Transmembrane pressure: 30 bar • Temperature: 20 ° C • Membrane: GE Duracon NF1 8040C35 • Volume Concentration Factor FCV: 2.5
    Allulose dimers are concentrated in the retentate (Flux 9). This retentate is purged from the circuit while the permeate (Flux 6) is recovered. FIG. 6 gives the detail of the permeation of the syrups as a function of the FCV.
    Step 6:
    Flux 6 passes through a two-stage evaporator with a pressure inside of 50 mbar. The first stage is at 38 ° C and allows to raise the dry matter to 35%. The second stage reaches 77% dry matter. The D-allulose syrup (Flux 7) is obtained at the end of this step.
    The characteristics of the syrup of the invention are listed in Table 1b (Flux 7).
    Table 1a: Flows and composition of the flows of steps 1 to 5 of Example 1
    Stage / Flow Characteristics Flux Step 1 Flow 1 Flow 2 - Mass flow (kg / h) 360 360Dry matter (%) 50 50Wealth Fructose (%) 94.5 71.5Glucose wealth (%) 2 2Wealth Allulose (%) 1 24Di-Allulose wealth (%) 1 1Wealth Other (%) 1.5 1.5 Step 2 / Step 3 Flow 2 Flow 3 Flow 8 Mass flow (kg / h) 360 348 12 Dry matter (%) 50 50 50Step 4 Flow 4 Flow 10 Flow 5 Mass flow (kg / h) 348 658 424 Dry matter (%) 50 20 10 Wealth Fructose (%) 71.5 93.2 4.4 Glucose wealth (%) 2 2.5 0.4 Wealth Allulose (%) 23.7 1.3 93.4 Di-Allulose wealth (%) 1.2 1.4 0.8 Wealth Other (%) 1.6 1.6 1Step 5 Flow 6 Flow 9 - Mass flow (kg / h) 306 118Dry matter (%) 5 23Wealth Fructose (%) 3.5 5.0Glucose wealth (%) 0.3 0.4Wealth Allulose (%) 95.8 92.2Di-Allulose wealth (%) 0.1 1.1Wealth Other (%) 0.3 1.3
    Table 1b: Flows and composition of Flow 7
    Step 6 Flow 7 - - Mass flow (kg / h) 19.9 Dry matter (%) 77 Wealth Fructose (%) 3.5 Glucose wealth (%) 0.3 Wealth Allulose (%) 95 Di-Allulose wealth (%) 0.5 Wealth Other (%) 0.7
    In the same process where no nanofiltration step is carried out, the Dallulose syrup obtained is similar to the difference that the amount of D-allulose (DiAllulose) dimers expressed as dry mass is 1.5%.
    EXAMPLE 2 Evaluation of the Crystallizability of Different D-Allulose Syrups
    Example 2 consists in preparing different syrups of D-allulose having a dry matter of 77% and a richness in D-allulose of approximately 95%.
    These syrups are prepared by adjusting the volume concentration factor of step 5 of nanofiltration so as to obtain different contents of Di-Allulose and / or by preparing syrups, by mixing the permeate or the retentate obtained with crystals of D- allulose or D-fructose and / or using nanofiltration membranes with a lower rejection threshold. This made it possible to adjust the contents of the various constituents while keeping the D-allulose content around 95%. The composition of the dry matter of the syrups is shown in Table 2.
    In order to assess the crystallisability of the syrups, a primer of sifted D-allulose crystal with an average particle size of 70 μm is introduced into each syrup in a proportion of 0.3% (primer mass / dry matter mass) .
    Each syrup thus primed is then placed for 4 weeks in a refrigerated enclosure at 4 ° C or 15 ° C.
    At the end of this period, the dry matter of the supernatant (or mother liquors) of the sample is measured by the Karl Fischer method. The more the syrup has crystallized, the more the supernatant has a low dry matter (since the dry matter of the syrup is concentrated in D-allulose crystals).
    Table 2: Composition of the various syrups and dry matter of the supernatant after storage 5
    Composition (% CPG) % MS of the supernatant after one month Echantillonot Dallulose D-allulose dimer Glucose Fructose Other 15 ° C 4 ° C 1 95.1 0.1 1 3.5 0.3 70.6 67.5 2 95 0.5 0.3 3.5 0.7 71.8 68.7 3 94.9 0.7 0.1 3.2 1.1 72.8 69.7 4 95 1.2 0.2 1.9 1.7 73.4 70.2 5 95 1.5 0.2 2 1.3 73.9 70.8 6 95.2 2.1 0.2 1.8 0.7 74.7 71.3 7 95 2.7 0.2 1.4 0.7 75.3 71.6 8 95 3 0.2 4.1 0.7 75.3 71.5 9 95.1 3.4 0.1 1 0.4 75.6 71.6 10 94.9 4 0 1 0.1 75.3 71.5 11 94.8 4.6 0 0.5 0.1 75.7 71.8 12 94.9 5 0 0.1 0 75.2 71.9
    These results are shown in Figure 8.
    These tests demonstrate that the dimers of D-allulose are quite specific compounds, which have a considerable influence on the crystallizability of a syrup of D10 allulose comprising it, unlike for example glucose or fructose.
    Thus, the lower the amount of D-allulose dimer in the syrup, the more the D-allulose syrup is crystallizable, even though the amount of D-allulose remains similar.
    Example 3. Manufacture of long-textured caramels
    A composition of long-textured caramels (hard caramels) is produced according to the recipe in Table 3 from the D-allulose syrup according to the invention (sample 2).
    Table 3. Caramel formulation
    Constituents Proportions Fresh cream 27.00 Skimmed milk powder 8.00 Allulose syrup 52.00 Butter 5.60 Salt 0.10 Water 6.10 Lecithin 0.20 Vanilla 1.00 Total 100.00Has nutritional dataa portion of 30 g: Calories (kcal) 99.90 Total carbohydrates (g) 18.82 Sugars (g) 18.51 Proteins (g) 0.50 Fat (g) 6.68 Texture long (7-9)
    a Nutritional data calculated according to product specifications or, from the Nutritional USDA's National Nutrient Database for Standard Reference Release 27, when these specifications are not available
    Conclusions:
    A long-textured caramel could be obtained, while having the advantage of having a reduced calorie content.
    EXAMPLE 4 Manufacture of Chewing Gum
    A chewing gum composition is produced according to the recipe below from the D-allulose syrup according to the invention (sample 2).
    Base gum (1) 28.0%
    Allulose powder
    58.0%
    Allulose syrup 3.5% Mannitol powder (average diameter: 160 pm) (2) 3.7% Mannitol powder (average diameter: 50 µm) (3) 0.1% Maltitol syrup (4) diluted to 60% dry matter 3.5% Intense sweeteners (5) 0.2% Perfumes 3.0%
    (1) Optima®, CAFOSA (2) Pearlitol® 160C, ROQUETTE (3) Pearlitol® 50 C, ROQUETTE (4) Lycasin® 80/55, ROQUETTE (5) GumSweet®, SWEETENER SOLUTIONS
    The gum base, the allulose and mannitol powders are placed in an enclosure at 55 ° C for 4 hours. The gum base, 60% of the allulose powder, the mannitol powder and half of the maltitol syrup are mixed in a gum mixer at 50 ° C. Then, the intense sweeteners, the rest of the allulose powder, the rest of the maltitol syrup, the allulose syrup and the flavors are added successively. The mixer is stopped and the composition obtained removed, then put into the form of chewing gum tablets.
    The chewing gum tablet has the advantage of having a good texture when chewing, which is explained by a high hardness.
    权利要求:
    Claims (11)
    [1" id="c-fr-0001]
    Claims
    1. D-allulose syrup comprising, in addition to D-allulose, a mass content of D-allulose dimer expressed as dry mass, determined by gas phase chromatography (GPC), of less than 1.5%.
    [2" id="c-fr-0002]
    2. D-allulose syrup according to claim 1 characterized in that it has a mass content of D-allulose dimer expressed in dry mass ranging from 0.1 to 1.4%, advantageously ranging from 0.2 to 1 0.3%, preferably ranging from 0.3 to 1.2%.
    [3" id="c-fr-0003]
    3. D-allulose syrup according to one of claims 1 or 2 comprising a D-allulose content greater than or equal to 75%.
    [4" id="c-fr-0004]
    4. D-allulose syrup according to claim 3 characterized in that it comprises, relative to its dry mass:
    • from 75 to 99% of D-allulose;
    • from 0 to 25% of D-fructose;
    • 0 to 10% glucose;
    • from 0 to 1.5% of D-allulose dimer, for example ranging from 0.1 to 1.4%, advantageously ranging from 0.2 to 1.3%, preferably ranging from 0.3 to 1.2 %.
    [5" id="c-fr-0005]
    5. D-allulose syrup according to one of the preceding claims characterized in that it has a dry matter greater than 50%, for example ranging from 65 to 85%, in particular ranging from 70 to 83%, for example 75 at 82%.
    [6" id="c-fr-0006]
    6. Method for manufacturing a D-allulose syrup according to one of the preceding claims, characterized in that it comprises:
    • a step of supplying a D-allulose composition comprising D-allulose dimers;
    • a nanofiltration step of said D-allulose composition to provide a retentate and a permeate;
    • a step of recovery of the nanofiltration permeate;
    • a step of concentrating this permeate to provide the D-allulose syrup according to one of the preceding claims.
    [7" id="c-fr-0007]
    7. Method according to claim 6 characterized in that, to provide the composition of D-allulose, is carried out a step of chromatography of a composition comprising D-allulose and D-fructose.
    5
    [8" id="c-fr-0008]
    8. Method according to claim 7 characterized in that the composition comprising D-allulose and D-fructose is obtained by epimerization of a Dfructose solution.
    [9" id="c-fr-0009]
    9. Use of a syrup according to one of claims 1 to 5 for the manufacture of
    [10" id="c-fr-0010]
    10 food or pharmaceutical products.
    10. Use according to claim 10 for the manufacture of chewing gum in the form of tablets or dragees, caramel with long texture, candies and sucking tablets, cookies, cookies, muffins, cakes, cakes base of
    [11" id="c-fr-0011]
    15 gelatin, chewing pastes, especially short-textured chewing pastes.
    1/6
    Flow 10 <
    D-fructose solution
    Flux 1 ψ
    Step 1: Epimerization
    Flow 2
    Ψ
    Step 2: Microfiltration ------------> Flux 8
    Flow 3
    V
    Step 3: Flux 4 demineralization
    Ψ
    Step 4: Chromatography
    Flux 5 ψ
    Step 5: Nanofiltration_______________ Flow 9
    Flow 6
    Ψ
    Step 6: Evaporation
    Flow 7
    V
    Crystallizable syrup
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    同族专利:
    公开号 | 公开日
    WO2018127669A1|2018-07-12|
    FR3061414B1|2021-07-16|
    JP2020505012A|2020-02-20|
    US20200085090A1|2020-03-19|
    KR20190101389A|2019-08-30|
    EP3565419A1|2019-11-13|
    MX2019008061A|2019-09-11|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JP2001354690A|2000-06-08|2001-12-25|Kagawa Univ|Method for isolating psicose|
    WO2011119004A2|2010-03-26|2011-09-29|Cj Cheiljedang Corp.|Method of producing d-psicose crystals|
    CN103059071B|2013-01-08|2016-03-16|华东理工大学|A kind of nanofiltration separation method of monose|
    CN103333935A|2013-05-24|2013-10-02|桐乡晟泰生物科技有限公司|Production technology of D-psicose|
    WO2015032761A1|2013-09-03|2015-03-12|Roquette Freres|Improved variant of d-psicose 3-epimerase and uses thereof|
    WO2015094342A1|2013-12-20|2015-06-25|Roquette Freres|Protein food product comprising d-allulose|
    FR3016628A1|2014-01-17|2015-07-24|Syral Belgium Nv|PROCESS FOR OBTAINING SYRUP RICH IN HIGH-PURITY SORBITOL|
    WO2016064087A1|2014-10-20|2016-04-28|씨제이제일제당|Method for preparing d-psicose crystal|
    CN104447888A|2014-12-04|2015-03-25|山东福田药业有限公司|Preparation method and application of allulose|
    WO2016135458A1|2015-02-24|2016-09-01|Tate & Lyle Ingredients Americas Llc|Allulose syrups|
    MX2017000827A|2014-07-21|2017-05-01|Roquette Freres|Sugar compositions for tableting by direct compression.|KR102064911B1|2019-03-21|2020-01-10|씨제이제일제당 주식회사|A novel compound derived from allulose|
    KR20210067301A|2019-11-29|2021-06-08|씨제이제일제당 |Composition for producing allulose and method of producing allulose using thereof|
    WO2021245230A1|2020-06-05|2021-12-09|Savanna Ingredients Gmbh|Allulose syrup|
    法律状态:
    2018-01-31| PLFP| Fee payment|Year of fee payment: 2 |
    2018-07-06| PLSC| Publication of the preliminary search report|Effective date: 20180706 |
    2019-01-30| PLFP| Fee payment|Year of fee payment: 3 |
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    2022-01-31| PLFP| Fee payment|Year of fee payment: 6 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1750104|2017-01-05|
    FR1750104A|FR3061414B1|2017-01-05|2017-01-05|D-ALLULOSE CRYSTALLIZABLE SYRUPS|FR1750104A| FR3061414B1|2017-01-05|2017-01-05|D-ALLULOSE CRYSTALLIZABLE SYRUPS|
    US16/471,778| US20200085090A1|2017-01-05|2018-01-05|Crystallisable d-allulose syrups|
    JP2019536517A| JP2020505012A|2017-01-05|2018-01-05|Crystalline D-allulose syrup|
    EP18700792.7A| EP3565419A1|2017-01-05|2018-01-05|Crystallisable d-allulose syrups|
    KR1020197019097A| KR20190101389A|2017-01-05|2018-01-05|Crystalline D-Allulose Syrup|
    PCT/FR2018/050027| WO2018127669A1|2017-01-05|2018-01-05|Crystallisable d-allulose syrups|
    MX2019008061A| MX2019008061A|2017-01-05|2018-01-05|Crystallisable d-allulose syrups.|
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