• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 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 greater 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:FR3061415A1
    申请号:FR1750106
    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) NON-CRYSTALLIZABLE SYRUPS OF D-ALLULOSE.
    (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 greater 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 3 061 415 - 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 less 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, starting from the composition resulting from the epimerization reaction, 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 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 for the analysis of this type of syrups. The syrups described in this application are presented as being crystallizable at low temperature.
    However, for certain applications, there may be an advantage in having a non-crystallized or even less crystallizable D-allulose syrup, even at low temperature. This is particularly the case when D-allulose must be used as a humectant since a compound exhibits this humectant function only when it is in the form of a solute, and therefore not crystallized. Other applications also require that the sugar does not crystallize in the final product to obtain the desired properties. For example, to obtain a soft texture, it is necessary that there is no crystallization of D-allulose in sauces, starch jellies, soft caramels, jams or fruit fillings. Similarly, it is preferable that there is no crystalline deposit in liquid solutions such as salad dressings or drinks. Food in the form of bars (nutritional bars, cereal bars, fruit and nut bars, etc.) are more tender if the sugar does not crystallize in the final product.
    It has also been observed that syrups can exhibit instability during storage by forming crystals in suspension over time, in particular when this storage is done at low temperature. In this case, and in particular when these crystals grow, the viscosity of the syrup can increase drastically and it may become necessary to reheat the syrup until the crystals in suspension are melted in order to be able to handle it again easily. It may thus have an interest in providing new syrups having improved stability in storage, which do not crystallize or little, and this even at low temperature.
    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. These D-allulose dimers are formed during the process and their presence in the D-allulose syrup is systematic.
    Going beyond this observation, the Applicant has also continued its efforts to provide, for a given dry matter and D-allulose content, new syrups having a less crystallizable character than those of the prior art. To do this, it has developed a process enabling it to supply syrups with an increased content of D-allulose dimers. This makes the syrup less crystallizable, which makes it easier to store it for later use, especially at low temperatures.
    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 (GC), greater than 1.5%.
    This syrup has the advantage of being less crystallizable than syrups of the prior art, or even non-crystallizable under certain temperature conditions, which allows it to be more stable on storage. This syrup can also be used advantageously in the aforementioned applications.
    Another object of the invention is a method for manufacturing the syrup of the invention. This process includes:
    • a step of supplying a D-allulose composition comprising D-allulose dimers;
    • a nanofiltration step of said D-allulose composition;
    • a step of recovering the nanofiltration retentate;
    • a step of concentrating this retentate to supply the D-allulose syrup.
    The use of a nanofiltration step makes it possible to recover a retentate enriched in D-allulose dimer and thus to obtain, after concentration, 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 production circuit of a non-crystallizable allulose syrup.
    Figure 2: Figure 2 shows a circuit for the production of a non-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 retentate taken in the method 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 retentate removed in the process of the invention, that is to say after nanofiltration.
    Figure 8: Figure 8 shows the dry matter of the supernatant 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 quantity of D-allulose dimers included in the syrup is enriched, ie that its mass content expressed in dry mass is according to the invention greater than 1.5%, made it possible to obtain a syrup less 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. The amount of these glucose-glucose dimers may be very small, or even nonexistent. In the syrup of the invention, the mass quantity of glucose-glucose dimers is generally less than 2%, often less than 1%, or even less than 0.2% or 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 D-allulose, a mass content of D-allulose dimer, determined by gas phase chromatography (GC), greater than 1.5%.
    It can be greater than 1.8% and in particular range from 1.9% to 20%, preferably from 2.0 to 15%, for example from 2.1 to 8%, or even from 2.4 to 5%.
    According to a variant, the syrup of the invention comprises D-fructose and D-allulose in a D-fructose / D-allulose mass ratio of between 50/50 and 40/60 and consists essentially of D-fructose, D-allulose and D-allulose dimers. This syrup has the advantage of having the same sweetening power as sucrose.
    According to another preferred variant, the syrup of the invention comprises a content of D-allulose expressed in dry mass greater than or equal to 75%. The syrup of the invention has the advantage of being able to have a poorly crystallizable character, even when it reaches this content of D-allulose. This is particularly surprising since it is known that the more a syrup comprises a majority of compound (here D-allulose), the more this syrup tends to have a crystallizable character. According to the invention, the presence of dimers of D-allulose from more than 1.5% by mass, expressed as dry mass, in the syrup makes it particularly less crystallizable.
    The syrup of the invention may have a D-allulose content expressed as 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 D-allulose syrup can advantageously comprise, relative to its dry mass:
    • from 75 to 99% of D-allulose;
    • from 0 to 20% of D-fructose;
    • 0 to 10% glucose;
    • from 1.5 (limit excluded) to 20% of D-allulose dimer, in particular from 1.9% to 20%, preferably from 2.0 to 15%, for example from 2.1 to 8%, or even from 2.4 to 5%.
    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 increase 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 allows the supply of a Dallulose syrup, the content of D-allulose dimers of which is richer 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 retentate and Flux 9 represents the permeate. 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 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 retentate 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 recovering the nanofiltration retentate;
    • a step of concentrating this retentate 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 retentate recovered can comprise, relative to its dry mass, from 0.8 to 20% of D-allulose dimers, for example from 1.5 to 15%, in particular of 2 at 5%. It can for example include, in dry mass:
    • from 75 to 99% of D-allulose;
    • from 0 to 20% of D-fructose;
    • 0 to 10% glucose;
    • from 0.8 to 20% of D-allulose dimers, for example from 1.5 to 15%, in particular from 2 to 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 retentate has a dry matter lower than 50%), it is necessary to carry out a concentration step, during which the content of D-allulose dimers can increase. The formation of D-allulose dimers can also occur during this concentration step, especially when the temperature is high. It is thus possible to select conditions which further increase the quantities formed in these dimers. The concentration step can be carried out under vacuum or at room temperature under vacuum. A vacuum step 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 100O. 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 greater than 1.5%. Generally, the mass content of D-allulose dimers in the syrup of the invention is greater than 1.8% and can in particular range from 1.9% to 20%, preferably from 2.0 to 15%, for example 2.1 to 8%, or even 2.4 to 5%.
    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.
    ίο
    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 T) of this D-fructose syrup with at least one recycled fraction which may be the raffinate (all or part of the raffinate) (Flux 10 or 12), this recycled fraction possibly comprising a greater 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, obviously, on the amount of D-allulose and D-fructose in the D-fructose composition supplied 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.cm -1 . It is also possible, before this demineralization step, to carry out a step of bleaching the composition comprising D-fructose and D-allulose, for example by passing over a column comprising active carbon.
    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 (Simulated Moving Bed SMB) type, of the Improved Simulated Moving Bed (ISMB) type, of the Divide Improved Simulated Moving Bed (DISMB) type. ), 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 include a step of recycling at least a portion of the nanofiltration permeate (Flux 9 in FIG. 2) and / or the raffinate (Flux 10 in FIG. 2).
    The syrup can be used for the manufacture of food or pharmaceutical products. The syrups of the invention can thus be used in the known applications of Dallulose and, in general, of sweeteners. The syrup of the invention is advantageously used in applications where it is preferable that there is no crystallization. Thus, the syrup of the invention is advantageously used for the manufacture of drinks, caramels, starch jelly, sauces, dressings, jams, fruit filling, nutritional bars, cereal bars, pizza, fruit and nut bars, dairy products such as yogurt or ice cream, sherbet or as a humectant.
    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 α-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. 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 D-allulose dimers and of glucose-glucose dimers
    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 non-crystallizable D-allulose 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. Is introduced into the tank a lyophilisate of the strain 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 supply 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 lOOkQ.cm -1 at 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: 10
    Allulose dimers are concentrated in the retentate (Flux 6). The permeate (Flux 9) is purged. FIG. 6 gives the detail of the permeation of the syrups as a function of the FCV.
    Step 6:
    Flux 6 passes through an evaporator. 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) 348 656 429 Dry matter (%) 50 20 10 Wealth Fructose (%) 71.5 93.7 3.6 Glucose wealth (%) 2 2.5 0.4 Wealth Allulose (%) 23.7 0.9 93.4 Di-Allulose wealth (%) 1.2 1.1 1.5 Wealth Other (%) 1.5 1.6 1.1Step 5 Flow 6 Flow 9 - Mass flow (kg / h) 67.1 363.3Dry matter (%) 29.3 6.4Wealth Fructose (%) 3.5 3.7Glucose wealth (%) 0.4 0.4Wealth Allulose (%) 91.8 94.8Di-Allulose wealth (%) 3.1 0.1Wealth Other (%) 1.2 1
    Table 1b: Flows and composition of Flow 7
    Step 6 Flow 7 - - Mass flow (kg / h) 25.5 Dry matter (%) 77 Wealth Fructose (%) 3.5 Glucose wealth (%) 0.4 Wealth Allulose (%) 91.8 Di-Allulose wealth (%) 3.4 Wealth Other (%) 1.2
    The syrup obtained cannot be crystallized at room temperature.
    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 dimers expressed in 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 of the syrups 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).
    The priming carried out during this test allows an accelerated study of storage stability, in particular at low temperature.
    Table 2: Composition of the various syrups and dry matter of the supernatant after storage
    Composition (% CPG) % MS of the supernatant after one month Sample D-allulose Dimer ofD-allulose 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 Dallulose syrup comprising it, unlike for example glucose or fructose.
    Thus, the higher the amount of D-allulose dimer in the syrup, the less the D15 allulose syrup can be crystallized, even though the amount of D-allulose remains similar.
    These tests demonstrate that the syrups comprising more than 1.5% of D-allulose dimers have very improved storage stability at low temperature. This is an advantage since the syrups can thus be more easily handled before use, without having to reheat the syrup (or by reheating it to a lesser extent) so as to at least partially melt it again.
    Example 3. Manufacture of short-textured caramels
    A short-textured (soft) caramel composition comprising the D-allulose syrup according to the invention (sample 10) was produced.
    Table 3 shows the composition of the caramel formulated.
    Table 3. Caramel formulations using D-allulose syrup
    Amount of ingredients (%) in the formulation Ingredients Formulation Full cream 27.00 Powdered milk 8.00 Allulose syrup 24.40 NUTRIOSE® FM06 23.10 Butter 5.60 Salt 0.10 Water 10.55 Lecithin 0.20 Sodium bicarbonate 0.05 Vanilla (2x) 1.00 Total 100.00 Nutritional data has produced 30gCalories (kcal) 100.90 Total carbohydrates (g) 18.80 Sugars (g) 8.94 Fibers (g) 8.13 Proteins (g) 0.50 Total fat (g) 6.69
    a Nutritional data calculated from product specifications or USDA's National Nutrient Database for Standard Reference Release 27, when these specifications were not available
    The soft caramel obtained from the syrups of the invention has an excellent texture, very short.
    Example 4. Making Ketchup Sauce
    A ketchup sauce comprising the D-allulose syrup according to the invention (sample 10) was manufactured as well as a reference ketchup sauce.
    Table 4. Ketchup sauce formulations
    Ingredients Reference Invention Tomato puree 35.12 35.12 Sucrose 14.15 0 D-allulose syrup 0 18.54 Modified starch (CLEARAMCH 2020) 2.44 2.44 Vinegar 13.66 13.66 Salt 0.49 0.49 Onion powder 0.49 0.49 Water 33.66 29.47 Total 100.00 100.00
    The amount of sugar by dry weight of the 2 sauces is equal but the amount of calories is reduced by 43% with the sauce of the invention. The sauce of the invention has a less sweet taste and is brighter, which is an advantage for a sauce of this type.
    The ketchup made from the syrup of the invention has a soft texture and without aggregates, which is synonymous with non-crystallization of D-allulose.
    Furthermore, the ketchup made from the syrup of the invention has an excellent flow, which is due to the fact that the sauce does not crystallize, even after storage for a week in the refrigerator.
    Example 5. Making barbecue sauce
    A barbecue sauce comprising the D-allulose syrup according to the invention (sample 10) was manufactured as well as a reference barbecue sauce.
    Table 5 Barbecue sauce formulations
    Ingredients Reference Invention Tomato sauce 45.64 45.64 D-allulose syrup 18.76 0.00 HFCS Glucose Fructose Syrup55 (77% DM) 0.00 18.76 Vinegar 18.26 18.26 Modified starch (PREGEFLOCH 20) 2.28 2.28 Liquid smoke 1.62 1.62 Salt 1.50 1.50 Garlic powder 0.63 0.63 Onion powder 0.53 0.53 Mustard powder 0.30 0.30 Paprika 0.20 0.20 Dye 0.13 0.13 Water 10.14 10.14 Total 100.00 100.00
    Method
    The ingredients in dry form are weighed and mixed together. In a blender, the tomato sauce and the water are mixed and the ingredients in dry form are added. After incorporating these ingredients in dry form, the syrup and vinegar are added and mixed well. The mixture is placed in a dish and heated until the water content is approximately 74%.
    Characteristics
    Reference Invention Dry matter 26.5% 27.3% Taste Sugar Slightly less sweet than the reference sauce Viscosity, texture Soft and viscous enough to be "hardenable" Soft and viscous enough to be "hardenable"
    Nutritional information for 35 g of product
    Reference Invention Calories (kcal) 26.7 11.4 Carbohydrates(g) 6.31 6.31 Sugars (g) 5.17 5.17 Fibers (g) 0.83 0.83 Proteins (g) 0.34 0.34 Fat (g) 0.29 0.29
    The sauce of the invention has a reduced calorie content of 57% while comprising the same amount of sugars.
    Although viscous, the sauce of the invention has a very soft texture, which is synonymous with non-crystallization of D-allulose.
    Example 6. Making of jam
    A jam comprising the D-allulose syrup according to the invention (sample 10) was produced as well as a reference jam.
    Table 6. Jam formulations
    Ingredients Reference Invention Strawberries 49.27 49.27 D-allulose syrup 0.00 49.27 Glucose-fructose syrupHFCS 55 (77% DM) 49.27 0.00 Modified pectin 0.45 0.45 Citric acid (solution to50%) 1.01 1.01 Total 100.00 100.00
    The strawberries are washed, crushed and the beans are removed. The strawberry puree, syrup and pectin are mixed and heated in a casserole dish. After a few minutes of boiling, the casserole is removed from the heat so as to obtain a dry matter of approximately 57%, the citric acid is added and the mixture is left to cool.
    Organoleptic characteristics
    Reference Invention Dry matter 57.4% 57.2% Taste Sugar Slightly less sweet and more acidic than the reference Viscosity, texture in the mouth Soft and spreadable Soft and spreadable
    Nutritional information for 17 g of jam
    Reference Invention Calories (kcal) 34.2 8.8 Carbohydrates (g) 8.62 8.59 Sugars (g) 8.28 8.31
    Observations:
    The jam made from D-allulose syrup does not turn brown during cooking. This is expected because the pH is acidic and does not include unmodified protein. The caloric content of the jam of the invention has the advantage of having a calorie content reduced by 74%. The color of the jam of the invention is slightly more colorful (more red) than the reference jam, which is an advantage for a jam.
    The jam made from the syrup of the invention also has the advantage of having a soft texture, similar to the reference jam using a very poorly crystallizable syrup (it comprises a mixture of glucose and fructose in almost equivalent amounts) .
    Example 7. Use of the syrup as an adhesive agent for a frozen pizza topping
    In this example, the D-allulose syrup according to the invention (sample 10) was used.
    Generally, the cheese on the toppings of frozen pizzas tends to come off the pizza. This uses a layer of adhesive agent, which can be a glucosefructose syrup, to improve adhesion. However, too rapid crystallization of the adhesive agent can cause the cheese to separate from the pizza, rather than causing it to adhere. The adhesive agent would have an advantage in being less sweet.
    Protocol
    A pizza dough is spread and then put for 8 minutes in an oven at 245 ° C.
    After cooking, the dough is cooled and then covered with pizza sauce. Then, the pizza is optionally pulverized using 4g of syrup (or water), 50 g of grated mozzarella is sprinkled then the pizza is optionally repulverized using 4g of syrup (or water).
    The pizza covered with aluminum foil is placed in the freezer for 4 days. Then she discovered aluminum foil. A first test consists in turning over the frozen pizza: the cheese that falls from the pizza is recovered. A second test is to do the same, turning the pizza over when it is thawed.
    The pizza is then cooked and a sensory analysis is performed.
    Table 7. Results obtained
    Adhesive agent Concentration Amount (g) of cheese lost (frozen) Amount (g) of cheese lost (thawed) Sensory analysis HFCS 42 50% solution 0 0 Too sweet SyrupDAllulose purity 95%, 75% DM 50% solution 0 0 Slightly sweet SyrupDAllulose purity 95%, 75% DM 10% solution 0 0 Taste not altered compared to the reference Control - 8 16 Reference Tap water tap water 5 14 Taste not altered compared to the reference
    No loss of cheese was observed for the pizza (thawed or not) using the adhesive agent obtained from the syrup of the invention, just like the agent HFCS 42, but which has a sweeter taste. than the pizza reference. The reference pizza loses 32% of cheese when thawed and then turned. According to the same test, if water is used as an adhesive agent, 28% of the cheese is lost.
    Example 8. Composition of Ice Cream
    The composition of ice cream reduced in sugar was carried out according to the following recipe:
    Skimmed milk powder 400 g Water 1801.2g Stabilizing 12g Sucrose 160g Allulose 440 g Vanilla 28g Full cream 1160g Total 4000 g
    The ice cream obtained has a creamy and soft texture on the palate.
    权利要求:
    Claims (9)
    [1]
    Claims
    1. D-allulose syrup comprising, in addition to D-allulose, a mass content of D-allulose dimer, determined by gas phase chromatography (GC), greater than 1.5%, preferably greater than 1.8%.
    [2]
    2. D-allulose syrup according to claim 1 characterized in that the content of D-allulose dimer ranges from 1.9% to 20%, preferably from 2.0 to 15%, for example from 2.1 to 8%, or even 2.4 to 5%.
    [3]
    3. D-allulose syrup according to one of the preceding claims characterized in that it has a D-allulose content greater than or equal to 75%.
    [4]
    4. D-allulose syrup according to one of the preceding claims, characterized in that it comprises, relative to its dry mass:
    • from 75 to 99% of D-allulose;
    • from 0 to 20% of D-fructose;
    • 0 to 10% glucose;
    • from 1.5 (limit excluded) to 20% of D-allulose dimer, in particular from 1.9% to 20%, preferably from 2.0 to 15%, for example from 2.1 to 8%, or even from 2.4 to 5%.
    [5]
    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]
    6. Method of manufacturing a D-allulose syrup according to one of claims 1 to 5 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;
    • a step of recovering the nanofiltration retentate;
    • a step of concentrating this retentate to supply the D-allulose syrup.
    1. Method according to claim 6 characterized in that a step of chromatography of a composition comprising D-allulose and D-fructose is carried out to provide the composition of D-allulose.
    [7]
    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.
    [8]
    9. Use of a syrup according to one of claims 1 to 5 for the manufacture of food or pharmaceutical products.
    [9]
    10. Use according to claim 9 for the manufacture of beverages, caramels, starch jelly, sauces, dressings, jams, fruit filling, nutritional bars, cereal bars, pizzas, bars fruit and nuts, dairy products such as yogurt or ice cream, sherbet or as a humectant.
    1/5
    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
    Non-crystallizable syrup
    类似技术:
    公开号 | 公开日 | 专利标题
    FR3061415A1|2018-07-06|NON-CRYSTALLISABLE SYRUP OF D-ALLULOSE
    JP2020195391A|2020-12-10|Allulose syrups
    EP0774210B2|2009-09-09|Sugarfree coating for preparing hard dragées and process for preparation of them
    FR2499576A1|1982-08-13|MALTITOL ANHYDROUS CRYSTALS, STARCH HYDROLYSATE, HYDROGEN, CRYSTALLINE, CONTAINING SUCH CRYSTALS, AND METHODS FOR THEIR PREPARATION AND THEIR USE
    EP3565419A1|2019-11-13|Crystallisable d-allulose syrups
    FR2951165A1|2011-04-15|PROCESS FOR THE PREPARATION OF A COMPOSITION COMPRISING A COMPOUND BASED ON VANILLINE AND ETHYLVANILLIN, COMPOSITION OBTAINED AND APPLICATIONS THEREOF
    WO2018127668A1|2018-07-12|Method for producing d-allulose crystals
    EP0607189B1|1996-11-27|Hydrated lipophilic composition and method for obtaining same
    CH659173A5|1987-01-15|FOOD COMPOSITIONS CONTAINING SWEETENESS MODIFIERS AND PROCESS FOR PREPARING SUCH COMPOSITIONS.
    WO2012164383A1|2012-12-06|Sweetness enhanced sugars and sugar like products
    CA1279225C|1991-01-22|Process for incorporating a low watersoluble substance, particularly aspartame, in a sugar based molded food product
    EP2704725B1|2015-03-18|Boiled sugar sweet comprising non-fructosylated-galactooligosaccharides
    WO2019048564A1|2019-03-14|Use of vanillin and/or ethylvanillin as a bitterness-masking agent
    EP1484983B1|2006-04-05|Sweet food base, the preparation method thereof and uses of same
    EP0148428B1|1986-12-17|Flavouring product
    EP3607832A1|2020-02-12|Taste improver
    US20150351425A1|2015-12-10|Composition for low fat ice cream, containing tagatose, low-fat ice cream using same, and preparation method therefor
    CH659172A5|1987-01-15|FOOD COMPOSITIONS CONTAINING SWEETENESS MODIFIERS AND PROCESS FOR PREPARING SUCH COMPOSITIONS.
    EP2249870B1|2015-03-18|Large particle size crystallised maltitol powder, method for preparing same and applications thereof, particularly in chocolate production
    FR3077959A1|2019-08-23|METHOD FOR MANUFACTURING RESISTANT PEAR DEXTRIN
    JPH069487B2|1994-02-09|Kneaded product or beverage containing stable aspartame
    JP2020124123A|2020-08-20|Cacao pulp juice dried powder, foods blended with the powder, and methods for producing them
    JPH0662732A|1994-03-08|Concentrate cow&#39;s milk, its production and confectioneries containing the same concentrated cow&#39;s milk blended therein
    FR2644324A1|1990-09-21|Improvement in the methods for preparing patisserie and confectionery products
    BE843067A|1976-10-18|PROCESS FOR PREPARING A DRIED EGG ALBUMEN POWDER
    同族专利:
    公开号 | 公开日
    MX2019008060A|2019-09-11|
    FR3061415B1|2021-07-16|
    WO2018127670A1|2018-07-12|
    EP3565420A1|2019-11-13|
    KR20190100222A|2019-08-28|
    JP2020506674A|2020-03-05|
    US20190328014A1|2019-10-31|
    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.|
    JP6762316B2|2015-03-31|2020-09-30|ロケット フレールＲｏｑｕｅｔｔｅ Ｆｒｅｒｅｓ|Chewing gum composition containing crystalline allulose particles|KR102004914B1|2016-10-10|2019-07-30|씨제이제일제당 |Plant-soaked solutions containing allulose and method for preparation thereof|
    JP6992175B2|2017-10-27|2022-01-13|サムヤン コーポレイション|Allose syrup and its manufacturing method|
    WO2020263992A1|2019-06-28|2020-12-30|Corn Products Development, Inc.|Fruit preps and other sweet sauces comprising sugar reduction solutions and starch|
    KR102332373B1|2019-11-29|2021-11-29|씨제이제일제당 주식회사|A composition comprising allulose dimer for inhibiting production of HMF|
    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 |
    2020-01-30| PLFP| Fee payment|Year of fee payment: 4 |
    2021-01-28| PLFP| Fee payment|Year of fee payment: 5 |
    2022-01-31| PLFP| Fee payment|Year of fee payment: 6 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1750106|2017-01-05|
    FR1750106A|FR3061415B1|2017-01-05|2017-01-05|NON-CRYSTALLIZABLE D-ALLULOSE SYRUPS|FR1750106A| FR3061415B1|2017-01-05|2017-01-05|NON-CRYSTALLIZABLE D-ALLULOSE SYRUPS|
    PCT/FR2018/050028| WO2018127670A1|2017-01-05|2018-01-05|Non-crystallisable d-allulose syrups|
    MX2019008060A| MX2019008060A|2017-01-05|2018-01-05|Non-crystallisable d-allulose syrups.|
    JP2019536510A| JP2020506674A|2017-01-05|2018-01-05|Amorphous D-allulose syrup|
    EP18700793.5A| EP3565420A1|2017-01-05|2018-01-05|Non-crystallisable d-allulose syrups|
    US16/471,717| US20190328014A1|2017-01-05|2018-01-05|Non-crystallisable d-allulose syrups|
    KR1020197019098A| KR20190100222A|2017-01-05|2018-01-05|Non-crystalline D-Allulose Syrup|
    [返回顶部]