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    • 专利摘要:
    Procedure for the preparation of candies with a high content of prebiotic oligosaccharides. The present invention comprises the transformation of food sugars containing D-fructose, into candies enriched in oligosaccharides with prebiotic activity by the use of carbon dioxide gas as catalyst, either alone or in combination with a food acid such as acetic acid, acid citric acid or phosphoric acid, in a homogeneous medium, by means of a process that does not require any separation stage or generates any residue. The resulting caramel exhibits prebiotic properties, favoring the development of a beneficial intestinal flora and a repairing effect on the damaged colon. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2671175A1
    申请号:ES201631484
    申请日:2016-11-18
    公开日:2018-06-05
    发明作者:José Manuel García Fernández；Loyda Ester ATENCIO GENES；Carmen Ortiz Mellet；François JÉRÔME；Karine De Oliveira Vigier；Maïte AUDEMAR；Julio Juan Gálvez Peralta
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；Universidad de Granada；Universidad de Sevilla；Centre National de la Recherche Scientifique CNRS；Universite de Poitiers；
    IPC主号:
    专利说明:

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    CANDY PREPARATION PROCEDURE WITH ELEVATED CONTENT
    IN PREBIOTIC OLIGOSACARIDS
    DESCRIPTION
    OBJECT OF THE INVENTION
    The present invention aims at a new method of obtaining candies rich in oligosaccharides with prebiotic activity. More specifically, the present invention comprises the transformation of food sugars into candies enriched in oligosaccharides with prebiotic activity through the use of carbon dioxide as a catalyst or the joint use of carbon dioxide with a food acid such as acetic, phosphoric or citric acids. An important advantage of the method is that it makes unnecessary the separation of the catalyst at the end of the process and does not generate any residue. In accordance with the invention, the starting food sugar may be D-fructose, sucrose or any oligo- or polysaccharide containing fructose as a constituent, including fructobioses such as palatinous or leucrose, fructooligosaccharides such as 1-kestose or the nosy, the fructans and the inulin. These starting sugars can be used alone or in combination in different proportions, as well as in combination with other or other sugars for food use, including glucose, galactose, maltose, lactose, raffinose or cyclodextrins. The products resulting from the activation of these sugars with carbon dioxide, obtained in accordance with this invention, have a high proportion of oligosaccharides that contain fructose and exhibit prebiotic properties, favoring the development of a beneficial intestinal flora, in particular of the genera Bifidobacteria and Lactobacillus, and exerting a reparative effect on the damaged colon.
    STATE OF THE TECHNIQUE
    Oligosaccharides that contain D-fructose in their structure, generically referred to as fructooligosaccharides, have been shown to have beneficial nutritional properties for both animal and human diets. These oligosaccharides modify the intestinal flora, particularly favoring an increase in the proportion of Bifidus type bacteria in the digestive tract. Consequently, candies containing a high proportion of this type of oligosaccharides have important nutritional advantages.
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    Candies are products that result from the heat treatment of sugars, such as sucrose, fructose, glucose or others. This heat treatment can be carried out on dry sugar or in the presence of water, in the absence or in the presence of acidic, basic additives, salts or nitrogen compounds. Its composition has been studied previously and basically consists of a volatile fraction in which the majority compound is 2-hydroxymethylfurfural (HMF) and a non-volatile fraction consisting of a variable proportion of the starting sugar or its monosaccharide constituents and by oligosaccharides formed from them during the caramelization process. Specifically, in the case of industrial candies prepared from sucrose in the presence of a food acid, the major components of this oligosaccharide fraction, which can reach 20% of the total, have a fructose dianhydride structure. Up to 13 different isomers with this general structure, resulting from the dimerization of D-fructose with the formation of two reciprocal glycosidic bonds, have been identified in candies. Higher oligomers, resulting from the addition of D-fructose or D-glucose units, from the hydrolysis of sucrose during caramelization, on a central nucleus of fructose dianhydride, as well as reversing glycooligosaccharides, are also present in the candy. Both fructose dianhydrides and their glycosylated derivatives have been shown to possess prebiotic properties.
    The preparation of candies enriched in fructose dianhydrides and fructooligosaccharides derived therefrom presents the difficulty associated with the reversible character of both the fructose dimerization reaction and the glycosidation reactions, as well as the competition between these reactions and dehydration reactions. nonspecific
    In US 5 454 874, Richards has described the preparation of candies with a high fructooligosaccharide content by means of a process consisting of intimately mixing sucrose and a food acid, preferably citric acid or tartaric acid, both finely divided components, and submit the mixture to a heat treatment (130-160 ° C). The product thus obtained contains between 20 and 50% fructooligosaccharides, including fructose dianhydrides and their glycosylated derivatives, with a range in the degree of polymerization (DP) ranging from 2 to 20.
    In WO 96/39444, the same author has extended the previous method to the preparation of candies enriched in fructose dianhydrides and higher oligomers
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    from the inulin polysaccharide by pyrolysis at 150-205 ° C. In this case, the composition of the resulting product has been studied in detail. Specifically, it is established that the relative proportions of the different fructose dianhydrides present do not correspond to that expected for a thermodynamic distribution of the different isomers.
    A problem inherent to the methods mentioned is that, being weak acidic food acids, they lead to conversions into fructooligosaccharides which, in general, are less than 50%. The fact that the entire catalyst remains in the final product further limits the proportion in which it can be used and will significantly affect the organoleptic properties of the resulting candies.
    An additional problem of the above procedures is that weak acids used as promoters of caramelization lead to kinetic distributions of fructose dianhydrides that, not being in thermodynamic equilibrium, can evolve over time by altering the composition of the product, even more if we have Note that the isomerization and non-specific dehydration reactions are also catalyzed by the acidic medium. In general, in a distribution of fructose dianhydrides close to the thermodynamic equilibrium, the majority isomer contains a unit of fructose in the form of pyranose, while in kinetic distributions the majority compound contains the two units of fructose in the form of furanose.
    In WO 2008/107506 A1, EM Rubio Castillo and other authors describe the preparation of candies enriched in fructose dianhydrides and higher oligomers from fructose or other food sugars containing fructose, alone or in combination with other food sugars , using solid catalysts such as zeolites, bentonite or acidic ion exchange resins in their acidic form. These catalysts are capable of promoting the formation of candies with a high content of fructose dianhydrides and glycosylated fructose dianhydrides under heterogeneous conditions, guaranteeing a thermodynamic distribution of fructose dianhydrides. Once free of the catalyst, candies obtained according to this method presented prebiotic properties. Thus, the products obtained according to this method favored the development of a beneficial intestinal flora, particularly increasing the proportion of Bifidobacteria and Lactobacillus in animal models. In addition, they showed a reparative effect on the damaged colon in an animal model that corresponds to diseases such as Crohn's disease in humans, so
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    they can be considered as useful nutraceuticals for the treatment of this pathology and other related disorders in both humans and animals.
    Although the method described in WO 2008/107506 A1 leads to potentially usable products as ingredients or additives in the preparation of animal feed or in the elaboration of specific products intended for human consumption, it has the disadvantage that, not Being the catalyst a food acid, it requires a separation process that guarantees that no traces of it remain in the final product.
    There is therefore a need for methods of preparing candies with a high content of prebiotic oligosaccharides derived from fructose dianhydrides that run under homogeneous conditions, which do not imply catalysts that are not suitable for consumption, that therefore do not require the removal of the catalyst. at the end of the process or generate waste, and that preferably lead to well defined distributions, close to the thermodynamic equilibrium, of the final constituents.
    DESCRIPTION OF THE FIGURES
    Figure 1. Structures of the fructose dianhydrides present in fructose and sucrose candies (except in 8, the two monosaccharide subunits are derived from D-fructose; Fru = D-fructose; Glc = D-glucose; f = furanose; p = pyranose).
    Figure 2. Relative proportions of the different isomeric fructose dianhydrides obtained by caramelizing the D-fructose (85% weight / volume in water) with carbon dioxide gas (20 bar) at 100 ° C for 48 hours.
    Figure 3. Relative proportions of the different isomeric fructose dianhydrides obtained by caramelization of D-fructose (85% weight / volume in water) with carbon dioxide gas (20 bar) and citric acid (5% weight / weight relative to initial fructose) at 90 ° C for 12 hours.
    Figure 4. Relative proportions of the different isomeric fructose dianhydrides obtained by caramelization of D-fructose (85% weight / volume in water) with carbon dioxide gas (20 bar) and citric acid (10% weight / weight relative to initial fructose) at 90 ° C for 12 hours.
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    BRIEF DESCRIPTION OF THE INVENTION
    A first object of the present invention is the production of candies with a high content of prebiotic oligosaccharides from food sugars containing fructose in their composition, mixtures of several of these sugars or mixtures of these with other sugars, by procedures that do not require separation of the acid catalyst used and that do not generate waste.
    A second object of the present invention is a method that maximizes the content of prebiotic oligosaccharides of the fructose dianhydride type and glycosylated fructose dianhydrides in candies, preferably favoring isomeric distributions of fructose dianhydrides close to the thermodynamic equilibrium.
    In accordance with these objects of the invention and others mentioned below, the present invention provides a process for the preparation of candies with a high content of prebiotic oligosaccharides which includes:
    (a) A food sugar as a starting product, this may be D-fructose, sucrose or any oligo or polysaccharide that contains fructose as a constituent, including fructobioses such as palatinous or leucrose, fructooligosaccharides such as 1-kestose or the nosy, the fructans and the inulin. These starting sugars can be used alone or in combination in different proportions, as well as in combination with other or other sugars for food use, including glucose, galactose, maltose, lactose, raffinose or cyclodextrins.
    (b) The use of carbon dioxide as a catalyst, alone or in combination with a food acid such as acetic acid, citric acid or phosphoric acid, under homogeneous reaction conditions.
    Preferably, according to the invention, the caramelization is carried out in the presence of water, at concentrations of total sugar comprised between 60-95% (weight / volume) in water and with constant effective stirring, at temperatures ranging between 70- 140 ° C, preferably between 90-115 ° C, and reaction times that can range from 1 hour to a week, preferably between 24 and 72 hours when the catalyst used is exclusively carbon dioxide and between 6 and 12 h when used carbon dioxide in combination with a food acid in weight / weight ratio relative to sugar
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    Total starting between 1% and 20%, preferably between 5 and 10%.
    The present invention also provides new candies with a high content of fructose dianhydrides and glycosylated fructose dianhydrides, comprised between 40-85%, preferably between 50-80%, with an isomeric composition in fructose dianhydrides close to the corresponding one for a thermodynamic distribution, without the need to remove the acid catalyst used as a caramelization promoter, as well as the use of these candies as prebiotics that, among other favorable effects, favor the development of a beneficial intestinal flora, such as Bifidobacteria or Lactobacillus, and that show a reparative effect on colon lesions.
    DETAILED DESCRIPTION OF THE INVENTION
    In accordance with the present invention, it has been found possible to prepare candies with a high content of fructose dianhydrides and glycosylated fructose dianhydrides from sugars for food use, using exclusively carbon dioxide (CO2) as a caramelization promoter. These oligosaccharides have prebiotic properties, exerting a reparative effect on lesions of the colon and modifying the intestinal flora, increasing the proportion of beneficial bacteria such as Bifidobacteria or Lactobacillus in the digestive tract of both animals (birds, pigs, rabbits) and humans. Candies with a high content of these oligosaccharides have, consequently, important nutritional advantages compared to conventional candies.
    The starting sugar can be D-fructose, sucrose or any oligo or polysaccharide that contains fructose as a constituent, including fructobiosae such as palatinous or leucrose, fructooligosaccharides such as 1-kestose or nystase, fructans and inulin . These starting sugars can be used alone or in combination in different proportions, as well as in combination with other or other sugars for food use, including glucose, galactose, maltose, lactose, raffinose or cyclod extrins. The caramel is prepared using a high concentration of total sugar in water, between 60-95% (weight / volume) and preferably between 70-90% (weight / volume), in an airtight container and under a pressure of Carbon gas that can vary between 1 and 40 bars, preferably between 10 and 30 bars, and at temperatures ranging from 70-140 ° C, preferably between 90-115 ° C.
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    In the event that the starting sugar is D-fructose, the addition of water results in solutions throughout the range of concentrations of the invention. In the case of other sugars such as sucrose or inulin, or when starting from mixtures of sugars, suspensions can be obtained initially which, during the caramelization process in the presence of the catalyst, eventually lead to homogeneous solutions. The preferred caramelization times under these conditions range from 1 to 168 hours (one week), preferably between 24 and 72 hours.
    In accordance with the present invention, in all cases the reaction is preferably carried out under intense, efficient and constant agitation, for example magnetic or mechanical, during the heating period. The final product, obtained without the need to carry out any catalyst separation stage and without residues being generated, is a homogeneous caramel of amber to dark mahogany.
    According to another method of the invention, candies with a high content of fructose dianhydrides and glycosylated fructose dianhydrides can be prepared from food use sugars using carbon dioxide in combination with a food acid, preferably acetic acid, citric acid or phosphoric acid, as a caramelization promoter. In this case, the caramelization times range between 1 and 48 hours, preferably between 6 and 12 hours.
    The proportion of food acid referred to the total initial sugar weight may vary, preferably between 1% and 20%, more preferably between 5 and 10%. Although the use of higher proportions of food acid does not present technical problems, it is preferred to adapt the proportion of catalyst to the minimum necessary so that conversions are obtained in prebiotic oligosaccharides such as fructose dianhydrides or glycosylated fructose dianhydrides greater than 50% in lower times at 12 hours at caramelization temperatures of 80-115 ° C.
    In accordance with the foregoing, the process for preparing a caramel with a high content of prebiotic oligosaccharides of the fructose dianhydride type and glycosylated fructose dianhydride according to the present invention consists, essentially, in heating in a hermetic reactor of a solution or suspension of Starting food sugars at a high concentration in water, under a pressure of carbon dioxide gas that can vary between 1 and 40 bar, in the presence or not of a food acid, with constant effective stirring and at a temperature between 70-140 ° C .
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    A preferred method for preparing candies rich in prebiotic oligosaccharides according to the invention is the heating of a 70-90% fructose solution (weight / volume) in water at 80-115 ° C under a carbon dioxide pressure comprised between 10 and 30 bars, for a period of 24-72 hours.
    Another preferred method for preparing candies rich in prebiotic oligosaccharides according to the invention consists in heating a 70-90% fructose solution (weight / volume) in water containing a food acid such as acetic acid, citric acid or Phosphoric acid in a weight / weight ratio between 5-10% relative to fructose, at 80-115 ° C under a carbon dioxide pressure between 10 and 30 bar, for a period of 6-12 hours.
    The composition of the final product resulting from caramelization can be determined by gel filtration chromatography and gas chromatography, using techniques such as mass spectrometry and proton and carbon-13 nuclear magnetic resonance. The degree of polymerization (DP) of the prebiotic oligosaccharides formed ranges from 2 to about 25, generally between 2-12 when the starting sugar is fructose and generally increasing to 2-25 when the starting saccharide material contains other sugars. Oligosaccharides have a wide variety of types of glycosidic bonds.
    Candies prepared in accordance with the present invention contain proportions of the starting sugars or their monosaccharide constituents that vary between 10-60% and of prebiotic oligosaccharides of the fructose dianhydride type and glycosylated fructose dianhydride between 40-85%. When the initial sugar contains a monosaccharide other than fructose, the resulting caramel may also contain varying amounts of reducing reversing oligosaccharides resulting from the self-glycosidation of said monosaccharide. For example, in the case of candies obtained from sucrose, the presence of higher glucobioses and glucooligosaccharides is detected in a proportion generally less than 10%.
    In candies prepared according to the present invention, the disaccharide fraction consists mostly of fructose dianhydrides, while the higher oligosaccharides essentially have a glycosylated fructose dianhydride structure. The isomeric distribution of the different fructose dianhydrides in the disaccharide fraction can be determined by gas chromatography. The protocol can be followed for this
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    described by Ratsimba et al. in the document J. Chromatogr. A. 1999, 844, 283-293. Chromatograms obtained from samples of the candies of the invention indicate the presence of 13 isomeric fructose dianhydrides. In the particular case of candies obtained from sucrose, a mixed dianhydride containing a fructose and glucose subunit is additionally identified in this fraction. The structures of these dianhydrides correspond to the 13 and 14 structures previously identified in industrial or homemade candies obtained by heat treatment of D-fructose or sucrose, respectively, in the presence of a food acid, shown in Figure 1, a to know:
    - a-D-fructofuranose p-D-fructofuranose 1,2 ’: 2,3’-dianhydride (compound No. 1 or DAF 1).
    - p-D-fructofuranose a-D-fructopyranose 1,2 ′: 2,3’-dianhydride (compound No. 2 or DAF 2).
    - p-D-fructofuranose p-D-fructopyranose 1,2 ’: 2,3’-dianhydride (compound No. 3 or DAF 3).
    - Di-p-D-fructofuranose 1,2 ’: 2,3’-dianhydride (compound No. 4 or DAF 4).
    - a-D-fructopyranose p-D-fructopyranose 1,2 ′: 2,1’-dianhydride (compound No. 5 or DAF 5).
    - p-D-fructofuranose a-D-fructopyranose 1,2 ′: 2,1’-dianhydride (compound No. 6 or DAF 6).
    - Di-a-D-fructofuranose 1,2 ’: 2,1’-dianhydride (compound No. 7 or DAF 7).
    - a-D-fructofuranosa a-D-glucopiranose 1,1 ’: 2,2’-dianhydride (compound No. 8 or DAF 8).
    - a-D-fructofuranose p-D-fructopyranose 1,2 ′: 2,1’-dianhydride (compound No. 9 or DAF 9).
    - a-D-fructofuranose p-D-fructofuranose 1,2 ′: 2,1’-dianhydride (compound No. 10 or DAF 10).
    - a-D-fructofuranose a-D-fructopyranose 1,2 ’: 2,1’-dianhydride (compound No. 11 or DAF 11).
    - Di-p-D-fructofuranose 1,2 ’: 2,1’-dianhydride (compound No. 12 or DAF 12).
    - p-D-fructofuranose p-D-fructopyranose 1,2 ′: 2,1’-dianhydride (compound No. 13 or DAF 13).
    - Di-p-D-fructopyranose 1,2 ’: 2,1’-dianhydride (compound No. 14 or DAF 14).
    An important feature of the invention is that the relative proportions of the different isomers of fructose dianhydrides in the resulting candies preferably correspond to distributions close to the thermodynamic equilibrium. Thus, unlike what is observed in candies obtained by processes that exclusively use food acids as catalysts, in which the majority isomer is always a difructofuranosidic isomer, preferably compounds No. 1, 4 or 10, the majority isomer in candies obtained in accordance with the present invention is compound No. 9, in which one of the two fructose subunits is in the form of pyranose and is the most thermodynamically stable isomer.
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    An important feature of the invention is that the prebiotic oligosaccharides with the structure of fructose dianhydrides and glycosylated fructose dianhydrides that constitute the major components of the candies object of the same are not toxic and are not hydrolysable or only partially during digestion. In the latter case, the products resulting from hydrolysis are food sugars and, consequently, devoid of toxicity. The candies with high content of fructose dianhydrides and glycosylated fructose dianhydrides of the present invention thus exhibit a reduced caloric power compared to other candies of different composition.
    Candies prepared according to the present invention have important nutritional advantages, derived from their high content of prebiotic oligosaccharides, in particular of fructose dianhydrides and glycosylated fructose dianhydrides and of the isomeric distribution close to the thermodynamic equilibrium thereof, in comparison with candies of different composition prepared previously. These characteristics are analogous to those described for caramel obtained using solid catalysts such as zeolites, bentonite or acidic ion exchange resins in their acid form in WO 2008/107506 A1, but with the important advantage that the process described in the present invention does not require any stage of catalyst separation or generate waste. In fact, in trials conducted on Wistar rats that have been induced a lesion in the colon to generate a model analogous to Crown disease in humans, the candies of the invention have been shown to have an important reparative effect, analogous to that described. for candies prepared according to the procedure described in WO 2008/107506 A1, while favoring the development of a beneficial intestinal flora of the Bifidus and Lactobacillus type in the intestinal tract.
    Candies prepared in accordance with the present invention have numerous applications and can, in general, be used as a substitute for any other candy. The caramel obtained can be mixed with additional sugars, vitamins, aromas, dyes, with other prebiotics, probiotics or any other substance necessary for the preparation of a certain edible product. The caramel obtained can also be discolored, for example by treating an aqueous solution thereof with charcoal or with a resin suitable for the adsorption of colored products, such as the Lewatit® S6823 A resin, without this process affecting the composition in fructose dianhydrides and glycosylated or fructose dianhydrides or
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    relative proportion of the different isomeric fructose dianhydrides.
    The candies with high content of fructose dianhydrides and glycosylated fructose dianhydrides of the invention have properties especially beneficial for the treatment and prevention of pathologies in both animals and humans, particularly pathologies that affect the digestive system and more particularly Crohn's disease. , ulcerative colitis, colon cancer or infectious diseases, for example those caused by E.coli or Salmonella. They can also be used in the preparation of specific nutraceuticals for the prevention and treatment of these pathologies. In general, the candies of the invention can be used as a substitute for other prebiotics in the preparation of products intended for food or health and welfare in animals and humans. The final proportion of prebiotic candy of the invention in a product capable of producing a prebiotic effect for any of these purposes can vary over a wide range, preferably between 1 and 30%.
    EMBODIMENT OF THE INVENTION
    The features and advantages of the invention are more apparent in view of the following examples, which are illustrative and not limiting.
    Example 1:
    An 85% solution (weight / volume) of fructose (30 g) in water (5 mL) was introduced into a stainless steel reactor and carbon dioxide gas was injected until a pressure of 20 bar was reached. The homogeneous mixture was heated at 100 ° C in the closed reactor with constant magnetic stirring for 48 hours, after which it was allowed to cool to room temperature and the reactor was depressurized to atmospheric pressure. The product obtained in this way is a mahogany candy.
    Candy analysis by gel filtration chromatography, using Sephadex G10 as stationary phase, and by gas chromatography using phenyl p-D-glucopyranoside as internal standard, following the protocol described in J. Chromatogr. A. 1999, 844, 283-293, indicates the presence of fructose (28%), fructose dianhydrides (47%) and higher fructooligosaccharides of DP 3-12 (22%). The rest (3%) is
    consisting essentially of 2-hydroxymethylfurfural (HMF) and melanoidins. The proportions
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    Relates of the different isomeric fructose dianhydrides, determined from the corresponding gas chromatogram, are shown in Figure 2.
    The mild acid hydrolysis of an aliquot of the caramel obtained or of the fraction containing the oligosaccharides of DP 3-12 led exclusively to fructose and fructose dianhydrides, indicating that these oligosaccharides have a fructose dianhydride structure fructose. The isomeric distribution profile of fructose dianhydrides resulting from hydrolysis is practically identical to that of the DAF fraction in the initial caramel shown in Figure 2.
    Example 2:
    The procedure of Example 1 was repeated exactly, except that an 85% solution (weight / volume) of fructose (180 g) in water (30 mL) was used. The product is a mahogany candy containing fructose (31%), fructose dianhydrides (40%) and superior fructooligosaccharides of DP 3-10 (27%). The rest (2%) consists essentially of 2-hydroxymethylfurfural (HMF) and melanoidines. The distribution profile of fructose dianhydride isomers is practically identical to that of example 1.
    Example 3:
    The procedure of Example 1 was repeated exactly, except that a gas carbon dioxide pressure of 1.2 bar was used and heated at 90 ° C for 72 hours. The product is a dark mahogany candy containing fructose (37%), fructose dianhydrides (45%) and superior fructooligosaccharides of DP 3-10 (16%). The rest (2%) consists essentially of 2-hydroxymethylfurfural (HMF) and melanoidines. The distribution profile of fructose dianhydride isomers is practically identical to that of example 1.
    Example 4:
    An 85% solution (weight / volume) of fructose (30 g) in water (5 mL) containing 5% (weight / weight) of citric acid (1.5 g) relative to the starting fructose was introduced into a reactor of stainless steel and carbon dioxide gas was injected until it reached a pressure of 20 bars. The homogeneous mixture was heated at 90 ° C in the closed reactor with constant magnetic stirring for 12 hours, after which it allowed to cool to temperature.
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    ambient and the reactor was depressurized to atmospheric pressure. The product obtained in this way is a mahogany candy containing fructose (38%), fructose dianhydrides (47%) and superior fructooligosaccharides of DP 3-10 (9%). The rest (6%) consists essentially of citric acid, 2-hydroxymethylfurfural (HMF) and melanoidins. The relative proportions of the different isomeric fructose dianhydrides, determined from the corresponding gas chromatogram, are shown in Figure 3.
    Example 5:
    The procedure of Example 4 was repeated exactly, except that a proportion of 10% (weight / weight) of citric acid (3.0 g) relative to the starting fructose was used. The product is a dark mahogany candy containing fructose (31%), fructose dianhydrides (48%) and superior fructooligosaccharides of DP 3-10 (9%). The rest (11%) consists essentially of citric acid, 2-hydroxymethylfurfural (HMF) and melanoidins. The relative proportions of the different isomeric fructose dianhydrides, determined from the corresponding gas chromatogram, are shown in Figure 4.
    Example 6:
    An 85% solution (weight / volume) of palatinose (30 g) in water (5 mL) was introduced into a stainless steel reactor and carbon dioxide gas was injected until a pressure of 20 bar was reached. The homogeneous mixture was heated at 90 ° C in the closed reactor with constant magnetic stirring for 24 hours, after which it was allowed to cool to room temperature and the reactor was depressurized to atmospheric pressure. The product obtained in this way is a mahogany candy containing fructose (0.5%), glucose (0.6%), palatinous (54%) and higher fructose glycosyl dianhydrides of DP 3-12 (43%). The rest (1.9%) consists essentially of 2-hydroxymethylfurfural (HMF) or glycosylated derivatives of HMF and melanoidins.
    Example 7:
    The procedure of Example 6 was repeated exactly, except that the reaction time was extended for 72 hours. The product obtained in this way is a dark mahogany candy containing fructose (1%), glucose (2%), palatinose (35%) and higher fructose glycosyl dianhydrides of DP 3-16 (55%). The rest (8%) consists essentially of 2-hydroxymethylfurfural (HMF), glycosylated derivatives of HMF and
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    melanoidins
    Example 8:
    In vivo assessment of the intestinal anti-inflammatory effect of candies obtained according to examples 1 and 2 in experimental colitis induced by sodium dextran sulfate (DSS) in rats.
    The anti-inflammatory effect of candies enriched in fructose dianhydrides and glycosylated fructose dianhydrides of the present invention obtained according to examples 1 and 2 was evaluated in vivo in rats in an experimental colitis model following the procedure described in WO 2008 / 107506 A1 and in comparison to the candy obtained under the heterogeneous conditions detailed in example 3 of said document. The experimental animals that were used in these experiences are Wistar rats, weighing 200-230 g, supplied by the Experimental Animal Service of the University of Granada. The selected experimental inflammation model consists of the administration in the drinking water of 5% DSS for one week. This model is characterized by generating an inflammatory process in the rat's colon, with numerous similarities with inflammatory bowel disease in humans (Crohn's disease), in terms of the tissue damage it generates and the production of mediators involved in the inflammatory response. To carry out these studies, different groups of animals (n = 10) received the diet supplemented with the appropriate proportion of the prebiotic candies in the examples. This treatment began two weeks before the incorporation of the DSS into the drinking water and was maintained until a week later, at which time the animals were slaughtered and colonic damage was assessed. In order to assess the effectiveness of prebiotic treatment, control groups of colitic animals (n = 10) that received the standard diet containing cellulose were used instead of prebiotic candy. Additionally, a white group (n = 10) was used that did not receive any dietary treatment and did not undergo intestinal inflammation.
    The macroscopic assessment of the inflammatory bowel process was performed by determining the weight / length ratio of the colon (macroscopic damage index, MDI). For the weight / length ratio of the colon in control animals that have not suffered any injury, the IDM is defined as 0.0, while this index reaches an average value of 7.5 for the control group that was treated with DSS and did not receive prebiotic candies in
    fifteen
    your diet In animals that received the candies of examples 1 and 2, this value decreased to 5.5 and 5.3, respectively, practically identical to that achieved with the prebiotic candy obtained under heterogeneous conditions according to example 3 of WO 2008/107506 A1. Given the aggressiveness of the model used, the data collected in this example 5 indicate a protection / regeneration power against inflammation of the colon very significant and completely analogous to that described for candies enriched with fructose dianhydrides and glycosylated fructose dianhydrides obtained under heterogeneous conditions. , with the important advantage of not needing to remove the catalyst at the end of the preparation process and of not generating waste.
    10
    Example 11:
    In vivo assessment of the effect of the candies of examples 1 and 2 on bacterial flora in rats.
    fifteen
    On the animals undergoing treatment with DSS and to which a diet containing the prebiotic candies of Examples 1 and 2 is supplied, as well as on the corresponding control groups, the Lactobacillus and Bifidobacterium count was counted. The population of these bacteria decreases in animals treated with
    20 DSS at 30 and 20%, respectively, of the values observed in healthy untreated animals. In the case of animals for which the candies of examples 1 and 2 have been included in their diet, a very significant recovery of the corresponding populations is observed, reaching values close to the initial ones.
    权利要求:
    Claims (17)
    [1]
    5
    10
    fifteen
    twenty
    25
    30
    35
    1. - Procedure for the preparation of candies with a high content of prebiotic oligosaccharides from:
    (a) at least one starting saccharide material containing D-fructose, and
    (b) carbon dioxide gas as an acid catalyst for caramelization, characterized in that the caramelization process comprises heating a solution of the starting saccharide material in water in an airtight container and under a pressure of carbon dioxide between 1 and 40 pubs.
    [2]
    2. - Procedure for the preparation of candies with a high content of prebiotic oligosaccharides according to claim 1 wherein the prebiotic oligosaccharides are of the type of fructose dianhydrides and glycosylated fructose dianhydrides and the starting saccharide material is D-fructose, sucrose or any oligo- or polysaccharide containing fructose as a constituent, particularly fructobioses such as palatinous or leucrose, fructooligosaccharides such as 1-kestose or nistose, fructans and inulin.
    [3]
    3. - Procedure for the preparation of candies with a high content of prebiotic oligosaccharides according to claims 1 or 2, wherein the starting saccharide material containing D-fructose is used in combination in proportions between 1:10 and 10: 1 with the less other sugar for food use, particularly glucose, galactose, sucrose, maltose, lactose, raffinose or cyclodextrins.
    [4]
    4. - Procedure for the preparation of candies with a high content of oligosaccharides
    prebiotics according to any one of claims 1 to 3 wherein it is added to the
    reaction mixture a food acid that is selected from acetic acid, citric acid and phosphoric acid in a weight / weight ratio relative to the starting saccharide material comprised between 1% and 20%.
    [5]
    5. - Procedure for the preparation of candies with a high content of oligosaccharides
    prebiotics according to any one of claims 1 to 4 characterized in that the
    concentration of the saccharide starting material in water is between 60 and 95% (weight / volume)
    5
    10
    fifteen
    twenty
    25
    30
    35
    [6]
    6. - Procedure for the preparation of candies with a high content of prebiotic oligosaccharides according to claim 5, characterized in that the concentration of the starting saccharide material in water is between 70 and 90% (weight / volume).
    [7]
    7. - Procedure for the preparation of candies with a high content of prebiotic oligosaccharides according to any one of claims 1 to 6, characterized in that the temperature at which the heating is carried out is between 70 and 140 ° C.
    [8]
    8. - Procedure for the preparation of candies with a high content of prebiotic oligosaccharides according to claim 7, characterized in that the temperature at which the heating is performed is between 80 and 115 ° C.
    [9]
    9. - Procedure for the preparation of candies with a high content of prebiotic oligosaccharides according to any one of claims 1 to 8, characterized in that the heating takes place during a period of time between 1 and 168 hours.
    [10]
    10. - Procedure for the preparation of candies with a high content in
    Prebiotic oligosaccharides according to claim 9, characterized in that the heating takes place over a period of time between 24 and 72 hours.
    [11]
    11. - Procedure for the preparation of candies with a high content in
    Prebiotic oligosaccharides according to any one of claims 4 to 8, characterized in that the heating takes place during a period of time between 6 and 12 hours when adding a food acid.
    [12]
    12. - Caramel with a high content of prebiotic oligosaccharides obtained by a process as defined in claims 1 to 11, characterized in that it contains at least 40% of prebiotic oligosaccharides of the fructose dianhydride type and glycosylated fructose dianhydride with polymerization degree between 3 and 25 and with an isomeric distribution of fructose dianhydrides, in which the major isomer is the 1,2'-2,1'-dianhydride p-fructopyranose aD-fructofuranose pD-fructopyranose.
    [13]
    13. - Candy according to claim 12, characterized in that it additionally contains: a) at least one other sugar different from fructose, particularly glucose, galactose, sucrose, maltose, lactose, raffinose, cyclodextrins or reversing oligosaccharides formed from these sugars.
    b) at least one component selected from the families of vitamins, flavorings, dyes, prebiotics or probiotics.
    [14]
    14. - Use of caramel, as defined in claims 12 and 13, to prepare a
    5 product intended for animal or human food, being in proportion
    between 1 and 30%, capable of inducing an increase of Bifidobacteria or Lactobacillus in the intestinal tract.
    [15]
    15. - Use of caramel, as defined in claims 12 and 13, for processing
    10 of pharmaceutical product intended for the prevention or treatment of pathologies, in
    animals or humans, being in proportion in weight preferably between 1 and 30%
    [16]
    16. - Use of caramel, as defined in claims 12 and 13, for processing
    15 of pharmaceutical product intended for the prevention or treatment of pathologies that
    they affect the digestive system, in animals or in humans, being in proportion in weight preferably between 1 and 30%.
    [17]
    17. - Use according to claim 16, wherein the pathologies of the digestive system are Crohn's disease, ulcerative colitis, colon cancer or infectious diseases.
    DRAWINGS
    image 1
    OH
    OH HO O
    image2
    HO
    O ^^ OH
    HO or. 0
    Or oh
    OH
    image3
    OH
    af, mp 1.2 ': 2.3'
    image4
    mp, ap 2.1 ': 3.2'
    OH
    OH
    image5
    HO O,
    HO ^^^^ O- ^ ÓH V HO
    OH
    OH OH
    3
    Pf, pp 2.1 ': 3.2'
    OH
    OR
    Mp, mp 1.2 ': 2.3'
    5
    ap, pp 1.2 ': 2.1'
    image6
    OH
    , ^ 0 <3o.
    OH OH OH HO OH
    7 8th
    HO
    Ó ”0 ->" OH
    OH 6
    Pf, ap 1.2 ': 2.1'
    OH
    OH HO ^ ^ 0, ~
    OH
    HO or
    7
    af, af 1.2 ': 2.1'
    OH OR
    aFruf, aG! cp 1.1 ': 2.2'
    or
    af, pp 1.2 ': 2.1'
    image7
    OH
    10
    af, mp 1.2 ': 2.1'
    image8
    OH
    image9
    hoOCKHó0
    Oh oh
    14
    pp, pp 1.2 ': 2.1'
    FIG. 1
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    同族专利:
    公开号 | 公开日
    ES2671175B1|2019-03-13|
    WO2018091759A1|2018-05-24|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US5454874A|1993-11-30|1995-10-03|University Of Montana|Production of caramel having a high content of fructose oligosaccharides and caramel product|
    ES2304223B2|2007-03-08|2009-05-01|Universidad De Sevilla|NEW CANDIES WITH ELEVATE CONTAINED IN PREBIOTIC OLIGOSACARIDS, PREPARATION AND USE PROCEDURE.|
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    ES201631484A|ES2671175B1|2016-11-18|2016-11-18|PROCEDURE FOR THE PREPARATION OF CARAMELS WITH HIGH CONTENT IN PREBIOTIC OLIGOSACARIDOS|ES201631484A| ES2671175B1|2016-11-18|2016-11-18|PROCEDURE FOR THE PREPARATION OF CARAMELS WITH HIGH CONTENT IN PREBIOTIC OLIGOSACARIDOS|
    PCT/ES2017/070764| WO2018091759A1|2016-11-18|2017-11-18|Method for preparing caramels with a high prebiotic oligosaccharide content|
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