CA1090194A

CA1090194A - Process for the production of sweet material with 1- sorbose

Info

Publication number: CA1090194A
Application number: CA276,349A
Authority: CA
Inventors: Hans R. Muhlemann
Original assignee: Individual
Current assignee: Individual
Priority date: 1976-12-09
Filing date: 1977-04-18
Publication date: 1980-11-25
Also published as: JPS5372869A; DE2706319B2; AR210934A1; GB1566821A; DE2706319A1; FR2373238A1

Abstract

ABSTRACT OF THE DISCLOSURE

There is provided a mixture of sucrose, sorbose and a mono, di, oligo and/or polysaccharide. The mixture is employed in food, fodder or food supplements as a sweetener.
The mixture reduces the calorie value of the sucrose.

Description

1090~9~
BACKGROUND OF THE INVENTION
In numerous civilized countries, approximately one third of the total calories intake is in the form of the refined sugar, sucrose. In Germany, Great Britain, Switzerland, Scandinavia and the United States the sugar consumption per person per year is in the range of 35-55 kg., of which approx-imately 30% is recognizable as sugar, such as powdered sugar, cube sugar~ syrups, sweet dainties, sugar pastries, etc. In 1973, each Swiss ate 10 kg. of chocolate. The English consumed 6.5 kg. each of sugar confectionary per year. 70% of the sugar in eating and drinking is probably identified as "sweet", but is not absolutely recognized as sugar. In numerous foods and food supplements in place of sucrose (or in admixture therewith) there is also used in relatively high amounts fruit sugar (fructose), grape sugar (glucose) or mixtures of fructose and glucose (invert sugar, isomerose) or glucose syrup (hydrolyzed starch) or lactose or maltose. These also have high calorie content.
Experimental investigations of caries were tried in past years with some success because of caries prevention by substituting the sweetness recognizable as sucrose by poorly fermentable or non-fermentable carbohydrates, e.g., hexitols and pentitols. Although there is a loss of 100 Swiss francs a person per year because of dental caries which can be traced backtothe frequent eating of sweets and because of periodontal disease resulting from treating dental carities, of much greater social medicine significance are the fat illnesses (overweight), circulatory,

-2-10~0194 vascular and metabolism illnesses (Diabetes mellitus) caused by the excessive total amount of carbohydrates eaten. On account of the fact that they supply the greatest portion of calories in the total amount of sugar eaten, of particular importance as sugar is the sucrose in sweet pastries, biscuits, cakes, sugar enriched confitures, compotes, fruit juices, sauces, sweetened drinks, etc. The results which are injurious to health are treated in the monograph of J. Yudken (Sweet and Dangeous, P. H. Wyden Inc., New York, 1972). Modern nutritional studies extensively share Yudkin's previous warning of caloric overweight. As long ago as 1969, a recommendation of the Federal Republic of Germany required the reduction of one-third in the calories in the form of sugar. Until now, this has been without great success. Limitations of the calories supply have paved the way for sweetening drinks and foods with calorie free sweeteners in place of sugar. The food and food supplement industries as well as housewives at the range cannot give up sugar in the preparation of foods because of the numerous favourable properties of sugar as l'sweetener with body", preserving agent, filler and binder.
Therefore, the question has been asked whether the caloric value of sucrose as well as of mono, di, oligo and poly-saccharides can be modified by the addition of other less biologically usable sweeteners, i.e., lower calorie supplying carbohydrates.

SUMMARY OF THE INVENTION
It has now been found in animal tests ,hat a ketohexose, l-sorbose when added to the disaccharide sucrose, as well as to the monosaccharides fructose, glucose and their mixtures, up to starch inhibits the obtaining of nutritive energy from these carbohydrates without causing digestive disturbances. Studies with people are in progress.
To understand the subsequent description of the experiments on which the present invention is based there must be considered several chemical principles. "Sugar", whether refined or non-refined sugar, whether from sugar cane or sugar beets, chemically consists of the disaccharide, sucrose, a glucose-fructose molecule, see below:
Grape Sugar Fruit Sugar d-Glucose d-Fructose HO ~ OH 2C ~ oH2H

H OH
OH H

Mo'. Gew. 162 Mol. Gew. 180 "Sugar"

(Sucrose) ~ 'L ~ <~cH2oH
OH OH

Mol. Gew. 342 1090:194 l-Sorbose also is a sugar and is a stereoisomer of fruit sugar (d-fructose) and differs from the latter only through the position of the hydroxyl group at the C5 atom.

CO CQ
HOCH HOCH
HCOH HCOH
H ~ ~ H

d-Fructose l-Sorbose = l-Sorbinose = 2-Oxo-l-Xylohexose In eating carbohydrates, there is differentiated between their availability as suppliers of energy:
(1) in the mouth for the oral microflora, or the bacteria-film on teeth;
(2) in the stomach-intestinal tract for the intestinal microorganisms; and,

(3) after the absorption unchanged or converted carbohydrate for the metabolism occurring in the total organism.
It has been shown (Muhlemann/Schneider: "The Effect of Sorbose on pH of Mixed Saliva and Interproximal Plaque,"
Helv. Odont. Acta, 19, pages 76-80, 1976), that l-sorbose can supply no energy to the bacteria-film on the teeth since it is lgO194 only slowly fermented to lactic acid, among others (glycolysis).
The hydrogen ion concentration (pH) does not drop below 5.7 in the film on the teeth ("Plaque") ! As a result, l-sorbose can be designated as "safe for teeth" in Switzerland based on the regulation of the Federal Health Office, Bern, January 22, 1969.
The poor fermentability of pure sorbose in human saliva is established in a French patent application (Publication No.
2,201,081, Nationally registered No. 72,34057).
Mixtures of sorbose and sucrose and other sugars in freshly recovered total oral flora under laboratory conditions and in pH-telementry of the plaque were scarcely less fermented than sucrose or glucose, fructose, etc., alone.
The admixture of sorbose with other carbohydrates as set forth in the patent claims therefore takes place not with the view of reducing their teeth damaging properties in the mouth. It has much more turned out that orally consumed sorbose reduces the caloric value of simultaneously introduced mono, di, oligo (e.g., starch dextrins) and polysaccharides (starch). Experiment I illustrates this.
Unless otherwise indicated, all parts and percentages are by weight.

:1090194 DESCRIPTION OF THE PREFERRED EMBODIMENTS

1 Experiment I
2 Fifteen Osborne-Mendel rat litters, each with four 3 animals, after weaning at the age of 32 ways were distributed

4 to four different diets. The basic starch diet 2000f (Process 1) contained grain meal 64%, low fat milk powder 28~, dry yeast 5%, 6 NaCl 1%, and a 2% addition of a polyvitamin, mineral salt and 7 amino acid preparative (Gevral PR).
8 In processes 2, 3 and 4, a portion of the starch was 9 replaced by sucrose, l-sorbose or their combination as set forth in Table I A:

13 Process 1 2000f basic starch diet .
14 Process 2 2000f + 30%.sucrose Process 3 2000f + 30% sorbose 16 Process 4 2000f + 30% sucrose + 30~ sorbose 18 Drinking water and feed were available to the animals 19 _ libitum; however, in the course of the 35 day test.period from the different processes there were determined on 8 litters 21 chosen by chance, 8 times during 3 days: daily duration of 22 eating and drinking, frequency of eating and drinking, con-?3 sumption of feed and drinking water, water loss through diarrhea, 24 cleanliness of the cases and animals.
During the first three days of the caries tests the ~090194 1 young animals were orally innoculated with a mixture of 2 Stre-~tococcus mutans OMZ 176 + ActinomYces viscosus OMZ 105(~Jy-l) 3 plus a feces suspension of caries active animals. During the 4 experiments the behavior of the animals, condition of health, diarrhoea,etc., were continously followed. Upon killing there 6 was determined the increase in weight tg) in grams during 7 the experiments, the autopsies and photographs of the small 8 and large intestines, the determination of the bacteria lining g on the rat molars (BB), the slight (LKF) and average (MFK) caries lesions in the fissures of the lower-jaw molars and the smooth 11 surfaces of the molars (GK).
12 The results, average values, average error of the 13 middle value (sx) are collected in Tables I B and I C.

TABLE I B
16 Attack with bacterial coating (BB), slight (LFK) and 17 advanced fissure caries (FFK), smooth surface caries (G~) during 18 a 35 day caries test, weight increase (grams):

20 Process BB LFK ~FK GF g 21 Basic starch diet 2.6 0.1 0.Q 1.1 144 22 + 30~ sucrose 2.2 7.7 4.0 7.5 159 23 + 30% sorbose 1.9 0.0 0.0 0.0 9Q
24 + 330% sSorbose 2-6 3-7 0.9 5 4 51 Sx 0.23 0.63 0.52 1.27 7.5 1090~9~

The pure basic starch diet as well as the diet containing 30% of sorbose in contrast to the sucrose mixture were non-carious. The admixing ~f sorbose partially reduced the caries promoting properties of sucrose. Sorbose and particu-larly the addition of sorbose to sucrose retarded the averaqe increase in weight of the animals. Worthy of mention is the lack of diarrhoea already 3-4 days after the beginning of the experiments in the sorbose or sorbose-sucrose fed animals which supports absorption of the sorbose. The animals were healthy, active and had a clean, white skin. The cages also were clean.
The lack of diarrhoea can also be seen from the normal consumption of drinking water (Table I C). The amount of drinking was inconspicuous in the sorbose-animals, with the sucrose/sorbose-animals it was slightly reduced.
Table 1 C

Several Recorded Eating and Drinking Behaviour of the Animals in Experiment 1 24 Hour Values Process Eating Eating Drinking Drinking Feed Amount Time Frequency Time Frequency EatenDrunk min. min. H20 g g Basic starch diet 313 12 46 33 13 29 + 30% sucrose 329 13 51 37 13 31 + 30% sorbose 265 12 48 32 11 28 + 30% sucrose 252 13 44 34 9 24 30% sorbose s- 19.5 1.0 3.1 1.1 0.4 1.8 x ~090194 Feeding of sugar substitutes, e.g., 30% sorbitol or 30% xylitol in the same basic starch diet as shown by other investigators produces severe diarrhoea and frequently high loss of animals, which was not the case in present Experiment I
although the addition of sorbose along to the basic starch diet through influencing the intestinal flora also led to slight swelling of the intestine (caecum, meteorismus). The simultaneous dispensing of 30% sorbose + 30% sucrose, however, in the autopsies showed a normally proportioned intestine with much less weight increase (Table I C). The missing caecum swelling in the sucrose-sorbose combination in Experiment I as well as in other combina-tions in Experiments II and III (see below) makes it highly improbable that there are formed the so-called "volatile fatty acids" by gas production with simultaneous formation of acetic acid, propionic acid and butyric acid (Seely et al., in "Energy Metabolism of Farm Animals," Ed. Kil. Blaxter et al., Orid Press, 1969, pages 93-102), as is the case in feeding sorbose alone and togethertherewi-th a restricted caloric effect. This can be - an intestinal, but probably less important mechanism of the caloric restriction.
The retarding of the increase in weight with obviously sound animals in Experiment I points additionally to a retarding action of the sorbose on the sucrose utilization as well as that of the already mentioned mono, di, oligo and 109019~

polysaccharide on the metabolism of the entire animal.
The mechanism for checking the increase in weight is completely different from that of another sugar substitute, xylitol, as can be seen in the independent Experiments II and III (Table II). After 19 or 33 days feeding of a basic starch diet substituted with 17~ of sucrose, fructose, glucose, sorbose or xylitol there were found the following increases in weight and diarrhoea indices.
TABLE II

Increase in Weight in Grams and Degree of Diarrhoea of Osborne-Mendel Rats After 19 or 33 Days Feeding of a 17% Substituted Basic Starch Diet (12 Animals per Procedure) Basic Starch Diet Increase in Weight After Diarrhoea Substituted With 19 Days 33 Days Index Exp. II III II III Exp. II

Non~- ~ 901911~147~140 rO'~TO'-Sucrose 85 142 0.25 0.2 Fructose-Glucose 1:1 92 147 0.3 0.2 Fructose Alone 93 151 0.2 0.0 Sorbose 68 69 118 116 0.9 0.1 Xylitol 59 114 2.2 1.4 Glucose 95 146 Glucose-~orbose 1:1 84 _ 127 _ * Average of determinations at 2, 5, 13 and 33 days of test (Degree of Diarrhoea 0, 1, 2 and 3).
** Index at the 33rd day of test --11~

1~)90194 1 The retardation of growth by xylitol depends on a 2 severe disturbance in the digestive tract (diarrhoea). The 3 retardation of the increase in weight by the substitution of 4 sorbose alone is similarly marked as that by xylitol). }~owever, there does not result an intestinal illness as a result thereof 6 as is shown by the degree of diarrhoea.
7 The effect on the conservation of energy (growth) 8 in Experiments I, II and III is not explainable by a theoreticall g considered reduction of the supply of starch.
` Total replacement of the starch in the basic diet, 11 e.g., by sucrose, only causes slight disturbances in growth 12 with Osborne-Mendel rats ~K. G. Konig and T. H. Grenby, 13 Arch. Oral Biol. 10, 43 (1965)).
14 Reference is also made to Experiments II and III
lS concerning this. The reduction of the portion of starch in 16 the basic diet of 64% to 47% by admixing 17% of glucose or 17 17% of fructose does not cause growth disturbances. However, 18 this same I7% substitution of the starch by a mixture of 1 19 part glucose and 1 part sorbose, however, resulted in a clear retardation of growth (from 140, 146, 147 or 151 grams to 127 21 grams). It is theorized that with the simultaneous presence 22 of sorbose and physiological energy metabolites (glucose, 23 fructose) in the organisms the recovery of energy and therewith 24 the growth is retarded by opposing influences. Through this the caloric value of an orally fed sorbose-monosaccharide or .

__ _ sorbose-disaccharide, etc., is reduced. It is a retarding effect supposedly based on the molecular asymmetry fructose-sorbose in accordance with Conforth (Science 193, page 121 (1976)).
Sorbose is produced by bacterial or catalytic dehydrogenation of sorbitol which occurs in nature. Sorbose is crystalline very similar to sugar. In contrast to fructose, sorbitol and xylitol, it is not hygroscopic and in combination with sucrose is non-laxative. It is colorless, odorless, chemi-cally stable and easily soluble in water. 50% sucrose-50% sorbose mixtures are completely compatible, stable and appear to be of the same crystal particle size as sucrose and are able to be used in cooking as "sugar". Sorbose melts at 165C without decomposition. Sorbose is caramelizable. The sweetening power of sorbose alone is double that of sorbitol, greater than that of d-glucose and about 0.6-0.75 that of sucrose. It is without after-taste. Mixtures of 1 part sorbose and 1 part sucrose have nearly the same properties for the senses as conventional sugar (sucrose). The mixture can be made still sweeter in foods and food supplements with calorie free sweeteners, e.g., saccharin.
The~acute, subacute and chronic toxicity of sorbose for animals and men have been investigated by Ch. Dupas (Le sorbose These de pharmacie, Univ. de Lille II, 1974). The findings are very favorable.
The present invention is directed to the admixture of logolg4 sorbose in an effective amount in all natural and synthetic sucrose, fructose, glucose, invert sugar, iscmerose, glucose syrups, lactose, maltose, oligodextrin and polysaccharide, e.~., starch, containing foods and ~ood supplements for reducing the calorie value or to a stopping up of the calorie intake not recognizable by the consumers so that there is an effortless prophylaxis of overweight (obesity) and its consequential effects on the circulation, vascular system and metabolism of the organism.
By the "admixture" of sorbose to sucrose or to mono, di, oligo and polysaccharides there is meant a mechanical mixing of the pure monohexose sorbose with, for example, the pure disaccharide, sucrose. Thereby there is formed a mixture utilizable in cooking as powdered or crystalline sugar. On the other hand sorbose can be mixed along with foods and food supplements wh~ch already contain naturally monosaccharides, ~ disaccharides, oiigodextrins or mixtures thereof or also contain starch.
The present invention makes possible to cook in cooking as previously was done with "sugar" (sucrose) or to dispense "sugar" on the table, whereby, however, the theoretical caloric content of this "sugar" (e.g., sucrose-sorbose mixture is not completely utilized in the organism.
The theoretically optimum mixing ratio with sucrose is 1:1. Under these conditions one molecule of l-sorbose compares with one molecule of d-fructose from the sucrose. The ~090194 1 claims of the invention, however, include both smaller and 2 larger amounts of sorbose based on the total of sorbose and 3 sucrose, since the absorption ratio in the intestine can 4 change according to the composition of a meal. Further research with people also can be carried out to optimize the 6 ratios in a particular feeding situation and the type of 7 carbohydrate composition.
8 The sweetening mixtures of the invention consist of 9 various categories:
1. Powdered sugar for use in cooking and on the 11 table -12 40 to 90 weight % sucrose and 13 10 to 60 weight % sorbose.
14 2. Confectionary Goods:
(a) Sugar containing chocolates, chocolate 16 compositions, e.g., 17 Sucrose 75-130 grams 18 Sorbose 75-20 grams 19 Eggs 4 Egg yoIks 4 21 Flour 100 grams 22 Chocolate powder 30-40 grams 23 In this example the amount of sorbose varies inversely 24 with the sucrose so that the total of sucrose and sorbose is 150 grams.

.. .. _ . .

1090~94 1 (b) Sugar containing pastries such as mocha cubes, 2 chocolate balls, Moor's heads, coverings, sweet fillings:
3 nougat, marzipan, praline (chocolate cream) compositions, almond 4 macaroons -e.~. almond macaroons 6 Fresh shelled almonds 250 grams ? Sugar (sucrose) 125-225 grams 8 Powdered sugar 100 grams 9 Sorbose 225-125 grams In this example the amount of sorbose varies inversely 11 with the sucrose so that the total of sucrose and sorbose is 12 350 grams.
13 (c) Sugar containing frostings and sweets, such as 14 cream frostings, sugar frosting, powdered sugar frostings, semi-frozen parfaits, shells, cassata, coupes (e.g., Danish, 16 tu~ti frutti, napoleons, etc.) -17 e.~. vanilla frosting 18 Milk 800 ml 19 Cream 200 ml Sucrose 125-225 grams 21 Glucose 50 grams 22 Sorbose 125-25 grams 23 Egg yolks 10 24 1/2 vanilla stalk In this example the amount of sorbose varies inversely 1 with the sucrose so that the total of sucrose and sorbose is 2 250 grams.
3 (d) Sugar containing cold drinks such as ice coffee, 4 ice cream soda, sherbets, frappes, sugar containing creams, vacherins, meringues, etc.
6 3. Sugar containing (sucrose, maltose, glucose, 7 invert sugar), energy imparting foods, food supplements and 8 ~efreshing agents in liquid or solid form with coooa (e.g., the typ-9 of Ovomaltine).
4. Infant and small child food preparations with 11 sucrose, lactose, honey, isomerose, glucose syrup, sweetened 12 condensed milk, sweetened dry milk.
13 5. Sweetened or unsweetened jams, marmalades, 4 sweet fruit, sweetened preserves, fruit syrups. There can be employed unsweetened, naturally sweet, or fructose containing 16 marmalades additionally sweetened with sorbitol, mannitol or 17 Lycasine~or with artificial sweeteners as well as sugared 18 (sucrose, glucose syrup, isomerose, fructos-e, etc.) ~9 The addition of sorbose to unsweetened ~sorbitol containing) confectionaries depends on the content of natural 21 sugars (fructose, glucose, etc.) -22 e.g. apricot marmalade 23 Filtered- fruit juice 1000 grams 24 -Sorbose 50-250 grams Sucrose- 250-45 grams Pectin ~090194 1 In this example the sorbose varies inversely with the 2 sucrose~
3 6. Sugared sweet drinks -4 e.g. mineral water 1000 ml sucrose 60-100 grams 6 sorbose 60-20 grams 7 citrate (flavor) 8 In this example the sorbose varies inversely with the g sucrose so the total is 120 grams.
7. Sugar containing doughs, baked goods, small 11 pastries, confectionary.
12 The sugar addition to dough can be partially replaced 13 with sorbose, for example, sweet butter dough, chocolate, Linzer 14 dough-, honey dough -e.~. sugar dough 16 flour 1500 grams 17 sucrose 400-700 grams 18 sorbose 400-100 grams 19 butter 700 grams eggs 6 21 egg yolks 22 lemon, leavening salt 23 In this example the sorbose varies inversely with 24 the sucrose so that the total of sorbose and sucrose is 800 grams.
The invention also includes sugar containlng honey 1090~94 ~Leckerle~' 1 pastry, "Basle V gingerbread, biscuits, "Mailanderli", 2 chocolate cream rings, chocolate bubbles, macaroons, nut 3 confectionary, almond stalks, chrabeli, amaretti, pretzels, 4 "Schoggibissen", "Totenbeinli", half moons, almond peaks, risotes, etc. -6 e.~. home biscuits 7 sucrose 300-500 grams 8 sorbose 300-100 grams 9 synthetic honey 150 grams butter 700 grams 11 flour 1000 grams 12 wheat powder 1000 grams 13 eggs 2 14 egg yolks 2 leavening salt 10 grams 16 milk 300 grams 17 lemon 18 In this example the amount of sorbose varies inversely 19 with the sucrose so that the total of sucrose and sorbose is 600 grams.
21 There are also included sugar containing cakes, filled 22 fruit loaves, special tortes such as Zuger cherry torte, 23 Engadiner torte, etc.
24 The compositions can comprise, consist essentially of or consist of the materials set forth.

1 The sorbose is usually present in an amount of 2 1:0.5 to 1:5 moles, per mole of the other saccharide. Preferabl~
3 the molar ratio is 1:1. With saccharides above disaccharides, 4 e.g., starch, the ratio of sorbose to saccharide can be 1:0.5 to 1:50 moles of sorbose per saccharide unit (in the case 6 of starch this would be l:O.S to 1:50 moles of sorbose per 7 glucose unit).

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
l. A sweetening composition comprising a mixture of 1-sorbose and another saccharide, the other saccharide being a mono-saccharide, a disaccharide, an oligosaccharide or a polysaccharide, the molar ratio of sorbose to other saccharide being from 1:0.5 to 1:50.
2. A composition according to claim 1 wherein the ratio of sorbose to other saccharide is from 1:0.5 to 1:5.0 on a molar basis.
3. A composition according to claim 1 wherein the other saccharide is a monosaccharide, a disaccharide, a trisaccharide or an oligosaccharide.
4. A composition according to claim 3 wherein the other saccharide is glucose, fructose, invert sugar, sucrose, lactose or an oligo dextrin.
5. A composition according to claim 4 wherein the other saccharide is glucose, fructose, invert sugar or sucrose.
6. A composition according to claim 5 wherein the other saccharide is sucrose.
7. A composition according to claim 6 wherein the sucrose is 40 to 90 weight % and the sorbose is 10 to 60 weight % of the total of sucrose and sorbose.
8. A composition according to claim 7 wherein the sucrose and sorbose molar ratio is 1:1.
9. A composition according to claim 2 wherein the molar ratio of sorbose to other saccharide is 1:1.
10. A food or food supplement comprising another food or food supplement and the sweetening composition of claim 1.
11. A food or food supplement according to claim 10 which is a beverage.
12. A beverage according to claim 11 which is coffee, tea, or chocolate.
13. A food according to claim 10 which is a solid food.
14. A food according to claim 13 which contains starch.
15. A food or food supplement according to claim 10 which is powdered sugar, chocolate, baked goods, frosting, sweet drinks, energy imparting food, infant food, confectionary, marma-lade, jelly or jam.
16. A food according to claim 10 which is a cake, pastry, pie or cookie or a cake mix, pastry mix, pie mix or cookie mix.
17. A food according to claim 10 which includes flour.
18. A food or food supplement according to claim 10 wherein the other saccharide is sucrose, glucose, fructose, invert sugar or lactose.
19. A food according to claim 10 also including starch.
20. In a process of preparing a food or food supplement containing a sweet material comprising a sugar, which is sucrose, glucose, fructose, invert sugar or lactose, the improvement comprising including in the sweet material 1-sorbose as a partial replacement for said sugar, the molar ratio of sorbose to sugar being from 1:0.5 to 1: 5 . O .
21. The process of claim 20 wherein there is employed 1-sorbose and said sugar in the molar ratio of sorbose to said sugar of 1:0.5 to 1:50.
22. The process of claim 21 wherein the food or food supplement also includes starch.
23. The process of claim 21 wherein the food or food supplement is a dairy product.
24. The process of claim 21 wherein the food or food product is a composition suitable for baking.