CA1096306A - Anticariogenic comestible - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Anticariogenic comestibles (i.e., food products that reduce the incidence and severity of dental caries) may be obtained by incorporating therein a cariostatic additive comprising a soluble aluminum ion containing salt and a member selected from the group consisting of adipic acid, ascorbic acid, and mixtures thereof. Dental health benefits of such products may be further enhanced by employing as a nutritive sweetening system therein a mixture of at least one first sweetening agent consisting of sorbitol and/or xylitol and at least one second sweetening agent consisting of dextrose and/or fructose, with the mixture containing at least about 75%
of the first agent by weight of the mixture where dextrose is the second agent and at least about 60% of the first agent where fructose is the second agent.

Description

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This invention relates to the production of comestibles. More specifically it is concerned with a candy product which is rendered anticariogenic through the use of a novel cariostatic additive.
The prior art has long sought a means to compensate for the cariogenic potential of comestibles, particularly foods containing high preponderances of sweeteners such as sucrose and other sugars. It has been theorized that, when sugars are placed in the mouth, they give rise to the production of acids which promote dental caries.
A contributing cause of dental caries in children is the adherence of highly refined sugars and their decomposition products to the dental plaque after ingestion, coupled with the slow rate of oral clearance, or the ability to produce high amounts of acid, or combinations of such factors.
A number of cariostatic agents have been evaluated in the past in systems wherein the agent is applied or consumed topically (i.e. directly on the teeth) in the form of a dentifrice (e.g., a toothpaste or a toothpowder). However, knowledge gained on the effectiveness of eariostatic agents used in sueh topieal applieations has not permitted predietion of efficacy for these eariostatie agents in other applieations, sueh as in foods, and partieularly in foods eontaining a substantial portion of sugars.
Unfortunately, known eariostatie agents have in general not provided any substantial degree of protection when used in foodstuffs. Thus, known eariostatic agents sueh as fluorides, ~ 2 -3~

I phosphates, vitamin ~, nitro~urlns, ammonium compo~nds, iodoacetic 2I acid and the like, when added separately to a food stuff containing 31 a high percentage of sugar, have little direct topical effect in a 4 1 foodstuff environment.
For the foregoing and other reasons, dental researchers 6 have continued their efforts to develop new anticariogenic agents 7 which not only demonstrate a high level of anticariogenic effec-81 tiveness but which are non-toxic, stable, and widely available. It gI has been suggested that aluminum salts may have a beneficial effect o¦ in reducing dental caries or in facilitating the uptake of fluoride 11¦ by the dental enamel. See, e.g., Manly et al., "Substances Capable 12 of Decreasing the Acid Solubility of Tooth Enamel", J. Dent Res.
151 28: 160 (1948); Regolati, et al., "Effects of Aluminum and Fluo-14 ride on Caries, Fluorine Content and Dissolution of Rat Molars", 15 1 Hel. Odon. Acta. 13: 59 (1969); and Kelada, "Electrochemical 16l Characteristics of Free and Complexed Fluorides in Drinking Water 17 l¦ and The Effects of Aluminum and Iron on Fluoride Incorporation Into Tooth Enamel," Univ. Michigan Thesis (1972).
lg ! In vitro studies have shown that pretreatment of enamel with aluminum solutions resulted in increased fluoride uptake when 21 followed by treatment with a fluoride solution; however, treatment 22 with combinations of aluminum and fluoride did not afford any added 23 benefit over that of fluoride alone. McCann, "the Effect of Fluo-24 ride Complex Formation on Fluoride Uptake and Retention in Human Enamel", Archs. Oral Biol. 14:521 (1969); and Gerhardt, et al., 26 "Fluoride Uptake in Natural Tooth Surfaces Pretreated with Aluminum 27 Nitrate", J. Dent. Res. 51:870 (1972). Moreover, the foregoing 28¦ techniques have dealt primarily with the use of aluminum in combi-29 ! nation with fluorides and have not focussed on the effect of alumi-30I num in the absence of fluoride.

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63~6 1 It has heretof~re ~een s~ggested that ~he addition of a

2 ¦source of aluminum to the diet may reduce the cariogenic potential

3 ~thereof. However, studies have to date suggested that aluminum is

4 ¦ ineffective as a dietary anticariogenic agent. Thus, Van Reen, et

5 ¦al., "Trace Elements and Dental Carries: Molybdenum, Aluminum, and

6 ¦Titanium", Helv. Odont. Acta., 11:53-59 (1967), concluded (p. 57)

7 ¦ that "Aluminum potassium sulfate when added to the drinking water 81 of rats to provide 10, 50, or 100 ppm of aluminum did not afford 9¦ any protection against dental caries. . . ." The same conclusion o¦ was reached with aluminum added to the dietrary ration fed rats, as 11¦ reported by Wynn et al., "Dental Caries in the Albino Rat on High 12¦ Sucrose Diets Containing Different Amounts of Aluminum", J. Nutri-1~ tion, 54:285-290 (1954), and with parenterally injected aluminum, 14 1 as reported by Kruger, "The Effect of "Trace Elements" on Experi-15 ¦I mental Dental Caries in the Albino Rat", Univ. of Queensland Papers, 161 1:1-28 (1959).
17 Nor has the use of aluminum salts in dentrifices demon-1~ strated a desirable result. Thus, while French Patent No. 3610M
19 describes a specific combination of aluminum lactate, aluminum 20 fluoride and calcium pyrophosphate, the abrasive interferes with 21 ¦ the aluminum by reacting therewith to form insoluble aluminum 22 ¦ phosphate. Similarly, U.S. Patent 3,095,356 uses aluminum salts 23 I such as aluminum fluoride to coact with insoluble sodium metaphos-24 phate abrasives to reduce the solubility of such abrasives and to 25 increase fluoride uptake, but without independent therapeutic 26 advantage being taken of the aluminum.
27 U. S . Patent No. 3,282,792 describes low pH stannous 28 fluoride dentifrices stabilized against precipitation and oxidation 29 of stannous tin ions through the use of hydroxyl substituted di-and 30 ¦ tri-carboxylic acids. However, nothing is said in the patent S2 ,1 lll -4-~L~9~i3~6 l egardirlg the use of aluminum Wlth respect to systems thnt do not 2 contain fluoride. Similarly, while U.S. Patent 3,937,806 teaches 3 ¦oral compositions comprising indium and fluoride to which malic 4 ¦acid is added to stablize the indium, the patent does not recognize S ¦that beneficial results may be achieved with aluminum and carbo-6 ¦xylic acids without incorporating fluoride.
7 I Canadian Patent No. 928,272 describes acidic dentifrices

8 ¦comprising a combination of surface active substances and albumen

9 ¦coagulating substances such as certain carboxylic acid salts of

10¦ aluminum and other metals. However, this patent likewise fails to 1¦ teach that significant dental health benefits can be achieved with 12 ¦ aluminum containing comestibles.
15¦ Thus, while some elements are known to inhibit dental 14¦ caries (e.g., F, Mo, Sr, and V) and while others are known to 15¦ promote caries (e.g., Se, Mg, and Cd), the preponderance of data on 16 ¦ aluminum indicates that it is dental caries inert as classified by 171 Navia, "Effect of Minerals on Dental Caries", in Dietary Chemicals 1~¦ v. Dental Caries, A.C.S., Washington, D.C. (1970).
19¦ U.S. Patent 3,772,431 concerns a mouthwash tablet contain-ing a effervescent couple (e.g., a solid basic material and a solid 21 lorganic acid such as fumaric, citric, tartaric), which produce CO2 22 ¦when dissolved in water, in combination with an astringent-desensitiz-23 ¦ing agent, which may (but need not) be an aluminum compound. In 24 ¦addition, the patent discloses the optional use of Vitamin C (as-251 corbic acid) as a mucin precipitating agent in combination with an 26 ¦ anti-microbial agent and a chelating agent. The patent, however, 27l does not suggest that any anticariogenic therapeutic effect is 28 achieved as a result of the aluminum compounds in such composi-29 1 tions. In fact, other essential constituents in the tablets are 30l incompatible with alumimum ions such that they are not therapeu-31 1I tically available.

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In sum, the prior art has not heretofore suggested a therapeutically effective system which provides biologically available aluminum in a comestible in the absence of fluoride.
Accordingly, the primary object of this invention is to provide means for overcoming the disadvantages of the prior art approaches to reducing the dental caries potential of sugar containing foodstuffs.
A related objective is to provide an effective aluminum containing cariostatic additive for use in sweetened comestibles such as candy.
A further object is to provide anticariogenic comestibles incorporating aluminum containing cariostatic additives of the character described.
Another object is to provide anticariogenic comestibles of the character described which incorporate a noncariogenic nutritive sweetening system.
A still further object is to provide new anti-cariogenic candies.
The foregoing and other objects, advantages, and features of this invention may be achieved by incorporating in comestibles anticariogenically effective and nontoxic amounts of a cariostatic additive comprising at least one soluble aluminum ion containing salt and a member selected from the group consisting of adipic acid, ascorbic acid, and mixtures thereof. Where such an additive is provided in a candy product, even very low levels of additive (e.g., amounts of aluminum as low as about 100 ppm) are effective since repeated ingestion of small amounts of the anticariogenic agent has been shown to have an accumulative effect.

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1 Desirably such additive containing comestib1es also 2 incorporate a noncariogenic nutritive sweetener comprising a mix-3 ¦ ture of at least one first sweetening agent selected from the group 4I consisting of sorbitol, xylitol and mixtures thereof and at least o~e second sweetening agent selected from the group consisting of 1~ ~eX ~ rOs~
6 ~cet~se, fructose and mixtures thereof. The mixture contains at 7 least about 75% of the first sweetening agent by weight of the 8 mixture where dextrose is the second agent and at least about 60%
9 of the first agent where fructose is the second agent. The sweet-ener is provided in the comestible in an amount effective to ll sweeten it.
12 Use of the cariostatic additive of this invention reduces l~ ¦ the acid solubility of dental enamel and, where the sweetening 14¦ system of this invention is also employed, there are obtained products which, when introduced into the mouth, exhibit: little or 16 no harmful lowering of the dental plague pH (indicating that the 17l formation of decay causing oral acids has been minimized)i little or no harmful decalcification of the dental enamel (decalcification 19 I being a precursor of dental caries formation); and rapid oral clearance.

22 DET ILED DESCRIPTION OF THE PREFERRED EMBOLI~ENTS

I In accordance with this invention, comestibles, especi-25 ¦ ally sweetened comestibles such as candy, have incorporated therein 261 anticariogenically effective and nontoxic amounts of an additive I comprising a mixture of one or more soluble aluminum ion containing 281 salts and a member selected from the group consisting of adipic 291 acid, ascorbic acid, and mixtures thereof.

1l -7-1~9(i30~i 1 1~ As used herein, the term "comesti~le" should be understood 2 ¦ to mean substantially any of the wide range of food products suit-3 ¦ able for ingestion by humans, including without limitation candies, 4 ¦ bakery products, chewing gum, prepared beverages, fruit preparations, 5 ¦ and the like.
61 As used herein, the term "ascorbic acid" should be under-7 ¦ stood to encompass its isomeric epimer, isoascorbic acid, also known 81 as erythorbic acid and D-erthro-hex-2-enonic acid qamma-lactone~
9¦ which may be substituted for it for purposes of this invention.
o¦ The adipic and/or ascorbic acid may be present at any

11 convenient level greater than 0 up to about 6% by weight of the

12 comestible. Preferably, the acid is present at a level of about 3%
by weight.
14 The particular soluble aluminum salt employed is not critical, and substantially any nontoxic water soluble aluminum ion 16 containing salt may be used. Suitable aluminum salts include alu-17 minum potassium sulfate, AlK(S04)2.12H2O; aluminum chloride, 1~ AlC13.6H2O; aluminum sodium sulfate, AlNa(SO4)2.12H2O; aluminum 19 ammonium sulfate, AlNH4(SO4)2.12H2O; aluminum sodium phosphate, 20 ¦ NaA13H14 (P04)8.4H20; aluminum sulfate, A12(SO4)3.18H2O; aluminum 21 nitrate, Al(NO3)3 and sodium aluminate, NaA102. Aluminum potassium 22 sulfate and aluminum sodium sulfate are preferred by reason of their 23 wide availability and established safety.
24 The anticariogenically effective and nontoxic amount of 25 ¦ the soluble aluminum salt should lie in the range capable of sup-26 ¦ plying about lOOppm up to about 1000 ppm aluminum ions, (0.01 - O.lC
27 weight percent, calculated as aluminum ion). Thus, where aluminum 28 potassium sulfate dodecahydrate and aluminum chloride hexahydrate 29 are employed, the respective salts are present in the range of about 30l 0.2 up to about 2% and about 0.1 up to about 1.0% by weight.
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1~63C~6 I The cari~static additlve of this inventi~n may be used in 2 ¦ all types of sweetened comestibles such as hard candies, taffies 3 I and carmels, chocolates and chocolate coatings and in other candy 4 ~ products. Preferably, however, the additive is provided in tab-5 ¦ leted and cooked hard candies. Where candy products are produced 6 ¦ from a variety of individual constituents (as in candies in which a 7 I cooked sugar based center may be coated with chocolate), the addi-81 tive of this invention may be employed in one or more of the con-9¦ stituents or in all of them.
lo¦ An important feature of this invention is the discovery 11 that, in comparison with other conventionally used carboxylic acids 12 such as citric acid and malic acid, ascorbic and adipic acids are 1~ relatively safe and do not decalcify the teeth when present in the 14 mouth during the rapid oral clearance period achieved with the 15 candies of this invention. In addition, these acids (1) do not 16 interfere with aluminum ions as do many other carboxylic acidsi (2) 17 1 help temporarily to reach pH of 3.5-4.5 in the mouth at which 1~ ¦ aluminum ions are most actively incorporated into dental enamel;
19l and (3) open the enamel apatite crystal lattice somewhat so alumi-num ions may better react with the enamel.
21 I Candy products produced in accordance with this inventon 22 ¦ are essentially the same as prior art candy products with the 23l exception that, by virtue of the addition of the cariostatic addi-24 tive of this invention, the candy products hereof may be safely 251 consumed without causing or promoting dental caries.
26¦ Thus, anticariogenic candy products produced in accor-27l dance with this invention may contain usual and customary comple-2~1 mentary ingredients conventionally found in candy products such as 291 colorings, flavorings, dairy and vegetable fats, foaming agents, 30l~ texturing agents such as crisped rice, nuts, and the like. How-31 ll ever, certain conventional candy ingredients are undesirable from a 32 ll ,1 _ 9 _ 1~9~i3~6 1 ¦ dental standpoint. For example, significant amounts of fats and 2 ¦ texturing agents such as crisped rice may adversely affect the oral 3 ¦ clearance of the candy. Nonetheless, by employing the additive of 4 ¦ this invention, the candies may be rendered less harmful to the 5 ¦ teeth.
6 ¦ Candies produced in accordance with this invention may be 7 ¦ prepared using the manufacturing techniques heretofore employed.
8 ¦ The additive may be added at any convenient point so long as it is g ¦ present in the final product at the desired level.
lo ¦ The compositions of exemplary anticariogenic candies 11¦ produced in accordance with this invention are given in the follow-12~ ing examples.
1~ 1 14 ¦ Example I - Tableted Candy 15 ¦ Constituent Parts by Weight 16¦ Sucrose 95.0 17l Adipic Acid 3.0 1~ Aluminum Potassium Sulfate 0.2 19 Magnesium Stearate 1.0 Flavorings, Colors, etc. 0.8 Example II - Cooked Hard CandY
22 Constituent Parts by Weight 23 Sucrose 98.0 Adipic Acid 1.0 26 Aluminum Chloride 0.5 Flavorings, Colors, etc. 0.5 29 Desirably, the cariostatic additive of this invention is 301 employed in sweetened comestibles containing, in place of the suc-I rose or other cariogenic sweetener, a noncariogenic nutritive 31li Il -10-9 ~ 3 ~ ~

I sweetlng system comprising a mixture of at least one first sweeten-21~ ing agent selected from the group consisting of sorbitol, xylitol 3¦ and mixtures thereof and at least one second sweetening agent 4 selected from the group consisting of dextrose, fructose and mix-tures thereof, with the mixture containing at least about 75% first 6 agent by weight of the mixture where dextrose is the second agent 7 and at least about 60% of the first agent where fructose is the 8 1 second agent.
9¦ Sorbitol is the preferred first agent, with dextrose being o¦ the preferred second agent on the basis of cost and availability.
11¦ Desirably, homogeneous mixtures of the first and second agents are 12~ employed.
1~ ¦ Where sorbitol-dextrose or xylitol~dextrose mixtures are 14 ~ employed, a 75% sorbitol and/or xylitol - 25% dextrose mixture is 15 ¦ preferred. Where fructose is employed, somewhat greater amounts of 16 1~ the second sweetening agent may be employed. Thus, about 40% fruc-17 Il trose is preferred in the case of sorbitol-fructose and xylitol-! fructose mixtures.
19ll Generally, the sweetening mixtures of this invention are 20 ¦ employed at the same levels that the sugar or other cariogenic Zl sweetening systems have been employed. Thus, where noncariogenic 22 nutritive sweetening systems are employed in accordance with this 23 invention in a candy product they are used preferably at a level of 24 about 40-100% by weight of the candy product.
251 Candy products produced in accordance with this invention 26 ¦ are essentially the same as prior art candy products with the excep-27 tion that, by virtue of the addition of the cariostatic additive and 28 the substitution of the noncariogenic nutritive sweetening system, 29 they may be safely consumed with a reduction of the incidence and 30 1! severity of dental caries.
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Il --11--1~)96306 I Candies produced in accordance with this invention may be2 prepared using the foregoing noncariogenic nutritive sweetening 3 system heretofore employed. Manufacturing techniques are generally 4 the same although certain modifications must be made by reason of 5 the use of sorbitol or xylitol as the principal constituent of the 6 sweetening system.
7 Thus, in the case of tableted candies, the same techni-8 I ques of mixing the ingredients and forming them into tablets are g ¦ used, but somewhat greater humidity control must be exerted because lo~ sorbitol and xylitol are desiccants. An agent such as magnesium 11 stearate may also be added at low levels to facilitate removal of 12 the tablets from the mold.
15l With knowledge of these properties of the sorbitol and/or 14 xylitol containing sweetening agents, one skilled in the art can 15 readily adapt existing candy processing techniques to the prepara-16 tion of other candy products pursuant to this invention.
17 1 The compositions of exemplary anticariogenic candies lB ¦¦ produced employing the nutritive sweetening system in accordance 19ll with this invention are given in the following examples.
20 1~
21 j Example III - Tableted Candy I J
22 ~ Constituent Parts by Weiqht 23 I Sorbitol 71.3 2~ Dextrose 23.8 Flavorings, Color, Etc. 0.7 26 Adipic Acid 3.0 28 Aluminum Potassium Sulfate 0.2 29 Example IV - Tableted Candy Constituent Parts by Weight 30 ll Sorbitol 81.0 31 l¦ Dextrose 14.0 1~ -12-I

i3~i 1 Ascorbic Acid 3 0 2¦l Flavoring, Color, etc. 0.5 3 j~ Aluminum Chloride 0.5 4 I Magnesium Stearate 1.0 6 Exa ple V - Tableted Candy 7 Constituent Parts bY Weight 8 Sorbitol 57.2 g Fructose 38.1 Adipic Acid 1.5 11 ¦ Ascorbic Acid 1.5 12 I Flavoring, Color, etc. 0.5 15 I Magnesium Stearate 1.0 14 l~l Aluminum Potassium Sulfate 0.2 15 1I Example VI - Tableted Candy 16¦~ Constituent Parts bY Weiqht 17 ll Xylitol 72.0 1~¦ Dextrose 24.0 19¦ Adipic Acid 3.0 20¦ Flavoring, Colors, etc. 0.2 21 ¦ Magnesium Stearate 1.0 22 ~ Aluminum Chloride 0.5 23 ¦ Example VII - Tableted Candy 25 ¦ Constituent Parts bY Weiqht 26 I Sorbitol 64.1 Dextrose 15.5 27 ~ Fructose 15.5 28 1¦ Adipic Acid 1.5 ¦ Ascorbic Acid 1.5 30l Flavorings, Colors, etc. 0.5 311j Magnesium Streate 1.0 32 ' ! Aluminum Chloride 0.5

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¦i Example VIII - Tableted Candy li 2¦¦ Constituent Parts by Wei~
3¦¦ Sorbitol 35-7 4 Xylitol 35.7 Dextrose 23.8 6 Adipic Acid 3.0 7 Falvoring, Colors, etc. 0.2 8 Magnesium Stearate 1.0 9~l Aluminum Chloride 0.5 10 1!
11l Example IX - Cooked Hard CandY
12 ¦ Constituent Parts bY Weight 15 1I Sorbitol (70% solution) 81.8 l4~1 Dextrose 17.3 15~ Adipic Acid 0.8 ll Falvoring, Color, etc. 0.2 16ll Aluminum Potassium Sulfate 0.2 17!l ~ Example X - TaffY
19 I Constituent Parts b~Y Weight 20 I Sorbitol (70% solution) 70.1 21 j Dextrose 16.3 22 Egg albumin ~45.27% solution) 2.4 23 92 degree coconut oil 8.9 24 Adipic Acid 1.7 Sodium Alginate 0-3 26 Calcium Acetate 0.1 27l Emulsifier 0.1 28l Flavoring, Color, etc. 0.2 29~ Aluminum Chloride 0.5 32 1!
li -14-!l ll 10~3~

Example XI - Chocolate Candy Coating 2~ Constituent Parts by Wei~ht 3¦ Sorbitol 42.0 4 1 Dextrose 14.0 51 Kaomel (hard butter) 30.9 61 Cocoa Powder 7.8 7 ¦ Non-Fat Dry Milk 4.2 8¦ Lecithin 0-3 g Salt 0.1 Vanilla Powder 0.9 11 Aluminum Potassium Sulfate 0.2 EXPERIMENTAL EVALUATIONS

14 1 The anticariogenic attributes of the products produced in

15 I accordance with this invention have been verified by the following 7 1 experimental studies.
A primary criterion in evaluating an anticariogenic agent is its ability to reduce the solubility of dental enamel, namely, 1l enamel solubility reductions ("ESR"). In vitro "ESR" studies are Il carried out in the following manner. Sound bovine incisors are ¦ mounted in self-curing acrylic resin, with the labial surface I exposed, and given a thorough prophylaxis with flour of pumice. A
23 "window" is then formed on the labial surface by dripping wax over 24 a 1.0 cm diameter aluminum foil circle. A sharp stylus is then used to circumscribe the foil wndow which is then pulled off expos-26 ing a round area of enamel of reproducible size.
27 The windowed teeth are decalcified 4 consecutive times 28 over 20-minute intervals with 25 mls aliquots of a 0.2 N acetic 29 acid solution (buffered to a pH of 4.0) at a stirring rate of 60 50 1! rpm using an ESR stirring apparatus. By the 4th decalcification, Il -15-1g;~963C}~

1 the amount of calcium and phosphorus being demineralized from the 2 teeth has reached a constant level. The teeth are then treated 3 with 25 mls of candy supernatant (1 part candy diluted with 3 parts 4 redistilled water to simulate the d:ilution that occurs in the mouth upon ingestion) stirred at a rate of about 60 rpm.
6 After treatment, the teeth are decalcified again with 25 7 ml portions of the acetic acid buffer for four additional 20-minute 8 intervals. The 5th and 8th decalcification solutions are referred g to as the first post-treatment decalcification (lst PTD) and 4th lo post-treatment decalcification (4th PTD), respectively.
11 The difference in the amount of calcium and phosphorus in 12 the 4th decalcification solution before treatment and that present 1~ in the 5th and 8th decalcification solutions after treatment, 14 divided by the amount of the 4th decalicification, times 100 is 15¦ used to determine the 1st PTD and 4th PTD ESR values. Calcium is

16¦ determined using atomic absorption spectroscopy, and phosphorus 17l using the Fiske-Subbarow method.
l~I In order to demonstrate that repeated ingestion of candy 19 incorporating the cariostatic additive of this invention over short periods of time has an accumulative effectiveness in reducing the 21 I solubility of dental enamel, the teeth are treated a number of 22 ¦ times of relatively short duration (e.g., 5 minutes, the typical 23 oral clearance time of candies of this type). Using this technique, 24 a grape flavored tableted candy having the formulation given in Example III was evaluated. For comparative purposes a candy of the 26 same formulation but without the aluminum salt was tested as a 27 control. The ESR data for the Example III candy was measured after 28 10 five minute treatments and also after 20 five minute treatments.
29 The ESR data, which are given in Table I, show that repeated 5-minute treatments with this dissolved candy causes an accumulated signifi-31 ¦¦ cant ESR effect. After 20 such treatments an ESR of 70% is obtained.32 1 !I -16-~09~63~i 21~ TABLE I

ll No. of 5-Min. ~A ESR (%) P ESR (%) 4 I Treatment Solution Treatments 1st PTD 4th PTD 1st PTD 4th PTD
I ~
5 ¦ Example III, but no ¦ AlK(S04)2.12H 0 61 (pH adJusted to 4.0) 7 ¦ (Average of 3 readings) 20 9 5 12 3 l Example III
9 (pH adjusted to 4.0) (Average of 3 readings) 10 41 30 44 25 Example III
12 (pH adjusted to 4.0) (Average of 3 readings) 20 69 43 74 43 While ESR evaluations are indicateive of the effective-16 ~ ness of an anticariogenic agent, it is also very desirable to

17 1l determine the amount of the agent actually taken up by the dental enamel in order to further establish its efficacy. Six windowed 1911 sound bovine incisors were treated with the candy of Example III
201~ diluted 1:3 with redistilled water. The teeth were treated 20 21 consecutive times over separate 5 minute intervals with 25 mls of 22 the candy solution. After treatment the teeth were decalcified for 23 30 seconds in 15.0 mls of 2.0 HC104, and the amount of calcium and 24 aluminum was determined. Calcium was determined by atomic absorp-tion, and alumlnum by the Aluminon method.
26 The data which are reported in Table II unequivocally 27 demonstrate that a substantial amount of aluminum ion reacts with 28 and is taken up into the tooth enamel. Treatment of teeth with 29l redistilled water in a similar manner resulted in a zero aluminum 30l uptake score. These accumulative aluminum uptake values correspond 32 l Il -17-3~
I

1 to and should be associated with the accumulative ESR values re-2 ¦ ported in Table I. Collectively they demonstrate the cariostatic 3 ¦ effectiveness of the additives of this invention.
4 l l Calcium Total g Aluminum Total g g Aluminum/
7 1 Tooth Ion ppm Calcium Ions ppm Aluminum g Calcium xlO 3 8 1 1 1.14 1710 0.79 11.85 6.93 9 1 2 0.89 1335 0.50 7.50 5.62 10 1 3 0.68 1020 0.54 8.10 7.95 11 1 4 1.22 1830 0.88 13.20 7.21 12 5 0.97 1455 0.88 13.20 9.07 6 1.00 1500 0.97 14.55 9.70 The anticariogenic effectiveness of the additives has also been shown in an in vivo rat study conducted as follows. Ten Il 35-day old Wistar strain rats were randomly distributed into two 1~ equal groups according to sex, body weight, and littermates. Group l9 2 rats served as the control and were fed a low fluoride corn meal diet and fluoride free water ad libitum. Group 1 rats were main-21 tained on the same regimen except that their corn diet was supple-22 mented with 3% adipic acid and 1% AlC13.6H20. At the end of 1 month, the rats were sacrificed, and the acid solubility of their mandibular molars was measured. The data are reported in Table 24 I III.
25 l 26 ¦ TABLE III
21 Phosphorous ESR Calcium ESR
28 Group Reps. Mean + b Mean + b No. (N) S.D. (ppm) Reduction -S.D. (ppm)Reduction 1 10 2.05+0.20 40.2 4.40+0.40 35.8 - (P S) - (P S) 31 2 10 3.43+0.20 ---- 6.85+~.68 ----Il -18-1~363(~6 2 These data show phosphorus and calci~m ESR's of 40% and 35%, re-s spectively, for rats fed a diet inco:rporating the cariostatic 4 ~ additive of this invention.
5 ¦ The anticariogenic effectiveness of the anticariogenic 6 ¦ candies of this invention has also been demonstrated in rats using 7 I the method described by Francis, "The Effectivenss of Anticaries 8 ¦ Agents in Rats Using an Incipient Carrious Lesion Method", Arch.
g Oral Biol., 11:141-148 (1966).

oI A total of 100 weanling (21 day old) Wistar strain rats were randomly divided into five equal groups according to sex, body 2 1 weight, and litter mates. The parents of the weanlings were placed on a noncariogenic low fluoride corn diet and fluoride-free re-4 I distilled drinking water one week prior to mating. The dames were I maintained on this same regimen during the pups' 21-day gestation 16~ period, birth, and 21-day weaning period in order to avoid exposure 17 1 of the pups to any exogenous sources of fluoride during their 1~¦ development. After weaning, the 21-day old rats were placed on a 19¦ high sucrose caries inducing diet and fluoride-free redistilled 201 water ad libitum. Once daily, five days per week for a 4 week I period, both the right and left molars of the mandibular were each 211 swabbed for 60 seconds with the respective topical anticariogenic 23 candy solution. A stick cotton swab was used to apply the solution l to the molars by freshly dipping into the candy solution at 15 24I second intervals. The topical candy solutions used for treatment 261 were prepared by dissolving the various experimental candes 1 part l by weight with 3 parts redistilled water. The basic candy formula 281 Example IIIwas employed wth the following variations:

29~ Group 1 - Control group - Example III without the AlK(SO4)2.
l 12H20 31l Group 2 - Example III

32 1I Group 3 - Example III with 6% AlK(SO4)2.12H20 I'l -19-1 1~963~6 1 Group 4 - Example III substituting dextrose for all of 2 the sorbitol 3 Group 5 - Same as Group 3, substituting dextrose for all 4 the sorbit:ol 51 The rats were housed in an air-conditioned room in cages 61 with raised screen floors, and the usual sanitary measures in the 7I care of laboratory animals were strictly followed. The lights were 81 time regulated to insure 12 hours of light and 12 hours of dark-9¦ ness.
o¦ The weight of the rats was determined initially and then 11¦ at the end of the one-month study. There were no statistical 12 differences in weight gain between the experimental groups and the 15I control group. In addition, not one single animal died during the 14 1 course of the study.
15 ¦ At the termination of the experiment the animals were 16¦ sacrificed by chloroform inhalation, and the teeth were stained 17 ~ with 1% silver nitrate, sectioned in half and graded for incipient

18 lesions. The data are reported in Table IV.

19 TABLE IV
21 Incipient Lesions 22 Group No. IncidenceReduction Se~,~erity Reduction 23 1 (Control) 27.3+1.6 ---- 58.4+5.8 ----24 2 24.4+2.510.6% 52.6+5.59.9%
2s 3 22.4+2.517.9% 49.7+6.114.9%
4 24.5+3.510.3% 57.0+10.23.0%
26 5 25.4+3.67.0% 57.6+12.21.4%

28 A statistical analysis of the data showed that the 11%
29 caries incidence reduction noted for Group 2 (3:1 sorbitol-dextrose candy containing .2% AlK(S04)2.12H20) was significant at the 98%

!1 -20-963~
I

1 ~ confidence level, while the 18% reduction obtained with Group 3 2 ¦ (3:1 sorbitol-dextrose candy containing 6% AlK(S04)2.12H20) was 3 ¦ significant at the 99% level. The 10% and 7% reductions noted for 4 ¦ Groups 4 and 5 respectively were not statistically significant.
5 ¦ These latter two groups were identical to Groups 2 and 3 respec-6 ¦ tively except that all the sorbitol in the candies was replaced by 7 ¦ dextrose. While Group 4 had, on the average approximately the same 81 number of lesions as Group 2, the lesions of Group 4 were much more 9¦ severe. The data demonstrate that the 3:1 sorbitol-dextrose candies o¦ containing AlK(S04)2.12H20 have a significant effect in reducing 11¦ dental caries in vivo. They also demonstrate that all candies are 12¦ to a degree benefited by the cariostatic additive system of this invention.
14 1 The criticality of the use of adipic and/or ascorbic acid 15 ~ in combination with the aluminum salt has also been verified experi-16¦ mentally. Windowed bovine teeth were treated using the described 17 1 ESR method, except that the teeth were given a single 20 minute 1~¦ treatment with solutions containing 37 ppm aluminum ions (supplied 19 as AlK(S04)2.12H20) with 1% by weight of various carboxylic acids

20 ~ with pH adjusted to 4Ø Calcium and phosphorus ESR data are given

21 ¦ the Table V and show that, in contrast to other acids which deacti-

22 ¦ vate aluminum or significantly reduce its effectiveness as an 231 enamel solubility reducing agent under these conditions, adipic and 24 I asorbic acids have a minimal effect, especially at the 4th post 26 treatment decalcification and are compatible with aluminum.

Il -21-1~963~

1 TABLE _V

Phosphorus ESR (%) Calcium ESR (%) 3 37 ppm aluminum Mean (+ S.D.) Mean (+ S.D.) 4 With 1h of 1 PTD l~t l~

5 No Acid 92.1 ( 5.0) 72.2 (+18.5) 90.4 (_ 6.0) 75.7 (+15.5) 6 ¦ Adipic Acid 85.7 (_ 5.8) 72.7 (+, 8.9) 81.7 ( 4-0) 70.7 (+ 8.6) 7 ¦ Asocorbic Acid 80.7 (_ 6.8) 70.7 (+12.8) 78.7 (+ 6.7) 72.1 (+10.3) 8 ¦ Glutaric Acid 77.9 (_ 5.2) 65.1 (_ 5.7) 70.0 ( 5.8) 64.1 ( 5.7) 9 ¦ Succinic Acid 71.5 (_12.5) 54.4 (+11.5) 64.3 (+10.8) 57.5 (+ 7.5) 10 ¦ Fumaric Acid 65.6 (_ 2.9) 52.2 (+ 5.6) 60.9 (+ 5.8) 52.4 (_ 8.4) 11 ¦ Tartaric Acid 7.9 ( 34.7) -25.2 (_54.0) 3.5 (+23.8) -15.5 (_41.4) 12 ¦ Citric Acid 11.4 (_ 6.8) -10.9 ( 10.7) 7.5 ( 8.7) - 8.8 (+10.3) 15 ¦ Malic Acid-12.5 (+26.6) -11.3 ( 17.7) -16.0 ( 22.4) - 6.3 (+16.0) 15 ¦ Control-Redistilled 16 ~ 2 -12.5 (_ 8.1)-26.4 (+,21.9)- 2.6 (+ 8.4)- 4.7 (+ 5.9) 17 l~ While the foregoing invention has been described with 1~ respect to candy products in particular, these technigues are 19l intended to and have utility in relation to other food products in which the invention additive may be employed.

23

24 28ll Il -22-

Claims (9)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An anticariogenic comestible comprising about 0,01 up to about 0.10% of at least one soluble aluminum ion containing salt, calculated as aluminum ion, and greater than 0 up to about 6% by weight of the comestible of a member selected from the group consisting of adipic acid, ascorbic acid and mixtures thereof.

2. A comestible, as claimed in claim 1, wherein the aluminum ion containing salt is aluminum potassium sulfate dodecahydrate, AlK(SO4)2.12H2O.

3. A comestible, as claimed in claim 1, wherein the aluminum ion containing salt is aluminum chloride hexahydrate, AlC13.6H2O.

4. A comestible, as claimed in claim 1, and further comprising as a nutritive sweetening agent a mixture of at least one first sweetening agent selected from the group consisting of sorbitol, xylitol,and mixtures thereof and at least one second sweetening agent selected from the group consisting of dextrose, fructose, and mixtures thereof, with the mixture containing at least about 75% of the first agent by weight of the mixture where dextrose is the second agent and at least about 60% of the first agent by weight where fructose is the second agent, the mixture being present in an amount effective to sweeten the comestible.

5. A comestible, as claimed in claim 4, wherein the first agent is sorbitol and the second agent is dextrose.

6. A comestible, as claimed in claim 4, wherein the first agent is sorbitol and the second agent is fructose.

7. A comestible, as claimed in claim 4, wherein the first agent is xylitol and the second agent is dextrose.

8. A comestible, as claimed in claim 4, wherein the first agent is xylitol and the second agent is fructose.

9. An anticariogenic candy product comprising:
about 0.1 up to about 1.0% by weight of the product of a soluble aluminum ion containing salt;
greater than 0 up to about 6.0% by weight of a member selected from the group consisting of adipic acid, ascorbic acid, and mixtures thereof; and at least about 40% by weight of a nutritive sweetening mixture of sorbitol and dextrose comprising at least 75%
sorbitol by weight of the mixture.