Carbohydrates in Confections - Advances in Chemistry (ACS

Carbohydrates in Confections JUSTIN J. ALIKONIS

Downloaded by UNIV OF NEW SOUTH WALES on September 9, 2015 | http://pubs.acs.org Publication Date: June 1, 1955 | doi: 10.1021/ba-1955-0012.ch006

Paul F. Beich Co., Bloomington,

Ill.

The large variety of products turned out by the confec-tionery industry require a remarkable flexibility in the carbohydrates that serve as major constituents of these products. Physical and chemical properties play a major role. Technological control of raw materials, formula-tions, processing, and finished confections is important. In choosing the various types of sweeteners the candy technologist is governed by the consumer, for it is only repeat sales that tell confectioners whether they are satisfying consumers.

A bout 70 f a r m products of v a r y i n g carbohydrate content f u r n i s h over 90% of a l l the r a w materials for over 2000 varieties of confections. This paper is limited to the sweeteners used i n confections, which on a dry basis are practically pure carbohydrates. Common sweeteners used i n confections are refined crystalline cane or beet sugar, brown sugars, liquid sugars, corn sirup, dextrose, sorbitol, starches, molasses, honey, and maple sugar. The 2000 varieties of confections seem like a large number, and probably the A C S member has sampled only a fraction of these. I f he is an average citizen, he has consumed about 18 pounds of candy annually and this adds up to over 2 billion pounds of carbohydrates to put our industry i n a billion-dollar-a-year class. To complicate the problems further, most of the 2000 varieties have hundreds of different variations. There are as many as 500 different formulas for nougats, and probably double that number of formulas for marshmallow. This situation provides a wide opportunity for candy research and development, which is growing rapidly i n importance. This report tries to convert trade terminology into technical terminology, and dwells on the functions of carbohydrates i n confections and the reason for the candy technologist's choice. The candy man is charged w i t h producing a type of confection, w i t h the highest quality, at a minimum cost, to have a long shelf life i n a l l types of weather conditions, be attractively wrapped, be consumed by the customer w i t h a satisfaction so as to return for a repeat sale, and, incidentally, be sold at a profit. Candymaking has been an a r t and w i l l remain an a r t i n many small shops throughout the country. Considerable credit is due thousands of candy men, who, w i t h no scientific t r a i n ing, have produced confections which are scientifically balanced i n formulas and procedures. M a n y of the secrets of the old candymaker were known physical and chemical phenomena. A s i n other food fields, there is no magic i n candymaking, for there is a reason for everything, but these reasons are often very complex because of the many factors involved (8). To evaluate effectively the functions of carbohydrates i n confections, i t is appropriate to consider first the composition of the commercial types and grades of sweeteners and jelling agents (Tables I to I V ) . The major factors considered by a candy technologist i n determining sweetener usage are differences i n physical and chemical properties of various sweeteners, their relative prices, i n some cases restrictions imposed by federal or state regulations and, to a lesser extent, advertising and sales programs, in-plant handling problems, consumer preference, and psychological factors. 57

In USE OF SUGARS AND OTHER CARBOHYDRATES IN THE FOOD INDUSTRY; Advances in Chemistry; American Chemical Society: Washington, DC, 1955.

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ADVANCES Table I.

Typical Composition of Sucrose Products Uninverted

Granulated Sugar Medium Moisture, % Total solids, % Sucrose, % Invert sugar, % Ash, % PH Relative Solution color


β

Clear

33 67 66.3 0.4 0.08 6.5-7.0 Clear

Water white

Light straw

Light straw

Clear Water white

SERrfS

0

Inverted Sirups

Sirups No. 2 sirups

33 67 66.6 0.1 0.008 6.5-7.0 Clear

0.04 99.96 99.90 0.03 0.01

cane

No. 1 sirups

Fine

0.02 99.98 99.95 0.01 0.005

Based upon eastern

IN CHEMISTRY

Partially

Totally

27 73 42.5 30 0.1 5 Water white Light straw

24 76 3.5 72 0.12 5 Water white Light straw

refiners' products.

Table II.

Typical Composition of Corn Sirups

e

Types of Sirup Regular Conversion Baume Refining

Intermediate

High

Acid 43 Carbon

Acid 43 Carbon

Acid 43 Carbon

Moisture, % 19.7 Color * Lovibond 0.81 Heat color f Series 2.7 D.E. 42.6 PH 5.0 S 0 , p.p.m. 30 Copper, p.p.m. 2 Iron, p.p.m. 3 Carbohydrates (as is), % 80.1 Carbohydrates (dry basis), % 99.7 Dextrose (as is), % 17.5 Maltose (as is), % 16.7 Higher sugars (as i s ) , % 16.2 Dextrine (as is), % 29.7 Viscosity (centipoises) at 100° F . 14,000 3

α

19.05 0.55 2.37 51.8 4.98 26.2 1.4 3.22 80.8

18.9 1.8 3.0 54.6 4.84 22.5 2.6 2.75 80.8

99.7 25.9 20.5 10.95 22.7

99.7 27.06 21.88 10.76 20.8

99.7 29.88 27.44 12.88 11.6

8970

9090

Composition of Refined Corn Sugar (Dextrose)

(Monosaccharide

formed

by complete

hydrolysis of cornstarch) Dextrose Hydrate

Moisture, % Dextrose (dry basis), % Ash Form Sweetness (basis sucrose 100%), Color

Table IV.

B. C.

7350

Based upon average analysis of eight principal corn sirup producers.

Table III.

A.

High Acid enzyme 43 Carbon and ion exchange 18.5 0.85 2.9 62.3 4.96 19.25 .975 1.8 81.5

%

9.0 99.9 Trace Crystals 70 White

Anhydrous Dextrose 0.25 99.9 Trace Crystals 75 White

Confectioners* Starches

M o l d i n g a n d d u s t i n g s t a r c h e s ( f o r m s p h y s i c a l shapes of c o n f e c t i o n s ) . U n m o d i f i e d c o r n s t a r c h i n powder f o r m , 9 9 % o f w h i c h w i l l pass 200-mesh sieve O i l - t r e a t e d m o l d i n g s t a r c h (uses same as A ) . P o w d e r e d s t a r c h b l e n d e d w i t h 0.1 to 0.5 u n s apon ifiable o i l T h i n b o i l i n g s t a r c h e s ( i n g r e d i e n t s o f c a n d y ) . A c i d modified c o r n s t a r c h d e s i g n e d to cook o u t at lower v i s c o s i t i e s a n d set back to firmer gel s t r e n g t h . A v a i l a b l e i n p e a r l or powdered f o r m s

The most important physical and chemical properties, considered i n their order of relative importance to the candy man, a r e : (1) relative sweetness; (2) solubility and crystallization characteristics; (3) density of liquid sweeteners and moisture In USE OF SUGARS AND OTHER CARBOHYDRATES IN THE FOOD INDUSTRY; Advances in Chemistry; American Chemical Society: Washington, DC, 1955.

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content of solid sweeteners; (4) hygroscopicity ; (5) flavor; (6) fermentation and preservative properties; and (7) molecular weight, osmotic pressure, and freezing point depression (19). Sweeteners v a r y considerably w i t h respect to these properties, as illustrated i n the tables. Requirements also v a r y widely, according to the qualities desired i n the particular type or class of confection. The large variety of products turned out by the confectionery industry require a remarkable flexibility f r o m the carbohydrates which serve as major constituents of these products. There have been some excellent papers on the sweeteners (11, 18,15).


Categories of Confections

F o r purpose of this discussion, confections are divided into three categories: hard candies or high boiled sweets, chewy confections, and aerated confections. The second and t h i r d categories are further subdivided into two classes, where the sugar solution is supersaturated (grained) or unsaturated (nongrained). Candies that g r a i n , which are of crystalline structure, include the fondant types, such as cream centers, crystallized creams, fudge, pulled grained mints, r i g i d grained marshmallows, and soft and hard type pan centers. The nongrained candy group consists of m a r s h mallows, taffies, chewy candies, such as nougats, caramels, and molasses kisses, jellies, and gums. There are many intermediate or hybrid types of confections combining the characteristics of both the grained and nongrained candies (9). Sugar is the universal g r a i n i n g agent. The regulators are corn sirup, invert sugar, sorbitol, and others that r e t a r d or prevent sucrose crystallization. Basic Properties of Individual Sweeteners

Sugar (sucrose) has the highest rate of solution, and the smaller the crystal size the more rapid the solution. It forms highly supersaturated solutions which withstand supercooling. Most important of the chemical reactions of sugar is its ability to hydrolyze to produce invert sugar. The color developed i n sugar solutions is the function of the p H , and color cannot be formed unless inversion has first taken place. Invert sugar sirups are known for being hygroscopic and retarding the crystallization of concentrated sugar solutions (16). Corn sirups are noted for retarding and controlling the crystallization of concentrated sugar solutions. This was formerly thought to be due to the dextrins present. Experience has shown that for practical purposes regular corn sirup, high conversion corn sirups, enzyme sirups, and invert sugar have equal effects and can be used interchangeably on a solids basis to control sugar crystallization i n such products as fondant, fudge, or other grained confections. Thus dextrins are not necessarily the controlling agent. In physical chemistry protective colloidal action was the explanation for the action of the dextrins. T o t a l solubility of the many sugars found i n corn sirup and moisture present i n the confection minimize the crystallization of the sucrose. Singly each sugar increases the tendency to c r y s t a l l i zation, but this factor of total solubility i n the liquid phase overbalances any such tendency. The important thing about corn sirups is that they affect the crystallization of cane sugar to a greater degree than invert sugar and without introducing excessive hygroscopic qualities. A candy man can produce most confections without corn sirup, but the sales hazards would be tremendously increased. Dextrins add viscosity, which increases the body of nongraining confections. Dextrose possesses the ability to change solubility characteristics and modify the relative sweetness of confections (12). Dextrose also tends to crystallize more slowly than sucrose and the solution at the same concentration is less viscous. Sorbitol, derived from dextrose, is a sugar alcohol, which seems to have plasticizing properties on confections. Besides having a narrow humectant range, i t has an effect on the sugar crystal which results i n keeping candies soft for extended periods of time. It appears to be gaining i n favor as a softening agent for not only grained but nongrained confections (1). Sweetness

Sweetness is a factor i n candymaking and something of a problem. Do customers eat candy because i t is sweet, or are some confections a bit too sweet? In In USE OF SUGARS AND OTHER CARBOHYDRATES IN THE FOOD INDUSTRY; Advances in Chemistry; American Chemical Society: Washington, DC, 1955.


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t u r n , is sweetness a detriment to greater consumption? The relative sweetness of maltose, dextrose, and corn sirups, using sucrose as a standard, varies directly w i t h the concentration and is almost twice as great i n high concentrations as i n low concentrations. A significant supplementary effect of dextrose and corn sirups i n combination w i t h sucrose was found (5). This effect is sufficient to give dextrose and h i g h conversion corn sirup the same sweetness as sucrose i n 2 5 % solutions consisting of two-thirds sugar and one-third dextrose or corn sirup. Regular corn sirup is as sweet as sucrose i n a 40% solution consisting of two-thirds sugar and one-third corn sirup. Thus the relative sweetness of other sugars, compared w i t h sucrose, varies w i t h the concentration. In a mixture of sugars, i f the sweetness values of the components are calculated i n terms of dextrose sweetness, the values become additive rather than supplemental as they appear to be when calculated i n terms of sucrose sweetness as the standard (3). The sugar and corn products industries, through the nature of their products, have given the confectioner a flexibility and a challenge to his creative abilities f o r producing new candy. Hard Candies

H a r d candies or high boiled sweets are essentially a highly supersaturated, supercooled solution of sucrose containing 1% or less of moisture. This solution, which may be likened to glass, is usually prevented from crystallizing by the addition of invert (or of invert formed i n the batch) or corn sirup, or both, depending upon the properties desired. They are usually compounded i n the ratio of 70 sugar to 30 corn sirup for open fire cooking, and 60 sugar to 40 corn sirup i n vacuumprocessed batches. If the h a r d candy is to be relatively slow dissolving, a larger proportion of corn sirup is used, as i n a banana caramel, which the kids want to last a l l d a y ; i f a quicker dissolving product is wanted, such as a clear mint, smaller amounts of corn sirup are used. C o r n sirup controls sweetness and reduces f r i a b i l i t y of h a r d candies, which are susceptible to fracture from mechanical shock, because of internal stresses induced by unequal cooling. Sirups of high dextrin content and low dextrose and maltose fractions are used to control hygroscopic properties. Formulations and processing techniques i n the manufacture of hard candy confections are designed to produce a product of low hygroscopicity, and different degrees of sweetness, ungrained, dense and brittle i n texture. Chewy Confections

Chewy confections or the nongraining type, such as kisses, caramels, gums, and jellies, are formulated w i t h sucrose, corn sirup, fat, and milk solids. The ratio of sugar solids to corn sirup solids, plus 12 to 15% of moisture, is such that the carbohydrates remain i n solution. The dextrins i m p a r t the body or chewy texture and i n caramels the m i l k solids contribute flavor and texture. N a t u r a l and artificial flavors are accentuated by the sugar, invert sugar, and corn sirup. F a t s , which are usually of the vegetable type because of their excellent shelf-life properties, are added to impart body and lubricating qualities. Emulsifiers such as lecithin, monoglycerides, Span 60, and Tween 60 are added to make the product more palatable (17). Standard 42 dextrose equivalent ( D . E . ) corn sirup has widest application, as i t contributes the desirable chewy characteristic without danger of excessive hygroscopicity. Gums and Jellies. Gums and jellies may be subdivided into two classes: those u t i l i z i n g starch as the gelling agent, and those u t i l i z i n g pectin as the gelling agent. Starch gums employ about 10% t h i n boiling starch which is gelatinized d u r i n g processing by the free water i n a sucrose-corn sirup solution cooked w i t h i t . It is essential to use excess water at the beginning of cooking to ensure complete gelatinization—i.e., about 1 gallon of water for every pound of starch i n the batch. N o excess water is necessary i n a new continuous method (A). Sucrose and corn sirup are present i n approximately equal proportions and are concentrated to about 76% solids before being cast into a cornstarch molding medium. On cooling, a firm, resilient, transparent gel results. Crystallization is prevented because of the high solubility of mixed sugar present and gelatinized starch. Although standard 42 D . E . corn sirup is i n most common usage for gum work, the enzyme-converted 53 In USE OF SUGARS AND OTHER CARBOHYDRATES IN THE FOOD INDUSTRY; Advances in Chemistry; American Chemical Society: Washington, DC, 1955.


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D . E . type has advantages due to its humectant properties and extra sweetness. U p to 2 5 % of the total sweetener may also be i n the form of refined corn sugar, which promotes sweetness, and reduces viscosity of the batch, enabling faster moisture evaporation and prolonging shelf life because of its hygroscopic character. H o w ever, a high ratio of dextrose to sucrose may cause g r a i n i n g i n the piece due to the relatively low solubility of the former (10). The introduction of corn sirup has revolutionized the commercial production of gum work. Pectin and low-methoxyl pectin jellies are compounds of sucrose, corn sirup, pectin, citric acid, water, and a buffer salt, concentrated by heat to a solids content of about 7 5 % , which is necessary for proper gel formation. A 50-50 mixture of sucrose and corn sirup is conventional practice. This ratio effectively inhibits g r a i n ing and gives the minimum difficulty from excess moisture absorption on the surface. Because the p H of pectin jellies must be adjusted to between 3.45 and 3.55 for proper setting of the pectin gel, significant quantities of invert sugar are formed f r o m the sucrose, g i v i n g rise to possible subsequent sweating problems. Accordingly, a corn sirup of relatively low dextrose equivalent is the logical selection, so as to avoid undue amounts of hygroscopic sugars i n the mixture. Sorbitol appeared to be effective i n a l l pectin jellies, whereas the M Y R J emulsifiers were more beneficial i n starch gum confections (1U). Unsaturated solutions, such as frappés and marshmallows, are not necessarily chewy, although tough marshmallow bars are certainly chewy. Both types of these products are formed w i t h sugar and corn sirup i n percentages r a r e l y i n excess of 55 to 45, respectively, w i t h water and an aerating agent, usually albumen or soy bean protein for frappés and gelatin for marshmallow work. A new diffusion method for producing foam candy continuously results i n longer shelf life because of smaller uniform a i r cells, and less gelatin or other whipping agents are required because of lessened " f a t i g u e " i n process (7). Because of the high proportion of corn sirup and the protection afforded by the protein colloids, the system remains unsaturated w i t h respect to sucrose. Concentration of the total solids without i n c u r r i n g supersaturation to a level safe from microbiological spoilage is made possible w i t h the corn sirup or invert fraction, which may be either standard 42 D . E . or special 52 D . E . type i n the case of uncoated goods, or special 52 D . E . and 63 D . E . enzyme or invert sugar i n the case of coated marshmallow products. Molasses, honey, or maple sugar is used i n a l l types of confections, mainly as a flavor. Honey has very good humectant properties. Aerated Confections

Aerated confections are the supersaturated solutions that f o r m grained confections such as creams, fondants, nougats, fudges, and grained marshmallow items. Fondants and creams are prepared by concentrating a sucrose, corn sirup, and water solution to around 8 5 % total solids, using a ratio of sucrose i n excess of that of corn sirup so that precipitation w i l l occur when the supersaturated solution is seeded or crystallization induced by mechanical means. This generally implies a proportion of 80 to 70 parts of sucrose to 20 to 30 parts of corn sirup. The m i x t u r e is usually boiled to 238° to 242° F . A g i t a t i o n or seeding is carried on at reduced temperatures of around 110° F . , so that the crystals so formed w i l l be of impalpable size. Some a i r is incorporated by the mechanical action of the equipment used i n making the fondant. I n the case of creams, the fondant is used as a seeding medium and a small percentage of egg or soya bean albumen i n the form of mazetta is used to import some a i r . The function of the corn sirup portion is to serve as a humectant that w i l l keep the products soft and palatable, and to permit concentration of soluble solids i n the liquid phase to a level of around 8 0 % , which w i l l prevent growth of microorganisms. A l l three types of corn sirups have applications, the special 52 D . E . and enzyme-converted 63 D . E . i m p a r t i n g effective humectant properties. Invert i n combination w i t h corn sirup gives excellent results. Refined corn sugar may be used i n limited amounts, but i t is not generally recommended because of its tendency to g r a i n off i n coarser crystals. Sorbitol w i t h corn sirup seems to give a more uniform and whiter cream and fondant. Fudges are similar to caramels, containing sugar, corn sirup, milk solids, and vegetable fats, but are slightly aerated by mechanical agitation w i t h the aid of In USE OF SUGARS AND OTHER CARBOHYDRATES IN THE FOOD INDUSTRY; Advances in Chemistry; American Chemical Society: Washington, DC, 1955.


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egg or soybean protein frappés. Soybean proteins are g a i n i n g favor because they b r i n g out the color of the cocoa powder or cocoa liquor used i n chocolate fudges. Ratio of sugar to corn sirup is higher, enabling precipitation of sugar crystals to f o r m short, crystallized texture. A l l three types of corn sirups have applications, as i n creams. Although the sirups of higher dextrose equivalents are used i n chocolatecoated bars, the quartermaster ration chocolate-type covered disks have 10% sorbitol to ensure a shelf life of the product for at least 2 years (6). Grained marshmallows are produced w i t h sugar, corn sirup, and an aerating agent, such as gelatin or albumen. A g a i n the corn sirup, invert sugar, or sorbitol serves to retain softness i n a supersaturated, aerated sucrose system. Refined corn sugar (dextrose) may be incorporated to 20 to 2 5 % of the total sweetener because of its hygroscopic qualities and higher fluidity qualities, permitting faster beating to the desired specific g r a v i t y of the product. Standard 42 D . E . and special 52 D . E . sirups are preferred for this item. Enzyme-converted sirups or invert sugar, i f used, should be used sparingly to avoid excessive softening due to absorbed moisture. W h a t holds true for grained marshmallows w i l l hold true for grained nougats. In this confection gelatin is seldom used and the aerating agent is usually egg albumen, soybean protein, or a 50-50 mixture. Vegetable fats are used to promote smoothness and palatability to the confections. Since a high percentage of nougat confections are coated w i t h chocolate or chocolate-type coatings, the 63 D . E . enzymeconverted corn sirups or invert sugar are usually used. Chocolate coatings are mixtures of sugar, cocoa butter, chocolate liquor, emulsifiers, and flavor, and i n some cases milk powder. The function of carbohydrates in confectionery coatings is practically limited to refined cane and beet sugars. A small percentage of dextrose and corn sirup solids is used on some special coatings, but these sweeteners tend to raise the viscosity of the coatings which call for more expensive cocoa butter or vegetable fat. In recent years, because of the commercial g r i n d coatings used on candy bars and on coatings for syndicate outlets i n which there is a coarser particle size distribution, as f a r as the d r y ingredients are concerned, more sugar and less vegetable cocoa butter and fats are being used. The sieve-size particles have less surface area than subsieve range particles, thus using less f a t and producing a lower viscosity i n the coating, which results i n considerable savings (18). The intensive use of "chocolate-type" coating which uses cocoa powder as a rule instead of chocolate liquor and vegetable butters other than cocoa butter, and white and colored vegetable coatings that w i l l withstand high temperatures and high relative humidities d u r i n g the summer months, has increased the use of this important carbohydrate, sugar (2). Choice of Sweetener

The competitive relationship between sugar and corn sweeteners is actually i n name only. I n choosing the type of sweetener, a candy technologist is actually governed by the consumer, for it is only f r o m repeat sales that confectioners are able to tell i f they are satisfying consumers w i t h their choice of carbohydrates in confections. Candy technologists w i l l continue to study the functions of carbohydrates in confections to give the highest quality possible. A l l they seek is good w i l l . "Good w i l l is the disposition of a pleased customer to r e t u r n to the place where he has been well t r e a t e d . " — U . S. Supreme Court. Literature Cited

(1) A l i k o n i s , J. J., Confectioner's J. and Mfg. Confectioner, 78 (June 1952). (2) A l i k o n i s , J. J., L a w f o r d , H., and K a l u s t i a n , P . , "Role of H a r d Butters i n Choco-late-Type Coatings," Ν. Y . Section, A m e r i c a n Association of Candy Tech -nologists, F e b r u a r y 1953. (3) Cameron, A. T., "Taste Sense and Relative Sweetness of Sugars and Other Sweet Substances," N e w Y o r k , Sugar Research Foundation, Rept. 9 (De -cember 1947). (4) Ciccone, V . R., "Cooking Starch Jellies Continuously," 6th Production Con -ference, Pennsylvania M a n u f a c t u r i n g Confectioners Association, April 1952. (5) Dahlberg, A . C., and Penczek, E . S., Ν. Y . State A g r . E x p t . Sta., Bull. 258 (1941). In USE OF SUGARS AND OTHER CARBOHYDRATES IN THE FOOD INDUSTRY; Advances in Chemistry; American Chemical Society: Washington, DC, 1955.


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(6) F a r r e l l , Κ. E . , and Alikonis, J. J., Food Technol., 7, 288-90 ( J u l y 1951). (7) Food Eng., 25, 56-8 (February 1953). (8) Jordan, S., "Confectionery Problems," Chicago, Ill., National Confectioners Association, 1930. (9) K i n g , J. Α., "Art of Candy M a k i n g vs. Science," 4th Production Conference, Pennsylvania M a n u f a c t u r i n g Confectioners Association, April 1950. (10) Koorman, J., Confectioner's J., 78, 44 ( M a r c h 1952). (11) Koorman, J., " W h a t Is Corn S y r u p , " Confectionery and Ice Cream World (June 1949). (12) K r n o , J. M., "Dextrose and Its Characteristics," 4th Production Conference, Pennsylvania M a n u f a c t u r i n g Confectioners Association, April 1950. (13) L a n g , L . , "The Role of Sugar i n Candy M a k i n g , " 3rd Production Conference, Pennsylvania M a n u f a c t u r i n g Confectioners Association, M a y 1949. (14) M a r t i n , L . F . , "NCA Candy Research Reports," New Orleans, L a . , Southern Regional Research Laboratory, 1951. (15) Meeker, E . W., Food Technol., 4, No. 9, 361-5 ( M a y 1950). (16) Meeker, E . W., Mfg. Confectioner, 31 (February 1951). (17) P r a t t , C. D., "Sorbitol and Emulsifiers in Candy," Boston Section, American Association of Candy Technologists, November 1952. (18) Slater, L. E . , Food Eng., 24, 62 ( J u l y 1952). (19) U . S. Dept. A g r . , Bull. 48 (June 1951). RECEIVED M a y

20,

1953.

In USE OF SUGARS AND OTHER CARBOHYDRATES IN THE FOOD INDUSTRY; Advances in Chemistry; American Chemical Society: Washington, DC, 1955.

Carbohydrates in Confections - Advances in Chemistry (ACS

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