One Hundred Years of Commercial Food Carbohydrates in the United States
Total Page：16
File Type：pdf, Size：1020Kb
J. Agric. Food Chem. 2009, 57, 8125–8129 8125 DOI:10.1021/jf8039236 One Hundred Years of Commercial Food Carbohydrates in the United States JAMES N. BEMILLER* Whistler Center for Carbohydrate Research, Department of Food Science, Purdue University, West Lafayette, Indiana 47907 Initiation and development of the industries producing specialty starches, modified food starches, high-fructose sweeteners, and food gums (hydrocolloids) over the past century provided major ingredients for the rapid and extensive growth of the processed food and beverage industries. Introduction of waxy maize starch and high-amylose corn starch occurred in the 1940s and 1950s, respectively. Development and growth of the modified food starch industry to provide ingredients with the functionalities required for the fast-growing processed food industry were rapid during the 1940s and 1950s. The various reagents used today for making cross-linked and stabilized starch products were introduced between 1942 and 1961. The initial report of enzyme-catalyzed isomer- ization of glucose to fructose was made in 1957. Explosive growth of high-fructose syrup manufacture and use occurred between 1966 and 1984. Maltodextrins were introduced between 1967 and 1973. Production of methylcelluloses and carboxymethylcelluloses began in the 1940s. The carrageenan industry began in the 1930s and grew rapidly in the 1940s and 1950s; the same is true of the development and production of alginate products. The guar gum industry developed in the 1940s and 1950s. The xanthan industry came into being during the 1950s and 1960s. Microcrystalline cellulose was introduced in the 1960s. Therefore, most carbohydrate food ingre- dients were introduced in about a 25 year period between 1940 and 1965. Exceptions are the introduction of maltodextrins and major developments in the high-fructose syrup industry, which occurred in the 1970s. KEYWORDS: Alginates; carrageenans; cellulose-based gums; guar gum; high-amylose corn starch; high-fructose syrups; modified food starch; waxy maize starch; xanthan This paper reviews major developments in food carbohydrate agricultural experiment station nurseries as a curiosity (4). How- ingredients over the past century from an industrial standpoint. ever, the early days of Word War II (even before the United States It focuses on the patent literature and on introductions of entered the war) endangered the supply of tapioca starch from products and processes, excluding later improvements to the Southeast Asia. The loss of this desirable food ingredient initiated basic products and processes. It also focuses on developments a search for a starch that would give similar clear, nongelling originating in the United States and U.S. patents. As will become pastes. Waxy maize starch was found to be a suitable replacement evident, most of the significant advances have occurred over the for tapioca starch. Hybridization and commercialization quickly past 70 years, in fact, during a 25 year period (1940-1965). The followed. Corn breeders at Iowa State University converted waxy major developments in the modification of carbohydrates for maize into a high-yielding hybrid. Commercialization was a joint nonfood applications also occurred during this period, but are effort of the American Maize Co. and the National Starch not covered in this review. Neither are processes that did not Products Co., which arranged for a waxy maize crop to be grown result in commercial products. under contract. Waxy maize starch was first produced commer- Of course, in terms of tonnages, the major refined carbohy- cially in 1942. Pastes of native waxy maize starch have high drate food ingredients are starch and sucrose. Most of the current viscosity and a long texture. They are only slightly cloudy and starch-producing companies have their roots in companies that exhibit a very low tendency to gel, making them more like the were founded before 1908, so their history is not covered here. pastes made from tapioca and potato starch than those made It can be found in ref 1. from normal corn and other normal cereal starches. Waxy maize A spontaneous mutant of maize (corn) called waxy maize, a starch became the base starch of choice for many food applica- mutant that produces an all-amylopectin starch (2, 3), originated tions in the United States. However, pastes of native waxy maize in China and was first reported in 1908. Within a year, it had been starch are too stringy and cohesive and break down too easily brought to the United States, where it was maintained in under shear to be acceptable for some, in fact, many, food applications. However, properly modified waxy maize starch *Telephone (765) 494-5684; fax (765) 494-7953; e-mail bemiller@ produces pastes of good clarity and stability and a relatively high purdue.edu. viscosity (see later discussions on cross-linking and stabilization © 2009 American Chemical Society Published on Web 08/31/2009 pubs.acs.org/JAFC 8126 J. Agric. Food Chem., Vol. 57, No. 18, 2009 BeMiller of starch). Today, waxy maize starch is the most widely used base treatment with an oxidant such as hypochlorite resulted in a starch for making modified food starches in the United States, so product that had the properties of a lightly cross-linked starch. the development of waxy maize starch as a commercial product At about the same time, George Felton and Herman Schopmeyer was a major development in the food starch industry. of American Maize Products Co. claimed reaction of granular In the mid-1940s, research was initiated at two locations, the starch with phosphoryl chloride and achieved a greater degree of goal of which was to produce the counterpart to waxy maize resistance to breakdown during cooking (26), in what is probably starch, that is, a starch containing mainly or entirely amylose the first commercial reaction of granular starch with a derivatiz- molecules. One project was that of Roy Whistler and Herb ing reagent. Kramer at Purdue University (5, 6). Other research involved the Particularly after the latter revelation, use of a large number of Northern Regional Research Laboratory, ARS, USDA, and bifunctional reagents was explored. Those reagents that resulted cooperating breeders (7-9). Quickly, it was determined that the in commercial cross-linked modified food starch processes and high-amylose (ha) gene found by Kramer et al. (5) and the products are the following. Moses Konigsberg of the National amylose extender (ae) gene characterized by Vineyard and Starch Products Co. claimed the use of epichlorohydrin in Bear (7) were the same gene (10). Hybridization of corn contain- 1950 (27). This reagent was used to make diether cross-linked ing the ae gene followed and resulted in increases in both starch starch products until it was voluntarily discontinued by the yield and amylose content. In 1958, a consortium of Bear member companies of the Corn Refiners Association to ensure Hybrids, American Maize Products Co., and National Starch worker and consumer safety. In 1957, Ralph Kerr and Frank and Chemical Co. commercialized the first high-amylose maize Cleveland of the Corn Products Refining Co. described the use of hybrid containing 53% apparent amylose content and now sodium trimetaphosphate (STMP) to make distarch phos- known as amylomaize-V (11, 12). phate (28). Carlyle “Corky” Caldwell and Otto Wurzburg, also Modified food starches were developed for three reasons: to of the National Starch Products Co., used adipic-acetic mixed minimize negative aspects of starch in terms of pasting and paste anhydride to produce dicarboxylic acid ester cross-links properties, to enhance the positive attributes of starches in either (1953) (29). Cross-linked starch products became widely used in their native or cooked states, and to provide functionalities that spoonable salad dressings, the commercial baking of pies, canned native starches cannot provide. Before the 1930s, little starch was pie fillings, and canned products such as cream-style corn. Cross- used in foods. (Uses of starch prior to 1928 and prior to 1954 are linked waxy maize starch became the starch ingredient of choice described in refs 13 and 14.) In foods, starch was used in baking for canned soups, sauces, gravies, and many other products. powders, pie fillings, sauces, and puddings (15). In the 1930s, A second major group of products made by derivatizing Kraft Foods began extending mayonnaise with a paste containing hydroxyl groups is that of the products known as stabilized normal corn starch and arrowroot starch. Later, combinations of starches or substituted starches. Development of stabilized/sub- normal corn starch and tapioca starch and normal corn starch stituted starches originally was the result of a need for pie fillings and locust bean gum were employed (16). that were more stable to cold temperatures (16). Corky Caldwell Before the 1940s, there were many attempts to derivatize of the National Starch Products Co. used acetic anhydride to starch, but almost all reactions were done on nongranular prepare low-DS granular starch acetates (1949) (30), although starch (17-19). There are two major kinds of chemical modifica- nongranular starch acetates had been known for many years tion;cross-linking and substitutions that result in paste stabili- before that (17,18). Jack Tuschoff and Clifford Smith of the A. E. zation (20, 21). Oxidation, acid-thinning, and various kinds of Staley Manufacturing Co. claimed the use of vinyl acetate to pregelatinization are also employed (20, 21). effect a transesterification reaction for the same purpose Starch molecules within granules are cross-linked by reacting (1960) (31). Use of vinyl acetate for acetylating starch was them with bifunctional reagents. The purpose of cross-linking is voluntarily discontinued by the member companies of the Corn to strengthen granules, largely, but not entirely, to make the Refiners Association because the byproduct of its reaction with starch more tolerant to food-processing conditions (high tem- starch is acetaldehyde. (Both epichlorohydrin and vinyl acetate peratures, high shear, low pH).