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1.

Introduction and History


The saccharides are among the most common organic compounds found in nature and glucose is by far the most abundant monosaccharide. D-Glucose (d-glucopyranose) [50-99-7], C6H12O6, Mr 180.159, is the primary six-carbon sugar (hexose) found in the juice of most fruits and berries. Starch ( Starch) and cellulose ( Cellulose) are composed of anhydroglucopyranose units connected through - and linkages, respectively, to form longchain polymers. Thus, a considerable portion of the human diet is composed of glucose in either the free or the polymerized state. When -linked polymers of glucose (starch) are ingested, acid and enzymatic processes convert these macromolecules to glucose in much the same way that it is made commercially. The digestive process begins in the mouth with the action of salivary amylase. Final digestion is accomplished by the action of numerous other enzymes in the small intestine. D-Glucose was probably known to early humans because it appears as granules in honey due to crystallization. However, despite the abundance of glucose in nature, the disaccharide sucrose sucrose has historically been the primary sweetener for humans. Sucrose is sweeter than glucose, and very pure crystals can be recovered from syrups extracted from sugar cane and sugar beets ( Sugar). Most glucose, on the other hand, is bound up as starch, requiring complicated manufacturing processes to release its sweetness. The growth of the glucose sweetener industry has been based upon a classic response to market needs for improved purity and functionality. Pure glucose was first obtained from grape juice by the German chemist A. S. Marggraf in 1747 [1]. Proust was one of the first to precipitate -dglucose crystals from grape juice in 1801 [2]. The synonym for d-glucose, grape sugar, owes its origin to this process. The first sweetener created from starch was the disaccharide maltose made in China about 1000 B.C. by the enzymatic hydrolysis of rice [3]. By 1781, it was known in Europe that starches could be treated with acids to produce a soluble, sweet-flavored substance [4]. This knowledge was little more than a laboratory curiosity until the Napoleonic Wars when the blockade of cane sugar imports from the West Indies provided incentive for the development of alternative sweeteners.In 1811, G. S. C. Kirchoff, who was looking for a substitute for gum arabic (used in the manufacture of porcelain), overcooked a mixture of potato starch and sulfuric acid [5]. The sweet, syrupy substance that resulted earned him a lifetime pension of 500 rubles per year from the Russian Emperor. Kirchoff recognized the commercial potential of his discovery and proceeded to improve the process. He succeeded in preparing a syrup that crystallized partially on standing, and from which a solid product (impure d-glucose) could be obtained by pressing the mass in cloth sacks. This solid material contained large quantities of uncrystallized syrup andwas quite impure. Nevertheless, serious attempts were made to manufacture the product on a large scale. However, the defeat of Napoleon at Waterloo made cane sugar available once again and the venture was abandoned. The French chemist Saussure determined that the acid conversion of starch was achieved through a hydrolytic reaction that cleaved the linkages between the anhydroglucopyranose units in starch by adding one molecule of water to each unit to produce the basic building block, d-glucose. It was also recognized that candies manufactured with glucose syrups were not cloyingly sweet as were those made from sucrose, thus allowing delicate flavors to reach the palate. As a result, the starch sugar industry developed in Europe (especially in Germany) and in the United States [6]. Early efforts to improve the quality of starch sugars were attempts to control the nonspecific nature of the acid hydrolysis. The market needed purer glucose, but early commercial production (1880 1920) of crystalline glucose required either repeated crystallization steps or crystallization from nonaqueous solvents. The only solid form of glucose available in quantity at lowprice at this time was a cast product; starch was acid converted to as high a degree as possible, evaporated to a thick syrup, and poured into molds where it hardened into solid blocks. It was subsequently removed from the molds, chipped into small pieces, and sold. In the United States in 1923, W illiam B. Newkirk (Corn Products Refining Company) received a patent for developing a commercially feasible process for the production of pure crystalline glucose [7]. By careful control of the conditions during the crystallization step, large, easily separable crystals could be produced economically and an industry was born. Although glucose and glucose-containing syrups can have functional advantages over sucrose (higher viscosity, greater solubility, bland flavor, etc.) in certain applications, the unmatched sweetness of sucrose prevented glucose-containing syrups from capturing more than about one-fifth of the caloric sweetener market in the United States. In many of its uses, sucrose in aqueous solution is treated with either acid or enzymes to produce invert syrup consistin of a 50 : 50 glucose fructose mixture (

Fructose). Thus, in a highly converted glucose syrup, isomerization of half of the glucose to fructose would make starch based syrups about as sweet as those made from sucrose. Glucose isomerization under alkaline conditions (see Section 2.3), which increases sweetness somewhat, results in a highly colored product with off-flavor. In 1957, a xylose isomerase enzyme was reported to convert glucose to fructose [8], and a US patent was issued to the Corn Products Refining Company in 1960 [9]. However, no industrial activity was immediately pursued in the United States, and glucose isomerase research shifted to Japan in the 1960s [10]. Once the economical enzymatic conversion of glucose to fructose had been demonstrated by the Japanese, the technology moved back to the United States. In 1965, the Clinton Corn Processing Company (United States) and the Japanese Agency of Industrial Science and Technology worked together to commercialize fructose-containing syrups made in the United States by enzymatic isomerization of glucose. At about the same time, the first batchwise production began in Japan. The degree of enzymatic isomerization of glucose to fructose depends on a number of operating parameters. Because higher fructose content is desired, higher operating temperature and/or increased reaction time is required. However, both of these process conditions reduce the effective enzyme productivity. Although enzymatic isomerization of glucose to fructose in excess of 50% db (dry basis) is possible, conversion to a 42% db fructose content was chosen as the best balance between increased sweetness and process economics. The first commercial shipment of 42% fructose syrup in the United States was made in 1968. This new sweetener began to replace sucrose in many liquid applications (see Table 1), but it was not sweet enough to satisfy the demands of the most important U.S. soft drink producers. By use of chromatographic separation techniques, the 42%fructose syrupwas enriched to a fructose content in excess of 90% db. Blending this enriched syrup with 42%fructose syrup, the sweetness level of total invert syrupwas matched at 55% fructose content. More than 50% fructose was required because the various glucose polymers remaining in the syrup, due to incomplete starch hydrolysis have a lower sweetening power. The first large-scale production of 55%fructose syrup began in 1978; by 1984, fructose syrups derived from glucose had replaced sucrose in nearly 100% of the soft drinks produced in the United States, substantially reducing sucrose consumption. Today, glucose-based sweeteners account for more than half of the total caloric sweeteners consumed in the United States (see Fig. 1) [12].

North America, led by the United States, is the dominant leader in the production and consumption of glucose fructose syrups, consuming 74.1%of theworld production of 11.8106 t (dry basis) today, followed by Asia and Oceania at 14.8 %, with European consumers using 7.1% and Latin America and Africa accounting for the remaining 4% [13]. This market dominance is expected to continue for the forseeable future the major market growth (on a percentage basis) expected in Asia [14] has not occurred, because genetically modified organism (GMO) regulations have

complicated maize procurement and lowsugar prices have reduced substitution incentives [15]. Consumption of glucose fructose syrups increased in the United States, on average, by 19% annually between 1980 and 1985and grew much faster than population (4% annually) between 1990 and 1995. The per capita nutritive sweetener consumption in the United States peaked about 1999; since then, per capita consumption of glucose fructose syrups has fallen about 1% per year [16]. Imports of sugarcontaining products may explain some of this reduction but reasons may also include reduced economic activity and a drop in the consumption of baked goods and cereal products in the United States [17]. Chromatographic enrichment to > 90% fructose syrups has allowed the economical production of crystalline fructose ( Fructose) [18]. New drying and encapsulation technology claims to be able to produce solid glucose fructose syrups [19], so that they can be used in certain dry applications as well.

2. Properties of Glucose
2.1. Structure
At the end of the 19th century, the general structure of glucose was elucidated by Emil Fischer. He found that the six carbon atoms of the glucose molecule are linked in a straight chain. At first glucose was thought to be an open polyhydroxy aldehyde. However, more than 99% of the molecules exist as a six-membered cyclic hemiacetal which is formed by reaction of the aldehyde group with the hydroxy group at C 5. As a result, glucose does not undergo the specific addition reactions (e.g., with ammonia or sodium bisulfite) that are typical for aldehydes. Glucose predominantly occurs in nature in the form of the d-enantiomer which is therefore important commercially. d-Glucose is generally believed to exist in three crystalline forms: anhydrous and -d-glucose crystals are both orthorhombic while -d-glucose monohydrate crystals are monoclinic (see Fig. 2). However, a fourth form, thought to be a hydrated form of -d-glucose, has been reported [22].

Conformation. In aqueous solution, dglucose exists as a mixture of the and 4C1 chair forms (approximately 62% and 38% when equilibrated at 31 C [23]) that mutarotate from one anomeric form to the other through the open chain aldehyde form (see Fig. 3). Chemical structure and conformation have been confirmed with the aid of high-field nuclear magnetic resonance spectrometry using superconducting magnets, advanced pulsars, and expanded computer capabilities to perform one and two-dimensional Fourier transform experiments [24].

2.2. Physical Properties


Some important physical properties of crystalline d-glucose are shown in Table 2. The large positive heat of solution of the crystalline monohydrate form imparts a unique cooling effect to the palate when incorporated into candy and icing in the crystalline state. Solubility is an important property of glucose since it is crystallized commercially from aqueous solution and many of its commercial uses involve water systems. The solubility of glucose in water is shown in Figure 4 [25]. Belowa temperature of ca. 100 C, the stable, crystalline form of d-glucose is the -form, which crystallizes as a monohydrate below ca. 50 C; above ca. 100 C, the -anhydrous form is most stable.

2.3. Chemical Properties


Above a pH of 6.3, the open aldehyde form of glucose rearranges to keto-d-fructose (Lobry de Bruynvan Ekenstein rearrangement Carbohydrates, see Fig. 3).

Glucose is a reducing sugar, i.e., it reacts with oxidizing agents such as cupric hydroxide. Cupric hydroxide oxidizes reducing sugars more rapidly if the copper is kept in solution by the formation of a complex salt with tartrate ion (Fehlings solution) or citrate ion (Benedicts solution) to form red cuprous oxide. Benedicts solution is the more stable and is not affected by uric acid; hence it is preferred for detection of glucose in urine. The inherent reducing property of glucose inhibits oxidative degradation in food; glucose maintains the bright red color of tomato catsup, red berry preserves, and red meats without the need for artificial antioxidants. Glucose is fermented rapidly and completely by yeast and other organisms. The degree of fermentation possible (or fermentable extract) of glucose and glucose-bearing syrups is shown in Table 3.