Aspartam Aspartame is a nutritive intense sweetener produced by combining the amino acid L-phenylalanine and L-aspartic acid by a methyl

ester link. Its full chemical name is (35)-3-amino-N [alpha-S-alpha methoxy carbonylphenythyl] succinic acid but it is often described by its synonym L-aspartyl-L_phenylalanine methyl ester. It was discovered by J.D Schlatter in 1965 in the laboratories of G.D Searle. There followed a period of rigorous testing before aspartame first appeared in the US market in 1981 under the brand name of NutraSweet. The brand was heavily promoted and contributed to the phenomenal commercial success of aspartame as a sucrose replacement in the 1980s and 1990s. Synthesis Although G.D Searle discovered and recognized the potential of aspartame as a sweetener, the Ajinomoto Company of japan developed and patented many of the processes for the commercial production of aspartame. Many further patents refining the original process have subsequently been granted to Ajinomoto and other companies. In the late 1970s Toyo Soda filed patents utilizing enzymes to link N-protected aspartic acid to phenylalanine methyl ester followed by crystallization and purification steps. This biocatalyst method is claimed to have greater specificity and therefore better yields. The method used by Holland Sweetener Company (HSC) is based on the Toyo Soda Patents. Raw materials for the production of aspartame are the two amino acids L-phenylalanine (produced by fermentation) and L-aspartic acid. The Toyo Soda process can use DL-phenylalanine, which is chemically synthesized and can offer cost-benefits over the purer optically active L form. Aspartic acid is produced by chemical synthesis. The reactive groups of the amino acid are first protected, with the exception of the group that will form the methyl ester link. The amino acids are then coupled either chemically or enzymatically and the reactive groups removed. This is followed by a series of crystallization steps to remove impurities. Crystallization methods can vary from static (Ajinomoto, NutraSweet) to stirred (HSC), and the technique employed will influence the type, size, shape and other properties of the crystal formed. This can influence the physical attributes of the product. Sensory properties Aspartame has a clean sweet taste and is approximately 180-200 times the sweetness of sucrose. Unlike many other intense sweeteners, its taste profile is good enough and its maximum sweetness intensity of 13-14% sucrose equivalence is high enough for it to be used as a sole sweetener. At the time of its approval in the UK and the USA in the early 1980s, it offered a very significant benefit when compared to other intense sweeteners-its sweetener profile being much more similar to sucrose than any other permitted intense sweeteners.

Relative sweetness (RS) of aspartame varies with concentration, as with all intense sweeteners. At threshold (0.34%) in water RS is 400 (where sucrose =1), at 10% sucrose equivalence it falls to 130. RS can also be affected by other factors including pH, temperature and application and is, therefore, difficult to predict. The generally quoted RS is 180-220 and this is a useful starting point for many formulations. Sweetness profile for aspartame is similar to sucrose-onset time is very slightly longer than sucrose, and in some applications has a slightly lingering tail, where this is not desirable it may be modified by blending with other intense sweeteners, sugars, or by adding naringin or aluminium potassium sulphate.

Synergy and flavor enhancement. Aspartame is synergistic with many bulk and intense sweeteners. Levels of synergy are dependent on concentration and blend constituent. Synergy has been reported with glucose, sucrose, fructose, polyols, saccharin, cyclamate, acesulfame K and stevia. It is interesting that combination of aspartame and sucralose do not appear to be synergistic with respect to sweetness intensity. Suppression has been reported with combinations of aspartame and sucrose in neutral solutions. This suppression changes to synergy when the pH is decreased. Aspartame is frequently blended with acesulfame K or saccharin. In these instance, sweetness intensity synergy is noted (up to 30%). Equally important in these blends is the taste modifying effects of aspartame on the bitter/ metallic side and tastes of acesulfame K and saccharin. Aspartame also has some flavour-enhancing properties, in particular soft fruit flavours can be enhanced. Aspartame salt An aspartame-acesulfame-K salt is now available. The two molecules are linked through an ionic bond and it has an RS of 350. The product is composed of 64:36 aspartame: acesulfame-K on a weight basis. In solution, the product dissociates to aspartame and acesulfame K. the product is non-hygroscopic, dissolves more quickly than aspartame and is said to have stability benefits in applications such as chewing gum. It was developed by HSC and branded as TwinSweet. Physicochemical properties. Aspartame is a white colourless crystalline substance and is regarded as ecologically safe and represents a bio-degradable non-regulated material. Solubility Solubility f aspartame in water (pH 6-7) at 25 C is approximately 1%. This can be increased by elevating the temperature and/or increasing the acidity. Use of some hydrocolloids, for example, CMC, has also been reported to significantly increase solubility, even at low temperature. Lowest solubility is at its isoelectric point at pH 5.4. Aspartame is sparingly soluble in others solvents.

Stability Dry In solid form at ambient temperature aspartame has excellent stability (more than 5 years), even at elevated temperatures. The best stability is achieved in systems with lower than 8% moisture. Liquid Aspartame is less stable in liquid systems and the stability is primarily a function of pH, temperature and time. The aspartame molecule slowly hydrolyses at low pH to produce a tasteless molecule aspartylphenylalanine (AP) and methanol. An alternative route at pH 5 and above is that aspartame may cyclise to form its diketo-piperazine (DKP) with the elimination of methanol. These conversion products can be subsequently hydrolysed to the individual amino acid-aspartic acid and phenylalanine. In liquid systems, stability of aspartame at different pH follows a bell-shaped cure the optimum pH for stability of aspartame is pH 4.2. it most stable in the pH range of 3-5 which, fortunately, is the pH range of many food systems. Stability decreases with increasing temperature. It should be noted from that within the pH range of 2.5-5.5 small change in pH towards the optimum of pH 4.2 can have a significant and positive impact on stability. Aspartame degradation in liquids during heat treatment is quite small, providing the pH is in the optimum range. High-temperature short-time (HTST) systems are the preferred method in order to minimize aspartame losses. Stability during storage of beverages containing aspartame follows first-order kinetics and, to an extent, is predictable if parameters of pH and temperature are known. Expected result can, however, be confounded by other interactions with ingredients that can have a positive or negative impact on stability and also perceived sweetness level. For example, synergy with other sweeteners can have an impact on perceived sweetness of beverages over time. Figure 6.7 shows a synergy curve for aspartame and acesulfame K. it can be seen that maximum synergy occurs when a 50:50 blend of aspartame and acesulfame-K is used. On storage the level of aspartame will decrease over time. As the level of aspartame decrease, the level of synergy also declines. So, in effect, the loss of aspartame on storage is amplified by addition impact of lower synergy. If, on the other hand, the beverage is formulated using a blend on the right-hand side of the curve, it can be seen that over time aspartame will also hydrolyse, but the synergy level between the two sweeteners will increase, compensating in part for the loss of aspartame. So the perceived sweetness of the beverage will reduce to a much lesser extent over time. Therefore, to maintain the sweetness level over time, it is recommended to formulate on the right-hand side of the curve. Aspartame stability can also be affected by some flavour compound; cinnamon and some terpene compounds appear to accelerate degradation.

Aspartame is made up of amino acid and under certain conditions can take part in maillard reactions and form brown-coloured compounds. Various factors can impact stability and perceived sweetness of aspartame-containing products, and due to synergy there is not always a direct relationship between level of aspartame in a product and acceptability. It is therefore advisable to perform full storage and acceptability trials on products using it. Physiological properties Aspartame is a nutritive sweetener, in that it is broken down in the body to its two constituent amino acid and methanol. The amino acid metabolites follow the normal routes of digestion and utilization in the body as they would, if generated from other food sources. Aspartic acid makes up approximately 40% of the aspartame molecule. It is absorbed in the intestinal lumen and plays an important role in nitrogen and energy metabolism, in the mitochondria. Phenylalanine makes up over half the aspartame molecule. It is an essential amino acid (i.e. the body cannot synthesise it) and it must, therefore, be obtained from foods for normal growth to be maintained. Adults require a minimum of 1-2 g of L-phenylalanine per day. The requirement for Lphenylalanine is highest in infants (where growth rate is rapid) and it reduces as growth rate decline. Methanol is a potentially harmful metabolite. Various studies have shown that even at abuse levels the methanol levels produced by aspartame consumption are barely measurable, insignificant and do not represent a health risk. Toxic level of methanol are round 200-500 mg/kg body weight. One 33 ml can of soft drink sweetened with aspartame at 550mg/l would, in theory, generate 18.3 mg methanol-approximately.26 mg/kg bw methanol in a 70 kg person. For comparison, a 220 ml glass of tomato juice would generate 47 mg methanol or 0.67 mg/kg bw in a 70kg person. The small amount methanol produced is likewise excreted from the body in an identical fashion to methanol produced from other food sources. (e.g. banana, tomato juice). Phenylketonuria The presence of phenylalanine as one the breakdown products of aspartames is relevant for consumers with phenylketonuria (PKU). These people are unable to convert the essential amino acid phenylalanine in to tyrosine, usually because of a defect in, or a deficiency of, the enzyme phenylalanine hydroxylase. In normal individuals, this enzyme converts phenylalanine to tyrosine, which is in turn catabolized. A deficiency in the enzyme leads to elevated levels of phenylalanine in tissues and accumulation of the end products of the transamination pathway of phenylalanine intake and, therefore, prevent elevated levels of L-phenylalanine in the blood until adolescence or adulthood. For this reason, it is a requirement in many markets for products using aspartame, particularly soft drinks that would normally be classed as phenylalanine-fre, to have a note on the pack that the product contains a source of phenylalanine. Oral health. Aspartame is not fermented by tooth plaque bacteria and is to be considered tooth friendly.

Blood glucose Aspartame does not affect blood glucose levels and is, therefore, suitable for use in foods for diabetics.

Appilication Aspartame is used in many areas of the food and pharmaceutical industry. Current estimates suggest that it accounts for 7% of the global sweetener market (bulk and intense). The major markets for the product are soft drinks and table-up sweeteners. However, it is also used in confectionery, pharmaceutical tablets and dry syrups, dairy products, dry-mix products and bars. It is not used to any great degree in baked goods, products that undergo extensive and prolonged heat treatment or liquid products at or near neutral pH that require a long shelf-life. It would not give the required stability in these products unless it was protected in some way, for example, by encapsulation. Use levels of aspartame vary with application and are also dependent on its use as a sole sweetener or in combination with other sweeteners. Table 6.2 gives examples of use levels of aspartame in various applications where aspartame is the sole sweetener. Use in manufacturing Aspartame is available in a number of physical forms from ultra-fine powder to granular product to aid dissolution, flow properties and granulation/direct compression properties. Soft drink In soft drink applications, it can be directly added to the syrup tank after the acid (to aid rapid dissolution) in dry form. Alternatively, a more concentrated premix of aspartame suspended in water can be added to prevent clumping and adhesion of the powder to the mixing tank. Yoghurts In stirred yoghurts, aspartame is usually incorporated with the fruit preparation after fermentation. In set yoghurts, aspartame is added after pasteurization, but before fermentation. Aspartame can be degraded by yoghurt cultures and, therefore, in processes where it is added before fermentation, it is important to increase the aspartame addition level by 15-30% to compensate for losses during fermentation. Alternatively, careful selection of yoghurt culture can significantly reduce these losses. Confectionery High-boiled confectionery: aspartame should be added at the end of the boiling process, along with flavours and other heat-sensitive ingredients to minimize process losses. Chocolate: ultra-fine aspartame should be used and added at the end of the conching process. Chewing gum: Aspartame should be added towards the end of the kneading process, when the last part of the bulking agent is added.

Analysis Usual method of aspartame analysis is high-performance liquid chromatography (HPLC). Perchloric acid titration may also be used.

Safety Aspartame is probably the most rigorously tested food ingredient to date. Prior to its approval in major markets, aspartame and its breakdown products underwent extensive tests to validate its safety. Its commercial success in the market during the 1980s and 1990 focused attention on the product. Despite the fact that aspartames metabolites bring nothing new to the diet and are handled by the body in the same way as they would from other foods, a number of reports linking aspartame to adverse safety effects appeared. These allegations, which were based on a series of anecdotal reports and poorly controlled studies, gained publicity via internet and popular press. Scientifically controlled peer reviewed studies have consistently failed to produce evidence of a causal effect between aspartame consumption and adverse health events. Additional reviews of aspartame safety covering studies done pre- and post-approval have been carried out by regulatory bodies. These have confirmed that aspartame is a safe and thoroughly tested food ingredient. The latest review of over 500 studies conducted by the SCF (Scientific Committee for Food of European Union) concluded that intake of its (aspartame) component parts can be compared with intakes of the same substance from natural food. Join expert committee for Food Additive (JECFA) have assigned aspartame an acceptable daily intake (ADI) of 40 mg/kg bw. Unlike most other intense sweeteners, this level is sufficiently high for aspartame to be used as a sole sweetener in application, such as soft drink. Food and Drug Administration (FDA) have assigned aspartame an ADI of 50 mg/kg bw. Regulatory status Aspartame is permitted in all major markets. The maximum use level is dependent on application and EU maximum use levels for some major application areas are detailed in table 6.3.