Digital Re-print May | June 2013

Additives for flour standardisation - Part II: Additives other than enzymes
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FEATURE

Additives for flour standardisation -

Part II:
Additives other than enzymes
by Lutz Popper, Mhlenchemie GmbH & Co. KG, Germany
he most commonly used material to strengthen gluten is ascorbic acid, also called vitamin C. The material itself is originally a reducing rather than an oxidizing agent, but it is converted into an oxidative substance, namely dehydroxy ascorbic acid (DHAA), through the action of flour enzymes during dough preparation. DHAA basically inactivates the glutathione molecules which break down the sulfur bonds between the gluten molecules (Grosch and Wieser, 1999). With this action, dough mixing results in sulfur bond protection without excessive breakdown, which in turn leads to dough with desired structure. Pure ascorbic acid is added to the flour in mills at rates of typically 0.5-3 grams per 100 kg of flour. This dosage may go up to 6-10 grams per 100 kg in very weak flours or for weakening applications like frozen dough. Ascorbic acid is mainly produced by complex biochemical processing of glucose and sold as powder with different granule sizes. There are also natural sources for ascorbic acid, for instance acerola fruit powder, but these are too expensive compared to the synthetic ones.

of 45 ppm), but the dosage tolerance is low, so even a slight over dosage may result in bucky doughs and rough bread surfaces. It is a flammable material and its usage in foodstuff is not permitted in the EU and several other countries.

Cysteine
L-cysteine, a sulfur-containing amino acid found in diverse proteins, breaks down the disulfide bonds between and within gluten molecules and becomes attached to the bond forming regions. This prevents gluten from getting stiff, and a mobile, flexible but still coherent structure is secured. This effect seems to be the opposite of ascorbic acids, but actually they seem to complement each other in some processes. This synergy is especially used in frozen dough processes: Ascorbic acid provides the necessary fermentation stability whereas cysteine gives extensibility to gluten strands which have shorten because of freezing.

Others
Other than the ones stated above, there are many oxidative materials and oxidation processes utilized throughout the world. Chlorination, usage of peroxides, iodates, persulfates, cystine and oxidative enzymes are some of these. All of these methods differ by their effects on flour/dough, and their pace of action.

Dough relaxation, softening, reduction

Dough with short gluten (low extensibility) is hard to process. In addition to this, gas produced during fermentation will not be able to expand the dough sufficiently and hence the volume of the end product will be small. Furthermore, for products like biscuits, crackers and wafers, the optimum processing conditions can be reached when gluten structure is weaker than normal. In these situations, reductive materials are used to break the disulfide bonds and provide gluten with more flexibility.

Others
Inactive yeast preparations are rich in reducing material, but their dosage (500 5,000 ppm) and price are relatively high, as compared to cysteine. Levels of other reducing agents like sodium metabisulfite and sulfur dioxide which are used as dough softening agents in biscuit and cracker production are limited to 50 ppm. This amount is not sufficient to observe a softening effect in strong flours. Furthermore, many countries require declaration if the concentration of residual sulfur dioxide exceeds 10 ppm

Potassium bromate
Potassium bromate as a strong oxidative is still used as flour improver in many countries in the world. The very long lasting effect of bromate starts later than the effect of ascorbic acid and allows easier processing of the dough. Bromate creates new disulfide bonds resulting in more resistant doughs but it also oxidizes glutathione and hence prevents gluten weakening, just like ascorbic acid but without the help of the flours enzymes. Usage of bromate in flour industry is prohibited in the EU and many other countries because of the health concerns and its unstable/fire-accelerating nature.

Table 1: Suggested emulsifiers with potential use in baking applications Emulsifier Common abbreviation Acetyl esters of monoglycerides Calcium stearoyl lactate Diacetyl tartaric esters of monoglycerides Ethoxylated mono- and diglycerides (polyglycerates) Glycerol monostearate (non self-emulsifying) Glycerol monostearate (self-emulsifying) Lecithin Lactyl esters of monoglycerides Mono- and diglycerides Polyglycerol ester Propylene glycol monostearate Polysorbate 60 Succinyl monoglyceride Sorbitane monostearate (e.g. SPAN 60) Sodium stearoyl lactate Sucrose esters AMG CSL DATEM EMG GMS GMS LC LMG MDG PGE PGMS PS 60 SMG SMS SSL SUE HLB Application and benefit

2.5-3.5 7-9 9.2 12-13 3.7 5.5 3-4 3-4 2.8-3.8 12-13 1.8 14.4 5-7 4.7-5.9 18-21 7-13
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Whipped cakes, volume Bread, shelf-life, volume Bread, shelf-life, volume High-fibre bread; shelf-life (combined with monoglycerides) Shelf-life Shelf-life Shelf-life, dough properties Whipped cakes, volume Bread, cakes, cookies, volume Whipped cakes, volume Whipped cakes, co-emulsifier Whipped cakes, co-emulsifier Yeast leavened baked goods; volume Whipped cakes, volume Bread, shelf-life, volume Bread, cake, volume

Azodicarbonamide
Azodicarbonamide (ADA) is utilized in flour industry because of its oxidative action. Its dosage is similar to ascorbic acid (with a recommended maximum
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FEATURE confirm this perception. Other emulsifiers strongly interact with the starch delaying retrogradation and staling and thus provide bread with improved and prolonged softness and freshness. Some have potent foaming ability because of their surface-active nature and Figure 1: Effect of reducing agents on the dough consistency are used as whipping agents for sponge cake in the final product. Figure 1 compares the and the like. They ease the mixing of water effect of cysteine and inactive yeast on the and fat and hence improve fat dispersion in extensibility and resistance towards exten- bakery products that contain larger amounts of fat, such as biscuits, or in liquid systems such as sion in a standard wheat flour dough. wafer batters. They also decrease the amount of necessary fat, contributing to cholesterol, Emulsifiers Emulsifiers are polar molecules that can calorie and cost reduction. interact with many constituents of Emulsifiers that interact with gluten during mixing process Lecithin strengthen the bonds between protein chains, Lecithin is an emulsifier which has been but they also provide a lubricating effect that used in bakery products for a long time. Once allows the chains to slide over each other eas- egg yolk was used as the source of lecithin, ily. They are involved in the stabilisation of the but nowadays concentrated lecithin obtained gas bubbles in dough by binding to the bound- from soy beans, canola or sunflower seeds ary layers. As a result, dough elasticity, oven is used. The most obvious benefit of lecithin rise and volume increase, and the crumb pore is to lower the stickiness of the dough and size reduces. The bakers will note an increase improve its machinability. Other than this, in the practical water absorption, although the lecithin softens the crumb due to its interacdough rheological measurements may not tion with starch. But its effect on volume is less than that of its synthetic counterparts. The dosage of lecithin is about 30-150 g per 100 kg of flour (0.03 0.15 %). Low dosages increase the processing quality of the dough, whereas high dosages increase dough stability and fermentation tolerance, improve crumb structure and prolong shelf life.

Mono- and diglycerides

These molecules are formed by breakingoff fatty acids from edible fats and oils. The forms that are preferred as flour improver are the ones that prevent staling best. This property is found in linear saturated fatty acids that interact best with starch, and the most effective of them all is glycerol monostearate. The dosage starts at 0.05 percent and may go up to one percent, especially in high-fat products.

Diacetyl tartaric esters of monoand diglycerides (DATEM)

DATEMs currently are the most effective emulsifiers for bread volume. They are various molecules formed by esterification of monoand diglycerides (obtained from edible oils) with mono- and diacetyl tartaric acid. Some of these molecules are more active than the others (Khler, 1999), but the effect of the mixture is better than any single type of pure emulsifier. DATEM is rather used in bread improvers. The optimum dosage is about 400 g per 100 kg,

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FEATURE but much lower dosages are used actually because of the high prices. We mentioned that the effect of lipolytic enzymes is comparable to emulsifiers. Recent studies are focused on producing carboxyl esteerases that may reduce DATEM usage, or replace it completely.

Bleachers
Even though customers are getting more and more aware of the fact that darker milled flours are richer in vitamin and mineral content, bread with a crumb as white as possible is preferred in many regions. Bleaching of the carotenoids which give the flour a dark colour, namely lutein, can be achieved with oxidative materials.

Sodium and calcium stearoyl lactylate (SSL and CSL)

These emulsifiers are formed by the esterification of stearic acid with lactic acid. They act like DATEM, with a slightly weaker effect on dough stability and baking volume. On the other hand, they are more effective in preserving the crumb softness. Furthermore, they are more suitable for bakery products that require a softer crust.

Soy Flour
The best-known legal material for this application is enzyme-active soy flour. A clearly visible effect can be achieved at dosages around 0.5 percent. There are two types of enzyme-active soy flour in the market: deoiled and untreated. The bleaching effect is related to the lipoxygenase enzyme in soybeans. Deoiled soy flour may have lost some or all enzyme activity during the process and hence may not be suitable for this purpose, but nevertheless there are enzyme-active, deoiled soy flours available. On the other hand, untreated soy flour may cause an unwanted bitter taste because of the enzyme urease. Because the soy flours bleaching effect is due to an enzymatic reaction, the bleaching only starts after contact with water, that is, during dough mixing.

Other emulsifiers
Other than the ones stated above, there are many more to be used in high-fiber products, cake bases etc. The distinctive property among them is the HLB value (HydophilicLipohilic Balance). This value shows if the emulsifier displays a more hydrophilic or lipophilic character. Emulsifiers for high bread volume yield rather have an HLB of 7 or higher, while emulsifiers that improve the shelf life of the crumb softness exert a lower HLB, probably because they have to be able to interfere with the non-polar interior of starch helices. Table 1 provides a list of common emulsifiers used in baking applications.

Powerful oxidatives
Benzoyl peroxide, potassium bromate and their derivatives cause bleaching because of their powerful oxidative effects. Added at dosages of 5-10 g per 100 kg, the effect of benzoyl peroxide starts during storage of flour and the process is completed in about 1-3 days. These chemicals pose health risks by undesired residues and reaction products remaining in the final food or at least because of their inflammable, fire-accelerating or even explosive nature. Furthermore, their usage in food is not permitted in the EU and in several other countries.

The properties of gluten added from outside are different from those of native gluten. The difference that can be observed by determining the water absorption and rheological properties, resulting from partial denaturation of the protein during the drying process. Because of this, a proper drying practice is the most important factor in preserving the function of vital gluten. Some manufacturers do not worry about keeping the quality of the protein, because vital gluten is sometimes still considered as a byproduct of starch production. Using this low quality vital gluten increases the protein content of the flour, but does not improve the gluten properties. The water absorption capacity of added vital gluten is lower than that of native gluten. A ratio of 1.3-1.5 parts of water per one part of vital gluten can often be observed, while this ratio goes up to 2.5-3 parts of water per one part of native gluten in flour. Also the structure of vital gluten becomes shorter because of the drying process. Because of this, softer wheat varieties are more suitable for producing valuable vital gluten. The colour of gluten is also an important criterion in the market. Vital gluten mostly has a grayish tone that will also contribute to colour of flour. This is not a desired quality though; bright white or yellowish tones are preferred in flour industry. The colour is affected by the wheat variety, extraction and drying methods.

Services
Mhlenchemies mission and practical knowledge lie in selecting and combining the individual raw materials described. The optimum composition brings about synergistic effects. Since wheat qualities fluctuate, Mhlenchemie helps mills to produce flours with consistent baking qualities. The samples of flour sent in by the mills are subjected to a rheological analysis in the company, and the results are used to develop specific compounds for each customer. Baking trials are then carried out to test the flour improvers for functionality before they are offered to the mill as Alphamalt. Besides customized products, Mhlenchemie offers whole systems. The EMCEbest WA series increases the water absorption capacity of doughs, and thus the yield, and results in a more succulent crumb and a longer shelf life. The EMCEgluten Enhancers can save on vital wheat gluten at 1/10 of its usage level, strengthen weak flours and make it possible to use composite flours. Mhlenchemie offers mills further support in their daily work in the form of seminars, laboratory equipment and technical training courses and helps with the quality control and improvement of flours on the spot.

Acidifiers and acidity regulators

With germination, high amounts of amylase are formed in grain. This enzyme works like amylase added to the flour, but has a stronger impact on lowering the Falling Number (FN). If there is too much cereal amylase, the baking properties are negatively affected and the FN is too low. To restore good baking properties, the dough may be acidified by natural lactic acid fermentation, resulting in a sour dough. This prevents the cereal enzymes from finding the optimum conditions and hence their activity decreases. But the taste and aroma developed during acidification of the dough may not be well received by everyone. Moreover, this process takes a long time. Other than natural acidification, agents that are allowed in foodstuff, like fruit acids, salts of these acids, carbonates and phosphates may be used. By careful adjustment of these, the pH range (acidity) of the dough may be altered to a level where the enzymes cannot work optimally. Most preferred of these additives are the ones that keep the pH value at a desired level regardless of the chemical changes in the dough, called buffering agents. A typical dosage is 50-200 grams per 100 kg of flour. It should be kept in mind that phosphates and carbonates add to the ash content of flour. For sprout-damaged wheat, it is advisable to lower the extraction of enzyme-rich outer layers of the kernels (that is, to decrease the milling yield) and produce a whiter flour that allows addition of ash-increasing improvers.
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Other agents
The colour lightening effect on crumb experienced with the usage of ascorbic acid, emulsifiers and some enzymes is mostly a physical illusion. Using these improvers, one can have smaller and more evenly distributed pores which cast less shadow and therefore the crumb seems whiter. Using lipases also may contribute to a bleaching effect provided that there is enough of oxygen in the dough. The unsaturated fatty acids produced by lipase are converted to hydroperoxides by the flours own lipoxygenase, and these molecules in turn bleach carotenoids.

Vital wheat gluten

Vital wheat gluten is produced by separating the water-insoluble proteins of wheat flour from the starch and soluble materials by a thorough washing process with water and drying of the resulting wet gluten. The material obtained via this process consists of around 80 percent gluten plus some remaining starch, lipids and nonstarch carbohydrates (Pomeranz, 1988). When added to the flour, vital wheat gluten increases the protein strength. This effect is easily detected with the help of flour analysis equipment like the Alveograph or the Extensograph.

More inforMation:
Website: www.muehlenchemie.de The first part of this article, which discusses enzymes and flour standardisation, is in the March/April 2013 issue of Grain and Feed Milling Technology. It is also online at www.gfmt.co.uk

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