Enzymes produced by naturally occurring fungal and bacterial microorganisms long have been used to ferment beer and wine, coagulate milk to produce cheese and make bread rise. These protein powerhouses act as highly specific natural catalysts, increasing biochemical reaction rates without the application of high temperatures or pressures.

Moreover, recent technology advances have resulted in enzymes that are able to perform many other targeted functions in baked goods, including shelf life extension, oxidation enhancement, machinability improvements and more.

In baking applications, minute amounts of enzymes go a long way.

“[An enzyme] is not changed or used up during a reaction,” notes Charles Morris, manager of research for ADM Arkady, Olathe, Kan. “For example, during fermentation, enzymes manufactured by yeast cells convert molecules of sugar into molecules of ethanol, but the yeast enzymes are not diminished in the process. That is why small amounts of commercial enzyme products yield such large results, thus being more economical to use compared to other processing methods.”

For the past 50-plus years, says Morris, bakers have relied on enzyme-active soy flour or malted barley flour and their lipoxygenase and amylase enzymes, respectively, to improve bread products. Enzyme-active soy flour is a natural emulsifier that not only acts as a bleaching agent and a dough strengthener, but also increases mixing tolerance and improves bread volume and texture. Some bakers now are avoiding enzyme-active soy flour for allergy reasons, but researchers have not yet developed a decent substitute for lipoxygenase when it comes to whitening the crumb in white pan bread, he adds.

Although bakers sometimes add malt syrup to the flour themselves, malted wheat or malted barley flour usually would be added to flour by millers.

“At the flour mill, the malted flour would typically be added during the final stage of milling through a continuous feeder,” says Morris. “The amount added would depend on the amylase level found in the wheat flour and the strength of the malt flour. Flour used for yeast-raised breads would have a 0.01% to 0.5% malted flour added. … Cake flour would not be treated with malted barley flour.”

Fifty years ago, production technologies for enzyme preparations were far less developed than they are now, notes Jan van Eijk, research director for Lallemand Advanced Baking Solutions, Montreal. In the 1980s, however, researchers began to realize that some enzymes worked better than others in performing specific functions.

“When you’re growing a microorganism, it can produce all kinds of enzymes,” explains van Eijk. “It’s usually a mix. There’s only one [activity] that you measure, and the other ones are called side activities — and the side activities could be important as well. And I think, from that point, what developed were a variety of enzyme preparations for [specific functions].”

But not all developments have been beneficial to the baking industry, van Eijk points out.

“Bacterial amylase left many bakers with a bad experience,” he says. “It’s a highly thermal-stable enzyme that survives the baking and that breaks down the starch. … Bakers had the idea that more is better, and that definitely wasn’t true with bacterial amylase. [As a result], many bakers didn’t like enzymes for a long time.”

For the most part, however, new developments have proved positive to the baking industry.

During the past decade or so, technology has evolved to allow manufacturers to produce much purer enzyme fractions, says Maureen Olewnik, vice president, Audits & Technical Services with the American Institute of Baking (AIB).

“Historically, those enzyme preparations were contaminated with other enzymes — [for example], alpha-amylase had traces of protease and other natural enzymes mixed in, making it difficult to assume that not all were active in the dough systems. Greater purity of the enzymes has allowed researchers to better understand functional traits and pinpoint the appropriate use of that activity.”

Other technical enzyme advances related to genetic modification began in Europe 10 to 15 years ago, and have since made their way to the United States.

The two biggest breakthroughs of the past 10 years, contends van Eijk, are in the areas of shelf-life extension and bromate replacement.

“I’d say 10 years ago, we started to see the better hemicellulases, and also the development of the crumb softening enzyme — the multigenic amylase — which was a big improvement over the bacterial amylase because it didn’t give an overdosing effect.”

At about the same time, enzyme-based dough conditioners, containing a mix of enzymes specific to the application, began to replace bromate in formulations, says van Eijk.

“We still see some development — not in the multigenic amylase, but in the hemicellulase, although it’s getting toward the end of the development stage, I would say,” he notes.

Without a doubt, bakers now can find an enzyme solution for virtually every application.

“Today’s offerings are very diverse and … act on all major parts of the flour in order to improve the quality of the finished product, as well as facilitate the manufacturing process,” notes Lars Obel, business director for food enzymes with Denmark-based Danisco A/S. “[They act on] starch for flour improvement and especially shelf life; protein for maturation and increased flexibility; non-starch polysaccharides for improved processing, and, lately, lipids for increased processing stability.

“The shelf-life enzymes are dominated by amylases, and they are combined to offer the exact breakdown of the starch component that further extends shelf life,” Obel continues. “For uniformity, it has traditionally been xylanases and, lately, glycol lipases that ensure a homogenous mix and facilitate interaction between components. For browning, standard alpha-amylase is used.”

Baking industry suppliers have developed a number of proprietary enzymes for specific baking applications.

Among its many enzyme products, Denmark-based Novozymes offers Novamyl, a widely used shelf life-extending amylase enzyme developed by the company approximately 10 years ago. According to Chrisophe Loretan, the company’s global marketing manager for cereal foods, Novamyl is so specific that bakers don’t run the risk of overdose.

“It certainly gives the best performance in American white panned bread,” says Loretan, “in which it is very widely used all over. It can also be used in other applications like donuts and brioche — and some customers use it in tortillas, but there I would say the cost-benefit ratio is not as good as with the white panned bread area.”

Novozymes is working to develop specific enzymes for tortilla and other dough segments to improve the cost-benefit ratio over the current Novamyl product, notes Loretan. It also recently introduced Novamyl SD, which works well in low-pH doughs used for premium sourdough and rye breads.

Another newer development for Novozymes is Lipopan F, a lipase that Loretan says can readily replace datem.

“In a lot of European countries, datem has been replaced to a very large extent by lipases over the last two or three years,” he notes. “During that time, we realized that Lipopan F can also do in some applications the job of reducing the dosage of SSL (sodium stearoyl-2-lactylate), which is the most common emulsifier here in the states. But it’s not really as cost-efficient as in the case of datem.”

Danisco’s acquisition of the biotechnology firm Genencor earlier this year served to only strengthen its technology platform, of which enzymes play a big role. In fact, a multi-year R&D effort from the combined Danisco and Genencor organizations resulted in the introduction of two new enzymes for the baking industry.

GRINDAMYL POWERBake is a strengthening enzyme — glycolipase — designed to help bakers process more uniform and higher-quality bread products, says Danisco. The second enzyme, GRINDAMUL MAX-LIFE, is a special amylase that helps maintain the soft, fresh texture in sandwich breads, preventing the development of a dry, hard crumb structure and crust.

Lallemand offers a range of enzyme-based dough conditioners under the Essential, Fermaid and Eagle names in North America, for breads, buns, crackers, pastry and more. In addition, it distributes the Novamyl baking enzyme concentrate and the Bakezyme range of fungal amylase, fungal amylase/protease, fungal glucoamylase and bacterial protease enzyme concentrates for blend and mix manufacturers.

ADM Arkady, too, offers a range of enzyme-based dough conditioner solutions, notes Morris. By using enzymes from several different enzyme manufacturers, the company is able to use the best selections to “focus on function at a competitive cost.”

Its Soft Cel enzymatic concentrated dough conditioner/softener improves the color, grain and texture of bakery goods while prolonging shelf life. The Imperial FD dough conditioner, designed for yeast-raised frozen bakery products, increases volume, imparts a silkier texture and results in a brighter, whiter crumb. It also imparts greater tolerance to the freezing cycle and extends shelf life through retardation of crumb firming.

ADM’s MC2 is a powdered source of fungal protease enzymes and fungal alpha-amylase enzymes that produces a controlled modification of the peptide linkages in dough systems’ gluten, says Morris, resulting in a more relaxed, extensible dough, reduced mixing time and improved grain and texture. Finally, the MLO mix reducer contains a fungal protease enzyme and can reduce mix time by 10% to 20% while improving machinability and more.

But product selection is more complicated than it might seem. For one thing, different enzymes require different substrates for the best performance. For that reason, some enzymes work better in white pan bread, for example, than they would in a chocolate chip cookie with a high sugar content.

“Enzymes are very specific in the jobs they perform,” Morris emphasizes. “For instance, amylase enzymes only work on starch; protease enzymes only work on protein; and so on. … For this reason, it is important to select the correct enzymes based on the pH, temperature and other conditions of the process.”

The format of the bakery good also is an important consideration.

“Obviously, if a white pan bread needs to remain soft for a long time, you’re thinking about multigenic amylase or something like that,” says van Eijk. “When you’re making a bun or a baguette, machinability is very important. So you would use some enzymes that you would not use in a white pan bread.”

Particularly important is the enzyme’s denaturation temperature, stresses Debi Rogers, AIB’s director of cereal chemistry. A par-baked product might not get the full effect of the enzyme, while freezing slows down activity but does not stop it.

“Frozen dough is still a very challenging area because of the freezing step and the redistribution of the water/ice crystals,” says Loretan. “[It’s] difficult for all functional ingredients, not only enzymes. Fungal alpha-amylase and hemicellulase are widely used. Novamyl works fine, as well.”

Of course, bakers can tap into the expertise of enzyme experts to find the right products for their needs — products that typically are offered in the form of bread improvers or enzyme-based dough conditioners.

“It all depends on what they want to achieve, and we’re there to help,” says van Eijk. “The enzymes are still pretty technical to understand, and they cannot scale them anyway, so the formulation is very important. The ratio used depends on application.”

In the United States, Novozymes has what it calls preferred bread improvers.

“We work very closely together with them,” says Loretan. “One of them is Innovative Cereal Systems [of Wilsonville, Ore]. They have a huge connect to the industry, which allows them to take our enzymes as a building block and distribute those to the customer. We also work closely with American Ingredients Co. and Lallemand Advanced Baking Solutions.”

New research and development efforts promise only to add to the already vast toolbox of existing enzymes.

Novozymes now is tweaking a newly developed lipase that could represent a cost-effective replacement for chemical emulsifiers such as SSL.

“We should be able to introduce that enzyme by in the near future,” says Loretan. “It [would] basically give to the bakers the ability to reduce their costs, for those who are currently using SSL, and still give the same performance as they have today.”

Also planned for introduction soon, notes Loretan, is an enzyme that can help reduce the formation of acrylamide — a worrisome chemical linked with cancer — in a number of baked goods and other foods.

“With this enzyme, it would be possible to reduce the formation or prevent the formation of acrylamide to a very high extent,” he says. “Companies would not have to apply different production procedures in their plants, which in most cases today is the solution they used to try to control the formation of acrylamide.”

Lallemand, too, is excited about a new type of lipase that could replace SSL and datem.

“We have seen some good effects with it,” says van Eijk. “We really think that is next. We have these [products] developed, and we’re very busy convincing bakers that that’s the way to go — it saves them some costs.” SF&WB