Carbohydrates as functional ingredients in baking
Senay Simsek, PhD Bert L. D'Appolonia Cereal Science and Technology of Wheat Endowed Professor North Dakota State University Department of Plant Sciences Cereal Science Graduate Program Bakery Products
Bakery products means products manufactured in a bakery; for example: bread, rolls, buns, cakes, cookies, crackers, doughnuts, pies, pastries, pretzels, and potato chips. Baked Products – Wide Variety
Pan breads Doughnuts Each type of bakery product Cookies has a unique formulation and Flatbreads Pancakes requires flour with different Muffins functionality and different Hearth breads types of functional ingredients Crackers to optimize quality Pastries Cakes Bagels Specialty breads Frozen/refrigerated dough Wheat Flour • Proteins • Gluten forming proteins • Gliadin and glutenin • Very important for bread • Gluten development is discouraged for cookie and cake • Starch • Important for cakes and cookies • Lipids • Arabinoxylan • Important for many baked goods • Bran in whole wheat Function of flour polymers in baking Wheat Proteins Gluten Albumin Forming Proteins
Wheat Globulin Endosperm 1. Viscoelastic properties 2. Important in dough Proteins Gliadin development
Glutenin
(Delcour and Hoseney 2010) Gluten in Bread
• Very important • When flour is mixed with water, the gluten swells to form a continuous network of fine strands. • This network forms the structure of bread dough and makes it elastic and extensible. Gluten Network in Dough
(Amend and Belitz 1990) Gluten in Cookies
Height • Needed for structure Spread • But not too much • Too little gluten = too much spread • Too much gluten = too little spread Gluten in Crackers • Unique role • Acts to make the cracker weaker and stronger at the same time.
Strong protein structure
Creates rigid, crispy, and continuous layers
Aides in formation of a small number of large gas bubbles, which
Separates the layers and reducing density
Increasing surface area
Increasing moisture loss rate
Resulting in a low moisture, crispy texture. Gluten in Cookies % Gluten 0 5 7.5 10 12.5 15
(Pareyt et al 2008) Starch
Distinct granules
Amylose and Amylopectin
Embedded in gluten matrix in dough
Partially hydrolyzed during fermentation
Undergo gelatinization during baking
Influences bread structure and texture
Main factor in staling
(Pyler and Gorton 2008) Starch Gelatinization
(Schirmer et al. 2015) Starch
• Starch Damage • Susceptibility to α-amylase • Formation of fermentable carbohydrate • Sustain adequate gas production by yeast • Formation of dextrins • Baking absorption
(Pyler and Gorton 2008) Starch in Dough and Bread
Proofed dough Bread crumb Bread crumb Blue/purple = Starch Green = Protein
(Hug-Iten et al. 1999) Staling: Starch Retrogradation Mechanisms of Retrogradation
• Over time swollen granules loose water as it migrates to dryer regions and evaporates • Starch also undergoes retrogradation • Irreversible process • Liberates water and collapses starch molecules into insoluble crystallites
(Pyler and Gorton 2008) http://www.classofoods.com/page3_3.html Arabinoxylan Functionality
Textural characteristics Shelf life Water binding capacity Stability of dough Cryo-stabilization Viscosity Intermolecular interactions Functions of Arabinoxylans in Baking
(Courtin and Delcour 2002) Arabinoxylans in Bread
• WEAX • WUAX • Increase stability • Disrupts gluten of gas cells matrix • Increase loaf • Lower loaf volume volume • Improved texture Arabinoxylans in Bread
Xylanase application in industry
Bread baking •Included in bread improver mixtures
Improvement of •Dough handling •Oven spring •Loaf volume
(Courtin and Delcour 2002) Arabinoxylan in Cookies Not desirable in soft wheat flours used for cookies or crackers
Arabinoxylans High water Increase cause: absorption viscosity
• Longer bake time • Poor cookie spread Arabinoxylan in Cookies
• Negative effects of arabinoxylan • Increased bake time • Decreased cookie diameter • Sugar syrup sequestration • Decreased dough plasticity • Increased checking (stress fractures)
(Kiszonas et al 2013) Function of Fat in Bread
What is fat? Specific function and use • Energy-rich moleculedepends made on from application glycerol and fatty acids • It is insoluble in waterand while type soluble of fat usedin organic solvents, and at room temperature can exist in a liquid or solid state.
In baking, fat contributes to:
• Stabilization of gas cells • Flavor enhancer and adder • Aids in slicing • Smooth mouthfeel • Tenderness • Silky texture • Moistness Functional Ingredients in Baking
Yeast nutrients
pH regulators
Oxidizing agents
Reducing agents
Emulsifiers
Gums and hydrocolloids
Enzymes
(Pyler and Gorton 2008) Emulsifiers
• Food • EMULSIFICATION • Encapsulation Low fat yoghurt • Films • Coatings • Gels
• FAT REPLACEMENT Emulsified beverages • Industrial
Encapsulation of flavors Emulsifiers in Bread Crumb softening emulsifiers
Mono-glycerides, SSL, CSL Softer, fresher crumb, fine crumb, shorter bite
Dough strengthening emulsifiers Strengthen dough, form complexes with SSL, DATEM, polysorbate-60 gluten, contribute to dough elasiticity
Some can be both Emulsifiers in Bread
Increase volume Improve crumb texture Improve softness (expansion in oven) Emulsifiers in Bread Any single emulsifier does not possess all of these functions
Functions Classifications • Improve dough handling • Origin (synthetic or • Improve rate of natural) hydration • Solubility • Greater tolerance • Functional groups • Improve crumb structure • Hydrophilic/lipophilic • Improved slicing balance (HLB) • Crust thickness • Potential for ionization • Emulsification of fats • Improved symmetry • Longer shelf life Carbohydrate Functional Ingredients
Two Main Groups • Native and modified Starches and • Cyclodextrins derivatives • Maltodextrins • Hydrolysates
• Tree exudates • Seed flours • Plant fragments Hydrocolloids • Fermentation • Seaweed extracts • Animal derived Uses in Bakery Products Bulking agents Gluten substitutes Fat replacers/mimetics Modification of dough rheology and texture Change water absorption Very Diverse Stabilizers Applications! Cryoprotectant Alter crumb structure and texture Increase moisture retention Extend shelf-life Gluten Free Baked Products
Comparison of the swelling mechanism (a) and appearance (b) of fermenting wheat dough and additive-free, gluten-free (GF) rice batter
(Yano 2019) Gluten Free Baked Products
Summary of the procedures for making additive-free rice bread and “cooking tips” for each step
(Yano 2019) Use in Gluten Free Formulation
• Maltodextrins • Alter starch gelatinization • Improve loaf volume • Inhibit staling • Chemically and physically modified starches • Improvement of volume and crumb softness • Resistant starch • Improve nutritional quality
(Naqash et al 2017) Hydrocolloids in Gluten Free Baking
Most frequently used hydrocolloids, in commercially available gluten-free breads
(Roman et al 2019) Gluten Substitute
• Hydrocolloids in gluten free bread • Improved volume • Improved crumb texture • Softer texture Control 1 + HPMC
Control 2 + HPMC
(Mariotti et al 2013) Gluten Substitute Flour Blend Rice Flour Wheat Flour • Hydrocolloids in gluten free crackers • Resulted in • Fewer & larger gas cells • Higher moisture • Interact with native rice 1% HPMC 1.5% HPMC 2.0% HPMC proteins → increased dough elasticity 1% CMC 1.5% CMC 2.0% CMC (Nammakuna et al 2016)
1% XN 1.5% XN 2.0% XN Fat Replacers
Fat replacers are defined by the American Dietetic Association as “an ingredient that can be used to provide some or all of the functions of fat, yielding fewer calories than fat” (ADA, 1998) Fat Replacers • Carbohydrate, protein or fat origin • Bind water and form paste that mimics texture and viscosity of fats
Complex carbohydrates • Inulin, maltodextrin, polydextrose, plant fibers
Gums and gels • Xanthan gum, oatrim, pectin, HPMC
Whole foods • Chia seed mucilage, bean puree, apple pomace Fat Replacers
• Ideal fat replacer ingredients for different bakery products
Product Fat Replacer
Biscuit Oatrim or bean puree
Cake Oleogels or inulin
Cracker Inulin
(Colla et al 2018) Fat Replacers in Cakes a Succinyl chitosan containing cakes obtained with different levels of fat reduction: a: 0%, b: 25%, c: 50%, d: 75%, e: 100%. b
Fat Hardening Hardness Chewiness Drying rate Reduction Rate c (N) (g) (g/100g/day) (%) (N/day)
0 130 922 27.8 3.85 d 25 132 1029 26.1 5.64 50 130 985 14.0 5.00 75 129 1186 35.4 4.00 e 100 111 960 49.2 3.46
(Rios et al 2018) Fat Replacers in Cakes Texture and Sensory Quality of Cake with OSA Mung Bean Starch as Fat Replacer Control 10% 20% 30% 40% Hardness (N) 43.2 46.3 49.4 50.4 56.5 Cohesiveness 1.52 1.65 1.777 2.11 2.14 Mouthfeel* 8.5 8.4 8.1 7.9 7.3 Texture* 8.2 8.0 7.7 7.6 7.2 Overall acceptability* 8.9 8.7 8.5 8.2 7.2 *Scored 1-10, 10 being the best
(Punia et al 2019) Fat Replacers in Cakes Cake with OSA Mung Bean Starch as Fat Replacer
Control 10% 20% 30% 40%
(Punia et al 2019) Cryoprotectants
Need increased stability to Must control ice crystal freeze/thaw cycles to formation and growth maintain dough quality
https://en.angelyeast.com Cryoprotectants Unfrozen Control
Good volume and shape Nice bright crumb color Good crumb structure Ice crystal formation during 9 Weeks Frozen freezing/re-freezing of dough damages gluten Poor volume and shape and dough structure. Dark yellow crumb color Dense crumb structure
(Steffolani et al 2012) Cryoprotectants
Percent Freezable Water in Frozen Bread Dough Containing Carboxymethyl Cellulose Sodium with Different Degrees of Substitution
• CMCNa with higher DS resulted in less freezable water • Less freezable water will prevent ice crystal formation
(Xin et al 2018) Cryoprotectants Loaf Volume of Bread from Frozen Bread Dough Containing Carboxymethyl Cellulose Sodium with Different Degrees of Substitution
• Adding CMCNa with higher DS better loaf volume • Bread from frozen dough with CMCNa was also softer than bread without CMCNa (data not shown)
(Xin et al 2018) Sugar Reduction
Cakes and cookies have similar formulas • High sugar • High fat • Differ in flour type and water level Sucrose is the most commonly used sugar for baking
Recent interest in healthier baked products with reduced sugar contents
Products with • Lower glycemic index • Prebiotic nutritional benefits Sugar Reduction
• Functionality of Sugar • Significant impact on gelatinization temperature • Starch gelatinization and cake quality • Major factor in determining cake volume and shape • Different sugars will change gelatinization temperatures Sugar Reduction Effect of Sugar Type on Gelatinization Temperature
DSC Thermograms
(Kweon et al 2016a and c) Sugar Reduction Cakes Formulated with Different Sugars
Ultrafine Fine Sucrose Sucrose
Ultrafine Sucrose Fine Sucrose
Fructose Glucose Xylose (Kweon et al 2016a) Sugar Reduction Cakes Prepared with Sucrose and Alternative Sugars
Sucrose
Sucrose Isomaltulose
Isomaltulose
Glucodry 314 Glucodry 314 Mylose 351
Mylose 351
(Kweon et al 2016b) Sugar Reduction Baking Time Minutes Effects of Process Parameters 0 Using Isomalutlose as a Sugar 5 Substitute in Cakes 10
15
20 Pre-dissolution of isomaltulose resulted in an inferior product 25
30
(Kweon et al 2016b) 35 Cross section Predisolved ‘As Is” Isomaltulose Isomaltulose Sugar Reduction Firmness of Cakes with Different Bulking Agents and Sucrose (control)
(Ronda et al 2005) Sugar Reduction Sensory Scores of Cakes with Different Bulking Agents and Sucrose (control)
(Ronda et al 2005) Sugar Reduction Cookies Formulated with Sucrose and Sugar Alternatives
Sucrose Isomaltulose
Glucodry 314 Mylose 351
Sucrose Isomaltulose Glucodry 314 Mylose 351
(Kweon et al 2016c) Sugar Reduction Cookies Formulated with ‘As Is’ and Pre-dissolved Isomaltulose L: ‘As Is’ R: Pre-dissolved
Similar to Cakes → Process effects Quality
(Kweon et al 2016c) Sugar Reduction Partial Sugar Reduction: Cookies Formulated with Blends of Sucrose and Glucodry314
0% 25%
50% 75% 100%
0% 25% 50% 75% 100%
(Kweon et al 2016c) Sugar Reduction Cookies Prepared with Sucrose (A) Tagatose (B) and Fructose (C)
Likeness rankings (1-9) of cookies containing tagatose and sucrose Sweetener Color Sweetness Texture Overall 100% Sucrose 6.13a 6.23a 5.42a 6.17a 50% Suc-Tag 5.89a 5.28b 5.51a 5.40ab 100% Tagatose 6.85b 4.79b 6.02a 5.17b
1 = dislike extremely 9 = like extremely, values within a column with the same letter are not significantly (P<0.05) different
(Taylor et al 2008) Arabinoxylan in Cookies • Arabinoxylan oligosaccharides (AXOS) for sugar replacement Flour substituted with AXOS (12, 23.5 and 34%)
Control
Sucrose substituted with AXOS (10, 20 and 30%) (Pareyt et al 2011) Quality and Shelf Life Crumb structure of control bread, bread with konjac glucomannan (KGM), and bread with konjac superabsorbent polymer (KSAP).
(Liu et al 2014) Quality and Shelf Life Hardness of crumb for control bread (▲), bread with konjac glucomannan (■), and bread with konjac superabsorbent polymer (●).
(Liu et al 2014) Quality and Shelf Life Moisture Loss During Storage of Cakes Prepared with Different Hydrocolloids
Control
(Gomez et al 2007) Quality and Shelf Life Hardness increase during aging of wheat bread from partially baked bread stored at subzero (frozen) or positive temperatures. Frozen storage: 42 days; positive temperature storage: 10 days. Ageing conditions: 24 h at 25 C.
(Barcenas and Rosell 2007) Hydrocolloids in Refrigerated dough What is refrigerated dough?
≈ $1.7 Billion Dollar Industry Challenges in Refrigerated Dough During storage:
1. Loss of strength (dough consistency)
2. Increased syruping Flour and Dough Quality
Xanthan Gum % 0 0.01 0.5 1.0 Moisture (%)b 12.6a 12.6a 12.6a 12.6a c Ash (%) 0.54a 0.55a 0.54a 0.55a Not Proximate Protein (%)b 13.0a 13.0a 13.0a 12.9a much Analysis change Total Starch (%)c 73.5a 73.0a 73.0a 72.4b Xylanase Activity b 1.4a 1.4a 1.4a 1.4a Absorption (%) 66.4c 66.4c 69.2b 70.2a Farinograph d Data PT (min) 7.5c 8.0c 14.0a 12.5b Stability (min) 12.5c 12.5c 22.0a 19.5b *Values in the same row not sharing a common letter are significantly different (P≤0.05) a All analyses were replicated (n≥2) and mean values were reported. ± represent the standard deviation. b As is c Dry Weight Basis d Peak Time e Mixing Tolerance Index f Brabender Units Degree of Dough Syruping Dough Consistency
Measured by Farinograph as the difference in BU between day 0 and the other storage days Summary
Improvement of Refrigerated Water Dough Usage Level Dough Quality by Sequestration Consistency Functional Carbohydrate – • Xanthan gum’s • At 0.5% level • Xanthan gum is Xanthan Gum hydrophilic nature xanthan gum was able to prevent allows for binding able to improve dough syruping at of water released the dough low levels by AX consistency Octenyl succinate starches as Emulsifiers and Fat replacers in bread Light Microscopy of Emulsion Droplets
Oil droplet
Starch
*20x magnification, N: native and M: modified. C: corn; T: tapioca; R: rice; P: potato; W: wheat. Dough Quality 2% Shortening 2% OSA Wheat 4% OSA Wheat 2% OSA Tapioca 4% OSA Tapioca 50 a 40 a f bc c b a c c 30 b b d d c d 20
grams force or mm or force grams 10
0 Stickiness Resistance Extensibility *OSA = Octenyl succinic anhydride **Columns for the same parameter with the same letter are not significantly different (P<0.05) Dough Quality Farinograph Absorption Farinograph Stability 64 20 a a 18 a 62 b b 16 ab b ab b 60 c 14 58 12 10 56 Minutes 8 54 6 % Absorption% (14% MB) 4 52 2 50 0 2% 2% Wheat Wheat Wheat Wheat 2%OSA 4%OSA 2%OSA 4%OSA Tapioca Tapioca 2%OSA 4%OSA 2%OSA 4%OSA Tapioca Tapioca Shortening Shortening
*MB = Moisture basis, OSA = Octenyl succinic anhydride **Values in the same graph with the same letter are not significantly different (P<0.05) Bread Quality
Volume (cc)
2% Shortening 930.00a
2% OSA Wheat 823.33b
4% OSA Wheat 773.33bc
2% OSA Tapioca 771.67bc
4% OSA Tapioca 746.67c
*OSA = Octenyl succinic anhydride **Values with the same letter are not significantly different (P<0.05) Bread Crumb Firmness Summary
OSA esterification improves the emulsification properties,
Size of the starch granule showed a strong influence on emulsification
Effects of esterification varied among starches of different botanical sources
Improved functional properties
Useful as emulsifiers or fat replacer for many baked products Binding of bitter flavors in whole wheat products by cyclodextrins Cyclodextrins
Structure Classification Conical Glucosidic Unit Structure Inclusion Complex Formation
Geometry
Size Conditions Hydrophobic guest
http://www.chm.bris.ac.uk/pt/polymer/images/wirach/fig2-animation.gif Applications
Cosmetic
Textile FoodFood
Pharmaceutical
Household Wheat Bran
Phenolic compounds are concentrated in bran layers
http://grain-gallery.com/en/wheat/images Phenolic Compounds in Wheat Antioxidants Free radical scavengers Inhibit lipid oxidation
Influenced by Genetics Environmental factors Other stressors
Conflicting data regarding relationship with wheat bran color
Elicit unacceptable flavors within plant foods and their products
Sensory properties associated with phenolics Bitter taste Astringency Sour taste Cereal flavor Germ-like flavor
Challacombe et al. 2012 Complexation with Pure phenolic acids 1H NMR β-CD
FA/β-CD Complex
CA/β-CD Complex
∆δ = δpure - δcomplex CO/β-CD Complex
1H-NMR-Spectra (500 MHz) of β-CD with and without the flavors Ferulic acid (FA), Coumaric acid (CO), Caffeic acid (CA
in) D2O in the range of 4.10 ppm to 3.50 ppm. SEM
A: Coumaric acid B: Caffeic acid C: Ferulic acid a) β-CD b) Phenolic acid c) Physical mixture d) Complex Quantum-chemically optimized structures
a) CA/β-CD complex b) (b) CO/β-CD complex c) (c) FA/β-CD complex Structures of complexes represented with calculated HOMO, LUMO and ESP Caffeic Acid (a) HOMO (b) LUMO (c) ESP Coumaric Acid (d) HOMO (e) LUMO (f) ESP Ferulic Acid (g) HOMO (h) LUMO (i) ESP Complexation with Wheat bran phenolic acid Extract 1H-NMR β-cyclodextrin
Ferulic complex
Caffeic complex
Coumaric complex
Caffeic/Ferulic complex
Coumaric/Ferulic complex
Caffeic/Coumaric complex
Caffeic/Ferulic/Coumaric complex
Wheat bran extract complex
*Each 5 mM in D2O in the range of 4.10 ppm to 3.50 ppm. Electrostatic Surface Potential
Caffeic acid and p-Coumaric acid and trans-Ferulic acid and β-cyclodextrin β-cyclodextrin β-cyclodextrin
Electrostatic Surface Potential (ESP) representation of phenolic acid positions within the cyclodextrin Conclusion
Undesirable flavors Undesirable aromas
Cyclodextrins Possible Application in Baking: Making of undesirable flavors or aromas by complexation with Removal of undesirable cylcodextrins flavors or aromas Take Home Message
There is a diverse range of carbohydrate based functional ingredients that can be utilized in a variety of ways to improve quality of baked products References
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Dr. Senay Simsek Department of Plant Sciences North Dakota State University Fargo, ND Email: [email protected] Website: http://www.wheatquality.com Instagram: @wheat.quality.carbohydrate.lab Facebook: Wheat Quality Carbohydrate Lab