Fat Mimetics for Food Applications

Miguel Ângelo Parente Ribeiro Cerqueira, Staff Researcher, International Iberian Nanotechnology Laboratory, Braga, Portugal Lorenzo Miguel Pastrana Castro, Staff Researcher, International Iberian Nanotechnology Laboratory, Braga, Portugal

Foreword xv

List of Contributors xvii

Preface xxi

Acknowledgements xxii

Editors xxiii

Section I Introduction to Fat Mimetics 1

1.1 Why Does the Food Industry Need Fat Mimetics? 3
Miguel Ângelo Parente Ribeiro Cerqueira and Lorenzo Miguel Pastrana Castro

1.1.1 The Role of Lipids in Foods and Human Nutrition 3

1.1.2 Current Status of Fats in the Food Industry 4

1.1.3 Food Trends and Fat Mimetics 5

1.2 Overview of the Structure-Property Relationship in Fat Mimetics 7
Reed A. Nicholson and Alejandro G. Marangoni

1.2.1 Introduction 7

1.2.2 Rheological Properties 8

1.2.3 Large Deformation Testing 10

1.2.4 Microstructure 11

1.2.5 Oil Binding Capacity 14

1.2.6 Conclusions and Next Steps 16

Section II Materials and Methods Used for the Production of Fat Mimetics 21

2.1 Natural Wax-Based Oleogels for Food Application 23
Bikash K. Pradhan, Satish Saigiri, Deepti Bharti, Doman Kim, and Kunal Pal

2.1.1 Introduction 23

2.1.2 Mechanism of Oleogelation 24

2.1.3 Bibliography Meta-Analysis 25

2.1.4 Natural Waxes 26

2.1.4.1 Candelilla Wax 26

2.1.4.1.1 Chemical Composition of CW 26

2.1.4.1.2 Physico-Chemical Properties of CW 26

2.1.4.2 Rice Bran Wax 27

2.1.4.2.1 Chemical Composition of RBW 28

2.1.4.2.2 Physico-Chemical Properties of RBW 28

2.1.4.3 Beeswax 28

2.1.4.3.1 Chemical Composition of BW 29

2.1.4.3.2 Physico-Chemical Properties of BW 29

2.1.5 Applications of the Natural Wax-Based Oleogels 29

2.1.5.1 Candelilla Wax 30

2.1.5.2 Rice Bran Wax 30

2.1.5.3 Beeswax 32

2.1.6 Conclusion 34

2.2 Phytosterols and Other Sterols 38
Artur J. Martins

2.2.1 Introduction 38

2.2.2 γ-Oryzanol-Sterols System 40

2.2.2.1 Crystallites and Oil Gelation 40

2.2.2.2 γ-Oryzanol-Sterols Mechanism 41

2.2.2.3 Hydrates 48

2.2.3 Other Combinations Including Sterols 50

2.2.4 Perspective on the Industrial Applicability 50

2.2.5 Conclusion 52

2.3 Lecithin 57
Thaís Jordânia Silva, Paula Kiyomi Okuro, Mayanny Gomes da Silva, Ana Paula Badan Ribeiro, and Rosiane Lopes da Cunha

2.3.1 Introduction 57

2.3.2 Lecithin Chemistry 58

2.3.2.1 Types and Composition 58

2.3.2.2 Technological Manufacture of Lecithin 59

2.3.2.3 Strategies of Lecithin Modification 62

2.3.2.3.1 Physical Modification 62

2.3.2.3.2 Enzymatic Modification 63

2.3.2.3.3 Chemical Modification 63

2.3.2.4 Lecithin Self-Assembly: Dependence of Solvent Medium 64

2.3.3 Exploring Techno-Functionalities of Lecithin 66

2.3.3.1 Conventional Fat: The Role of Lecithin as Crystallization Modifier in Lipid Systems 66

2.3.4 Application of Lecithin in Alternative Oil-Structuring Routes 68

2.3.4.1 Oleogels 68

2.3.4.2 Emulsion Strategies 72

2.3.5 Beyond Oil-Structuring Purposes: Role of Lecithin as an Emulsifier and in the Vehiculation of Bioactive Components 73

2.3.6 Food Applications 74

2.3.6.1 Margarines 75

2.3.6.2 Bakery Products 76

2.3.6.3 Chocolate 77

2.3.6.4 Dairy Products 77

2.3.7 Final Remarks and Perspectives 78

2.4 Mono‐ and Diglycerides 88
Sofia Melchior, Stella Plazzotta, Sonia Calligaris, and Lara Manzocco

2.4.1 Introduction 88

2.4.2 Monoglycerides and Diglycerides 88

2.4.3 Fat Mimetics Based on Mono- and Diglycerides 89

2.4.3.1 Hydrogels 90

2.4.3.1.1 Effect of Compositional Factors 91

2.4.3.1.2 Effect of Processing Factors 92

2.4.3.2 Oleogels 92

2.4.3.2.1 Effect of Compositional Factors 93

2.4.3.2.2 Effect of Processing Factors 94

2.4.3.3 From Oleogels to Oleofoams 95

2.4.3.3.1 Effect of Compositional Factors 96

2.4.3.3.2 Effect of Processing Factors 96

2.4.3.4 Gelled Emulsions 97

2.4.3.4.1 Oil-in-Water Gelled Emulsions 97

2.4.3.4.2 Effect of Compositional Factors 98

2.4.3.4.3 Effect of Processing Factors 99

2.4.3.5 From O/W Gelled Emulsions to High Internal Phase Emulsions (HIPE) 100

2.4.3.6 Water-in-oil Gelled Emulsions 100

2.4.3.7 From W/O Gelled Emulsions to High Internal Phase Emulsions (HIPE) 102

2.4.4 Food Applications 102

2.4.5 Novel Functionalities of MG and DG Fat Mimetics 104

2.4.6 Conclusions 105

2.5 Oleogels Based on Fatty Acids and Fatty Alcohols: Toward Oil Foams 112
Anne-Laure Fameau and Alejandro G. Marangoni

2.5.1 Introduction 112

2.5.2 Structure and Properties of Oleogel Based on Fatty Acids or Fatty Alcohols 113

2.5.2.1 Definition and Properties of Fatty Alcohol 113

2.5.2.2 Definition and Properties of Fatty Acids 114

2.5.2.3 Fatty Alcohols as Oleogelators 116

2.5.2.4 Fatty Acids as Oleogelators 117

2.5.3 Mixture of Fatty Acids and Fatty Alcohol to Improve Oleogel Properties 117

2.5.3.1 Effect of R on the Crystal Structure 118

2.5.3.2 Effect of R on the Microstructure of the Oleogels 119

2.5.3.3 Effect of R on the Thermal Behavior and Solid Fat Content of Oleogels 119

2.5.3.4 Effect of R on Oleogel Properties: Mechanical Strength and Stability 120

2.5.4 Oil Foams Based on Fatty Acids and Fatty Alcohols 122

2.5.4.1 Definition of Oil Foams Stabilized by Crystalline Particles 122

2.5.4.2 Oil Foams Based on Fatty Acids and Fatty Alcohols 123

2.5.4.3 Controlling Oil Foam Properties by Tuning the Ratio between Fatty Alcohol and Fatty Acids 125

2.5.4.4 Application of Oil Foams to Develop Food Products 127

2.5.5 Conclusion and Perspectives 128

2.6 Proteins as Fat Replacers in the Food Industry 133
Davanam Srikanth, Dharani Gopi, Sunil, C. K., Karunairaj Michael, and Ashish Rawson

2.6.1 Introduction 133

2.6.2 Fat Mimetics 135

2.6.3 Protein-Based Fat Mimetics 137

2.6.3.1 Animal Protein-Based Fat Replacers 138

2.6.3.1.1 Casein 138

2.6.3.1.2 Whey Protein 139

2.6.3.1.3 Microparticulated Whey Protein 139

2.6.3.1.4 Simplesse & Dairy-Lo 140

2.6.3.1.5 Egg White Protein 140

2.6.3.1.6 Plasma Protein 141

2.6.3.1.7 Collagen Protein 141

2.6.3.1.8 Gelatin Protein 142

2.6.3.2 Plant Protein-Based Fat Replacers 142

2.6.3.2.1 Soy Protein 142

2.6.3.2.2 Corn Zein Protein 142

2.6.3.2.3 Wheat Gluten Protein 143

2.6.3.2.4 Pea Protein 144

2.6.3.2.5 Lupin Protein 144

2.6.4 Properties of Protein-Based Fat Mimetics 144

2.6.5 Factors Affecting the Acceptability of Protein-Based Fat Mimetics 145

2.6.5.1 Sensory Attributes 145

2.6.5.2 Nutritional Properties 146

2.6.5.3 Hygienic Aspects 146

2.6.5.4 Cost 146

2.6.5.5 Health Aspects 146

2.6.5.6 Marketing 146

2.6.5.7 Convenience 147

2.6.5.8 Heat Stability 147

2.6.6 Applications of Protein-Based Fat Mimetics 147

2.6.6.1 Bakery Products 147

2.6.6.2 Chocolate and Confectionery Products 148

2.6.6.3 Dairy Products 148

2.6.6.4 Meat Products 149

2.6.6.5 Other Applications 149

2.6.7 Future of Protein-Based Fat Mimetics 150

2.7 Polysaccharide-Based Oleogels 155
Andrew J. Gravelle

2.7.1 Introduction 155

2.7.2 Direct Polymeric Structuring 156

2.7.2.1 Ethylcellulose 156

2.7.2.2 EC-Based Hybrid Oleogelation Systems 158

2.7.2.2.1 Monoacylglycerol 159

2.7.2.2.2 Stearyl Alcohol and Stearic Acid 160

2.7.2.2.3 Lauric Acid 163

2.7.2.2.4 Behenic Acid 163

2.7.2.2.5 Lecithin 164

2.7.2.2.6 EC/MAG Binary and Ternary Blends (Edible Shortenings) 165

2.7.2.3 EC-Based Oleogels in Food Applications and Nutrient Delivery 167

2.7.2.4 Chitin 170

2.7.3 Indirect Structuring 171

2.7.3.1 Emulsion-Templating 172

2.7.3.2 Aerogel-Templating 177

2.7.3.2.1 Foam-Templating 178

2.7.3.2.2 Supercritical CO 2 -Derived Templates 181

2.7.4 Conclusion 183

Section III Methodologies for the Characterisation of Fat Mimetics 193

3.1 Rheology and Texture Analysis 195
Luiz Henrique Fasolin, Carolina Siqueira Franco Picone, Gabrielli Nunes Clímaco, and Felipe de Andrade Maia

3.1.1 Introduction 195

3.1.2 Rheology Principles 195

3.1.2.1 Large Deformation Tests 198

3.1.2.1.1 Rheological Behavior/Viscosity Measurements 198

3.1.2.1.2 Time-Dependence 199

3.1.2.2 Small Deformation Tests 201

3.1.2.2.1 Transient Tests 201

3.1.2.2.2 Oscillatory Tests 203

3.1.3 Texture Principles 205

3.1.3.1 Fundamental Tests 208

3.1.3.1.1 Uniaxial Compression 208

3.1.3.2 Empiric Tests 209

3.1.3.2.1 Puncture 209

3.1.3.2.2 Spreadability 209

3.2 Application of Small-Angle X-Ray Scattering and Small-Angle Neutron Scattering to Fat Mimetics 214
Elliot Paul Gilbert

3.2.1 Introduction 214

3.2.2 Fundamentals of Small-Angle Scattering 216

3.2.2.1 SAS Instrumentation 221

3.2.2.2 SAS Experiment and Data Collection 222

3.2.2.3 Data Analysis and Interpretation 222

3.2.3 Recent Experimental SAS and USAS Examples to Oleogels 226

3.2.3.1 Oleic Acid–Sodium Oleate 227

3.2.3.2 Natural Waxes 233

3.2.3.3 β-sitosterol (and Other Phytosterols) with γ-oryzanol 234

3.2.3.4 Lecithin 235

3.2.3.5 Mono‐, Di- and Triglycerides 237

3.2.3.6 Carbohydrate and Proteins 239

3.2.4 Conclusions and Outlook 239

3.3 Sensory Evaluation of Fat Reduction in Foods 245
Patricia Severiano-Pérez, Aurora Pintor-Jardines, Mariel Calderón-Oliver, and Hector Escalona-Buendía

3.3.1 Introduction 245

3.3.2 Generalities on Fat Replacement and Sensory Evaluation 246

3.3.3 Effect of Fat Replacement in Food Products 247

3.3.3.1 Cereal and Baking Products 252

3.3.3.2 Meat Products 252

3.3.3.3 Dairy Products 256

3.3.4 Conclusion and Final Considerations 259

3.4 Gastrointestinal Fate of Lipid-Based Formulations as Fat Mimetics 265
Maria A. Azevedo and Catarina Gonçalves

3.4.1 Introduction 265

3.4.2 Lipid Digestion 266

3.4.2.1 In Vitro Models 266

3.4.2.2 Factors Affecting Lipid Digestion 267

3.4.3 Conclusion 273

3.5 Nutritional and Functional Properties of Fat Mimetics 277
Xiao-Wei Chen and Xiao-Quan Yang

3.5.1 Introduction 277

3.5.2 Emerging Fat Mimetics 278

3.5.2.1 Oleogels 279

3.5.2.2 Templated Oleogels 283

3.5.2.3 Emulsion Gels 287

3.5.2.4 Structured Emulsions 291

3.5.3 Multifunctionality of Fat Mimetics in Food Applications 294

3.5.3.1 Replacement of Saturated Fats 295

3.5.3.2 Reducing Energy Intake in Diets 297

3.5.3.3 In Vitro and In Vivo Digestion 298

3.5.3.4 Controlled Delivery Carriers and Release of Bioactive Molecules 298

3.4.3.5 Texture Design and Modification 299

3.5.3.5 Reduction in Lipid Oxidation 301

3.5.4 Conclusion and Outlook 302

Section IV Food Applications 313

4.1 Processed Meat Products 315
Yogesh Kumar, Akhoon Asrar Bashir, and Poonam Choudhary

4.1.1 Introduction 315

4.1.2 Definition and Classification 316

4.1.3 Type of Fat Mimetics 317

4.1.3.1 Carbohydrate-Based Fat Mimetics 317

4.1.3.1.1 Starch and Starch Derivatives-Based Fat Mimetics 322

4.1.3.1.2 Cellulose-Based Fat Mimetics 323

4.1.3.1.3 Dietary Fiber-Based Fat Mimetics 325

4.1.3.1.4 Gelling and Bulking Agent-Based Fat Mimetics 327

4.1.3.1.5 Gum-based Fat Mimetics 330

4.1.3.2 Protein-Based Fat Mimetics 331

4.1.3.3 Fat-Based Fat Mimetics 332

4.1.4 Conclusion 332

4.2 Fat Mimetics in Dairy Products 343
Ainaz Alizadeh and Mitra Soofi

4.2.1 Introduction 343

4.2.2 The Characteristics of Milk Fat 344

4.2.3 The Role of Milk Fat in Dairy Products 345

4.2.3.1 Milk Fat and Dairy Product’s Sensory Characteristics 345

4.2.3.2 Milk Fat and Dairy Products Texture 345

4.2.3.3 Milk Fat and Dairy Products Melting Properties 346

4.2.4 Issues with Low-Fat Dairy Products 346

4.2.5 Fat Mimetics in Dairy Products 346

4.2.5.1 Carbohydrate-Based Fat Mimetics 347

4.2.5.2 Protein-Based Fat Mimetics 349

4.2.5.3 Lipid-Based Fat Mimetics 349

4.2.5.3.1 Oleogels as a Possible Fat Mimetics 350

4.2.6 Applications of Fat Mimetics in Different Dairy Products 352

4.2.6.1 Cheese 352

4.2.6.2 Ice Cream 355

4.2.6.3 Yogurt 358

4.2.6.4 Dairy Dessert and Beverages 360

4.2.7 Conclusion 361

4.3 Margarine and Fat Spreads 366
Filip Van Bockstaele, Ivana A. Penagos, Kato Rondou, and Koen Dewettinck

4.3.1 Introduction 366

4.3.1.1 Definitions and Legislation 366

4.3.1.2 Microstructure 367

4.3.1.3 Formulation 370

4.3.1.4 Processing 370

4.3.1.5 Properties 371

4.3.2 Alternative Structuring Approaches for Margarines and Fat Spreads 372

4.3.2.1 Stabilization Mechanisms 372

4.3.2.2 Network Stabilization – Continuous Phase 375

4.3.2.2.1 Waxes 375

4.3.2.2.2 Mono- and Diglycerides 379

4.3.2.2.3 Ethylcellulose 381

4.3.2.2.4 Phytosterols 382

4.3.2.2.5 Lecithin 383

4.3.2.3 Network Stabilization–Dispersed Phase 383

4.3.2.4 Bigels 385

4.3.3 Conclusion 386

4.4 Baked Products 392
Ilkem Demirkesen, Suyong Lee and Behic Mert

4.4.1 Introduction 392

4.4.2 Fat Mimetics in Bakery Products 393

4.4.2.1 Fat Mimetics in Bread Formulation 394

4.4.2.2 Fat Mimetics in Cookie/Biscuit Formulation 397

4.4.2.3 Fat Mimetics in Cake/Muffin Formulation 406

4.4.3 Conclusion 414

Section V Industrial Perspective 419

5. 1 Molecular Gels–Barriers, Advances, and Opportunities 421
Michael A. Rogers

5.1.1 Introduction 421

5.1.2 Reliance Serendipitous Discovery 421

5.1.3 Solvent Confluence on Gelation Outcome 422

5.1.3.1 Dissecting Gelator and Solvent Molecular Features that Drive Self-Assembly–A Step Toward Rational Design 423

5.1.3.2 Solvent Complexity of Edible Oils–An Opportunity for Advancement 427

5.1.4 Emerging Low Molecular Mass Organogelating Technologies 431

5.1.4.1 Peptide Gelators 431

5.1.4.2 Sugar Gelators 432

5.1.4.3 Lipids Gelators 432

5.1.4.4 Mixed System Gelators 434

5.1.5 Polymeric Gelation 437

5.1.5.1 Emerging Polymeric Organogelating Technologies 438

5.1.6 Conclusion 439

5.2 Research and Development Toward the Commercialization of Fat Mimetics 447
Miguel Ângelo Parente Ribeiro Cerqueira, Buse N. Gürbüz, and Lorenzo Miguel Pastrana Castro

5.2.1 Introduction 447

5.2.2 Research & Development in Fat Mimetics 448

5.2.3 Patents and Commercial Products 448

5.2.4 Conclusion 474

Index 495