Coffeine Chemistry, Analysis, Function and Effects

Edited by

Victor R Preedy School of Medicine, King's College London, UK Email:

Publishing

Contents

Caffeine in Context

Chapter 1 Caffeine and Nutrition: an Overview 3 Carlos Guedes, Märlison Jose Lima de Aguiar

and Rejane

1.1 Introduction: Caffeine and its Effects on the Organism 3

Pharmacodynamics and of Caffeine 6 1.3 Caffeine-Nutrition Interaction: Effects on

Physiological Processes 7 Caffeine-Nutrition Interaction: Latent Inhibition

Model of Attention 8 1.5 Caffeine-Nutrition Interaction on Cortical Spreading

Depression 1.6 Concluding Remarks 13 Summary Points 14 Key Facts of Latent Inhibition (LI) Key Facts of Cortical Spreading Depression (CSD)

and Explanations of Key Terms 16 Abbreviations 18 Acknowledgements 18 References 18

Chapter 2 Caffeine as an Ingredient in Sugar Sweetened Beverages 22 Lynn J. Riddell, Dhoungsiri Sayompark, Penny Oliver and Russell S. J. Keast

2.1 Introduction: Caffeine Consumption Patterns 2.2 Caffeine in the Body

Food and Nutritional Components in Focus No. 2 Caffeine: Chemistry, Analysis, Function and Effects Edited by Victor R Preedy © The Royal Society of Chemistry 2012 Published by the Royal Society of Chemistry, www.rsc.org

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Contents

2.2.1 Withdrawal from Caffeine 24 2.2.2 Is Caffeine a Drug of Dependence? 25

2.3 Caffeine as a Flavor Agent 26 2.4 Flavor Preferences 28 2.5 Caffeine in Sugar Sweetened Beverages 29 2.6 SSB Consumption 29 2.7 SSB and Body Weight 30

2.7.1 Cross Sectional Studies 30 2.7.2 Prospective Studies and Weight Change 30 2.7.3 Intervention Trials of SSB and Body Weight 31 2.7.4 Studies Finding no Association between SSB

and Weight Change 2.8 Linking Caffeine in SSB and Development of

Overweight and Obesity 31 2.9 Caffeine in SSB Impact Body

Weight? 32 2.10 Conclusion 33 Summary Points 34 Key Facts 34

35 Abbreviations 35 References 35

The Chemistry of Caffeine

Chapter 3 The Chemistry of Caffeine 41 Jose Joäo Carvalho, Franziska Emmerling and Rudolf J. Schneider

In Lieu of an Introduction: Caffeine Trivia 3.1 Nomenclature and Generic Properties 43 3.2 Properties 44 3.3 Spectral Data 47 3.4 Technical Substance, Identification and Impurities 47 3.5 Crystal Structure 48 3.6 Hazard Classification 49 Summary Points 50 List of Abbreviations 50 References 50

Chapter 4 Chemistry and Crystal Structures of Complexes of Caffeine and Tea Catechins 53

Ishizu and Hiroyuki Tsutsumi

4.1 Introduction 53 4.2 Stereochemical Structures of Complexes of Caffeine

and Catechins 55

Contents ix

4.2.1 Complex of Caffeine and CA 55 4.2.2 Complex of Caffeine and EC 59 4.2.3 Complex of Caffeine and CA, EC 61 4.2.4 Complex of Caffeine and Cg 63

4.3 Conclusion 65 Summary Points 66 Key Facts of Caffeine and Catechins 67 Key Facts of Complex of Caffeine and

Catechins 67 Key Facts of Complex of Caffeine and Galloylated

Catechins 68 Definitions of Words and Terms 68 Abbreviations 69 References 69

Chapter 5 Synthesis of Labeled Caffeine 72 Frederic Balssa

5.1 Introduction 72 5.2 Strategies for Caffeine Labeling 72

5.2.1 Synthesis of Labeled Caffeine by Hydrogen Exchange 73

5.2.2 Synthesis of Labeled Caffeine through Total Synthesis 73

5.2.3 Synthesis of Labeled Caffeine by Partial Synthesis with a Xanthine Derivative 73

5.3 Syntheses of Labeled Caffeine 74 5.3.1 Caffeine 74 5.3.2 Caffeine 75 5.3.3 Caffeine 76 5.3.4 Syntheses of Caffeine 76 5.3.5 Syntheses of Caffeine 79 5.3.6 Syntheses of Caffeine 83

5.4 Characterization of Labeled Caffeine 83 5.4.1 Characterization by Nuclear Magnetic

Resonance 84 5.4.2 Characterization by Mass Spectrometry 84

Summary Points 84 Key Facts of Labeled Caffeine 84 Definitions of Words and Terms 85 Abbreviations 85 References 85

Contents

Chapter 6 Diffusion of Caffeine in Different Aqueous Media at Physiological Temperature 89 Ana C. F. Ribeiro, Victor M. M. Lobo, Cecilia I. A. V.

and Miguel A. Esteso

6.1 Introduction 89 6.2 Theoretical Aspects

6.2.1 Concepts of Diffusion 6.2.2 Taylor Dispersion Technique

6.3 Experimental Aspects 93 6.3.1 Diffusion of Aqueous Caffeine 6.3.2 Diffusion of Caffeine in the Presence of 6.3.3 Diffusion of Caffeine in the Presence of

CD 95 6.4 Conclusions Summary Points Key Facts of the Cyclodextrins 97 Key Facts of the Diffusion Definitions of Words and Terms 97 Abbreviations 98 Acknowledgements 98 References 98

Analysis

Chapter 7 Analysis of Caffeine by Liquid Chromatography-Mass 103

Daniel Perrone and Adriana Farah

7.1 Introduction 103 7.1.1 Caffeine Sources 104 7.1.2 Pharmacokinetics and Physiological Effects of

Caffeine 105 7.2 Analysis of caffeine and related Compounds by

7.2.1 Food 107 7.2.2 Water 112 7.2.3 Biological Matrices

7.3 Concluding remarks 121 Summary Points 121 Key Terms of Caffeine Analysis Key Facts of Caffeine Analysis List of Abbreviations 123 References

Contents xi

Chapter 8 Simultaneous Determination of Caffeine and Phenolic Compounds in Tea and Coffee 130 Carolyne B. Faria, Juliana M. Prado, A. Rostagno, Flavio L. Schmidt, M. Angela A. Meireles

8.1 Introduction 8.2 Determination of Alkaloids and Polyphenols in Tea

and Coffee 131 8.3 Sample Preparation 131 8.4 Analysis of Alkaloids and Polyphenols in Tea and

Coffee 139 8.5 Conclusions 148 Summary Points 148 Key Facts of the Chemical Composition of Tea and Coffee 149 Key Facts of Phenolic Compounds 149 Key Facts of Determination of Caffeine and Phenolic

Compounds in Tea and Coffee 150 Definition of Words and Terms List of Abbreviations 151 References 152

Chapter 9 Analysis of Caffeine in Dietary Products by Multiple Injection Capillary Electrophoresis 154 Ahmad Amini

9.1 Introduction 9.2 Methodological Considerations 9.3 Separation of Caffeine and Acetaminophen by

Capillary Electrophoresis 9.4 Conversion of the Single Injection Method to Multiple

Injection Mode I 160 9.5 Method Validation 162

9.5.1 Specificity and Selectivity 162 9.5.2 Linearity 162 9.5.3 Precision 164 9.5.4 Accuracy 167 9.5.5 Robustness 167

9.6 System Suitability and Acceptance Criteria 168 9.7 Determination of Caffeine in Dietary Products 170 9.8 Conclusions Summary Points Key Facts Key Terms List of Abbreviations 175 References 175

Contents

Chapter 10 Determination of Caffeine in Various Coffee Types by Capillary Electrophoresis Through the Anionic Complex with 3,4-Dimethoxycinnamate 179 Thiago Nogueira and Claudimir Lucio do Lago

10.1 Introduction 179 10.2 Capillary Electrophoresis with Capacitively Coupled

Contactless Conductivity 00 DETECTION The Formation of rc-Complexes of Caffeine and

Chlorogenic Acids and Analogues 184 10.4 The with Cinnamic Acid Derivatives

as A Mobile Version of Caffeine and the Resulting Electrophoretic Method

10.5 Validation of the Method 186 10.6 Decaffeinated Coffee and the Need For a Better Limit

Detection 188 10.7 Conclusion 189 Summary Points 189 Key Facts 190 Definition of Words and Terms List of Abbreviations 191 References 191

Chapter 11 Analysis of Caffeine and Related Compounds by Automated Flow Methods 193 Paraskevas D. Tzanavaras and Constantinos K. Zacharis

Introduction 193 11.2 Automated Flow Injection Techniques 194

11.2.1 Flow Injection Analysis 195 11.2.2 Sequential Injection Analysis 196 Flow Injection

Techniques 197 Determination of Caffeine and Related Compounds

by Coupling of to Separation Techniques 198 Determination of Caffeine and Related Compounds

by Flow Optosensors 201 Determination of Caffeine and Related Compounds

by Detection 202 Various Flow Injection Methods for the

Determination of Caffeine and Related Compounds 204 Determination of Caffeine by Coupled to

Amperometric Detection 204 On-line Extraction of Caffeine from Solid and

Slurry Samples 204

Contents xiii

Method for the Determination of Theophylline 206

Summary Points 206 Key Facts 207 Key Facts on Flow - Sequential Injection Analysis 207 Key Facts on Sequential Injection Chromatography 207 Definitions of Words and Terms 208 List of Abbreviations 209 References 210

Chapter 12 Analysis of Caffeine by 213 Jose Joäo Carvalho and Rudolf J. Schneider

12.1 Development of Immunoassays for Caffeine 213 12.2 Enzyme Immunoassay for Caffeine 215

12.2.1 Works 215 12.2.2 A Detailed Experimental Protocol 215 12.2.3 Quantifying Caffeine in Beverages, Tablets

and Shampoo 219 12.2.4 Immunoassay Cross-Reactivity - Selectivity

Towards Caffeine 220 12.2.5 the Results with an LC-MS-MS

Method 222 12.3 Final Considerations 225 Summary Points 225 Definition of Words and Terms 226 List of Abbreviations 226 References 227

Chapter 13 Quantification of Caffeine Use 230 Merideth Addicott

13.1 Introduction 230 13.2 Estimation of Dietary Caffeine Consumption 231

13.2.1 Methods 231 13.3 Standardized Caffeine Content 235

13.3.1 Beverage Sampling 236 13.3.2 Studies 237

13.4 Caffeine Use Validation with Physiological Caffeine Concentrations 237

13.5 Conclusion 239 Summary Points 240 Key Facts about Methylxanthines in Coffee, Tea, and Cocoa 240 Definition of Words and Terms List of Abbreviations 242 References 242

Contents

Function and Effects

Chapter 14 Caffeine and the Brain: An Overview 247 Acquas, Maria Antonietta De Luca, Sandro Fenu,

Rosanna Longoni and Spina

14.1 Introduction 247 14.2 Pharmacokinetic and Pharmacodynamic of Caffeine 248

Effects of Caffeine on in vivo Neurotransmitters Release 249 14.4 Effects of Caffeine on of Synaptic

255 14.5 Caffeine in Neurodegenerative Diseases:

and Alzheimer's 257 Key Facts 260 Summary Points 261 Definitions of Words and Terms 262 List of Abbreviations 263 References 263

Chapter 15 Caffeine and Cognitive Performance 268 Ana Adan and Josep Maria

15.1 Introduction 268 15.2 The Difficulty of Cognitive Performance 269 15.3 Effects of Caffeine on Attention and Psychomotor

Tasks 270 Effects of Caffeine on Memory and Executive

Function Tasks 272 Effects of Caffeine in Subjective Activation and Affect 273

15.6 Caffeine Combined With Other Substances 277 15.7 Caffeine Use in Children and Aged Subjects 278 15.8 Methodological Difficulties to in the Future 279 Summary Points 281 Key Facts 282 Definitions of Words and Terms 282 List of Abbreviations 283 References 283

Chapter 16 Neuroprotective Effects of Caffeine in Deprivation 287 A. Alkadhi, A. Zagaar, Ibrahim A. Alhaider

and H Alzoubi

16.1 Introduction 287 16.2 Sleep and Sleep 289

Contents xv

16.2.1 Neurochemistry During Sleep 289 16.2.2 Sleep Architecture 290

16.3 Nutrition, Metabolism and Sleep 290 16.4 Sleep deprivation 292

16.4.1 Sleep Disruption and Neural Function 293 Caffeine and Adenosine 295

16.5.1 Adenosine Pharmacology 296 16.5.2 Caffeine Pharmacology 296 16.5.3 Caffeine and Cognitive Function 297 16.5.4 Caffeine, Sleep Deprivation and LTP

Impairment 298 Caffeine and Neuroprotection 299 Effects of Caffeine on Neural Signaling

Pathways 301 Summary Points 304 Definitions of Words and Terms 305 List of Abbreviations 306 References 307

Chapter 17 Caffeine and Exercise Performance 314 Todd A. and Ailish C. White

Introduction 17.2 Mechanisms Explaining Ergogenic Effect of Caffeine 315 17.3 Recommended Dosing, and Form of Caffeine

Ingestion 317 17.4 Tolerance and Withdrawal of Caffeine 318

17.5 Effects of Caffeine on Exercise Performance 318 17.5.1 Caffeine and Endurance Exercise 318 17.5.2 Caffeine and Exercise 319

Caffeine and Resistance Training 319 17.5.4 Caffeine and Team Sport Performance 325 17.5.5 Caffeine and Sprint Performance 325

Summary Points 325 Key Facts of Caffeine's as an Ergogenic Aid 326 Definitions of Words and Terms 327 List of Abbreviations 327 References 328

Chapter 18 The Effects of Caffeine on Ventilation and Pulmonary Function During Exercise 337 Robert F. Chapman, Daniel P. Wilhite and Timothy D. Mickleborough

18.1 Introduction 337 18.2 Effects of Caffeine on Ventilatory Drive 338

Contents

18.2.1 Central and Periphery Chemosensitivity Changes with Caffeine 338

18.2.2 Caffeine and Ventilation During Exercise 339 Potential Ergogenic Effects of Increased Exercise

Ventilation 342 Potential Negative Consequences of Increased

Ventilation During Exercise 343 18.5 Effects of Caffeine on Pulmonary Function 345 18.6 Summary 347 Summary Points 347 Key Facts of Ventilatory Control During Exercise 348 Definition of Words and Terms 349 List of Abbreviations 349 References 350

Chapter 19 Dietary Caffeine and Young Children: for Health 353 William J. Warzak, Shelby Evans, Luis F. Morales Knight, Laura Needelman and Rebecca K.

19.1 The Prevalence of Caffeine 353 Trends in Caffeine Consumption 354

19.3 The Effects of Caffeine on Children 355 19.4 Effects 355 19.5 Sleep Effects 356 19.6 Diuretic Effects 357 19.7 Maternal Consumption 357

Recommended Intake 358 19.9 Future Research 359 Summary Points 361 Key Facts of Caffeine 362 Definitions of Words and Terms 363 List of Abbreviations 365 References 365

Chapter 20 Caffeine and Type 2 Diabetes 369 Atsushi Goto and Liu

20.1 Introduction 369 20.2 Type 2 Diabetes: Pathophysiology and Risk Factors 369 20.3 Coffee Intake and Type 2 Diabetes 370

20.3.1 Evidence 370 20.3.2 Potential Mechanisms 370

20.4 Caffeine Intake and Type 2 Diabetes Risk 371 20.4.1 Evidence 371 20.4.2 Evidence 372

Contents xvii

20.5 Conclusion 376 Summary Points 376 Key Facts: 377

1. Key Facts of Insulin 377 2. Key Facts of SHBD 377 3. Key Facts of Sex Differences in T2D Risk 378

Definitions of Words and Terms 378 List of Abbreviations 379 References 379

Chapter 21 Caffeine and Apoptosis 382 Weinong Han, Yu- Ying He

21.1 Introduction 382 21.2 Caffeine and p53 383

Caffeine and 1 21.4 Caffeine and 387 21.5 Conclusion and Perspective 388 Summary Points 388 Key Facts of AKT 389 Key Facts of ATR 389 Key Facts of ATM 390 Key Facts of Apoptosis 390 Key Facts of UV 391 Key Facts of PTEN 392 Definitions of Words and Terms 392 List of Abbreviations 395 Acknowledgement 396 References 396

Subject Index 400