4 Reducing Human Hair Including Permanent Waving and Straightening Introduction Reduction of the Disulfide Bond

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1 1 Morphological, Macromolecular Structure and Hair Growth Introduction General Structure and Growth Variation in Fiber Diameter on Different Parts of the Head Functions of Hair on Different Parts of the Body Hair Growth Development of the Follicular/Hair Apparatus with its Essential Structures Hair Follicle Cycling and Hair Growth Extra Long Hair Excessive Hair Growth Hair Loss (Alopecia) Hair Density or the Number of Hairs/Unit Area Male Pattern Baldness Hair Loss Among Women Pregnancy and its Effects on Scalp Hair Alopecia Areata, Universalis and Other Forms of Hair Loss A Mechanism for Hair Growth/Hair Loss and Change in Hair Size Treatments for Hair Loss Surgical Treatment of Hair Loss Hair Multiplication or Hair Induction Treatments for Hair Loss Hair Extensions or Hair Weaves The Cuticle, Cortex, Medulla and Cell Membrane Complex The Cuticle The Cortex, its Cells, Macrofibrils, Matrix and Intermediate Filaments ix

2 x 1.8 Stretching Hair and Stress Strain Models Feughelman s Two Phase Model Wortmann and Zahn s Model Other Models/Modifications and Some Concerns Fractographic and Damaged Hair Concerns with These Models Swelling Behavior of Hair The Origin of Hair Fiber Curvature Structures in the Cortex Associated with Curvature The Structure of the Cell Membrane Complex General Differences for Cuticle-Cuticle CMC Versus Cortex-Cortex CMC The Cuticle-Cuticle CMC Bilayers Versus Monolayers in the Cuticle-Cuticle CMC Thickness of the Cuticle Beta Layers Globular Versus Glycoproteins in the CMC The Cortex-Cortex CMC Covalently Bound Internal Lipids of Animal Hairs Differences in Cuticle-Cuticle, Cortex-Cortex and Cuticle-Cortex CMC The Structure of the Cuticle-Cortex CMC The Formation of the CMC in Developing Hairs The Medulla References Chemical Composition of Different Hair Types Introduction The Amino Acids and Proteins of Different Types of Hair Whole-Fiber Amino Acid Studies Aging Influences on Hair Chemical Composition of the Different Morphological Components Cuticle Proteins of the Cell Membrane Complex Lipids of the Cell Membrane Complex The Effects of Menopause on the Lipids in Hair and the Hair Surface The Composition of the Cortex The Composition of the Medulla N-Terminal and C-Terminal Amino Acids and SCMK Fractionation N-Terminal Amino Acids C-Terminal Amino Acids Fractionation Procedures

3 xi 2.6 Major Protein Fractions of Hair and Gene Expression The KAP Proteins of Human Hair Type I and II Keratin Proteins (IF Proteins) of Human Hair Tricohyalin Protein Other Protein Fractionation Methods Diet and Hair Composition The Analysis and Origin of Protein Fragments from Damaged Hair: Useful Methodology for the Future Water: A Fundamental Component of Human Hair Trace Metals in Human Hair Transition Metals and Free Radical Reactions Functional Groups that Bind Specific Metals Regions of the Fiber that have a High Affinity for Metals Simulated Swimming Pool and Copper Binding to Hair Metals that Bind to Hair do so Specifically A Proposal for Free Radical Oxidation of Disulfide in Hair by Alkaline Peroxide Heavy (Toxic) Metals in Human Hair Other Disorders Related to Accumulation of Metals in Human Hair References Genetic Control/Involvement in Hair Fiber Traits Introduction The Genetics of Hair Form: Hair Diameter and Curvature Evolution to Hairless Bodies, Dark Skin and Highly Coiled Scalp Hair Helpful Websites for SNP Nomenclature and Its Relationship to Hair Form and Pigments Evolution of Coiled Scalp Hair to Straighter Hair Forms The Genes and SNPs Involved in Hair Form Hair Pigmentation and Genetics Melanin Granules of Different Hair Types The More Important SNPs and Genes for Hair Pigments Some Other Hair Traits Related to Genetics Hair Abnormalities Hair Analysis for Drugs and Forensic Studies Forensic Studies and DNA Analysis References

4 xii 4 Reducing Human Hair Including Permanent Waving and Straightening Introduction Reduction of the Disulfide Bond Equilibrium Constants, Redox Potentials, and ph Equilibrium Constants and Chemical Structure Equilibrium and Removal of One of the Reaction Products Equilibrium and Use of Excess Reactant Cystinyl Residues of Different Reactivities in Keratin Fibers Kinetics of the Reduction Factors Affecting the Rate of the Reduction Reaction Effect of Temperature on the Reaction Rate Effect of Hair Swelling and Hair Condition on the Reaction Rate Effect of Mercaptan Structure on the Reaction Rate Reduction of Hair with Sulfite or Bisulfite Summary of Chemical Changes to Hair by Permanent Waving Reduction of Keratin Fibers with Other Reagents Sulfides Steam and/or Alkali Amines Cyanide A Phosphine Miscellaneous Reducing Agents Reactions of the Mercaptan Group Oxidation of Reduced Keratin Fibers Nucleophilic Displacement Treatment of Reduced Hair with Dithioglycolate Ester Derivatives of Polyoxyethylene Nucleophilic Addition Reactions Free-Radical Addition and Polymerization Reactions Water Setting Human Hair Set and Supercontraction Swelling: During and After Treatment Permanent Waving of Human Hair Cold Wave Formulations and Making Cold Wave Products Acid Waves Properties of Cold-Waved Hair The Nature of the Cold-Wave Process

5 xiii 4.12 Hair Straightening and Hair Straightener Products Hair Straightener Compositions Reactions of Hair Straighteners Damage by Hair Straightening Products Why Alkaline Hair Straighteners Are Permanent and Reductive Are Not But Reductives Provide Some Permanence for Curling Depilatories Safety Considerations for Permanent Waves References Bleaching and Oxidation of Human Hair Introduction Hair-Bleaching Compositions Reactions of the Proteins of Human Hair with Bleaches Chemical Oxidation of the Disulfide Bond Proposed Mechanisms for Oxidation of Disulfide Bonds by Alkaline Peroxide Oxidation of Other Amino Acid Residues Hydrolysis or the Action of Alkalinity Summary of Chemical Bleaching of Hair Proteins by Peroxide Oxidation of Hair Proteins and the Cell Membrane Complex by Sun and UV Light Damage by Shampoos and Conditioners and Irradiation Wet Versus Dry State Failure and Oxidative Exposure CMC Lipids Degraded by Both UV and Visible Light Short Term Irradiation Attacks CMC Lipids Producing Internal Step Fractures Long Term Irradiation Produces Fusion Reactions Across Structural Boundaries Fusion Reactions at Peptide Bonds from Free Radicals at Alpha Carbon Atoms Photoprotection by an Oxidation Dye Other Physical Effects from Photochemical Reactions with Hair Other Photochemical Reactions with Hair Fibers Summary of Sunlight Oxidation of Hair Proteins Mechanisms for Free Radical Reactions in Human Hair The Formation of Sulfur Type Free Radicals in Keratin Fibers Proposal for the Photochemical Mechanism for C S Fission of Disulfides Photochemical Reaction of Disulfide with Hydroxyl Radical in Aqueous Solution

6 xiv Photochemical Reactions of Thioesters in Hair Carbon Based Free Radicals from Tryptophan and Phenylalanine Free Radicals from Allylic and Tertiary Versus Alpha Hydrogens Chlorine Oxidation of Human Hair Peracid Oxidation of Human Hair Hair Pigment Structure and Chemical Oxidation Hair Pigment Production and Pigment in Different Hair Types Eumelanins and Pheomelanins: Their Biosynthesis and Proposed Structures Degradation Products of Melanins Biosynthetic Pathway for Mixed Melanogenesis Casing Model for Mixed Melanogenesis ph and Melanogenesis Proposed Structures for Eumelanin and Pheomelanin Degradation Products of Hair Pigments and Different Hair Colors Chemical Oxidation of Hair Pigments Photochemical Degradation of Melanins Photoprotection of Hair Summary of Some Physical Properties of Bleached Hair Safety Considerations for Hair Bleaches References Interactions of Shampoo and Conditioner Ingredients with Hair Introduction General Formulation for Shampoos and Conditioners Aging/Temperature Stability Color Stability Preservation Against Microbial Contamination Viscosity Control in Shampoos and Conditioners Ingredient Structures and Making Procedures and Formula Examples for Shampoos and Conditioners Cleaning Soils from Hair and Cleaning Mechanisms Hair Soils and Detergency Mechanisms Soils from Hair Products Environmental Soils Detergency Mechanisms and Surface Energy of Different Hair Types Perceptions in Cleaning Hair and Subjective Testing of Shampoos Shampoo Performance Hair Effects and Discernibility Versus Perception

7 xv Different Tests to Evaluate Shampoo Performance Shampoo Foam or Lather Sorption or Binding of Ionic Ingredients to Hair Binding to the Hair Fiber Surface Overview of the Binding of Shampoos and Conditioners to Hair Transcellular and Intercellular Diffusion Sorption Theory Equilibria and Kinetics of Ionic Surfactant and Dye Interactions with Keratin Fibers The Chemical Potential (Affinity) Heat of Reaction Oxidative Theories of Dyeing Kinetics of Ionic Reactions with Keratin Fibers Diffusion Coefficients and Diffusion into Keratin Fibers The Binding of Ionic Groups to Hair Hydrogen Ion Interactions with Keratin Fibers Hydroxide Ion Interactions with Keratin Fibers Damage to Hair from Shampoos, Grooming, and Weathering Hair Damage Damage Involving Cuticle Fragmentation and Scale Lifting Fracturing Hair by Tensile Extension Damage by Removal of Structural Lipids Hair Breakage by Grooming Actions Dandruff, Scalp Flaking and Scalp Care The Cause of Dandruff Antidandruff Treatments and Hair Shedding (Telogen Effluvium) Antidandruff Ingredients and the Evaluation of Dandruff Effect of Medium (Delivery) on Antidandruff Efficacy Effect of Residence Time on Antidandruff Efficacy Toxicity, Regulation, Product Safety and Skin Irritation Regulation and Safety Issues (USA) Eye Irritation Skin Irritation Principles for the Relative Skin Irritation by Surfactants Support for the Principles of Surfactant Skin Irritation Sensitization and Phototoxicity Safety Considerations for Shampoo and Conditioner Products References

8 xvi 7 Dyeing Human Hair Introduction Oxidation Dyes or Permanent Hair Dyes Compositions and Dyeing Conditions Summary of the Reactions of Oxidation Dyes Mechanisms for Oxidation Dye Reactions Matrix Compounds The Formulation of Permanent Hair Dyes Usage Instructions The Allergy Test The Strand Test Regulatory Activities Related to Oxidation Hair Dyes Synopsis of Oxidation Dyeing of Human Hair Semipermanent Hair Dyes Formulation of Semipermanent Hair Dyes Usage Instructions for Semipermanent Hair Dyes Color Fading and Light Fastness of Permanent and Semipermanent Dyes Analysis of Semipermanent Hair Dyes Temporary Hair Dyes or Color Rinses Formulation of Color Rinses Usage of Color Rinses Other Dyes for Hair Metallic Dyes Formulation of a Lead Acetate-Sulfur Hair Dye Novel Permanent Dye Using a Dye-Metal Ion Complex Vegetable Dyes Natural-Based Oxidative Hair Coloring Fiber Reactive Dyes Photoprotection of Hair by Hair Dyes Hair Dyeing and Luster Safety Considerations for Hair Dyes Gray Hair and Graying of Human Hair The Process of Graying of Scalp Hair The Onset and Incidence of Graying The Effect of Hair Color on the Perception of Graying The Age that Graying Begins A Second Large Study of Graying of Hair Best Estimates of % Little Gray, % Moderate Gray and % Completely or Total Gray in 5 Year Age Increments Hair Graying and Hair Fiber Diameter Hair Graying and Scalp Hair Density Versus Age

9 xvii Sensitivity of Gray Hair to Light Radiation and Free Radical Reactions Sudden Graying Whitening of Hair References Polymers in Hair Products Introduction The Binding of Preformed Polymers to Hair Chemical Bonding and Substantivity Molecular Size and Substantivity Isoelectric Point of Hair and Polymer Substantivity Desorption and Breaking Multiple Bonds Penetration of Polymers into Hair Cationic Polymers and Their Interactions with Hair Interactions of Quaternized Cellulosic Polymers with Hair Cationic Polymer Surfactant Complexes Polyethyleneimine Polyquaternium-6 and -7 Formerly Quaternium-40 and -41 (Merquats) Other Cationic Polymers Other Polymers Polypeptides and Proteins Neutral and Anionic Polymers Some Newer Polymer Types for Hair Care Nanochemistry, Nanoparticles and Hair Care Cosmetics Hair Fixatives Hair Sprays Some Hair Fixative Formulations Mousses Setting/Styling Lotions and Gels Evaluation of Hair Fixative Products Silicone Polymers in Hair Care Products In-Situ Polymerizations in Hair Oxidation Dye Reactions as In Situ Polymerization Reactions In-Situ Polymerization of Vinyl Monomers in Hair Mechanism of Action Solvent System and Its Effect on Polymerization Polymerization into Chemically Altered Hair Evidence for Polymer in the Hair Safety Considerations for Polymers References

10 xviii 9 The Physical Properties of Hair Fibers Introduction Tensile Extension and Deformations Definitions and Conditions Important to Tensile Extension The Effects of Relative Humidity on Tensile Extension of Hair Tensile Properties and Fiber Diameter Tensile Properties and Temperature Twisting and Stretching Normal Hair and Hair with Natural Twists Tensile Properties of Different Geo-Racial Groups Chemical Bleaching of Hair and Tensile Properties Permanent Waving Hair and Tensile Properties Alkaline Straightening and Tensile Properties Dyes and Surfactants and Tensile Properties ph and Tensile Properties Light Radiation and Tensile Properties Hair Abnormalities and Tensile Properties Reductive Polymerization in Hair and Metal Salts and Tensile Properties Other Approaches to Evaluate Stretching Properties of Hair Vibration Methods Stress Relaxation Stretch Rotation Set and Supercontraction Bending and Fiber Stiffness Bending Methods Stiffness and Linear Density Stiffness and Relative Humidity Bending Stiffness and Hair Damage Bending Stiffness and Hair Fiber Curvature Bending and Possible Cuticle Contributions Torsion and Fiber Rigidity Torsion Methods Rigidity and Moisture Torsion and the Cuticle and Elliptical African Hair Torsional Behavior of Damaged Hair Damage to Hair by Twisting Density of Hair (Mass/Volume) Dimensions, Swelling and Effects of Fiber Shape on Reactivity Methods to Determine Hair Fiber Dimensions Fine Coarse Hair

11 xix Variation in Fiber Cross-Sectional Shape with Emphasis on Diameter and Ellipticity Effects of Fiber Cross-Sectional Shape on Properties and Reactivity Scale Type of Mammalian Hair is Related to Hair Fiber Diameter Hair Fiber Curvature Factors Related to the Origin of Fiber Shape A Historical View of Approaches to Measure Hair Curvature Curvature by the STAM Method can be Approximated from Ellipticity Variation of Curvature Across Populations and Countries Water (RH), ph and Solvents and the Dimensions of Hair Hair and Wool Have Similar Water Binding Amounts and Groups Variation of Fiber Surface Area with Diameter The Swelling of Human Hair Changes with ph Solvents and Swelling of Human Hair Hair Swelling by Permanent Wave Agents Swelling Test for Hair Damage Hair Fiber Friction Methods for Measuring Friction on Hair Fibers Relative Humidity and Friction Friction and Fiber Diameter The Directional Friction Effect Mandrel and Comb Composition and Fiber Friction Normal Room Temperatures do not Affect Hair Friction Bleaching (Oxidation of Hair) Increases Hair Friction Permanent Waving Increases Hair Friction Shampoos and Hair Friction Conditioners and Hair Friction Mechanical Fatiguing, Extension Cycling and Scale Lifting References Definitions of Consumer Relevant Hair Assembly Properties and How These are Controlled by Single Fiber Properties Introduction Combing Ease Methods to Evaluate Combing Ease Treatment Effects on Combing Ease Breakage of Hair During Grooming Actions Evidence that Hairs Don t Break from Tensile Elongation by Combing or Brushing

12 xx Hair Fibers Bend and Loop Around Other Hairs Forming Tangles Which Break Hairs by High Localized Forces from Pulling a Comb or Brush Through a Tangle Hair Fibers by Combing or Brushing Break into Short and Longer Segments Hair Breakage Increases with Hair Fiber Curvature Curly Hair Forms Knots Which Also Break on Impact at the Site of the Knot Hair Chemically or Physically Damaged Breaks Easier than Non-Damaged Hair Hair Fibers with Twists Contain Flaws and Can Break Prematurely Hair Breakage Correlates with Combing and Brushing Forces and the Location of the Break on the Fiber Corresponds to Where the Higher Combing Forces Occur Fatiguing and Hair Breakage Where Hair Fibers Break Favors a Mechanism Involving High Localized Stresses Summary of Hair Breakage as a Complex Multifactorial Phenomenon Split Ends, Types, Their Occurrence and Formation Hair Treated with Free Radical Cosmetics and Sunlight are Susceptible to Splitting Causes of Split Hairs and Split Ends Mechanisms for Formation of Splits Flyaway Hair Static Charge and Flyaway Methods Relevant to Static Flyaway Triboelectric Series Moisture Content and Resistance Temperature and Static Charge Impurities on the Fiber Surface can Influence Static Charge The Amount of Static Generated is Virtually Independent of Rubbing Velocity Decreasing Rubbing or Combing Forces Decreases Static Charge The Sign of the Charge is Related to the Direction of Rubbing Effect of Ingredients on the Static Charge

13 xxi 10.6 Hair Shine or Luster The Scale Angle and the Specular to Diffuse Reflectance Ratio Hair Shine Methods Fiber Alignment, Orientation, and Hair Shine Shine Increases with Ellipticity but Decreases with Curvature and Twists Dark Hair (Natural or Dyed) is Shinier than Lighter or Gray Hair Shampoos, Sebum, and Hair Shine Hair Sprays Decrease the Shine of Single Hairs Permanent Waves and Visual Assessment of Hair Shine Oxidation of Hair and Visual Assessment of Hair Shine Abrasion of Hair Decreases Hair Shine Hair Body Body Definition and its Relationship to Single Fiber Properties Methods to Evaluate Hair Body Treatment Effects and Hair Body Relative Scalp Coverage or Hair Amount Style Retention Style Retention Definition and its Relationship to Single Fiber Properties Methods Relevant to Style Retention Style Retention and Hair Treatments Hair Manageability Hair Manageability Definition and Single Fiber Properties Treatment Effects and Hair Manageability Hair Handle or Feel How Consumer Hair Assembly Properties Change with Age Infancy to Childhood: Approximately the First Year of Life Childhood to Puberty: Approximately Age Puberty to Young Adult: Approximately Age Young Adult to Middle Age: Approximately Middle Age to and Including Advanced Age: Approximately 45 and Up References Appendix Index

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