Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Dr. Lisa Mauer Associate Professor Department of Food Science Purdue University
Overview
Definitions of food additives Regulatory information Classification of food additives Specific categories and uses of food additives Organic Shelf-Life
Introduction
Definitions and functions
Food additive categories Functions of direct food additives Utilization of food additives Functions
Sweeteners Acidulants Thickeners and stabilizers Emulsifiers Flavors Colors Vitamins Preservatives Antioxidants Enzymes
Regulations
Regulations
Regulations
FCC
Other countries
FAO/WHO Joint Expert Committee on Food Additives (JECFA)
Judges safety of food ingredients on a worldwide basis Establishes acceptable daily intakes for specific food additives Many countries contribute to JECFA activities
Regulations
Regulations
Regulations
Regulations
Regulations
Regulations
Food Labeling
21 CFR 101
Recall Guidelines
21 CFR 7.40
Regulations
Regulations
Regulations
Regulations
Regulations
Regulations
Regulations
Regulations
Food/Ingredient Analysis
Association of Official Analytical Chemists
AOAC Official Methods of Analysis www.aoac.org
AOAC Methods
45. Vitamins and Other Nutrients 45.1 Chemical Methods 45.2 Microbiological Methods 45.3 Bioassay Methods 45.4 Nutritionally Related Components 46. Color Additives 46.1 Separation and Identification of Color Additives in Foods, Drugs, and Cosmetics 46.2 Intermediates 46.3 Subsidiary and Lower Sulfonated Dyes 46.4 Metals and Other Elements 46.5 Halogens 46.6 Miscellaneous 47. Food Additives: Direct 47.1 General Methods 47.2 Antioxidants 47.3 Chemical Preservatives 47.4 Emulsifying Agents 47.5 Enzymes 47.6 Miscellaneous 48. Food Additives: Indirect 33. Dairy Products 33.1 Sampling 33.2 Milk 33.3 Cream 33.4 Evaporated and Condensed Milk 33.5 Dried Milk, Nonfat Dry Milk, and Malted Milk 33.6 Butter 33.7 Cheese 33.8 Ice Cream and Frozen Desserts 34. Eggs and Egg Products 35. Fish and Other Marine Products 36. Flavors 36.1 General Methods 36.2 Vanilla Extract and Its Substitutes 36.3 Lemon, Orange, and Lime Extracts, Flavors, and Oils 36.4 Almond Extract 36.5 Cassia, Cinnamon, and Clove Extracts 36.6 Flavor Extracts and Toilet Preparations 37. Fruits and Fruit Products
Regulations
Regulations
Regulations
Regulations
EU: E Numbers
E numbers are codes for food additives and are usually found on food labels throughout the European Union. The numbering scheme follows that of the International Numbering System (INS) as determined by the Codex Alimentarius committee. Only a subset of the INS additives are approved for use in the European Union, giving rise to the 'E' prefix.
Wikipedia.com
EU: E Numbers
In the European common market, E numbers are given to additives as they are approved. E-numbers are numerical designations which have been developed within the European Community (EC) for declaration of foodstuff additives. There are a number of sources for lists of E-numbers on the Internet, including:
http://www.elc-eu.org/approved.htm http://www.fst.rdg.ac.uk/foodlaw/additive.htm http://www.eurunion.org/legislat/Foodstuffs/ENumbers.htm
The UK Food Standards Agency publishes a listing of E numbers split into major additive categories (colours, preservatives, etc.). Copies are available on the Internet in pdf format at: http://www.food.gov.uk/multimedia/pdfs/elist_numbers.pdf The numbering system is being adapted for international use by the Codex Alimentarius Commission who are developing an International Numbering System (INS). This largely uses the same numbers (but without the E).
Wikipedia.com
Regulations
Regulations
E Numbers
E Numbers
Wikipedia.com
Wikipedia.com
Regulations
Regulations
E Numbers
Wikipedia.com
Regulations
Regulations
www.faia.org.uk (United Kingdom) www.foodlaw.rdg.ac.uk/uk/reg-ni.htm (Northern Ireland) www.foodstandards.gov/uk/scotland/regulations (Scotland) www.foodstandards.gov.au (Australia, New Zealand) www.inspection.gc.ca/english/reg/rege.shtml (Canada) Many others
Classifications
1. GRAS ingredients
Classification of Additives
Exempt from regulation because their extensive use has produced no known harmful effects
Classifications
Classifications
1.
2.
Secondary direct
Substances added to foods for a specific purpose but which are removed from the final product before consumption
Propellant gases in pressurized foods
3.
Indirect
Become part of the food in trace amounts as the result of packaging, handling, or storage practices. Have no function in the finished product
Packaging migrants, VCM from plastics
FDA website
Classifications
Classifications
1.
1. Processing Additives
Substances used at the industrial level to facilitate the processing, storage, handling, or packaging of foods, and in general are not functionally active in the final food product, although they may, using good manufacturing practices, remain in the final product at low concentrations. Substances that are intentional constituents of the final food product and generally remain functionally active following processing.
2.
3.
4.
5.
Classifications
Classifications
10
20
30
33.3 27.2 26.7
40
Antimicrobial Agents
Antimicrobial Agents
Antimicrobial Agents
Antimicrobial Agents
Antimicrobial Agents
What is the specificity to act against certain microorganisms Can it be applied to a food and food process application? Does it meet prescribed regulatory requirements?
Safe for human consumption, effective in small concentrations, does not hide any food defects, listed on the label when applicable
Food composition
Moisture content Presence of other inhibitors (salt, sugar, spices) pH
Contamination
Sanitary condition of ingredients and equipment Processing methods (temperature, filtration , radiation) Types of microorganisms present
Antimicrobial Agents
Antimicrobial Agents
Types of Antimicrobials
Organic acids Parabens Hydrophilic compounds Sulfites Nitrites Hydrogen peroxide Bacteriocins Antibiotics Wood smoke Naturally occurring enzymes Others
Organic acids
Organic acids are generally used in foods that have a pH < 5.5.
Usually used against spoilage organisms that grow at low pH (yeast, mold, some bacteria) Can be used against pathogens
Lower pH
Antimicrobial Agents
Antimicrobial Agents
Organic Acids
stronger acids have higher K values, lower pK values weaker acids have lower K values, higher pK values pK = pH when the ratio of dissociated ions to undissociated acid is equal to 0.5 pK = pH when half of the acid (50% of it) is dissociated and the other half is undissociated For effective use of organic acids as antimicrobials, want pH of food < pK of acid The undissociated form of the acid is more active and can cross cell membranes
Antimicrobial Agents
Antimicrobial Agents
More active against yeast and mold than bacteria Used in fruit juices and drinks, jams and jellies, pie fillings, fresh fruit cocktails, pickles, condiments
Antimicrobial Agents
Antimicrobial Agents
Broad spectrum of antimicrobial activity but more effective against yeast and mold than bacteria Effective up to pH 6.5 Neutral flavor Frequently used in:
dried fruits (0.02-0.05%), pie fillings (0.05 0.1%), beverage syrups (0.1%), fruit drinks (0.025-0.075%)
Antimicrobial Agents
Antimicrobial Agents
Parabens
Functions: broad spectrum antimicrobial agents
Due to high pKa values, they are effective at high pH
Hydrophilic Compounds
Sulfites:
Mechanism unknown but thought to disrupt critical enzyme systems More effective against molds and yeasts than bacteria At low pH (<4.5) and low aW the fungicidal effect is much more pronounced Types: sulfur dioxide, sodium sulfite, sodium bisulfide, sodium metabisulfites Use levels: vary by country, 200-300 ppm in US Used in: soft fruits, fruit juices, lemon juices, beverages, wines, sausages, pickles, fresh shrimp Note: approx. 1% of population is sensitive to these compounds
Types: methyl, ethyl, butyl, propyl Use levels: 10 100 ppm (0.01 0.1%)
Nonalcoholic and alcoholic beverages, fruit fillings, jams/jellies, pickles, convectioneries, salad dressings, spreads, mustards
Antimicrobial Agents
Antimicrobial Agents
Hydrophilic Compounds
Nitrites
Both oxidizing and reducing agent Primarily used to control the growth and toxin production of Clostridium botulinum Work best in low pH foods (pH 5-6) and in the presence of reducing agents (ascorbate, erythorbate, cysteine) and with sorbate Used mostly for heat processed meat, poultry, and fish that has been vacuum packaged
Hydrogen Peroxide
Used to facilitate the destruction of foodborne pathogens alone or with other means of preservation (heat). Solutions of 0.05 0.1% are recommended Natural catalase in foods will detract from effectiveness Used in cheese and liquid egg processing Also used as sanitizing agent on equipment and packages
Antimicrobial Agents
Antimicrobial Agents
Bacteriocins
Byproducts that bacteria produce to attack other microorganisms
Peptides, proteins, or protein complexes Inhibitory to closely related bacteria
Antibiotics
Secondary metabolites synthesized by many types of microbes Inhibitory to a wide range of microbes Antibiotic resistance is a concern
Nisin is the only commercial bacteriocin approved for food use in US (for processed cheese, effective against Listeria monocytogenes)
10
Antimicrobial Agents
Antimicrobial Agents
Wood Smoke
Usually used to impart desirable flavor for meat products and to improve texture and color attributes
Can be applied as liquid smoke or by burning hardwoods Production of formaldehyde and other inhibitory compounds leads to antimicrobial properties
Temperature and time of heating, degree of surface drying (aW), concentrations of chemicals produced all impact bactericidal and bacteriostatic properties Used for smoked meat, fish, cheeses
Antimicrobial Agents
Other antimicrobials
Antioxidants (BHA, BHT) Flavoring agents (spices, essential oils) Emulsifiers (fatty acids and esters) Ethylene oxide gase (surface sterilents)
Antioxidants
http://www.althealth.co.uk/services/info/misc/antioxidants1.php
Antioxidants
Antioxidants
Definition of Antioxidants
General:
All substances that inhibit oxidation reactions
Food Antioxidants
Oil-Soluble
BHA BHT TBHQ Propyl gallate Tocopherols Thiodipropionic acid Dilauryl thiodipropionate Ascorbyl palmitate Ethoxyquin
Water-Soluble
Ascorbic acid Erythorbic acid Glucose oxidate/catalase Gum guaiac Sulfites
Compounds that interrupt the free radical chain reaction involved in lipid oxidation Compounds that scavenge singlet oxygen
11
Antioxidants
Antioxidants
BHA
Butylated hydroxyanisol Often used in edible frying fats and oils, salad oils, shortenings, nut meats, orangeflavored fruit drinks, processed fruits containing carotene pigments Often used in combination with other antioxidants
Antioxidants
Antioxidants
BHT
Butylated hydroxytoluene Often used as antioxidant for waxes used in packages and wrappers
TBHQ
Often the best synthetic antioxidant Widely used in oils
12
Antioxidants
Antioxidants
Propyl Gallate
Often used as a synergist in combination with BHA and BHT
Fruit juices 120-200 mg/kg Max. 200 mg/kg Nectars 300-500 mg/kg Max. 500 mg/kg Canned fruit 1000-3000 mg/kg Max. 2000 mg/kg Prevention of discoloration in: Olives 100-500 mg/kg Flavor protection in: Citrus beverages 150-200 mg/l Wine 25-100 mg/l Max. 200 mg/kg Max. 200 mg/kg
Antioxidants
Antioxidants
Tocopherols
Best antioxidant activity = 80% gamma and 20% delta mixture of natural tocopherols Nutritional vitamin E = alpha tocopherol Possible replacement for synthetic antioxidants
Antioxidants
Antioxidants
Sulfites
Sulfur dioside, sodium sulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite, potassium metabisulfite Retard enzymatic browning and reduce destruction of carotene and ascorbic acid
SO2 solutions 0.2-0.5%
Sulfites (cont.)
FDA limits for residual sulfur dioxide equivalent levels in foods
Jams and jellies: 30 ppm Nut products: 25 ppm Dried fruits: 2000 ppm Fruit juice concentrates: 1000 ppm Single-strength fruit juice: 200 ppm Maraschino cherries: 150 ppm Wine: 275 ppm Vinegar: 75 ppm
Some people are very sensitive to sulfites Possible replacements: EDTA, blend of erythorbic and citric acids
13
Antioxidants
Antioxidants
Gum Guaiac
Resin containing complex phenolic compounds More effective in animal fats than vegetable oils Approved antioxidant for natural flavoring substances used in conjunction with fruit flavors
Spice Extracts
Spice extracts do not have specific FDA approval for use as antioxidants and thus cannot be promoted as such However,
Rosemary-based extracts have high antioxidant capacities
Used in processed meat and poultry
Antioxidants
Colors
Colors
Color Psychology
. a lasting color impression is made within 90 seconds and accounts for 60 percent of the acceptance or rejection of an object.
14
Colors
Colors
Colors
Certified Colorants
Dyes Colorants that function by dissolution Pigments Insoluble colorants that function by dispersion Both dyes and lakes must have every batch certified by the FDA in the US
Certified Colors Compounds of known structure, produced by chemical synthesis and conforming to high purity specifications established by the FDA.
FD&C Certified Dye and Lake Colors Approved for use in the US
15
Colors
Colors
White Light
Colors
Colors
Strong Light Metal Ions Micro-Organisms Excessive Heating Oxidizing and Reducing Agents
16
Colors
Colors
Certified Lakes
Lakes Extensions of the water soluble dyes on a substratum of alumina hydrate Color by dispersion Common carriers: water, propylene glycol, glycerine, sugar syrup, oil
te hi
t gh Li
Colors
Colors
Any application in which they can be suitably and uniformly dispersed Lakes are also used in products where color migration or bleed is not desired.
Icings & Frostings Compound Coatings Dry mix products Semi moist pet food Pharmaceuticals Cosmetics Plastics Inks
Colors
Colors
Market Forms
Dyes Primary Powder Primary Granules Powder Blends Powder Monoblends Cut Colors and Blends Liquid Colors Lakes Primary powders Powder blends Dispersions
17
Colors
Colors
Colors
18
Colors
Colors
Yogurt Seasonings Mustard Cereals Dairy Candy/Confection Applications Salad Dressings Chewing Gum
Beverages Ice Cream Frozen Novelties Cereal Yogurt Salad Dressing Fruit Preparations Baked Goods Confections Ice-cream Cones Sausage Casings Cheese Eggnog
Colors
Colors
Colors
Colors
Carmine Applications
Beverages Dairy Products Yogurt Ice Cream Tomato Extenders Confections Surimi Cosmetics Pharmaceuticals
Anthocyanins
Yellow-Red Black Currant Elderberry Hibiscus Blue-Red Red Cabbage Grape Skin Extract Grape Juice Conc. Black Carrot
19
Colors
Colors
Anthocyanin Properties
Alcohol Soluble Change shade with change in pH Varying shades of red Most stable at pH less than 3.8
Anthocyanin Applications
Beverages Fruit Preps Confections
pH 8.0 (unstable)
Colors
Colors
Colors
Colors
Exempt Colorants
Exempt Shades Easy to Obtain Yellow Orange Red Exempt Shades Difficult to Obtain Blue Green
Opacifier Pastel Candies Pet Foods Dairy Products Mozzarella Cheese Cottage Cheese Cream Cheese Low fat / No fat (replaces opacity) Salad Dressings
20
Colors
Colors
Colors
Labeling of Exempt Colorants Cannot use the term natural Several Options Artificial Color (Added) Color Added Colored with name of color Colorant name (color) Do not need to declare titanium dioxide by name
Flavor Definition
Legal Definition
Flavors are mixtures of ingredients whose exact composition is usually known only to their supplier and which are sold in bulk to food and beverage manufacturers. They are labeled as FLAVORS according to definitions found in the code of federal regulations title 21, part 101. The composition of flavors are considered trade secrets
Flavor: Definition
Sensation: The sum of those characteristics of any material taken in the mouth, perceived principally by the senses of taste and smell and also by the general tactile and pain receptors in the mouth as received and interpreted by the brain (Hall, 1968) A substance which may be a single chemical entity, or a blend of chemicals of natural or synthetic origin whose primary purpose is to provide all or part of the particular flavor effect to any food or other product taken in the mouth (Society of Flavor Chemists)
21
Flavors
Flavor: Definition
A composite of chemosensations: taste, olfaction, and trigeminal (nerve) sensations
Without olfaction/ability to smell, food no longer has as much flavor (noticed by anosmics or you when you have a cold)
Flavors
Flavors
21CFR 101.22
To create a totally new taste To enhance, extend, round out, or increase the potency of flavors already present To supplement or replace flavors to compensate for losses during processing To simulate other more expensive flavors or replace unavailable flavors To mask less desirable flavors (NOT hide spoilage)
Flavors
Flavors
22
Flavors
Flavors
Flavors
Flavors
Nature Identical
Flavors
Regulatory Labeling
Kosher (Parve, Dairy) Non-Kosher (contains meat, grape skin, etc.) Halal (contains no alcohol) GMO free Allergens (Peanut, Soy, egg, etc.)
23
Flavor Houses
Bell www.bellff.com Degussa www.degussa.com Dragoco www.dragoco.com Firmenich
www.firmenich.com www.givaudan.com
McCormick
www.mccormick.com
Sensient www.sensienttech.com
Takasago
www.takasago.com
Wild www.WILDflavors.com
Examples:
5ribonucleotides (5 inosine monophosphate) Glutamate (monosodium glutamate) Yeast extracts and vegetable hydrolysates Maltol and ethyl maltol used to enhance flavors for sweet goods and fruits used at 50 ppm
21 CFR
Nutrient:
A chemical compound (such as protein, fat, carbohydrate, vitamins, or minerals) that make up foods.
24
Vitamin Definition
Organic compounds, usually of low molecular weight, that are essential nutrients for normal body growth and functions The human cannot synthesize vitamins
Except vitamin D with exposure to sunlight Therefore vitamin sources must be external (food and/or dietary supplements)
Vitamins
There are 13 recognized vitamins Classified as fat soluble or water soluble Each has unique chemistry and RDI Each must be considered in food processing and formulation
Concentration and bioavailability will influence food quality
Types of Fortification
Restoration
Restore losses due to processing and handling
Standardization
Enrich to meet current food standards
Fortification
Enrich to meet a specific nutritional profile
Replacement
A modified or new product replacing a standard product (reduced, low, non-, light, etc.)
Why Fortify?
Processing can reduce vitamin content or bioavailability
Heat sensitive vitamins
D, E, thiamin, riboflavin, pyridoxine, pantothenic acid, folic acid
Why Fortify?
Variation of vitamins in plants
Growth conditions, genetic variation, postharvest practices Soil conditions (moisture, fertilizer) Washing, blanching, cooking will decrease vitamin content Vitamin C content dramatically decreases after harvest and with maturity of plant Milling of cereals reduces vitamin content
Flours usually fortified with B vitamins (thiamin, riboflavin, niacin)
25
Classes of Vitamins
Fat soluble
A (retinol) D (cholecalciferol, D3) E (tocopherol) K (phytonadione, K1)
Water soluble
B vitamins
Thiamine (B1), riboflavin (B2), niacin/niacinamide (B3), pyridoxine (B6), cyanocobalamin (B12), folic acid, pantothenic acid, biotin
C (ascorbic acid)
26
B Vitamins
Thiamin (B1) Riboflavin (B2) Niacin/niacinamide/nicotinamide (B3) Pyridoxine/pyridoxal (B6) Cyanobalamin (B12) Folic acid Pantothenic acid Biotin
Sensitive to oxidizing and reducing agents Split by sulfite Off flavor and aroma potential Good stability in crystal form
Very stable not sensitive to heat, light, air, alkali Best to use niacinamide in foods since niacin is a vasodilator
27
Mineral Definition
An inorganic substance Something neither animal nor vegetable A solid homogeneous crystalline chemical element or compound that results from the inorganic processes of nature (or synthetic substance with same chemical composition and crystalline form)
28
Types of Minerals
Elements Salts
Most minerals added to foods are salts
Elements
30 elements are required or beneficial to humans 7 are macronutrients 7 are micronutrients 18 added to foods for nutritional purposes 12 added to foods for nutrition and functional properties
Added to foods as salt forms
Complexes Ash
Minerals are the constituents in foods that remain as ash after incineration
Elements
MAIN ELEMENTS Calcium Phosphorus Potassium Chlorine Sodium Magnesium TRACE ELEMENTS Iron Fluorine Zinc Silicon Copper Boron Vanadium Arsenic selenium Manganese Iodine Nickel Molybdenum Chromium Cobalt
29
Sodium
Sodium is the anion in the salts of many inorganic and organic compounds (improves solubility) Seasoning/flavor Preservative (lowers aW) Can use to salt in proteins
Magnesium
Solubility properties White color (milk of magnesia) Part of hard water
Desired for brewing because dissolved magnesium (and calcium) salts increase acidity of the wort
Aluminum
Sodium aluminum phosphate
Provides acid in baking powders Hydrated Al3+ reacts with bicarbonate (HCO3-) to release CO2
Silicon
Silicon dioxide = anticaking or freeflow agent
Flours, powdered soups, powdered coffee whiteners, baking powder, dried eggs
Aluminum calcium silicate anticaking agent Aluminum hydroxide used to bind water soluble dyes to form lakes
Phosphorus
Buffering pH stabilization Acidification or alkalization Sequestering of metals Chelation of metals Water-binding in protein foods Emulsification Anticaking Antimicrobial preservation Leavening
Sulfur
In foods, use oxo-species of sulfur
Bisulfite, sulfite, sulfurous acid, metabisulfite, sulfur dioxide
Sulfur dioxide
Preserving dried fruits and vegetables (color) Retard growth of unwanted organisms in wine Antioxidant properties
30
Chlorine
Chlorine and chlorine dioxide gases used to bleach flour Improves solubility of salts in water
Potassium
Anion of many salts good solubility Potassium ion used to help gel carrageenan Potassium hydroxide used to peel fruit
Calcium
Calcium chloride used as firming agent for canned foods
Tomatoes, potatoes, apple slices
Titanium
Titanium dioxide used as white color (levels up to 1% finished weight allowed)
Confectionary panned goods (jelly beans), icings, sugar syrups
Calcium ion active ingredient in leavening agents (monocalcium phosphate) = fast acting leavening agent Monocalcium phosphate acidulant
Bromine
Calcium and potassium bromate used as bleaching agents and dough conditioners (improve strength, grain, texture, water absorption, crumb resiliency) Being phased out of use because is possible carcinogen
Tin
Not widely used Stannous chloride used as food preservative Tin salt retains color in asparagus
31
Acidulants
Acidulants
Types of Acidulants
Acetic acid Adipic acid Citric acid Fumaric acid Lactic acid Malic acid Phosphoric acid Tartaric acid
Acidulants
Acidulants
Tartness comparisons
At equal concentrations, acidulants vary in their ability to depress pH and the level of acidic taste or tartness intensity
Acid Citric, anhydrous Fumaric Tartaric Malic Adipic Phosphoric (85% soln.) % to replace anhydrous citric acid 100 67-72 80-85 78-83 110-115 55-60
32
Acidulants
Acidulants
Citric Acid
The most versatile and widely-used food acidulant Characteristics:
excellent solubility, extremely low toxicity, chelating ability, pleasantly sour taste
FDA designates citric acid and its sodium, potassium, and calcium salts as GRAS for general purpose uses
Preservative, sequestrant Flavor enhancer Antioxidant synergist with ascorbic or erythorbic acid Prevent crystallization of honey
Acidulants
Acidulants
Malic Acid
Second major acid next to citric Strongly associated with apples Used in fruit-flavored sodas (apple or berry flavors), may mask high-intensity sweetener off-tastes in sugar-free drinks (synergism with aspartame) Blends of citric and malic acid may exhibit some better taste characteristics
Phosphoric Acid
Not recognized as an acidulant in Japan The only inorganic acid extensively used as a food acidulant, least costly of the food acidulants, gives the lowest attainable pH Has a characteristic flavor and tartness and is almost entirely used in cola-flavored carbonated beverages Sometimes used as buffering agent in jams and jellies to adjust acidity for maximum gel formation Food-grade phosphoric acid mostly supplied as 75% aqueous solution
Acidulants
Acidulants
Fumaric Acid
Use in mixtures with 0.3% dioctyl sodium sulfosuccinate (DOSS) and 0.5% calcium carbonate to speed solubility Used as modified acid for use in dry beverage powders, frozen fruit concentrates Increases strength of gelatin gels and acts as a calcium liberator incorporated in alginate preparations Stabilize suspended matter in in flashpasteurized and frozen juice concentrates and inhibits development of off-odors and darkening
Adipic Acid
Often used in dry food products (it is nonhygroscopic and may extent shelf-life in humid conditions) Adds supplementary flavor to grapeflavored products
33
Acidulants
Acidulants
Lactic Acid
Has a mild taste relative to other food acids Often sold as 50% and 80% solutions that are colorless and odorless Used in frozen desserts, jams, jellies to add slight tartness without masking natural fruit Used as gelling agent for demethylated pectins (dietetic/sugar-free jams/jellies)
Tartaric Acid
EC regulations indicate this should not be used in sparkling waters Widely used in cranberry and grape flavored foods and beverages Used in candies with citric acid to produce tart and sour flavors
Acidulants
Vinegar
Cider vinegar (US), wine vinegar (EU), malt vinegar (UK) 4-8% solution of acetic acid has similar taste to cider vinegar Vinegar powder used in dry seasonong blends
Sequestrant
Sequestrant
Definition of Sequestrant
To sequester = to withdraw from use Ingredients added to form complexes with metal ions and thereby stabilize foods
Any molecule with an unshared electron pair can form complexes with metal ions in a favorable physical environment
Types of Sequestrants
EDTA Polycarboxylic acids
Citric acid Malic acid Tartaric acid Oxalic acid Succinic acid
Polyphosphoric acids
Adenosine triphosphate phyrophosphate
34
Sequestrant
EDTA
The EDTA molecule can bind to metal ions by forming six bonds to it - two from nitrogen atoms in amino groups and four from oxygen atoms in carboxyl groups.
Sweeteners
Nutritive Nonnutritive
Sweeteners
Definition of Sweeteners
Nutritive:
Ingredients that are metabolized and provide calories May also function as flavor, body, bulk, texturizing, aW lowering, and viscosity agents and lower the freezing point
Sweetness
Sucrose is the standard against which sweeteners are measured in terms of quality taste and taste profile
Nonnutritive:
Ingredients that are non-caloric Many high-intensity sweeteners fall in this category (>30 times sweeter than sucrose)
Sweeteners
Sweeteners
Polyols
Mannitol Lactitol Isomalt Xylitol Sorbitol Maltitol Hydrogenated corn syrup
35
Sweeteners
Sweeteners
Table 13.3
Economics of Sweeteners
Sweeteners
Alitame
2000x sweeter than sucrose Approved for use in foods, beverages, and as table top sweeteners in Australia, New Zealand, Chile, Colombia, China, Indonesia, and Mexico. Approval is pending in USA, Brazil, Canada
36
Sweeteners
Sweeteners
Cyclamate
30 x sweeter than sucrose Banned in some countries (including US), reapproved in over 50 countries Enhance fruit flavors, even in low concentrations, and can mask some natural tartness of citrus fruits Has lower specific gravity and osmotic pressure than sucrose syrups, therefore do not draw water out of canned fruits
Glycyrrhizin
US FDA GRAS status to ammoniated glycyrrhizin for use as flavor enhancer and natural flavoring agent Japan used as a sweetener
Sweeteners
Nonhesperidin DC
2000x sweeter than sucrose Currently used in Belgium, Holland, Germany Often coupled with other sweeteners (aspartame and aceK) Recommended for fruit juices and nectars
Sweeteners
Stevioside
300x sweeter than sucrose Approved for sweetening use in Japan, Republic of Korea, Brazil
37
Sweeteners
Sweeteners
Thaumatin
3000x sweeter than sucrose Used primarily as a flavor enhancer Approved in US, EU, Japan, others
Tagatose
0.9x as sweet as sucrose Has the bulk of sucrose, is almost as sweet, but provides only 1.5 kcal/g Declared GRAS by manuracturers selfdetermination process
Production of Polyols
Use of Polyols
Polyol Functionality
Polyols are derived from sugars, but they are not processed by the body like sugars. Polyols have many advantages such as reduced calories as compared to sugar, reduced insulin response, ability to be labeled "sugar-free" and "no sugar added", do not promote tooth decay, and do not brown in bakery applications (i.e. no Maillard reaction). Polyols are used mostly in confectionery, food, oral care, pharmaceutical, and industrial applications. Some characteristics of polyols are fewer calories, pleasant sweetness, ability to hold moisture, and improved processing. Polyols serve as humectants, bulking agents, and freeze point depressants.
38
Polyol Functionality
Sweet Cool Not fully digested in body Non-cariogenic Beneficial to colon health Laxative effects
39
Emulsifiers
Emulsifiers
Emulsion Examples
Water in oil examples: margarine and butter water is the dispersed phase and oil the continuous phase Oil in water examples: milk, ice cream, mayonnaise oil is dispersed phase and water the continuous phase
Emulsifiers
Emulsifiers
Emulsifier Chemistry
H RCOO RCOO H C C C H Amphoteric - lecithin H H O O P O OH
+
N(CH3)3
stearic
Nonionic 1-monoglyceride
40
Emulsifiers
Emulsifiers
Water
Oil
3.
3.
Emulsifiers
Emulsifiers
Selecting Emulsifiers
Product design involves determining:
the problem knowing what the emulsifier can & cannot do on basis of food system functionality, will an emulsifier solve that problem? select the appropriate emulsifier/s optimize usage levels
Emulsifiers
Selecting emulsifiers
Emulsifiers
Common Emulsifiers
Lecithins (phospholipids); baked goods, chocolates, cooking sprays, confections, instantized foods Mono and diglycerides; bakery, frozen desserts, icings, toppings, peanut butter Sucrose esters; wide range of HLB dependent on ester number Sorbitans (Spans 60); toppings and cake mixes Polysorbates
Tween 60- cake mixes and icing; Tween 65- ice cream, custards; Tween 80- oils in diet foods, vitamin-mineral preps, fat-soluble vitamins
Functionality Cost $
Plastics vs. powders
Low Fat
Flavor impact problems
Regulations
MG & DG not regulated, polysorbates more highly regulated (U.S.)
Synergism
Work best in combination with each other
41
Emulsifiers
Emulsifiers
Emulsifiers
Emulsifiers
ORCH2O S OH O
N(CH3)3
surfactant micelle
Nonionic 1-monoglyceride
Emulsifiers
Emulsifiers
Phospholipids
Lecithin:
important emulsifier in the food industry by-product of processing crude soybean oil complex of phospholipids, glycolipids, TAGs, small quantities FAs, sphingolipids fractionation new products of variable functionality Hydrophilic-Lipophilic Balance (HLB) = High or Low Food technologists calculate:
HLB values = (hydrophilic values) - (lipophilic values) + 7
Bulk
lipid phase
Oil-in-water emulsion
H2O
Melting & Solidification Stability Whipping Qualities Viscosity & De-emulsification Melting & Solidification
H2O
Water-in-oil emulsion
Lipid
42
Emulsifiers
Emulsifiers
Phospholipids
HLB of 2-6: good W/O emulsifier, retards wetting HLB of 7-9: good wetting agent HLB of 10-18: good O/W emulsifier, wetting of fat powders Wetting:
High surface tension
H2O
Lecithin
fatty acid part
Market products are paste lecithin & powdered lecithin of high purity.
Either of choline, ethanolamine, inositol, serine
P
phospholipid
Uses: viscosity control & wetting, anti-spattering & anti-staling, also used in chocolate
Enzyme-digested or enzyme-treated lecithin is improved through strengthening the hydrophilicity by a treatment with phospholipase Enzyme-digested Lecithin
fatty acid part
Enzyme-Digested Lecithin
fatty acid part Hydroxyl group
( < 90)
H2O
( > 90)
P
phospholipid
P
phospholipid
Emulsifiers
Emulsifiers
Monoglycerides (MG)
fatty acid part hydroxy group hydroxy group
Glycerine + plant/animal oil/fat produced by interesterification Uses: emulsifier W/O, foaming agent, starch modifying agent, anti-foam, anti-tack, antibacterial, anti-staling, & softening A very stable oil, peroxide value not increased at 97 C for 1,000 h. Stable -crystals Uses: added to hydrogenated fats (margarines), coatings, plasticizer, solvent, & powdered foaming agent
Foaming ability > emulsifier ability Uses: in shortenings for cakes, desserts, & foam aeration for cream, by itself or with MGs, & gloss enhancement
Diglycerides
fatty acid parts
hydroxy group
Citric Acid Esters of Monoglycerides Highly hydrophilic emulsifier, stable fatty acid part crystal structure
hydroxy group citric acid
Uses: margarine, dairy products (in coffee whitener & cream), an emulsion stabilizer for mayonnaise & dressings because of strong acid-resistance
Emulsifiers
Emulsifiers
Insoluble in cold water, dispersible in hot water, soluble in hot alcohol, fats & oils. SMG complexes with starch & reacts with protein Uses: dough modifying agent, emulsifier for shortening
Dispersible in water, soluble in oil Hydrophilicity & lipophilicity greatly change with degree of polymerization and the type of fatty acid, HLB range 3-13 Uses: various (i.e., in many types of food as an O/W & W/O emulsifier for milk products containing acid & salt, and a modifier to control fat crystallization
( )n
fatty acid part hydroxy group
n
n = ~ 2-10
Dispersible in cold & hot water, soluble in fats/oils, hydrophilic emulsifier, acid resistant Uses: emulsification & foaming of margarine, mayonnaise & dressing, acts on starch & protein, & a dough modifier
n
n = ~ 2-10
43
Emulsifiers
Emulsifiers
Sucrose ester
fatty acid part
Sorbitol Monoester Many types of sorbitan esters, each with different kinds of fatty acids & fatty acid part various degrees of esterification
hydroxy group
hydroxyl group
Uses: emulsifying & dispersing agent for cream & bacteriocidal agents for canned coffee
Emulsifiers
Emulsifiers
Emulsion Destabilization
Creaming - density differences; droplet size critical Flocculation - droplet aggregation; interaction of adsorbed macromolecules between droplets, pH and ionic strength play a role as well Coalescence - droplet collision that breaks interfacial film; pH, salts, temperature, emulsion volume all involved Oswald Ripening - droplet collision that produces smaller and smaller particles that eventually dissolve and float above the aqueous layer; frozen foods
Emulsifier Applications
Baked Goods
largest use of emulsifiers (over 55%) Dough Conditioning (SSL, polysorb, DATEM,
ethoxylates and succinylated mono and diglycerides
Emulsifiers
Emulsifiers
Emulsifier Applications
Foaming/Aeration (monoglycerides, PGME,
polysorbates)
Emulsifier Applications
Confectionary and Coatings
prevention of fat bloom sorbitan tristearate, lactylated monoglyceerides lecithins in chocolate (scavenges free water) monoglycerides often used to enhance fat dispersion and improve eating in caramels and toffees
OR
Calcium Stearoyl-2-Lactate (CSL) stearic acid lactic acid Unreacted stearic acid & salt, nCa partially neutralized with calcium, an m anionic emulsifier with a strong Usually m = 2, n = 1/2 ability to bind protein
Uses: by itself limited to emulsifying applications mainly for cream, widely used as a major emulsifier in combination with other emulsifiers with different functions
o
Sorbide Monoester
Sorbitan Monoester
44
Emulsifiers
Emulsifiers
Emulsifier Applications
Dairy and Aerated Foods foam promotion with stability arising from proteins in system; emulsifier promotes fat crystal agglomeration to form matrix propylene glycol esters, acetylated and lactylated monoglycerides used coffee whiteners use emulsifiers for dispersion and rapid hydration ice cream usually used additional gums (CMC, guar, locust bean, and carrageenan) to stabilize
Emulsifier Applications
Fat Reduction
better fat dispersion and smaller droplets for better mouthfeel even at reduced fat levels emulsifiers used in full fat will require modification in reduced fat systems combinations of emulsifiers work better
Emulsifiers
Emulsifiers
Emulsifier Regulations
In USA:
GRAS:
Lecithin, mono and di-glycerides, DATEM, triethylcitrate
Emulsifier Regulations
In Japan:
On positive list of food additives:
Glycerin fatty acid esters Sorbitan fatty acid esters Propylene glycol fatty acid esters Sucrose fatty acid esters Lecithin
All others governed by multipurpose additive regulations stating use in specific products at set levels
In Europe:
Classified under EEC Council Directive reference numbers
e.g. mono and diglycerides: E471 Western Europe no food use of sorbitan esters Germany no propylene glycol esters
Leavening agents
45
Leavening agents
Leavening agents
Baking soda
Sodium bicarbonate, soluble white chemical compound with a slight alkaline taste Above 60 C, 2NaHCO3 When exposed to an acid NaHCO3 + HX
Leavening agents
Leavening agents
Baking soda
Cream of Tartar (potassium acid tartrate) (1835) -> development of the first baking soda gas release: 70/0/30 (relative percentages of gas release at mixing/bench/cooking) Sodium Aluminum Sulfate (SAS) (1885) 0/0/100 Sodium Acid Pyrophosphate (SAPP) (1900s) several grades based on particle size: 40/8/52, 36/8/56, 32/8/60, 28/8/64, 22/11/67 Other modern leavening agents: - monocalcium phosphate monohydrate (60/0/40) - coated monocalcium phophate (15/35/50) - sodium aluminum phosphate (22/9/69) - dicalcium phosphate dihydrate (0/0/100)
Baking Powder
Baking soda (about 30%) + acidulants + starch (25-40%) Home use: Phosphate (monocalcium phosphate) or SAS Commercial: Variable; mainly SAPP + monocalcium phosphate Double acting: two kinds of acidulants (room temp + high temp) Single acting: contain only room-temp acidulants Can substitute baking powder for baking soda One year shelf-life and lose activity over time
Leavening agents
Leavening agents
Ammonium bicarbonate
Bakers ammonia Slight ammonia odor and soluble in water -> alkaline soln. The aqueous solution of this salt liberates carbon dioxide and ammonia on heating NH4HCO3 NH3 + H2O + CO2 used in food industry before the introduction of baking soda
Yeast
Saccharomyces cerevisiae yeast cells convert carbohydrates into carbon dioxide and alcohol. More yeast needed in sweet breads because excess sugar will have negative osmotic effect on the cells Compressed fresh yeast (70% H2O) Granulated dry yeast (8% H2O)
46
Polydextrose
Polymer of D-glucose (dextrose) containing bound sorbitol and citric acid with MW 22,000 Daltons Soluble in water aW profile similar to sucrose used to lower aW in foods Depresses freezing point Energy 1 kcal/g Bulking and fat sparing agent
Functions of Polysaccharides
Interactions with water
Texture Thickener Gel formation
Digestibility
Dietary fiber
Starch
Starch
Amylopectin
47
Starch
Starch
Corn Starch
Maize, Waxy Maize and High Amylose 5-35 Micrometer Granules Waxy Maize: 0% Amylose Maize: 27% Amylose High Amylose: 55-95% Amylose
Tapioca Starch
5-35 Micrometer Granules Truncated Spheres Bell Shaped 17% Amylose
Starch
Starch
Potato Starch
20-100 Micrometer Granules Large Lenticular Granules 20% Amylose
Wheat Starch
Bi-Modal Granule Distribution 2-10 micrometer 20-35 micrometer Large Lenticular and Small Spherical Granules 27% Amylose
Starch
Starch
Potato
20% Amylose Salve Consistency Clear
Dent Corn
27% Amylose Firm Gel
Wheat
27 % Amylose Soft Gel
Clear
Slightly Opaque
Slightly Opaque
48
Starch
Starch
Starch Modifications
Native Starch Chemical Modification
Dextrinization Oxidation Thinning Crosslinking Substitution
Physical Modification
Instantize Agglomerate
Starch
Starch
Thinning/Thin-Boiling
Increases:
Paste Clarity Gel Strength
Thin-Boiling
Confection Jellies Bakery Fillings Gelled Products Meats Salad Dressings Baked Goods Meats Dairy Coatings
Decreases:
Hot Paste Viscosity
(Thin-Boiling)
Starch
Starch
Crosslinking
Increases:
Temperature Stability Acid Stability Shear Stability
Crosslinking
High Acid
Tomato based sauces, salad dressings
Hot Fill
Pie fillings, bakery glazes
Decreases:
Viscosity Rate of Hydration
Aseptic
Puddings, cheese sauces
Retorted
Soups, gravies, sauces
49
Starch
Starch
Substitution
Increases:
Freeze/Thaw Stability Water Holding Capacity Peak Viscosity Clarity
Substitution
Substituting Agents
Propylene Oxide Acetic Anhydride Octenyl Succinic Acid
Starch Terms
Hydroxypropyl (HP Starch) Acetylated Starch OS Starch
Decreases:
Retrogradation Pasting Temperature
Starch
Starch
Acetylated Starch
1st Generation in Substituted Starches Better Moisture Control over Unmodified Starches Increased Clarity
Hydroxypropylated Starch
Provides Exceptional Freeze/Thaw Stability Improved Paste Clarity Increased Moisture Control Better Control of Retrogradation
Starch
Starch
Octenylsuccinate Starch
Lipophilic Characteristics Helps Control Fat Provides Moisture Barrier Excellent Encapsulation Properties
Combined Modifications
Crosslinking
+
Substitution
Benefits of Both
50
Starch
Starch
Combined Modifications
Frozen Foods Processed Foods Neutral and Acidic Systems Aseptic and Retorted Foods Meats Dairy
Starch Modifications
Native Starch Chemical Modification Physical Modification
Instantize Agglomerate
Starch
Starch
Instant Starches
Dry an d ook -c Pre
Preswel l and
Dry
Pre-Gel Pre-
Granular
Starch
Starch
Instant Starches
Pregelatinized
Rapid Hydration Pre-Cooked Few Intact Granules Grainy Appearance
Granular/CWS
Rapid Hydration Pre-Swollen Intact Granules Cook-up Quality without Heat
Smooth Texture Superior Surface Gloss
Pre-gelatinized
Granular/CWS
51
Starch
Agglomerated Starches
Agglomeration
Starch
Agglomerated Starches
No Need for Diluent Ideal for Hot Water Dispersion Cook-up Quality Versatile for Processing
Instant Starch
Gums
Gums
Gums
Acts as an emulsifier
Gum tragacanth
Stable to heat and acid
Used in salad dressings and sauces Clarity and brilliance in frozen pie fillings
Both used in ice creams for binding water, decreasing ice crystal size, stabilizer, texture
52
Gums
Gums
Xanthan gum
Carrageenan
Interacts with locust bean gum and milk proteins Chocolate milk -> stabilize chocolate suspension Chemically set gels with potassium ion
Gellan
Requires monovalent or divalent cations to form a gel High gel strength and low syneresis
Alginates
Form gels at room temp. in presence of calcium ion Icing on donuts texture, gel, and stickiness
Gums
Gums
Pectin Functions
Commercial pectin obtained from:
Citrus peel (lemon and lime) and apple pomace
Methylcellulose
Thermogelation (gels when heated, melts when cooled)
Grease barrier in fried foods
Pectin with > 50% carboxyl groups in methyl ester form are high-methoxyl (HM) pectins Pectins with < 50% carboxyl groups in methyl ester form are low-methoxyl (LM) pectins
Gums
Gums
Pectin
Virtually impossible to dissolve without high shear and or high temperature Food uses:
Jelly Fruit on the bottom yogurt
Pectin Functions
HM pectin
Solutions gel when sufficient acid and sugar are present Lower pH convert charged carboxylate groups to uncharged and these can form junction zones High concentrations of sugar (at least 55%, often 65%) competes for water of hydration and assists junction zone formation
53
Gums
Pectin Functions
LM pectin
Gel only in the presence of divalent cations (only calcium used in food industry) Divalent cations provide cross-bridges (form junction zones) Increasing concentration of calcium increases gelling temperature and gel strength Gel formation does not require sugar can be used for diet formulations
GRAS
CFR 182.1480 184.1724
Humectants Humectants
Additives which are used to keep food moist. Humectants are hygroscopic, i.e. they absorb moisture from the atmosphere, and thus are able to counteract the normal drying effects caused by evaporation. Typical foods kept moist by humectants include cake icings, confectionery, shredded coconut and dried fruit. Common humectants include GLYCEROL, MANNITOL, SORBITOL, CALCIUM LACTATE and POTASSIUM LACTATE, and PROPYLENE GLYCOL.
Enzymes
54
Enzymes
Enzymes
Enzyme Functions
Speed up reactions Reduce viscosity Improve extractions Carry out bioconversions Enhance separations Develop functionality Create/intensify flavor Synthesize chemicals
1.
Groups of Enzymes
Oxidoreductases
Catalyze oxidations or reductions
2.
Transferases
Catalyze a shift of a chemical group from a donor to an acceptor substrate
3.
Hydrolases
Catalyze hydrolytic splitting of substrates
4.
Lyases
Catalyze removal or addition of chemical groups to substrates (excluding hydrolysis)
5.
Isomerases
Catalyze intramolecular rearrangements
6.
Ligases (synthetases)
Catalyze combinations of substrate molecules
Enzymes
Enzymes
Unwanted
Lipid hydrolysis producing hydrolytic rancidity in lipid containing foods Thinning of tomato paste Browning of fruits
One is an isomerase
Intramolecular rearrangement Glucose isomerase
Enzymes
Enzymes
55
Enzymes
Enzymes
Enzymes
Enzymes
Control :
Enzyme Type
Most commercial pectinase is produced by Aspergillus niger (mold) Often combination of pectin methylesterases and polygalacturonases
pH
Want maximum activity
Limited denaturation with maximum conversion of reactant to product
Time
Depends on the dosage of the enzyme and variety of fruit (15 min 2 hours) The more the enzyme, the less time is needed
Amylases
Used to hydrolyze starch to sugar Remove starch from:
Fruit juices and extracts Flavoring extracts Prepare starch-free pectin (important that this contains no pectinases)
By removing oxygen:
Prevent off flavors in citrus concentrates and drinks Prevent enzymatic browning of fresh frozen fruits Prevent iron pickup in canned fruit drinks
56
Enzymes
Enzymes
Proteases in milk
Proteases in milk degrade proteins and significantly affect flavor and protein stability Control
Enzyme Type
General protease Native to milk (e.g. plasmin) Produced by psychrotrophic microbes
Temperature
Very high temperature is needed to inactivate the enzymes Pasteurization and other milk processings are not inactivate all the enzymes, some still remain active
Enzymes
Enzymes
Temperature
Not recommended to heat
Temperature
Inactivated by denaturation (> 50C)
pH
Lower pH to reduce activity using organic acid
57
Enzymes
Enzymes
Inhibitor
Sulfite
Substrate removal
Remove O2 using vacuum package, MAP, CAP Remove copper
Radiation
D37 = 30-70 kGy
pH
Inactivated at pH < 3 and > 9.5
Enzymes
58