Food Chemistry, part 1

Dr. Clower CHEM 4201

Food Chemistry

Definition Components of food Behavior of these components Example:

Ethanoic acid a-D-glucopyranosyl-(1,2)-b-D-fructofuranose p-hydroxybenzyl and indoylmethyl glucosinolates S-propenylcysteine sulfoxide b-carotene phosphatidylcholine

Components of Food

Monosaccharides, disaccharides, polysaccharides Lipids Proteins Vitamins Minerals

Colors Flavors Preservatives Water Other components (caffeine, toxins, etc.)

Metabolic Pathways

Anabolism and catabolism

Carbohydrates Lipids Proteins (amino acids) Nucleotides

All relate to citric acid cycle

How does this relate to nutrition?

Molecules from outside the body (food)

Nutrients

Definition Macronutrients

Carbohydrates Fats Proteins Minerals Vitamins

Micronutrients

Carbohydrates

Monosaccharides Disaccharides Polysaccharides Fiber Requirements Artificial sweeteners

Fats

Saturated Unsaturated Trans fats Cholesterol Requirements

18

Linolenic acid

Linoleic acid

OH

Protein

Biological value Nitrogen balance Requirement

Government Food Guides

Government Food Guides

USDA Food Guide Pyramid

Government Food Guides

And today

Minerals

Inorganic substances Cofactors Macrominerals

Na, K, Cl-, Mg, P Ca Cr Mn Cu, Zn, I, Fe

Microminerals

Acrodermatitis enteropathica Goiter

Vitamins

Organic compounds Necessary for metabolic processes Insufficient synthesis in the body

Recommended Daily Values

Fat-soluble
Water-soluble
Figure from Lippincotts Biochemistry, 2nd ed., 1994

Vitamins

Water-soluble

Fat-soluble

Thiamine Riboflavin Niacin Pyridoxine Biotin Folic acid Cobalamin Ascorbic acid Pantothenic acid

Vitamin Vitamin Vitamin Vitamin

A D K E

Thiamine

Vitamin B1 Biologically active form Function

thiamine pyrophosphate (TPP) Also can have TTP

cofactor in oxidative decarboxylation of aketo acids (TCA, AA degradation) RC(O)COOH to RC(O)OH + CO2 Other coenzymes also involved in process Role of B1: H between S and N is very acidic; when removed makes an ylide pork, whole grains, legumes, tuna, soy milk 0.5 mg/1000 Cal intake or min 1 mg/day req. increase with high carb diet or elevated metabolic needs decreased ATP production impaired cellular function Beri-Beri Wernicke-Korsakoff Syndrome, aka cerebral Beri-Beri
O O P O O P O O O S HO S

N+

H2N

ATP

Sources RDA

AMP

N+

Deficiency

H2N N

Riboflavin

Vitamin B2; vit G? Biologically active forms

Flavin mononucleotide (FMN) Flavin adenine dinucleotide (FAD) Electron transfer FMNH2, FADH2 Redox reactions (TCA, glycolysis, etc.) Needed for good vision and healthy skin Milk, mushrooms, tomatoes, liver, green leafy vegetables 1.1-1.3 mg/day Growth retardation Ariboflavinosis

Function

OH OH

OH OH N N O

Sources

RDA

NH N O

Deficiency

Cheilosis Glossitis Stomatitis

Niacin

Nicotinic acid, Vitamin B3 Biologically active forms

Function

NAD+, Nicotinamide adenine dinucleotide NADP+ Nicotinamide (readily deaminated, also in diet)
HN O

Sources

Coenzymes in redox reactions (TCA, FA synthesis, gluconeogenesis, etc.) DNA repair Unrefined grains, fortified cereal, meat, fish, tomatoes, mushrooms, milk, liver, rice Metabolism of tryptophan when AA is abundant (needs riboflavin and B6)

HN

RDA

Deficiency Toxicity

14-16 NE/day (NE = niacin equivalents = 1 mg niacin or 60 mg tryptophan)

Pellagra = rough skin in Italian Skin inflammation, heartburn, nausea, liver damage

NH2

Pyridoxine

Vitamin B6, pyridoxal, pyridoxamine Biologically active form Function

pyridoxal phosphate (PLP)

Sources RDA

Coenzyme for transamination reactions, esp. AAs (neurotransmitters) Decarboxylation of carboxylic acids Wheat, corn, egg yolk, liver, potato, banana, fish, chickpeas 1.3-1.7 mg Induced by TB drug isoniazid (supplement given) Dermatitis, fatigue Depression, confusion Convulsions, seizures Microcytic hypochromic anemia Epidemic in 1950s Neurological disorders at > 2 g /day

Deficiency

Toxicity

Biotin

B7 Biologically active form

H S HN OH

Function

Binds to lysine residue of enzyme

Cofactor in carboxylation reactions, carrier of CO2 (acetyl-CoA to malonyl-CoA, synthesis of fatty acids) Regulation of gene expression Almost all food, esp. milk, egg yolk, tomato, almond, peanuts, avocado, mushroom Also synthesized by intestinal bacteria

N H

Sources

RDA

Deficiency

At least 30 mg/day
Deficiency does not occur naturally unless eat 20 raw egg whites per day (protein avidin binds biotin irreversibly and excreted) Why raw?

Folic acid

Biologically active form

Tetrahydrofolate (THF) Stimulates digestive acids; appetite Receive one carbon fragments from donors and transfer them in AA synthesis and nucleotide synthesis

Function

Sources

Green leafy veggies (foliage), organ meats, legumes, okra, whole grain cereals
400 mg/day, more during pregnancy and lactation Megaloblastic/macrocytic anemia and growth failure Once, most common vitamin deficiency in US; now fortified cereals Absorption inhibited by many medicines, so a problem with the elderly

RDA

Deficiency

Cobalamin

Vitamin B12

Function

Corrin ring system with Co in center Synthesis of Met Methylmalonyl-CoA to succinyl-CoA Transfer of methyl groups Produce red blood cells

Degradation of odd-chain FA, enter TCA

Sources

RDA

Liver, whole milk, cottage cheese, oysters, salmon, clams, eggs, shrimp, pork, chicken (animal sources) 2.4 mg/day Caused by pernicious anemia Methylmalonic acidemia (MMA)

Deficiency

Ascorbic Acid

Vitamin C Function

Sources

Reducing agent, readily oxidized by O2 React with free radicals that can damage DNA, proteins, lipids, etc. Reduces Fe(III) to Fe(II) for absorption Hydroxylation processes (synthesis of collagen) Citrus, potato skins, tomatoes, green veggies, blueberries, peppers, papaya, strawberries 10 mg/day to prevent scurvy 75-90 mg/day recommended; more if you smoke b/c of free radicals in smoke

OH HO

HO

OH

RDA

Deficiency

Toxic

Scurvy = swollen and bleeding gums, loose teeth, red spots on skin from internal bleeding Weakened connective tissue, slow-healing wounds, anemia
Metabolize to oxalate GI problems, so cap dosage at 2 g/day

Pantothenic acid

Vitamin B5 Function

Sources

Component of CoA (transfer of acyl groups, most commonly acetyl) Component of fatty acid synthase complex Eggs, liver, yeast, yogurt, salmon, turkey, sunflower seeds, mushrooms
4-5 mg/day Rare due to abundance in foods Not well characterized Burning feet syndrome

HO

HN

HO

OH

RDA

Deficiency

Vitamin A

Collective term for retinol, retinal, retinoic acid Formed from oxidative cleavage of b-carotene (in liver) Function Sources

Aldehyde: visual cycle/process Alcohol, carboxylic acid: growth, reproduction

RDA

Liver, kidney, cream, butter, egg yolk (animal sources) Yellow and green veggies: carotene precursors (pumpkin, sweet potato, carrots) 700-900 RE RE = retinol equivalent = 1 micro-g retinol or 12 micro-g b-carotene Hyperkeratosis Night blindness Xerophthalmia Levels over 7500 RE

H3C

CH3

CH3

Beta-carotene CH3

H3C

Deficiency

CH3 CH3 CH3

CH3

CH3

H3C

CH3

H3C

CH3

Toxicity

CH2OH Retinol (vitamin A)

CH3

Vitamin D

Group of compounds, steroids with open B rings Most prevalent = D3 D3 active form = 1,25dihydroxycholecalciferol Function

Sources

Regulate Ca and P absorption during bone growth

RDA

Diet: D2 (milk additive, plant sources) and D3 (animal sources) Precursor: intermediate in cholesterol synthesis Formed in skin non-enzymatically from steroid 7-dehydrocholesterol 5 mg D3
Soft bones, impaired growth and skeletal deformities in children (Rickets) Also caused by antiepileptic drugs Most toxic (stored, slowly metabolized)

Deficiency

Toxicity

Vitamin K

Phylloquinone or menaquinone Function

O CH3 CH3 O CH3 CH3

Synthesis of blood-clotting proteins

K1 = plants; K2 = animals, bacteria in intestine Cabbage, cauliflower, spinach, egg yolk, liver 90-120 mg/day Unlikely due to synthesis and wide distribution in food Injection for infants Jaundice

Sources

Vitamin K1 (phylloquinone)

RDA

Deficiency

O CH3 CH3 O CH3 CH3

Toxicity

Vitamin K2 (menaquinone)

Vitamin E

a-Tocopherol Function

Antioxidant, prevent oxidation of polyunsaturated FAs in membranes by O2 and free radicals

Vegetable oils, liver, eggs, nuts, seeds, spinach, tomatoes
CH3 HO CH3 H3C CH3 O CH3 CH3 CH3 CH3

Sources

RDA

15 mg

Deficiency

Associated with defective lipid transport/absorption Hemolytic anemia

Least toxic of fat-soluble vitamins

Toxicity

Olestra

Artificial, noncaloric fat substitute (indigestible)

FDA warning

This Product Contains Olestra. Olestra may cause abdominal cramping and loose stools. Olestra inhibits the absorption of some vitamins and other nutrients. Vitamins A, D, E, and K have been added.
O R C O CH2 H H O R C H O C R O R O O C O O R H O O H O C R H O O H O CH2 O C R O O O CH2 R C H

R = (CH2)7CH=CH(CH2)7CH3