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Vitamins

• Essential organic substances needed in small


amounts by the body
▫ Regulate & support chemical reactions
• Not a source of energy, promote energy-yielding
reactions
• Deficiencies occur if absent from the diet
• Fat-soluble & water-soluble vitamins
• Content in food can be affected by:
▫ Exposure to light, heat, air, water
Vitamins cont..
• Coenzymes
▫ Small, organic molecules
▫ Type of cofactor: combine with inactive enzymes
to form active enzymes that catalyze reactions

• Antioxidants
▫ Donate electrons to free radicals
▫ Protect molecules or parts of cells from attack
Vitamins cont..
• 13 required vitamins

Fat-soluble
• Vitamins A, D, E & K (ADEK)

Water-soluble
• B-group vitamins involved in energy metabolism
▫ Thiamin B1, riboflavin B2, niacin B3, pantothenic acid B5,
biotin B7
• Pyridoxine B6
• Folate B9
• Vitamin B12
• Vitamin C
Fat-Soluble Vitamins
= ADEK

• Dissolve in organic solvents


• Absorbed along with fat, require bile for
digestion
• Transported like fat in chylomicrons, VLDL,
LDL
• Not readily excreted; can cause toxicity
• Concerns of deficiencies in people with fat
malabsorption
Vitamin A
• Role in growth & development, cell differentiation,
vision & immune function

Includes:
• Retinoids (Preformed Vitamin A) = biologically active
▫ Retinal, retinol & retinoic acid
▫ Found in animal products

• Carotenoids (Provitamin A)
▫ Found in plants (yellow-orange pigmented materials)
▫ Beta-carotene, alpha-carotene, lutein, lycopene, zeaxanthin
▫ Must be converted to retinoid form; intestinal cells can
convert carotenoids to retinoids
Absorption of Vitamin A
• Requires bile, digestive enzymes, integration
into micelles
• Dependent on the fat in the diet
• 90% of retinoids can be absorbed
• Only ~3% of carotenoids are absorbed
• Intestinal cells can convert carotenoids to
retinoids
Transport and Storage of Vitamin A
• Transported via chylomicrons to the liver
• Transported from the liver as retinol via retinol-
binding protein to target tissue
• Carotenoids can be transported via VLDL
• Liver stores 90% of vitamin A in the body
• Reserve is adequate for several months
Functions of Vitamin A

• Retinol
▫ needed for reproduction
• Retinoic acid
▫ supports growth & cell maturation
• Retinal
▫ needed for night & colour vision
Functions of Vitamin A: Vision
• Cones in the retina
▫ Responsible for vision under bright lights
▫ Translate objects to colour vision
• Rods in the retina
▫ Responsible for vision in dim lights
▫ Translate objects to black & white vision
▫ Have a pigment – rhodopsin (protein opsin bound
to retinal)
▫ Light changes cis-retinal to trans-retinal changing
shape of opsin  nerve impulse
▫ Fresh cis-retinal required
Functions of Vitamin A:
Growth & Development

• Retinoic acid is necessary for cellular


differentiation
• Retinoic acid triggers specific receptors on DNA
for differentiation
• Important for embryo development, gene
expression
Function of Vitamin A:
Cell Health & Maintenance

• Epithelial cells line the outside (skin) &


external passages (mucus forming cells) within
the body
• Retinoic acid influences how epithelial cells
differentiate & mature
• Without vitamin A, cells will deteriorate
▫ Leads to xerophthalmia (major cause of blindness)
▫ Leads to follicular hyperkeratosis (skin disorder)
Carotenoids & Cancer
• Role in cell development, immune-system & as
an antioxidant
• Megadoses are not advisable (toxicity effects)
• Mixed results in cancer/vitamin A studies
• Foods rich in vitamin A & other phytochemicals
are advised
• Carotenoid lycopene may protect against
prostate cancer
Sources of Vitamin A
• Retinoids (Preformed A)
▫ Liver, fish oils, fortified milk, eggs

• Carotenoids (Proformed A)
▫ Dark-green leafy vegetables , yellow-orange
vegetables/fruits

RDI ~ 750 µg/day


Vitamin D (Calcitriol)
• Required for healthy bones, muscle & overall health

Dietary sources
• Vitamin D2 from plants (ergocalciferol)
• Vitamin D3 from animals (cholecalciferol)

Endogenous
• Synthesis of Vitamin D3 from a cholesterol
derivative (7-dehydrocholesterol)
• Sunlight required for activation
• Liver and kidney involved in conversion to calcitriol
(active form)
Vitamin D Synthesis
Absorption, Metabolism & Storage
• ~80% of vitamin D consumed is incorporated
into micelles
• Absorbed in the small intestine & transported
via chylomicrons
• Transported through the lymphatic system
• Stored in fat tissue
• Activated when calcium is inadequate
• Excretion of vitamin D mainly via bile
Functions of Vitamin D
• Hormone like functions
▫ Helps to regulate blood calcium level for optimum
neuromuscular function

• Increase calcium absorption


▫ Activates synthesis of calbindin (calcium-binding protein in
small intestine)

• Mobilisation of calcium from bones & reduces


calcium excretion (calcium reabsorption in the
kidneys)
• Parathyroid hormone (PTH) increases synthesis of
vitamin D (calcitriol) when blood calcium levels low
Role in Bone Formation
• Calcitriol creates a supersaturated calcium &
phosphorus solution which allows bone
mineralisation; strengthening bones

Results of low vitamin D:


• Rickets (in children)
▫ Reduced calcification of growing ends of bones
(epiphyses)
▫ Bones bow under pressure

• Osteomalacia (soft bone) is rickets in the adult


Rickets
• Enlarged head,
joint & rib cage

• Deformed pelvis

• Bowed legs
Food Sources of Vitamin D
• Fatty fish (salmon, herring)
• Egg yolks
• Liver
• Fortified products:
▫ Eg. Margarine, milk, cereals
Vitamin E
• Important part in the body’s antioxidant
network

• 8 naturally occuring forms


▫ Includes tocopherols (x4) & tocotrienols (x4)
▫ α, β , γ , δ variants

• Most active form is -tocopherol


Absorption, Metabolism & Storage
• Amount absorbed is dependent on fat intake
• Transported via chylomicrons to the liver
• Transported via VLDL, LDL, HDL from the liver
• Found concentrated in areas where fat is found
▫ Eg. liver, brain, adipose tissue
• Excreted via bile and urine (much in faeces due
to limited absorption)
Function of Vitamin E
• Redox Agent
▫ Undergoes oxidation & reduction
• Able to donate an electron to oxidising agents (free
radicals)
• Acts primarily in lipid-rich areas
▫ Protects PUFAs within the cell membrane &
plasma lipoproteins
• Prevents the alteration of cell’s DNA & risk for
cancer development
Free Radicals
• Unstable compounds with unpaired electrons
• Form & accumulate in our bodies as a result of:
▫ Cigarette smoke
▫ Air pollutants, such as ozone, nitrogen dioxide
▫ Some food preservatives, including nitrites
▫ Aerobic activity
▫ Metabolism of fats
• Production is a normal result of cell metabolism &
immune function
• Destructive to cells; set off a chain reaction
• Results in lipid peroxidation
Vitamin E Deficiency
• Deficiency is rare – most commonly seen in
premature & low-birth weight infants,
conditions with fat malabsorption (eg. cystic
fibrosis, coeliac disease)

• Characterised by:
▫ Premature breakdown of RBCs & haemolytic
anaemia
• Lead to:
▫ Peripheral neuropathy
Food Sources of Vitamin E
• Plant oils
• Wheat germ
• Sweet potato
• Peanuts
• Margarine
• Nuts and seeds
• Actual amount is dependent on harvesting,
processing, storage and cooking
Vitamin K (“Koagulation”)
• Phylloquinone (K1 from plants) & menaquinone
(K2; synthesised by bacteria)
• 40%-80% of dietary vitamin K is absorbed
• Stored in liver as menaquinone & in the plasma
as phylloquinone
• Role in the coagulation process (blood clotting)
• Calcium-binding potential
▫ Formation of osteocalcin (binds calcium;
involved in bone formation)
Blood Clotting
• Vitamin K essential for formation of
prothrombin & at least 5 other clotting factors
(factors VII, IX, X, and proteins C and S)

• Acts as a cofactor in -carboxyglutamate (Gla)


synthesis
▫ CO2 added to glutamate residues to form Gla
▫ Gla residues strongly bind to calcium – essential for
clotting process

• Osteocalcin also has Gla residues


Blood Clotting Process
Vitamin K Deficiency
• Characterised by bleeding disorders
▫ Low prothrombin activity
• Results from:
▫ Malabsorption syndromes & obstructive jaundice
(limited bile secretion)
▫ Long-term antibiotic use
• Newborns at risk of haemorrhagic disease due to
low Vitamin K levels (poorly transported across
placenta) & sterile gut (no bacteria to produce
Vitamin K)
Food Sources of Vitamin K
• Liver
• Green leafy vegetables
• Broccoli
• Peas
• Green beans
• Resistant to cooking losses
• Limited vitamin K stored in the body

• Toxicity unlikely; readily excreted


Water-Soluble Vitamins
• B-group vitamins (n=8) & vitamin C
• Dissolve in water
• 50-90% of B vitamins absorbed
• Transported throughout the water medium of
the body
• Easily excreted; not stored in the body
• Subject to cooking losses
B-Group Vitamins
The B group vitamins involved in Energy
metabolism

• Thiamin (B1)
• Riboflavin (B2)
• Niacin (B3)
• Pantothenic Acid (B5)
• Biotin (B7)
Thiamin (Vitamin B1)
• Central role in the generation of energy from
Carbohydrates (CHOs)
• Also involved in DNA & RNA production & nerve
function
• 80% in the body is in its active form:
Thiamin Pyrophosphate (TPP)

• Found in a large number of tissues


• Transported by RBCs; excess readily excreted in the
urine
Biological Roles of Thiamin
Decarboxylation:
▫ Removes CO2 from CHOs & some amino acids
▫ Essential co-enzyme for the conversion of:
CoA CO2
Pyruvate >>>>>>>>>> acetylCoA
(TPP)

Also involved in the synthesis of DNA & RNA:


▫ Aids conversion of 6-carbon glucose into 5-carbon
sugars used to form DNA & RNA
 ribose and deoxyribose
 ribo-nucleotides (DNA & RNA)
Thiamin Deficiency
Beri-beri:
• Impairs the nervous, muscle, GI, cardiovascular
systems
• Nervous system especially affected
• Glucose metabolism is severely disrupted
▫ Pyruvate cannot be converted to acetyl-CoA
• Described as either wet or dry beri-beri
Thiamin Deficiency

Wet beri-beri

• Cardiovascular system is affected

• Oedema, enlarged heart, heart failure

• Results from the accumulation of pyruvate & lactate


(cannot be metabolised)
▫ Leads to vasodilation & fatigue
Thiamin Deficiency

Dry Beri-Beri

• Affects nervous & muscular system

• Muscle weakness & wasting, poor coordination, loss


of nerve transmission

• Wernicke-Korsakoff syndrome
Wernicke-Korsakoff Syndrome
• Predominantly seen amongst alcoholics
▫ Alcohol diminishes thiamin absorption, increases
thiamin excretion & alcoholics may consume poor
quality diet

1. Wernickes Encephalopathy
▫ Ophthalmoplegia (paralysis of the eye muscle)
▫ Nystagmus (constant, involuntary eye movement)
▫ Ataxia (impaired muscle coordination)

2. Korsakoff Psychosis
▫ Confused, loss of recent memory
Food Sources of Thiamin
Found in a wide variety of foods
• Whole grains and cereals
• Legumes
• Pork
• Wheat germ
• Yeast
• Fortified flour
Riboflavin (Vitamin B2)
• Involved in energy production
• Component of 2 coenzymes
▫ FAD - flavin adenine dinucleotide
▫ FMN - flavin mononucleotide

• Oxidation-reduction reactions
▫ Act as oxidising agents

• Additional roles;
▫ Synthesis of Glutathione peroxidase (antioxidant)
▫ Utilisation of vitamin B6
▫ Conversion of tryptophan to niacin
Riboflavin Deficiency
• AKA Ariboflavinosis
▫ Usually occur in combination with other deficiencies

• Symptoms:
▫ Inflammation of throat, mouth (stomatitis)
▫ Inflammation of tongue (glossitis)
▫ Cracked lips (cheilosis)
▫ Moist, red, scaly skin (seborrheic dermatitis)

• Occurs within 2 months


Food Sources of Riboflavin
• Milk and Dairy products
• Wholegrains
• Liver
• Mushrooms
• Oysters
• Brewer’s yeast
Niacin
Nicotinic Acid & Nicotinamide
• Central role as a component of electron
transportation in energy yielding reactions

Co-enzyme forms are:


• NAD - nicotinamide adenine dinucleotide
• NADP - nicotinamide adenine dinucleotide
phosphate

• Oxidation-reduction reactions to produce energy


Niacin Deficiency
• Lack of niacin results in major damage to
cellular respiration & energy metabolism

Pellagra
• Dermatitis (on parts of the skin exposed to the
sun)
• Diarrhoea (inflammation of the entire GI tract)
• Dementia (depressive psychosis, tremors,
delirium )
• Death
Endogenous Synthesis of Niacin
• Made from Tryptophan, essential amino acid (AA)
▫ 60mg of tryptophan leads to 1mg Niacin
• So when calculating the adequacy of niacin in food,
account for the amount of tryptophan

• Niacin Equivalent (NE) =


dietary niacin (mg) + dietary tryptophan(mg)
60
Food Sources of Niacin
• Mushrooms
• Meat and Fish
• Yeast extracts
• Coffee beans
Pantothenic Acid B5
• Central role in energy metabolism as a component
of Coenzyme A
• Essential for the formation of acetyl CoA from
breakdown of CHOs, protein, ETOH & fats
• Also important in the synthesis of fatty acids, several
amino acids, cholesterol & steroid hormones
• Deficiency is extremely rare
▫ Pantothenic acid is widely distributed in foods
• Can also be produced by microorganisms in the
large intestine
Biotin B7
• Important in energy metabolism as a coenzyme that
carries carbon dioxide

Co-enzyme for:
• Carboxylation
▫ (carbon dioxide fixation)
• Decarboxylation
▫ (removal of carbon dioxide)
• Deamination
▫ (removal of a NH2 group)
Biotin Deficiency
• Symptoms rarely seen in humans
• Can be produced in humans by feeding large
amounts of raw egg
• An egg protein (avidin) strongly binds biotin,
destroyed by cooking
• Rare congenital deficiencies in children - nervous
system dysfunction, alopecia & immune system
dysfunction

• Symptoms are neurological


▫ Fatigue, depression, nausea
Water-Soluble Vitamins cont..

• B-Group Vitamins involved in Haematopoiesis


▫ Pyridoxine (Vitamin B6)
▫ Folate (Folic acid, B9)
▫ Vitamin B12

• Vitamin C
Vitamin B6
• Coenzyme role central to amino acid metabolism

• 3 Forms: Pyridoxine, pyridoxal and pyridoxamine


▫ Interconvertible
• Active coenzyme form is pyridoxal phosphate (PLP)
• Absorbed passively; binds to Albumin for transport in
the blood
• Unlike other B group vitamins, B6 is stored in muscle
bound to glycogen phosphorylase
Biological Roles of Vitamin B6
Co-enzyme for:
• Transaminases (for amino acid synthesis)
▫ Amino group (NH2) is passed from one amino acid to
another

• Deaminases
▫ Removal of NH2 producing ammonia
▫ Important for
 non-essential AA metabolism
 providing carbon skeletons for gluconeogenesis
Biological Roles of Vitamin B6
• Synthesis of haemoglobin
▫ Co-enzyme in early protein step

• Niacin Synthesis
▫ Tryptophan to niacin pathway

• Steroid hormone receptor binding


Vitamin B6 Deficiency
• Anaemia
• Dermatitis
• Convulsions
• Depression
• Confusion
• Weakened immune function
Food Sources of Vitamin B6
• Meat, fish, poultry
• Wholegrains
• Banana
• Spinach
• Avocado
• Nuts
Folate
• Required for synthesis & maintenance of new cells
• Essential for single carbon group transfer
▫ methyl groups - CH3
• Folate coenzyme form:
▫ 5-methyl tetrahydrofolate (THF)
• Closely linked to Vitamin B12
▫ B12 is required to activate folate and vice versa
▫ Needed for DNA synthesis
• Involved in the synthesis of 2 purines in DNA
▫ Deoxyuridylate (U) & Thymidylate (T)
Folate Deficiency
• Deficiency common
• Important for actively dividing cells
▫ Red blood cells
▫ Epithelial cells of the intestinal tract

• Signs of Deficiency of Folate


▫ Anaemia:
 Immature RBC (megaloblasts or macrocytes)
▫ Changes in cells of the gastrointestinal tract

• Strong link with folate in pregnancy & the


occurrence of neural tube defects (NTDs)
▫ E.g. Spina bifida
Food Sources of Folate
• Largest amounts in
▫ Yeast
▫ Liver
▫ Meats
▫ Leafy green vegetables

• Highly susceptible to cooking & oxidation

• Active absorption but bioavailability poor -


approximately half not absorbed →
supplementation required
Vitamin B12
• Required for RBC formation, neurological function
& DNA synthesis

• Active form is cyanocobalamin


▫ Cobalt containing organic molecule

• Coenzyme role
▫ Removal of methyl groups from THF (folate metabolism)

• If vitamin B12 is deficient then folate accumulates as


the MTHF form
▫ Producing an effective deficiency in folate
Absorption of Vitamin B12
• HCl & pepsin in stomach releases B12 from foods
then binds to ‘R protein’

• Requires ‘intrinsic factor’ (glycoprotein carrier)


for intestinal absorption
▫ Secreted from the stomach
▫ In old age, gastritis is common
Vitamin B12 Deficiency
• Impairment of DNA formation
▫ Megaloblastic anaemia, changes in WBC, platelets and
epithelial cells.
• Important in the development & maintenance of
nerves
▫ Loss of nervous function (neuropathy)
• Additional Symptoms
▫ Neurological disorders
▫ Loss of memory & mental slowness
Food Sources of Vitamin B12
• Animal products
• Organ meats
• Seafood
• Eggs
• Milk

• Miso (soybean paste), spirulina (sea algae) and


yeasts have no biologically active vitamin B12
Vitamin C
• Electron donor in many process
▫ Including synthesis of collagen

• Ascorbic Acid & Dehydroascorbic Acid

• Structure closely related to glucose

• Only required by a limited number of animals:


primates (including humans), guinea pigs, some
birds, bats, fish & insects
Roles of Vitamin C
Antioxidant Roles
• Has two hydrogens which can be donated to bind to oxygen
radicals
▫ Becomes dehydro form
• Increases iron absorption by converting Fe3+ to Fe2+
Role in Collagen Formation
• In synthesis of collagen
• Helps to convert 2 AA:
▫ Proline to Hydroxyproline
▫ Lysine to Hydroxylysine
• Necessary for the structural strength
Role of Vitamin C
Role in Stress
• Vit C plays a role in the synthesis of norepinephrine
& epinephrine
• During both physical, emotional & infection there is
increased production of oxygen radicals

Role in the Common Cold


• Very little evidence
• Vitamin C may reduce histamine production
• Vitamin C may protect against upper respiratory
tract infections
Vitamin C Deficiency
• Scurvy
▫ Deficiency after 20-40 days
▫ Repair & growth of connective tissues are
impaired
▫ Walls of blood vessels burst easily
 Small patches of subcutaneous bleeding
 Deep bruising
 Wounds fail to heal & old scars open
Food Sources of Vitamin C
• Citrus fruits
• Potatoes
• Cauliflower
• Broccoli
• Green peppers
• Strawberries
• Spinach

• Easily lost through cooking, sensitive to heat,


iron, copper & oxygen
Water Soluble Vitamins Fat Soluble Vitamins

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