Food

Chemistry
0711-2101
DEPARTMENT OF NUTRITION & FOOD ENGINEERING
DAFFODIL INTERNATIONAL UNIVERSITY
Today’s topic

Chemistry of Vitamins & Minerals

Lecture objectives
To learn about:

Chemical Stability &

Structure
Composition Degradation

of Vitamins
& Minerals
 Vitamins
Vitamins are minor but essential constituents of food. They are required for the normal growth, maintenance
and functioning of the human body. Preservation during storage and processing of food is important. Vitamin
losses can occur through chemical reactions which lead to inactive products. It can also occur during extraction
or leaching in the case of water-soluble vitamins during blanching and cooking.

The vitamin requirement of the body is usually adequately supplied by a balanced diet. A deficiency can result in
hypovitaminosis and, if more severe, in avitaminosis. Both can occur not only as a consequence of insufficient
supply of vitamins by food intake, but can be caused by disturbances in resorption, by stress and by disease.

An assessment of the extent of vitamin supply can be made by determining the vitamin content in blood plasma,
or by measuring a biological activity which is dependent on the presence of a vitamin, as are many enzyme
activities.
 Vitamins
Vitamins are usually divided into two general classes:
1. Fat-soluble vitamins: 2. Water-soluble vitamins,
➢Thiamin (B1)
➢Vitamin A (Renitol)
➢Riboflavin (B2),
➢Vitamin D (Calciferol) ➢Nicotinamide (niacin or B3)
➢Vitamin E (α-Tocopherol) and ➢Pantothenic acid (B5)
➢Pyridoxine (B6)
➢Vitamin K1 (Phylloquinone)
➢Biotin (B7)
➢Folic acid (B9)
➢Cyanocobalamin (cobalamin or B12)
➢Ascorbic acid (C)
 Retinol (Vitamin A)
Retinol (I) is of importance in protein metabolism of cells which
develop from the ectoderm (such as skin or mucouscoated linings
of the respiratory or digestive systems). Lack of retinol in some way
negatively affects epithelial tissue (thickening of skin,
hyperkeratosis) and also causes night blindness.

Furthermore, retinol, in the form of 11-cis-retinal (II), is the

chromophore component of the visual cycle chromoproteins in
three types of cone cells, blue, green and red (λmax 435, 540 and
565 nm, respectively) and of rods of the retina.
 Retinol (Vitamin A)
Vitamin A occurs only in animal tissue; above all in fish liver oil, in livers of mammals, in milk fat and in egg yolk. Plants are
devoid of vitamin A but do contain carotenoids which yield vitamin A by cleavage of the centrally located double bond
(provitamins A). Carotenoids are present in almost all vegetables but primarily in green, yellow and leafy vegetables and in
fruit which is often used for yellow coloring. Animal carotenoids are always of plant origin, derived from feed.

Stability & Degradation

Food processing and storage can lead to 5–40% destruction of vitamin A and carotenoids. In the absence of oxygen and at
higher temperatures, as experienced in cooking or food sterilization, the main reactions are isomerization and
fragmentation. In the presence of oxygen, oxidative degradation leads to a series of products, some of which are volatile.
This oxidation often parallels lipid oxidation (cooxidation process). The rate of oxidation is influenced by oxygen partial
pressure, water activity, temperature, etc. Dehydrated foods are particularly sensitive to oxidative degradation.
 Calciferol (Vitamin D)
Cholecalciferol (vitamin D3, I) is formed from cholesterol in the skin through photolysis of
7-dehydrocholesterol (provitamin D3) by ultraviolet light (“sunshine vitamin). Similarly,
vitamin D2 (ergocalciferol, II) is formed from ergosterol. Most natural foods have a low
content of vitamin D3. Fish liver oil is an exceptional source of vitamin D2. The D-
provitamins, ergosterol and 7-dehydrocholesterol, are widely distributed in the animal
and plant kingdoms. However, the most important vitamin D source is fish oil, primarily
liver oil. The vitamin D requirement of humans is best supplied by 7-dehydrocholesterol.

Stability & Degradation

Vitamin D is sensitive to oxygen and light. Its stability in food is not a problem, because
adults usually obtain a sufficient supply of this vitamin.
 α-Tocopherol (Vitamin E)
The various tocopherols differ in the number and position of the methyl groups on the ring. α-Tocopherol has the highest
biological activity). Its activity is based mainly on its antioxidative properties, which retard or prevent lipid oxidation.
Thus, it not only contributes to the stabilization of membrane structures, but also stabilizes other active agents (e. g.,
vitamin A, ubiquinone, hormones, and enzymes) against oxidation. Vitamin E deficiency is associated with chronic
disordes (sterility in domestic and experimental animals). Its mechanism of actionis not fully elucidated. The main
sources are vegetable oils, particularly germ oils of cereals.

Stability & Degradation

Losses occur in vegetable oil processing into margarine and shortening. Losses are also encountered in intensive lipid
autoxidation, particularly in dehydrated or deep fried foods
 Phytomenadione (Vitamin K1, Phylloquinone)
The K-group vitamins are naphthoquinone derivatives which differ in their side
chains. Blood clotting factors (prothrombin, proconvertin, Christmas and Stuart
factor) as well as proteins which perform other functions belong to the group of
vitamin K-dependent proteins which bind Ca2+ ions at Gla. Deficiency of this
vitamin causes reduce prothrombin activity, hypothrombinemia and hemorrhage.
Vitamin K1 occurs primarily in green leafy vegetables (spinach, cabbage,
cauliflower), but liver (veal or pork) is also an excellent source

Stability & Degradation

Little is known about the reactions of vitamin K1 in foods. The vitamin K compounds are destroyed by light and alkali. They
are relatively stable to atmospheric oxygen and exposure to heat.
 Thiamine (Vitamin B1)
Thiamine, in the form of its pyrophosphate, such as pyruvate dehydrogenase, transketolase, phosphoketolase and α-
ketoglutarate dehydrogenase, in reactions involving the transfer of an activated aldehyde unit. Vitamin B1 deficiency is
shown by a decrease in activity of the enzymes mentioned above. The disease known as beri-beri, which has neurological
and cardiac symptoms, results from a severe dietary deficiency of thiamine. Vitamin B1 is abundant in cereals, yeast,
vegetables (such as potatoes), meat (pork, beef, fish), eggs, and animal organs (liver, kidney, brain, heart), as well as in
human and cow's milk. However, refining processes like flour milling and rice polishing remove much of the vitamin found
in the bran.

Stability & Degradation

Thiamine stability in aqueous solution is relatively low. Thermal degradation of thiamine, which also initially yields the
thiazole and pyrimidine derivatives, is involved in the formation of meat-like aroma in cooked food Thiamine is inactivated
by nitrites, probably through reaction with the amino group attached to the pyrimidine ring.
 Riboflavin (Vitamin B2)
Riboflavin is the prosthetic group of flavine enzymes, which are of
great importance in general metabolism and particularly in
metabolism of protein. Riboflavin deficiency will lead to accumulation
of amino acids. A specific deficiency symptom is the decrease of
glutathione reductase activity in red blood cells. The most important
sources of riboflavin are milk and milk products, eggs, various
vegetables, yeast, meat products, particularly variety meats such as
heart, liver and kidney, and fish liver and roe.
Stability & Degradation
Riboflavin is relatively stable in normal food handling processes. Losses range from
10–15%. Exposure to light, especially in the visible spectrum from 420–560 nm,
photolytically cleaves ribitol from the vitamin, converting it to lumiflavin: Lumiflavin
 Nicotinamide (Niacin, Vitamin B3)
Nicotinic acid amide (I), in the form of nicotinamide adenine dinucleotide (NAD+) or its
phosphorylated form (NADP+), is a coenzyme of dehydrogenases. Its excretion in urine
is essentially in the form of N1-methylnicotinamide (trigonelline amide, II), N1-methyl-
6-pyridone-3-carboxamide (III) and N1-methyl-4-pyridone-3-carboxamide (IV).

Initial vitamin deficiency reduces NAD+ and NADP+ in liver and muscles, while levels
remain normal elsewhere. Pellagra, a classic deficiency disease, causes skin, digestion,
and nervous system issues. Initial symptoms are nonspecific. The vitamin occurs in
food as nicotinic acid, either as its amide or as a coenzyme. Animal organs, such as
liver, and lean meat, cereals, yeast and mushrooms are abundant sources of niacin

Stability & Degradation

Nicotinic acid is quite stable. Moderate losses of up to 15% are observed in blanching of vegetables. The loss is 25–30% in
the first days of ripening of meat.
 Pantothenic Acid (Vitamin B5)
Pantothenic acid is the building unit of coenzyme A (CoA), the main carrier of acetyl and other acyl groups in cell
metabolism. Pantothenic acid occurs in free form in blood plasma, while in organs it is present as CoA. The highest
concentrations are in liver, adrenal glands, heart and kidney. Animal proteins, avocado, broccoli &cabbage family, eggs,
legumes and lentils, milk, mushrooms etc. contain vit. B5

Stability & Degradation

Pantothenic acid is quite stable. Losses of 10% are experienced in processing of milk. Losses of 10–30%, mostly due to
leaching, occur during cooking of vegetables.
 Pyridoxine (Pyridoxal, Vitamin B6)
Vitamin B6 activity is exhibited by pyridoxine or pyridoxol (R = CH2OH), pyridoxal (R =
CHO) and pyridoxamine (R = CH2NH2). The intake of the vitamin occurs usually in the
forms of pyridoxal or pyridoxamine. Pyridoxine deficiency in the diet causes disorders
in protein metabolism, e. g., in hemoglobin synthesis. An indicator of sufficient
supply is the activity of glutamate oxalacetate transaminase, an enzyme present in
red blood cells. This activity is decreased in vitamin deficiency.

Stability & Degradation

The most stable form of the vitamin is pyridoxal, and this form is used for vitamin fortification of food. Vitamin B6 loss is
45% in cooking of meat and 20–30% in cooking of vegetables. During milk sterilization, a reaction with cysteine transforms
the vitamin into an inactive thiazolidine derivative.
 Biotin (Vitamin B7)
Biotin is the prosthetic group of carboxylating enzymes and therefore plays an
important role in fatty acid biosynthesis and in gluconeogenesis. Biotin deficiency
rarely occurs. Consumption of large amounts of raw egg white might inactivate biotin
by its specific binding to avidin. Biotin is not free in food, but is bound to proteins.

Stability & Degradation

Biotin is quite stable. Losses during processing and storage of food are 10–15%.
 Folic Acid (Vitamin B9)
The tetrahydrofolate derivative (II) of folic acid (I, pteroylmonoglutamic acid, PGA) is the cofactor of enzymes which transfer single
carbon units in various oxidative states, e. g., formyl or hydroxymethyl residues. Folic acid deficiency, from diet insufficiency or
absorption issues, is detected by decreased levels in red blood cells and plasma, correlating with altered blood cell patterns,
impacting neural tube development and causing various diseases. Folate is naturally present in a wide variety of foods, including
vegetables (especially dark green leafy vegetables), fruits and fruit juices, nuts, beans, peas, seafood, eggs, dairy products, meat,
poultry, and grains

Stability & Degradation

Folic acid is quite stable. There is no destruction during blanching of vegetables, while cooking of meat gives only small losses. Losses in
milk are apparently due to an oxidative process and parallel those of ascorbic acid. Ascorbate added to food preserves folic acid.
 Cyanocobalamin (Vitamin B12)
Cyanocobalamin was isolated in 1948 from Lactobacillus lactis. Due to its stability and availability, it is
the form in which the vitamin is used most often. In fact, cyanocobalamin is formed as an artifact in
the processing of biological materials. Cobalamins occur naturally as adenosylcobalamin and
methylcobalamin. Deficiency of vitamin B12 is usually caused by impaired absorption due to
inadequate formation of “intrinsic factor” and results in pernicious anemia. Vitamin B12 is present in
foods of animal origin, including fish, meat, poultry, eggs, and dairy products

Stability & Degradation

The stability of vitamin B12 is very dependent on a number of conditions. It is fairly stable at pH 4–6, even at high temperatures. In
alkaline media or in the presence of reducing agents, such as ascorbic acid or SO2, the vitamin is destroyed to a greater extent.
 L-Ascorbic Acid (Vitamin C)
Vitamin C is fully absorbed and distributed throughout the body, with the highest concentration in
adrenal and pituitary glands. Scurvy results from a dietary deficiency of ascorbic acid, with a small
portion of vitamin C pool excreted in urine, primarily as oxalic acid only at very high intakes.
Insufficient vitamin supply is indicated by low plasma levels (0.65 mg/100ml); vitamin C is abundant
in various plant sources but can be lost during storage, and most commercially available ascorbic acid
is synthesized, with genetically modified microorganisms being cost-effective.

Stability & Degradation

Ascorbic acid is readily oxidized to dehydroascorbic acid, which exhibits weaker biological activity,
with complete loss of activity when converted to 2,3-diketogulonic acid.
 Minerals
Minerals are the constituents which remain as ash after the combustion of plant
and animal tissues. Minerals are divided into:
Main elements in the human body
• The main elements (Na, K, Ca, Mg, Cl, P) are essential for human beings in
amounts >50 mg/day. Sulfur also belongs to this group.
• Trace elements (Fe, I, F, Zn, Se, Cu, Mn, Cr, Mo, Co, Ni) are essential in
concentrations of <50 mg/day; their biochemical actions have been elucidated.
• Ultra-trace elements (Al, As, Ba, Bi, B, Br, Cd, Cs, Ge, Hg, Li, Pb, Rb, Sb, Si, Sm,
Sn, Sr, Tl, Ti, W) are elements whose essentiality has been tested in animal
experiments over several generations and deficiency symptoms have been found
under these extreme conditions.
 Nutritional and Toxicological Aspects of Minerals
Mineral Function Deficiency Effects Adverse Effects from Food Sources
Excessive Intake
Calcium Bone and tooth mineralization, blood Increased risk for osteoporosis, Excessive intakes rare; may cause kidney Milk, yogurt, cheese,
clotting, hormone secretion, nerve hypertension, and some cancers. stones and milk alkali syndrome. fortified juices, tofu,
transmission kale, broccoli, fish
bones.

Phosphorus Bone mineralization; DNA and RNA Deficiency rare due to ubiquitous Impaired bone formation, kidney stones, Present in virtually all
synthesis; phospholipid synthesis, distribution in foods; low intakes may decreased Ca and Fe absorption, iron and foods. High-protein
energy metabolism, cell signaling impair bone mineralization. zinc deficiency due to high phytate foods (meats, dairy,
intakes. etc.), cereal products,
and cola beverages (as
H3PO4) are especially
rich sources
Magnesium Cofactor for numerous enzymes Deficiency is rare except Rarely occurs except Green leafy vegetables,
in certain clinical from overconsumption milk, whole grains
situations; patients of Mg supplements;
recovering from cardiac causes intestinal
surgery are often distress, diarrhea,
hypomagnesemic cramping, and nausea
Sodium Predominant cation in extracellular Deficiency is rare except in endurance Chronically high intakes may lead to Most foods are naturally
fluid; controls extracellular fluid sports. Deficiency may cause muscle hypertension in salt-sensitive persons low in Na. Processed and
volume and blood pressure; required cramping. prepared foods contain
for transport of many nutrients into varying levels of added
and out of cells Na
 Nutritional and Toxicological Aspects of Minerals
Mineral Function Deficiency Effects Adverse Effects from Food Sources
Excessive Intake
Iron Oxygen transport (hemoglobin and Deficiency is widespread. Effects Iron overload leading to increased risk Red meat, cereal
myoglobin), respiration and energy include fatigue, anemia, impaired for some cancers and heart disease. products, beans,
metabolism (cytochromes and iron– work capacity, impaired cognitive fortified foods, green
sulfur proteins), destruction of function, impaired immune response, leafy vegetables.
hydrogen peroxide (hydrogen and poor pregnancy outcomes.
peroxidase and catalase), and DNA
synthesis (ribonucleotide reductase)
Zinc Cofactor in Growth retardation, Inhibition of Cu and Fe Red meat, shellfish,
metalloenzymes, impaired wound absorption, impaired wheat germ, fortified
regulation of gene healing, delayed immune response foods.
expression sexual maturation,
impaired immune
response, and diarrhea
Iodine Required for synthesis of thyroid Goiter, mental retardation, decreased Rare in iodine replete persons, Iodized salt, seaweed,
hormones fertility, miscarriage, cretinism, and hyperthyroidism in iodine deficient seafood, dairy products
hypothyroidism. persons. (if I is added to feed or
iodine containing
sanitizers are used).
Selenium Antioxidant (as component in Myocarditis, osteoarthritis, and Hair and nail loss, skin lesions, nausea, Cereals grown on high-
peroxidases) increased risk for some cancers. increased risk for some cancers. Se soils, meat from
animals supplemented
with Se
 Nutritional and Toxicological Aspects of Minerals

Mineral Function Deficiency Effects Adverse Effects from Food Sources

Excessive Intake
Lead None, not an essential None Learning and behavioral problems in Contamination of foods
nutrient children, anemia, kidney damage. from Pb-soldered cans,
exhaust from cars
burning leaded gasoline,
some ceramic glazes

Mercury None, not an essential None Numbness, vision and hearing loss, Fish (especially long-
nutrient
kidney damage. lived carnivorous fish).

Cadmium Unknown Depressed growth in rats Kidney damage, bone disease, cancer. Grains and vegetables
grown on Cd-
contaminated soils.
Minerals in Food Processing
there are metal ions, derived from food itself or acquired during food processing and storage, which interfere with the quality and visual
appearance of food. They can cause discoloration of fruit and vegetable products and many metal-catalyzed reactions are responsible
for losses of some essential nutrients, for example, ascorbic acid oxidation. Also, they are responsible for taste defects or off-flavors, for
example, as a consequence of fat oxidation. Therefore, the removal of many interfering metal ions by chelating agents) or by other
means is of importance in food processing.
Mineral losses in food processing