Part II Biochemistry IUG, Fall 2013 Dr. Tarek Zaida 1 The branch of chemistry that deals with the different molecules, their structure, composition, and chemical processes in the living cell

Carbohydrates  Carbohydrates occur in all plants and animals and are essential to life.  Through photosynthesis, plants convert atmospheric carbon dioxide to carbohydrates, mainly cellulose, starch, and sugars.  Cellulose is the building block of rigid cell walls and woody tissues in plants, whereas starch is the chief storage form of carbohydrates for later use as a food or energy source.  Some plants (cane and sugar beets) produce sucrose, ordinary table sugar.  Another sugar, glucose, is an essential component of blood.  Two other sugars, ribose and 2-deoxyribose, are components of the genetic materials RNA and DNA. 2

The word carbohydrate arose because molecular formulas of these compounds can be expressed as hydrates of carbon. Glucose, for example, has the molecular formula C 6 H 12 O 6, which might be written as C 6 (H 2 O) 6. Carbohydrates are now defined as: 1. polyhydroxyaldehydes, 2. polyhydroxyketones, or 3. substances that give such compounds on hydrolysis. 3

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For example, hydrolysis of starch, a polysaccharide, gives first maltose and then glucose. 5

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Glyceraldehyde is the simplest aldose Dihydroxyacetone is the simplest ketose. Each is related to glycerol in that each has a carbonyl group in place of one of the hydroxyl groups. Other aldoses or ketoses can be derived from glyceraldehyde or dihydroxyacetone by adding carbon atoms, each with a hydroxyl group. In aldoses, the chain is numbered from the aldehyde carbon. In most ketoses, the carbonyl group is located at C-2. 10

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Naming Monosaccharides Carbohydrate nomenclature is unique we do not name monosaccharides using the IUPAC rules. Monosaccharide names end in ―ose 12

Naming Monosaccharides 13

Naming Monosaccharides 14 Examples:

Name each of the following monosaccharides as an aldose or ketose & according to its number of C atoms. 15

1. Plants catch up CO 2 from air & H 2 O from soil 6CO 2 + 6H 2 O sun light C 6 H 12 O 6 + 6O 2 The above reaction is called photosynthesis (formation of carbohydrates from CO 2, H 2 O and sun light) 16 enzymes, chlorophyll glucose

2. The carbohydrates produced during photosynthesis are monosaccharides. Plants build disaccharides from monosaccharides: C 6 H 12 O 6 + C 6 H 12 O 6 C 12 H 22 O 11 + H 2 O 17 Disaccharideglucose

3. Plants as well as animals can combine many molecules of monosaccharides into large polysaccharide molecules: nC 6 H 12 O 6 polymerization (C 6 H 10 O 5 ) n + nH 2 O Polysaccharides in plants are: - Cellulose in stalk and stem - Starch in roots and seeds - Mono & disaccharides are found in fruits 18

Oxygen – Carbon dioxide cycle 1. Plants pick up CO 2 from air, water from soil to build carbohydrates (monosaccharides). 2. Animals can not do that, so they have to rely on plants to get their carbohydrates CO 6 H 12 O 6 + 6O 2 6CO 2 + 6H 2 O + energy The above reaction is the reverse of photo- synthesis. 19 Krebs cycle

During Photosynthesis:  Energy from the sun needed for aerobic reactions.  During catabolism of carbohydrates in animals same amounts of energy is liberated from oxidation of food.  So energy from metabolism in animals comes from the sun through plants that store solar energy in carbohydrates. 20

Stereoisomerism Stereoisomers: Are compounds having the same molecular formula but a different structural formula. Stereoisomers have structures that are mirror image of one another If you put your left hand on top of your right hand, you will see that they are not superimposable 21

22 H HH H methaneMirror image

In general any object with a plane of symmetry is achiral Any object or molecule does not have a plane of symmetry it is chiral If there are 4 different atoms attached to a central carbon atom, it is said to be chiral 23

Stereoisomers in Carbohydrates Carbohydrates are chiral molecules since they have carbon atoms carrying four different groups. The simplest three carbon sugar is glyceraldehyde. This sugar exists as a pair of enantiomers. 24

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Two forms of glyceraldehyde (D and L) have the same physical properties except they behave differently in the way they rotate polarized light and the way they are affected by catalysts. 26

Remember: Compounds with n chiral carbon atoms has a maximum of 2 n possible stereoisomers and half that many pairs of enantiomers (mirror images). This aldotetrosose, has 2 chiral carbon atoms and a total of 2 2 = 4 possible stereoisomers (2 pairs of enantiomers). 27

The D and L Forms of Sugars: Drawing Sugar Molecules 28 Fischer Projections (or open chain) represent three-dimensional structures of stereoisomers on a flat page.

A chiral carbon atom is represented in the Fisher projection as the intersection of two crossed lines 29

Bonds that point above the page are shown as horizontal lines. Bonds that curve behind and below the page are shown as vertical lines. 30

Fischer Projections of Sugar Molecules 31 In a Fischer projection, the aldehyde or ketone carbonyl group of a monosaccharide is always placed toward the top of the page.

Fischer Projections of Sugar Molecules Example 32

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Fischer projection of glucose: 34

Monosaccharides are divided into two families: D form and L form sugars. D: the –OH group on the chiral C furthest from the C=O comes out of the plane of paper and points to the right. L: the –OH group on the chiral C furthest from the C=O comes out of the plane of paper and points to the left. The D and L relate directly only to the position of –OH group on the bottom carbon in a Fischer projection. 35

D: the –OH group on the chiral C furthest from the C=O comes out of the plane of paper and points to the right. L: the –OH group on the chiral C furthest from the C=O comes out of the plane of paper and points to the left. 36

Chiral Drugs Many enzymes will interact with only one particular enantiomer In human body, enzymes will react with carbohydrates of D- form, but will react with proteins of L-form. Some drugs are enantiomers: 1. Ibuprofen used in pain relief 2. Indinavir used in Aids 3. Levofloxacin used as antibiotic 37

some important pentoses and hexoses, and their derivatives 1. D-glucose, also called dextrose or blood sugar, is the most important monosaccharide in human metabolism. 38

2. D-fructose, or fruit sugar, is most common natural ketose. Honey contains about is 38% fructose 39

In deoxy sugars a hydrogen atom replaces one or more of the -OH groups in a monosaccharide. D-ribose and its derivative D-2-deoxyribose (deoxy = minus one oxygen atom) are found in various coenzymes and in DNA. 40

The Cyclic Form of Monosaccharides – A monosaccharide contains both an alcohol and an aldehyde group. – It can react with itself to form a cyclic hemiacetal. 41