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CARBOHYDRATES
Lecture Class of Dr. Carmen P. Sanchez

I. Definition Carbohydrates chemically defined as polyhydroxyaldehydes or ketones and their derivatives. There is more carbohydrate material in nature than all organic substances combined. Carbohydrates are also known as saccharides. They are made up only of 10% of the organic matter of the living cell. Carbohydrates are the most abundant constituent of many foods and are the source of a large part of the heat and mechanical energy of the body. II. Importance 1. Preferential source of energy by the body tissues 2. A form of stored chemical energy. 3. Form of structural units within the cell 4. Other diverse functions – carbohydrates in combination with other organic compounds become components of biologically important substances a. antigen-antibody interaction b. filtration barriers c. cell lubrication d. protective cell coats e. regulatory functions f. transport functions g. cell membrane components h. blood coagulation i. catalytic function 5. Source of carbon in the synthesis of other cell components III. Classification of Carbohydrates (Based on the number of saccharide units present in their molecules) A. Monosaccharides-simple sugars; consist of a single polyhydroxy aldehyde or ketone unit. Depending of the number of C. 1. Triose C3H6O3 Aldotriose – with aldehyde group Ex. Glyceraldehyde Ketotriose – with ketone group Ex. Dihydroxyacetone

2. Tetrose C4H8O4 erythrose erythrulose

3. Pentose C5H10O5 - xylose - ribose - deoxyribose - arabinose

2 rhamnose 4. Hexose C6H12O6 - glucose - galactose - mannose - fructose 5. Heptose C7H14O7 - mannoheptose - mannoheptulose The important monosaccharides are the pentoses and the hexoses. a. Pentoses Aldopentose – ribose Ketopentose – deoxyribose b. Hexoses Aldohexoses – glucose, galactose, mannose Ketohexoses – fructose B. Oligosaccharides – with chains of 2 to 6 monosaccharide units linked together by glycosidic bonds. Most important member are: 1. Disaccharides Sucrose Lactose Maltose 2. Trisaccharides Raffinose = = = glucose + fructose glucose + galactose glucose + glucose

- glucose + galactose + fructose

[Disaccharides and trisaccharides are sweet; starches and cellulose are tasteless] C. Polysaccharides They consist of long chains of monosaccharide units in a linear or branched arrangement. They yield more than 6 molecules of monosaccharide on hydrolysis. 1. Homopolysaccharides - polymers of a single monosaccharide Ex. Starch group - starch - glycogen - inulin - dextrin Cellulose group - cellulose - hemicellulose - pentosan (gum arabic)

3 - hexosan ( agar-agar) - hexopentosan 2. Heteropolysaccharides - contain more than one kind of Monosaccharide D. Derived Carbohydrates compounds Ex. 1. 2. 3. 4. 5. derivatives resulting from conversion to

by chemical reactions. Sugar acids Sugar alcohol Sugar amines Deoxysugars Glycosides

IV. Structure of Carbohydrates The Conventions for representing carbohydrates A. Fischer or Linear Projection B. Haworth Projection or Ring structure The Fischer or Linear Projection – - open chain in a vertical manner - lowest numbered carbon at the top - most oxidized end of the molecule has the lowest number CHO I H – C - OH I HO – C – H I H – C – OH I H – C – OH I CH2OH Glucose CHO I HO – C - H I HO – C – H I H – C – OH I H – C –OH I CH2OH Mannose CHO I H – C – OH I HO – C – H I HO –C – H I H – C – OH I CH2OH Galactose CH2OH I C=O I HO – C –H I H – C – OH I H – C – OH I CH2OH Fructose

Haworth Projection or ring structure (hexagonal or pentagonal formula) 1. Cyclic or ring structure is formed between the aldehyde and an alcohol to form a hemiacetal bond or between a ketone and an alcohol to form hemiketal. The formation of the ring structure creates another asymmetric C (C1anomeric C ) and the sugar can therefore exist in 2 stereoisomers forms (anomers). The phenomenon of Mutarotation strongly supports that sugar exist in cyclic forms in solution.

4 C I H – C – OH I HO – C – H I H – C – OH I H–C I CH2OH HO – C I H – C – OH I HO – C – H I H – C – OH I H–C I CH2OH beta D – glucose

o

o

Alpha D – glucose 2. Hexagonal or pentagonal formula Rules in transforming cyclic to hexagonal: a. those on the right side - below b. those on the left side - above

Alpha-D-glucopyranose

Beta-d-glucopyranose

Fructofuranose

Terminologies: 1. D and L configuration – determine the orientation or position of the H and OH groups around the C atom adjacent to the terminal 1o alcohol. Where: If the OH is on the right side – D isomer If the OH is on the left side – L isomer Both D and L sugars of the same compound have identical properties such as boiling points and solubilities in various solvents but they differ in optical activity. 2. Asymmetric C – the carbon atom with 4 different substituents attached to its 4 valences. Isomerism depends upon the number of asymmetric carbon atoms The number of possible isomers of a compound depends on the number of asymmetric carbon atoms (n) and is equal to 2n. Glucose = 24 3. Optical Activity – shown by asymmetric C wherein if a beam polarized light is passed in a solution of an optical isomer, it will rotated on the right. (d) or (+), or to the left (l) or (-). Sugar is: Dextrorotatory – plane of polarized light is rotated clockwise Levorotatory – if counterclockwise

5 4. Stereoisomers – compound with the same structural formula but with a different spatial configuration. - substituent on the same side – Cis - substituent on the opposite side – Trans 5. Epimers – isomers differing as a result of variation in configuration of the OH and H on carbons 2,3 and 4. Ex. Glucose is an epimer to mannose on C2 Glucose in an epimer to galactose on C4 6. Mesostructure – isomers which are optically inactive due to internal compensation 7. Racemic or DL mixture – mixture of equal amount of D and L isomers and exhibits no optical activity. 8. Anomers – pair of stereoisomers differing on the orientation of OH on the anomeric carbon which is C . Anomers are pairs of stereoisomers which are related to each other. Ex. Alpha-D-glucopyranose and Beta-D-glucopyranose IV. Importance of Carbohydrates and their Characteristics A. Monosaccharides 1. D-Glucose Also called dextrose or grape sugar Yellowish white or colorless, crystalline, freely soluble in water found in fruit juices, formed by complete hydrolysis of starch the only sugar present in the blood about 0.1% has reducing property, forms osazone and saccharic acid fermented by yeast in diabetes mellitus, glucose is increased in the blood and finds its way into the urine 2. D-Fructose also called levulose or fruit sugar the sweetest sugar, 173.3% sweet found in fruits, vegetable, honey prepared by hydrolysis of inulin can be converted to glucose in the liver has reducing property and forms osazone also found in the urine of patients with diabetes mellitus gives a cherry red color with Seliwanoff’s resorcinol HCl reagent 3. D-Mannose produced upon hydrolysis of plant mannose and gums

6 sugar frequently found in glycoproteins constituent of prosthetic polysaccharide globulin has reducing property, may form osazone 4. Dof albumin and

Galactose found in plants as pectin less sweet and less soluble than glucose galactose + glucose = lactose (milk sugar) can be changed to glucose in the liver has reducing property, forms a characteristic osazone crystal with HNO3 forms an insoluble mucic acid not fermented by yeast appears abnormally in the urine of nursing infants suffering from digestive disturbances

B. Disaccharides 1. Maltose 2. Lactose lactic

Intermediate product of the action of amylase on starch relative sweetness is 32.5% sweet, crystalline, fermented by yeast produces osazone crystal also called milk sugar yields glucose and galactose on hydrolysis beta lactose has been recommended for infant feeding a reducing sugar sour milk that is formed after the conversion of lactose into acid by microorganisms.

3. Sucrose fructose -

most important sugar from the dietary standpoint 100% sweet also called cane sugar, disaccharide of glucose and fructose no reducing property, no free anomeric carbon no reaction to phenylhydrazine to form osazone no mutarotation, readily hydrolyzed yielding a crude mixture called invert sugar because of the strongly levorotatory an inert sugar because the –CHO group in its structure is linked with the ketone group of fructose

C. Polysaccharides Most complex, white, tasteless, amorphous compounds Non-fermentable by yeast, mostly antigenic 1. Starch makes 50-70% of the solid substance of most cereals found in cereals, potatoes, legumes, some vegetables, some bulbs, tubers

7 responsible for the deep blue color with iodine b. amylopectin – 80-85% $ branch chain that gives red color with iodine because they do not coil effectively. 2. Glycogen also called animal starch, storage polysaccharide gives red color with iodine yields maltose on hydrolysis with maltase its molecule is highly branched, molecular weight is very high (1as source of energy 3. Inulin found in tubers, roots of dalias, garlic, onions soluble in hot water, no reaction with iodine used for the determination of GFR 5M) found mostly in the liver as storage material and in the muscles insoluble in water, gives a blue color with iodine solution constituents: a. amylase – 15-20% non branching helical structure

4. Dextrins - intermediary product of starch hydrolysis - Erythrodextrin gives a red color with Iodine as it reaches certain degree of branching on hydrolysis - as hydrolysis proceeds, the red color disappears assuming the name achrodextrin - used as a mucilage as those at the back of stamps - widely used in infant feeding because when mixed with milk, the formation of large, heavy curds on milk in the baby’s stomach is prevented 5. Cellulose - chief framework constituent of plants - cannot be digested by humans due to the beta linkage and therefore forms a bulk in the diet - no reaction with iodine, insoluble in water - furnishes roughage which stimulate peristalsis, thus promoting the evacuation of the bowel - it is constructed solely from glucose units joined by beta 1-4 linkages 6. chitin - found in the shells of crustaceans, exoskeletons of insects 7. others - Glycosaminoglycans – intercellular substance in tissues - Glycoproteins – sugar conjugated to proteins - Sialic acid – found in human ganglioside - These serve as biological lubricants

8 D. Derived Monosaccharides They contain functional groups other than carbonyl and hydroxyl groups. These are the carbohydrates converted to compounds by chemical reactions. Upon oxidation, sugar acids result upon reduction sugar alcohols are derived. 1. Sugar Acids a. aldonic acid – aldehyde group is oxidized ex. Glucose to gluconic acid or aldonic acid b. Aldaric Acid - both aldehyde and primary alcohol groups are oxidized ex. Glucose to saccharic acid or aldaric acid c. Uronic acid – primary alcohol is oxidized Ex. Glucose to glucoronic acid 2. Sugar alcohol - reduction of sugars to sugar alcohol a. Glucose - sorbitol or glucitol b. Mannose – mannitol c. Galactose – Dulcitol or galactitol VI. General properties of Carbohydrates A. Physical Properties 1. mono and disaccharides are white crystalline substances; starches are amorphous powder while cellulose is fibrous 2. mono and disaccharides are readily dissolved in water 3. mono and disaccharides are sweet; starch and cellulose are tasteless B. Chemical Properties 1. Reducing Action Forms the basis for both qualitative and quantitative test for sugars. Sugars that contain free aldehyde or ketone group possess reducing properties. These reducing action is manifested by color changes or precipitation when the sugar solution is heated with alkaline solutions of metals. Among these tests are: a. Fehling’s or Benedict’s test Cu(OH)2 →Cu2 O + 2 H2O + O2 b. Tollen’s test or silver mirror test 2AgOH + R-CHO → 2Ag + R-COOH + H2O c. Nylander’s test 2Bi (OH)3 → 2Bi + 3O + 3 H2O d. Picric Acid test C6H2OH (NO2)3 → C6H2OHNH2 NO2)2 e. Barfoed’s test – distinguishing mono from disaccharides cupric acetate in acetic acid → cuprous oxide

9 2. Osazone Formation All sugars except sucrose form yellow crystalline osazone crystals when treated with excess phenyl hydrazine. The individual sugar maybe identified by the characteristic structure and melting point of the osazone formed. 3. Fermentation It is the breaking down of complex substances by the use of enzymes. All sugars, except lactose and most polysaccharides undergo fermentation through the aid of specific enzymes, yeast is commonly used to produce fermentation in sugars. 4. Action of alkalis Moore’s Test When a solution of reducing sugar is heated with an alkali (NaOH), it turns yellow to orange and finally dark brown, liberating the odor of caramel. This is due to the liberation of aldehyde which subsequent polymerizes to form a resinous substance, caramel. Glucose, fructose or mannose when allowed to stand in the presence of weak alkali (BaOH) is converted into a mixture containing all the three sugars and whichever one of them is used the same proportion of the three sugars is always reached at equilibrium. This tautomeric change is known as Lobry de Bruyn von Eckenstein transformation, in which anyone sugar is readily converted to the other two forms. 5. Action of Acids a. dilute acids ---- hydrolysis b. strong mineral acids monosaccharides with concentrated acids and at boiling temperature are dehydrated forming: pentose → furfural hexose → hydroxymethyl furfural and its derivatives These condense with a number of compounds to yield colored products. a. Molisch’s test ( a general test for carbohydrates) When sugar solution is treated with Molisch’s reagent (alpha naphtol) and concentrated H2SO4, a violet color forms at the junction of the two liquids. b. Seliwanoff’s Test

10 This is a specific test for ketose sugar like fructose which forms rapidly hydroxymethyl furfural as a result of dehydration. This condenses with resorcinol to form red colored compounds. c. Iodine Test With iodine, uncooked starch gives a violet color but cooked starch forms a blue color heating makes the color disappear but the blue color returns on cooling. d. Anthrone test A blue or green color is produced with anthrone reagent and concentrated sulfuric acid with sugar. e. Bial’s Orcinol HCl test A green solution is produced with HCl and orcinol reagent with pentoses. f. Tauber’s Benzidine test A violet color is produced with benzidine + sugar.

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