CARBOHYDRATE

PROGRAM KBK FK-UKI

Prof. Dr. Drh. Maria Bintang, MS

Kepala Departemen Biokimia Kedokteran FK-UKI

REFERENCES
Lehninger.

2008. Principles of biochemistry 5rd Ed. Michael W. King. 2006. Medical Biochemistry. Murray R K, Granner D k, Mayers P a & Rodwell V w. 2009. Harpers Illustrated Biochemistry. 28th Ed. Pratt,C.W.and Cornely K. 2004. Essential Biochemistry. Wiley International Edition. Stryer, Lubert 1995. Biochemistry.4th Ed.

CARBOHYDRATE DEFINITION
Latin word " sacchararum" = sweet taste of sugars. It means a "hydrate of carbon with formula of carbohydrate isCx(H2O)y (classic) It is that the compounds are polyhydroxy aldehydes or ketones (modern) Initially synthesized in plants by photosynthesis.

CARBOHYDRATE FUNCTIONS

Source energy : Glucose, fructose and starch Store energy : starch in plants or glycogen in animals and humans Provide energy through metabolism pathways and cycles Form structural components in plant cells and tissues : cellulosa Carrier genetic information : DNA, RNA

CARBOHYDRATE CLASSIFICATION

According to the number of individual simple sugar units : Mono, di and polysaccharides According to the functional groups :
Aldoses, contain the aldehyde group : glucose, galactose, ribose. Ketoses contain the ketone group : fructose Reducing, sugars oxidized by Tollens' reagent (or Benedict's or Fehling's reagents) : glucose, galactose, fructose, maltose, lactose Non-reducing, sugars not oxidized by Tollens' or other reagents : Sucrose and all polysaccharides

Monosaccharides can be categorized according to their value of 'n,'

n 3 4 5 6 7 8 Category Triose Tetrose Pentose Hexose Heptose Octose

ALDOSES

KETOSES

CARBOHYDRATE ACCORDING SIMPLE SUGAR UNITS Carbohydrates

Monosaccharides Disaccharides Polysaccharides Glucose Galactose Fructose Ribose Maltose Lactose Sucrose Cellobiose Starch Glycogen Cellulose Hemicelluloce

Derivatives of Monosaccharides

Acids and Lactones : made by mild oxidation of an aldose, (to form an aldonic acid) Alditols : made by reducing the carbonyl group of a sugar and resulting polyhydroxy compounds are called alditol (erythritol, D-mannitol, and D-glucitol/ sorbitol) Amino Sugars : made by replacing a hydroxyl of a sugar with an amine group (beta-Dglucosamine and beta-D-galactosamine) Glycosides formed by elimination of water between the anomeric hydroxyl of a cyclic monosaccharide and the hydroxyl group of another compound

Formed an aldonic acid

beta-D-glucosamine and beta-Dgalactosamine

Glycoside

Cyclic Forms of Monosaccharides

Structural form of many monosaccharides may be that of a cyclic hemiacetal. Five and six-membered rings are favored over other ring sizes because of their low angle and eclipsing strain Cyclic structures of this kind are termed Furanose (five-membered) or pyranose (six-membered)

Haworth formula

Pyranose forms of hexoses

Oligosaccharides
Glycosidic bonds between monosaccharides give rise to oligosaccharides and polysaccharides. The simplest oligosaccharides, the disaccharides : sucrose, lactose,trehalose, maltose,gentiobiose, and cellobiose. Oligosaccharides are also found as part of glycoprotein and play a role in cell recognition/identity

Disaccharides

Polysaccharides

Polysaccharides are polymers of monosaccharide units The monomeric units of a polysaccharide are usually all the same (homopolysaccharides), though there are exceptions (heteropolysaccharides). It differ in the composition of the monomeric unit, the linkages between them, and the ways in which branches from the chains occur

.. Polysaccharides

Polysaccharides homopolysaccharides: Glucose : glucans (structure in fungi, glucoses

joined by beta 1->3 or beta 1->6 bonds ) Mannose : mannans Xylose : xylans ( polymers of D-xylopyranose)

Polysaccharides heteropolymers :
Glucopyranose and mannopyranose joined by beta 1>4 linkages with beta 1->6 branches to other substituents. The glucomannans and xylans are often grouped together and called hemicellulose.

Polysaccharides

Structures and Roles of some Polysaccharides

Polysaccharide Name Glycogen Cellulose Chitin Amylopectin

Monomeric Unit D-Glucose D-Glucose N-Acetyl-Dglucosamine D-Glucose

Linkages alpha 1->4 links with extensive alpha1->6 branches beta 1->4 beta 1->4

alpha 1->4 links with some alpha 1>6 branches alpha 1->4

Amylose

D-Glucose

Polysaccharide polymers

Polysaccharides

.. Polysaccharides

Polysaccharides for energy storage in almost all higher organisms : Animals use glycogen, Plants use starch (amylose and amylopectin). Plants use different polysaccharides : cellulose for structural purposes in their cell walls. The exoskeleton of many arthropods and mollusks is composed of chitin, polysaccharide of N-acetyl-Dglucosamine The most important compounds in this class, cellulose, starch and glycogen are all polymers of glucose

Glycogen is a storage Carbohydrate found in animals Starch is a storage Carbohydrate found in plants Cellulose Plant is a structural carbohydrate (woody material, cotton fibers) It is rather insoluble and most animals cannot digest cellulose All of these are polymers of glucose

Starch
Major carbohydrate reserve in plant tubers and seed endosperm where it is found as granules Stored in chloroplastsof plants The largest source of starch is corn (maize),wheat, potato, tapioca and rice Consists of two types of molecules: amylose (normally 20-30%) amylopectin (normally 70-80%)

. Starch

Starch stored in chloroplastsof plants Amylopectin (without amylose) be isolated from 'waxy' maize starch and amylose (without amylopectin) isolated after specifically hydrolyzing the amylopectin with pullulanase

Amylose
Forms a colloidal dispersion in hot water whereas amylopectin is completely insoluble Long polymer chains of glucose units connected by an alpha acetal linkage All of the monomer units are alpha -D-glucose, and all the alpha acetal links connect C 1 of one glucose to C 4 of the next glucose

Amylopectin

The acetal linkages are alpha connecting C 1 of one glucose to C 4 of the next glucose The branches are formed by linking C 1 to a C 6 through an acetal linkages. Has 12-20 glucose units between the branches. Natural starches are mixtures of amylose and amylopectin. In glycogen, the branches occur at intervals of 8-10 glucose units, while in amylopectin the branches are separated by 10-12 glucose units.

Cellulose

Polysaccharide polymer consisting linear with many glucose monosaccharide units long polymer chains of glucose units connected by a beta acetal linkage so it is makes it different from starch All of the monomer units are beta-D-glucose, and all the beta acetal links connect C 1 of one glucose to C 4 of the next glucose Cellulose is a major component of the cell walls plants, and is difficult to digest by human because lacking enzymes to breakdown the beta acetal linkages

Cellulose: Beta glucose is the monomer unit in cellulose, as a result of the bond angles in the beta acetal linkage, cellulose is mostly a linear chain. Starch: Alpha glucose is the monomer unit in starch, as a result of the bond angles in the alpha acetal linkage, starch-amylose actually forms a spiral much like a coiled spring.

Compare Cellulose and Starch Structures

Cellulose structure

Glycogen
Polymers consisting monosaccharide units (-Dglucose) connected by an alpha acetal linkage All the alpha acetal links connect C 1 of one glucose to C 4 of the next glucose and branches are formed by linking C 1 to a C 6 through an acetal linkages The branches occur at intervals of 8-10 glucose units, while in amylopectin the branches are separated by 12-20 glucose units. synthesized and stored mainly in the liver and the muscles

Structure of Glycogen

CARBOHYDRATE IMPORTANT REACTIONS

Carbonyl group (alone) Oxidation to a carboxylic acid group Reduction to a hydroxyl group Cyanohydrin reaction (and reaction with other nucleophiles) 2. Hydroxyl groups : Ester formation Oxidation to carbonyl Ether formation Reduction to deoxy Cyclic acetal Replacement with NH2, SH, or X 3. Both carbonyl and hydroxyl groups Cyclic hemiacetals (pyranose/furanose) Formation of acetals (glycosides) Aldose/ketose isomerizations
1.

DISEASES OF CARBOHYDRATE METABOLISM DISODER

1. 2. 3. 4. 5.

Diabetes mellitus Lactose intolerance Fructose intolerance Galactosemia Glycogen storage disease

BUKU ACUAN PRAKTIKUM BIOKIMIA

LIPID
PROGRAM KBK FK-UKI

Prof. Dr. Drh. Maria Bintang, MS

Definition of Lipid

Lipids : hydrophobic or amphipathic small molecules that may originate entirely or in part by carbanion-based condensations of thioesters (fatty acids, polyketides, etc.) and/or by carbocation-based condensations of isoprene units (prenols, sterols). Lipids are biomolecules which are insoluble in water but soluble in organic solvents like ether and chloroform.

The functions of lipids

source of energy for the body. parts of the membranes found within and between each cell In the myelin sheath that coats and protects the nerves Organ padding Body thermal insulation Hormone synthesis Fat soluble vitamin absorption

Classification of Lipids

Simple Lipids :
Phospholipids

Neutral fats (Triglycerides)

- Waxes

Conjugated Lipids (polar lipids) :

- Cerebrosides - Sulfolipids

Derived Lipids:
Fatty acids Fatty alcohols Fatty aldehydes - Hydrocarbons - Vitamins A, D, E, K

Miscellaneous:

Soaps Coloring matters

- Oxidative polymers - Thermal polymers

Lipid class
Monogalactosyldiacylglycerol Digalactosyldiacylglycerol
Sulfoquinovosyldiacylglycerol Triacylglycerol Phosphatidylcholine Phosphatidylethanolamine Phosphatidylinositol Phosphatidylglycerol Others

Potato tuber
6 16
1 15 26 13 6 1 15

Apple fruit
1 5
1 5 23 11 6 1 42

Soybean seed
trace trace
trace 88 4 2 2 trace 5

Clover leaves
46 28
4

Rye grass
39 29
4

Spinach cloroplasts
36 20
5

7 5 1 6 3

10 5 2 7 4

7 3 2 7

Table The lipid class compositions (weight % of the total lipids) of various plant tissues

Simple Lipids
These are esters of fatty acids with various types of alcohol, distinguished into fats and oils Fats are esters of fatty acids and glycerol. A fatty acid is an organic acid with a hydrocarbon chain ending in a carboxyl (COOH) group

Fatty acid
Fatty acids are merely carboxylic acids with long hydrocarbon chains with length may vary from 10-30 carbons (most 12-18) A fatty acid : Saturated and unsaturated Saturated if there are no double bonds between carbons of the molecular chain ex : Palmitic acid (16 C) and stearic acid (18 C). Unsaturated if one (mono) or more (poly) double bonds occur between the carbon atoms of the chain ex : oleic acid (18 C,1 double bond) , linoleic acid (18 C,2 double bond) and linolenic acid (18 C,3 double bond)

Saturated

unsaturated

Acid Name
SATURATED

Structure

Melt Point Symbol

+44
+63 +70 +16 -5 -11 -50 12:0 16:0 18:0 18:19 18:29,12 18:39,12,15 20:45,8,11,14

Lauric
Palmitic Stearic Oleic Linoleic Linolenic Arachidonic

CH3(CH2)10COOH
CH3(CH2)14COOH CH3(CH2)16COOH CH3(CH2)7CH=CH(CH2)7COOH CH3(CH2)4(CH=CHCH2)2(CH2)6COOH CH3CH2(CH=CHCH2)3(CH2)6COOH CH3(CH2)4(CH=CHCH2)4(CH2)2COOH

UNSATURATED

 Fatty acid

The unsaturated fatty acids have lower melting points than the saturated fatty acids. The geometry of the double bond is almost always a cis configuration in natural fatty acids. These molecules do not "stack" very well. The intermolecular interactions are much weaker than saturated molecules. As a result, the melting points are much lower for unsaturated fatty acids.

Triglycerides / triacylglycerol (TAG)

Main constituents of vegetable oils and animal fats Have lower densities than water At normal room temperatures may be solid ("fats" or "butters" ) or liquid (oils) A chemical compound formed from one molecule of glycerol and three fatty acids

Biosyntesis triacylglycerol pathway

Percent Fatty Acid Present in Triglycerides

Fat or Oil Saturated Palmitic Butter Lard Beef Corn oil Soybean Peanut Olive 29 30 32 10 7 7 6 Stearic 9 18 25 4 3 5 4 Unsaturated Oleic 27 41 38 34 25 60 83 Linoleic 4 6 3 48 56 21 7 Other 31 5 2 4 9 7 -

Animal Origin

Vegetable Origin

Wax

A simple lipid which is an ester of a long-chain alcohol and a fatty acid Found in nature as coatings on leaves and stems. Prevents the plant from losing excessive amounts of water. Example : Carnuba, Beeswax, Spermacetic Many of the waxes mentioned are used in ointments, hand creams, and cosmetics. Paraffin wax, used in some candles, is not based upon the ester functional group, but is a mixture of high molecular weight alkanes. Ear wax is a mixture of phospholipids and esters of cholesterol.

WAXES

Wax
Carnauba Beeswax

Alcohol

Fatty Acid

Used
in floor,candies, polishes, varnishes, cosmetic products,

CH3(CH2)28CH2-OH CH3(CH2)24COOH CH3(CH2)28CH2-OH CH3(CH2)14COOH

secreted by bees to make cells for honey and eggs

found in the head cavities and blubber of the sperm whale

Spermacetic CH3(CH2)14CH2-OH CH3(CH2)14COOH

Phosphoglycerides or Phospholipids
Esters of only two fatty acids, phosphoric acid and a trifunctional alcohol - glycerol Characterized : fatty acid chain and the phosphate/amino alcohol The long hydrocarbon chains of the fatty acids are of course non-polar

Structure of a phospholipid, phosphatidate

Phosphoglycerides or Phospholipids

The phosphate group has a negatively charged oxygen and a positively charged nitrogen to make this group ionic There are other oxygen of the ester groups, which make on whole end of the molecule strongly ionic and polar There are two common phospholipids: Lecithin contains the amino alcohol, choline. Cephalins contain the amino alcohols serine or ethanolamine

Lecithin
Found in egg yolks, wheat germ, and soybeans Extracted from soy beans for use as an emulsifying agent in foods Major component in the lipid bilayers of cell membranes (cholesterol & phospholipid) Lecithin contains the ammonium salt of choline joined to the phosphate by an ester linkage

Cephalins
Posphoglycerides that contain ehtanolamine or the amino acid serine attached to the phosphate group through phosphate ester bonds Found in most cell membranes, particularly in brain tissues Important in the blood clotting process as they are found in blood platelets

Steroids

Derivatives of terpenes have tetracyclic skeleton, consisting of three fused sixmembered and one fivemembered ring are lipids with the principle function of signaling chemical biological activities. Widely distributed in animals Include such well known compounds as cholesterol, sex hormones, birth control pills, cortisone, and anabolic steroids

Steroid hormone

Terpenes
A majority of these compounds are found only in plants, but some of the larger and more complex terpenes (squalene & lanosterol ) occur in animals Considered to be made up of isoprene ( more accurately isopentane ) units, an empirical feature known as the isoprene rule

Classification monoterpenes sesquiterpenes diterpenes Isoprene Units 2 3 4 Carbon Atoms C10 C15 C20

sesterterpenes
triterpenes

5
6

C25
C30

Lipid storage disorder

The body's store of fat is constantly broken down and reassembled to balance the body's energy needs with the food available. Groups of specific enzymes help the body break down and process fats. Certain abnormalities in these enzymes can lead to the buildup of specific fatty substances that normally would have been broken down by the enzymes. Over time, accumulations of these substances can be harmful to many organs of the body. Disorders caused by the accumulation of lipids are called lipidosis. Other enzyme abnormalities result in the body being unable to properly convert fats into energy. These abnormalities are called fatty acid oxidation disorders

.. Lipid storage disorders

Lipid storage disorders (or lipidoses) are a group of inherited metabolic disorders in which harmful amounts of lipids (fats) accumulate in some of the bodys cells and tissues. Types Lipid storage disorders
Niemann-Pick disease Fabry disease Farbers disease Gangliosidoses = Tay-Sachs disease Krabb disease Metachromatic leukodystrophy Wolmans disease

THE AND

1. Carbonyl group

a. Oxidation to a carboxylic acid group Tollens test

Fehlings test

Glucose oxidase

Glucose to glucitol (sorbitol)

b. Carbonyl group reduction

Periodate oxidation
can be used to quantitatively measure the number of adjacent hydroxyls in a molecule. It is used in the determination of polysaccharide structure The reaction is most rapid at pH 3-5

c. Oxidation of non-anomeric hydroxyl groups

Hydrogen peroxide
A non-specific oxidant Depolymerizes oligo- or polysaccharides Involves a free radical mechanism Employs an Fe+2 catalyst Fe+2 + HOOH Fe+3 + HO. + OH-

Esters
Reaction of alcohol with acid anhydride or acid chloride forms an ester Usually done in the presence of a base such as triethylamine, pyridine, sodium acetate, sodium hydroxide, (know as the Schotten-Bauman technique) and is done to shift the equilibrium toward the product ester

2. Hydroxyl groups

Use of acid anhydrides

Etherification of some polysaccharides Modifies their properties Makes them more useful Examples (derivatives of cellulose) Methyl (-CH3) Carboxymethyl (-CH2COO-Na+) Hydroxypropyl (-CH2CH(OH)CH3)

Etherification

Cyclic acetals

The hydroxyl groups on carbohydrates react with aldehydes or ketones to form cyclic acetals Common carbonyl compounds include acetone and benzaldehyde Sometimes such acetals occur naturally, as in xanthan gum

http://www.cfs.purdue.edu/class/f&n630/Virt _Class_2/CHOreactions.htm http://www.elmhurst.edu/~chm/vchembook/ 550lipids.html http://www.nicerweb.com/bio1151b/Locked/ media/ch05/polysaccharides.html