Carbohydrates Notes:

All carbohydrates have the general formula CnH2nOn side note --- this can be re-written as Cn(H2O)n and thus you can see the carbon component and the water (hydrate) component; HOWEVER, this name is not an indicator of the actual structure of carbohydrates- the name is just showing what the early scientists originally believed. Carbohydrates are polymers of monosaccharides (a.k.a sacchraides). These polymers are called polysaccharides. A polymer is basically a large molecule that can be hydrolyzed into a generic repeating unit. Monomers all have the same general backbone structure. They can be categorized into two main groups: aldoses and ketoses. aldoses- carbohydrates that contain an aldehyde o backbone of aldoses (in Fischer projection) ~ all aldoses have the CHO at the top and the CH2OH at the bottom ~ the number of horizontal lines in between can be variable (between 1-4) and indicate carbons at the convergence points ~ the attachments of each of these middle carbons must be an OH on one side and an H on the opposite ~ different monomers have different orientations and orders of each of these attachments (OH-H vs. H-OH) ~ the second to last C is the most important in terms of the attachment order because it differentiates between a D aldose and L aldose if the OH group attached to the second to last carbon atom is on the left, the saccharide is denoted with an L in front of the monomer name. if the OH group attached to the second to last carbon atom is on the right, the saccharide is denoted with a D in front of the monomer name. the number of carbons in the atoms depends on the monomer if there are three carbons- triose if there are four carbons- tetrose if there are five carbons- pentose if there are six carbons- hexose thus, a monomer with an aldehyde, six carbons, and a OH on the right of the second to last carbon atom would be named D-aldohexose o see Carbohydrate Lecture Supplement to see all the various D-Aldoses you dont need to memorize each of themjust be familiar with the backbone structure.

three aldoses that may be beneficial to memorize are glucose, galactose, and ribose

D-(+)-glucose

D-(+)-galactose

D-ribose

ketoses- carbohydrates that contain a ketose o backbone of ketoses (in Fischer projection) ~ all ketoses have the CH2OH at the top and a carbonyl at the second carbon (this is actually just a ketone, but in Fisher projections, they are shown in this way) they all have the CH2OH at the bottom ~ the same rules apply to ketoses as those of aldoses as far as the number of middle carbons, orientation of attachment groups, and D vs. L--- the only real difference between aldoses and ketoses is there functional group (and aldehyde vs. a ketone) thus, a monomer with a ketose, five carbons, and a OH on the left of the second to last carbon atom would be named L-ketopenthexose

For the rest of our discussions of carbohydrates, we will continually use glucose as our example because this is the most important monomer and most abundant monomer. We will see the reason for this in a little bit. Monosaccharides are actually in an equilibrium between their acyclic and cyclic forms. The equilibrium lies favorably towards the cyclic form. (This phenomenon explains why aldoses dont really act like aldehydes. Its because for a majority of the time, they are in cyclic form and in this form, the aldehyde doesnt exist, but is rather turned into an ether.) When the ring formed by a monomer has five members, it is called a furanose When the ring formed by a monomer has six members, it is called a pyranose

Using glucose as an example of linear vs. ring equilibrium:

The ring forms when the OH group on the second to last carbon of D-glucose attacks the carbon attached to the carbonyl --- this carbon (attached to the carbonyl in the acyclic form) is called an anomeric carbon. o D-glucose (acyclic) then forms a new bond within itself and becomes Dglucopyranose (the mechanism is not important- just memorize the glucose structure and glucopyranose structure) o The anomeric carbon in the cyclic form is the only one attached to two oxygens. Alternatively, it is the carbon forming the ring-ether that is not attached to the CH2OH group. o The ring has one carbon ether and one CH2OH attachment (see diagram above) Also, notice that the attachments on the left side of the Fischer projection are oriented above the ring. The attachments on the right side of the Fisher projection are oriented below the ring. The cyclic form of glucose explains why it is so common- all the hydroxyl attachments (maybe with the exception of the anomeric hydroxyl, which will be discussed later) are in equatorial positions. This means that there is a minimum amount of stress. In pyranoses and furanoses (cyclic forms) there is yet another equilibrium--- between the alpla conformation and beta conformation o See the diagram above- If the CH2OH attachment and anomeric hydroxyl (the OH attached the anomeric carbon) are trans to each other, then the ring is alpha. If the CH2OH attachment and anomeric hydroxyl (the OH attached the anomeric carbon) are cis to each other, then the ring is alpha.

Disaccharides Disaccharides are two monomers linked together by a glycosidic bond (glycoside). Definition of glycoside- an acetal (C-O-C-O-C) at the anomeric carbon of a saccharide The important disaccharides to remember are: o maltose- 1,4 alpha glycoside links between glucose o lactose- 1,4 beta glycoside links between glucose and galactose o sucrose- 1,1 alpha glycoside links between glucose and fructose Look in thinkbook lecture supplements to see how the bonds look

Polysaccharides Many monosaccharides linked together The important ones to remember are: o cellulose- 1,4 beta links made by plants used as support substances- strong due to hydrogen bonding indigestible by humans because of the nature of the beta links o starch- 1,4 alpha links made by plants as energy storage digestible by humans because they are alpha links composed of two different polymers amylase- 1,4 alpha links amylopectin- 1,4 alpha and 1,6 alpha (this is what causes the branching) o glycogen a lot like amylopectin, however there are less 1,6 alpha links, so there is less branching