Lipids: Fats, Oils, Waxes, etc.

All Lipids are hydrophobic at one end and hydrophilic at the other end.
That’s the one property they have in common.
This group of molecules includes fats and oils, waxes,
phospholipids, steroids (like cholesterol), and some other related compounds.

The Glycerol Molecule

Fats and oils are made from two kinds of molecules: glycerol (a type of alcohol with a hydroxyl group on each of its three carbons) and three fatty acids joined by dehydration synthesis. Since there are three fatty acids attached, this molecule is known as a triglycerides. “Bread” and pastries from a “bread factory” often contain mono- and diglycerides as “dough conditioners.” Can you figure out what these molecules would look like? The main distinction between fats and oils is whether they’re solid or liquid at room temperature, and this, as we’ll soon see, is based on differences in the structures of the fatty acids they contain.

Structure of Fatty Acids: The tail of a fatty acid is a long, uncharged, string of carbons and hydrogens (a hydrocarbon chain) making it hydrophobic. The head of the molecule as the 'acid' group of a carbon atom double bonded to an oxygen atom and the carbon is attached to an -OH group. Since the hydrogen of the -OH group commonly is removed when in a water environment, this 'acid' end of the fatty acid molecule has a negative charge associated with it. For this reason we consider the head portion hydrophilic. Fatty acids are the main component of soap, where their tails are soluble in oily dirt and their heads are soluble in water to emulsify and wash away the oily dirt.

The terms saturated, mono-unsaturated, and poly-unsaturated refer to the number of hydrogens attached to the hydrocarbon tails of the fatty acids as compared to the number of double bonds between carbon atoms in the tail. Fats, which are mostly from animal sources, have all single bonds between the carbons in their fatty acid tails, thus all the carbons are also bonded to the maximum number of hydrogens possible. Since the fatty acids in these triglycerides contain the maximum possible amount of hydrogens, these would be called saturated fats. The hydrocarbon chains in these fatty acids are, thus, fairly straight and can pack closely together, making these fats solid at room temperature.

Oils, mostly from plant sources, have some double bonds between some of the carbons in the hydrocarbon tail, causing bends or “kinks” in the shape of the molecules. Because some of the carbons share double bonds, they’re not bonded to as many hydrogens as they could if they weren’t double bonded to each other. Therefore these oils are called unsaturated fats. Because of the kinks in the hydrocarbon tails, unsaturated fats can’t pack as closely together, making them liquid at room temperature. Many people have heard that the unsaturated fats are “healthier” than the saturated ones. Hydrogenated vegetable oil (as in shortening and commercial peanut butters where a solid consistency is sought) started out as “good” unsaturated oil. However, this commercial product has had all the double bonds artificially broken and hydrogens artificially added (in a chemistry lab-type setting) to turn it into saturated fat that bears no resemblance to the original oil from which it came (so it will be solid at room temperature).

In unsaturated fatty acids, there are two ways the pieces of the hydrocarbon tail can be arranged around a C=C double bond. In cis bonds, the two pieces of the carbon chain on either side of the double bond are either both “up” or both “down,” such that both are on the same side of the molecule. In trans bonds, the two pieces of the molecule are on opposite sides of the double bond, that is, one “up” and one “down” across from each other. Naturally-occurring unsaturated vegetable oils have almost all cis bonds, but using oil for frying causes some of the cis bonds to convert to trans bonds. If oil is used only once like when you fry an egg, only a few of the bonds do this so it’s not too bad. However, if oil is constantly reused, like in fast food French fry machines, more and more of the cis bonds are changed to trans until significant numbers of fatty acids with trans bonds build up. The reason this is of concern is that fatty acids with trans bonds are carcinogenic, or cancer-causing.

We need fats in our bodies and in our diet. Animals in general use fat for energy storage because fat stores 9 KCal/g of energy. Plants, which don’t move around, can afford to store food for energy in a less compact but more easily accessible form, so they use starch (a carbohydrate, NOT A LIPID) for energy storage. Carbohydrates and proteins store only 4 KCal/g of energy, so fat stores over twice as much energy/gram as fat. By the way, this is also related to the idea behind some of the high-carbohydrate weight loss diets. The human body burns carbohydrates and fats for fuel in a given proportion to each other. The theory behind these diets is that if they supply carbohydrates but not fats, then it is hoped that the fat needed to balance with the sugar will be taken from the dieter’s body stores.

Fat is also used in our bodies to
a) cushion vital organs like the kidneys and
b) serve as insulation, especially just beneath the skin.

Phospholipids

Phospholipids are made from glycerol, two fatty acids, and (in place of the third fatty acid) a phosphate group with some other molecule attached to its other end. The hydrocarbon tails of the fatty acids are still hydrophobic, but the phosphate group end of the molecule is hydrophilic because of the oxygens with all of their pairs of unshared electrons. This means that phospholipids are soluble in both water and oil.

An emulsifying agent is a substance which is soluble in both oil and water, thus enabling the two to mix. A “famous” phospholipid is lecithin which is found in egg yolk and soybeans. Egg yolk is mostly water but has a lot of lipids, especially cholesterol, which are needed by the developing chick. Lecithin is used to emulsify the lipids and hold them in the water as an emulsion. Lecithin is the basis of the classic emulsion known as mayonnaise.

Our cell membranes are made mostly of phospholipids arranged in a double layer with the tails from both layers “inside” (facing toward each other) and the heads facing “out” (toward the watery environment) on both surfaces.

Cholesterol

The general structure of cholesterol consists of two six-membered rings side-by-side and sharing one side in common, a third six-membered ring off the top corner of the right ring, and a five-membered ring attached to the right side of that. The central core of this molecule, consisting of four fused rings, is shared by all steroids, including estrogen/estradiol, progesterone, corticosteroids such as cortisol/cortisone, aldosterone, testosterone, and Vitamin D. In the various types of steroids, various other groups or molecules are attached around the edges. Know how to draw this central structure.

Cholesterol is not a “bad guy!” It is the precursor to our sex hormones and Vitamin D. Vitamin D is formed by the action of UV light in sunlight on cholesterol molecules that have “risen” to near the surface of the skin. At least one source I read suggested that people not shower immediately after being in the sun, but wait at least 1/2 hour for the new Vitamin D to be absorbed deeper into the skin. Our bodies make about 2 g of cholesterol per day, and that makes up about 85% of blood cholesterol, while only about 15% comes from dietary sources.

Many people have heard the claims that egg yolk contains too much cholesterol, thus should not be eaten. An interesting study was done at Purdue University a number of years ago to test this. Men in one group each ate an egg a day, while men in another group were not allowed to eat eggs. Each of these groups was further subdivided such that half the men got “lots” of exercise while the other half were “couch potatoes.” The results of this experiment showed no significant difference in blood cholesterol levels between egg-eaters and non-egg-eaters while there was a very significant difference between the men who got exercise and those who didn’t.

Lipoproteins

Lipoproteins are clusters of proteins and lipids all tangled up together. These act as a means of carrying lipids, including cholesterol, around in our blood. There are two main categories of lipoproteins distinguished by how compact/dense they are. LDL or low density lipoprotein is the “bad guy,” being associated with deposition of “cholesterol” on the walls of someone’s arteries. HDL or high density lipoprotein is the “good guy,” being associated with carrying “cholesterol” out of the blood system, and is more dense/more compact than LDL.