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27)
The chemistry of lipids is all about how structure affects function. This
is generally the case with biomolecules (true of carbohydrates, peptides,
proteins)
Since the fats and oils are esters, their chemistry fits in well with the
previous chapters on carboxylic acid derivatives; reactions of these
molecules are similar
We will discuss information that is not covered in the textbook. Take careful
notes in class.
Chapter 27: 14, 17, 20, 22, 24, 25, 33, 35, 38, 46
Lipids: Structure, Function & Chemistry
1. Waxes (27.1)
Structure: Esters of long-chain fatty acids and long-chain alcohols
Function: Coatings, protection against environment
Example: Carnauba wax (palm leaves) : CH3(CH2)30-COO-(CH2)33CH3
Amphiphilic = Structures which have both nonpolar areas and polar or charged
areas. This will affect how these molecules aggregate together.
Fatty acids: Common long-chain carboxylic acids are shown in Table 27.1
Some key points about fatty acid structure & properties:
3) Unsaturated fatty acids in nature are always cis (Z) isomers; puts a kink in
the chains & affects 3-D structure (trans-fatty acids only form synthetically)
OH HOOC R1 O C R1
H 2C H 2C O
HC OH + HOOC R2 HC O C
R2
O
H2 C HOOC R3 H2 C
OH
O C
R3
Condensation of glycerol with three fatty acids produces a molecule of fat or oil
1) TAG that are solid at room temperature are classified as fats (animal-based)
2) TAG that are liquid at room temp. are classified as oils (vegetable-based)
3) In general, the more unsaturated the fatty acids in a TAG, the less solid it is
4) Most liquid TAG come from plant sources (olives, corn, safflower)
6) 3-D structure of fatty acids affects packing which in turn affects melting point
(Figure 29.3)
d) Lipid peroxidation
and antioxidants
a peroxy radical
an alkyl hydroperoxide
Key point: Fatty acid oxidation contributes to cardiovascular disease.
Oxidation of LDL initiates formation of plaque (solid buildup) in blood vessels and
onset of atherosclerosis and heart disease.
Cell membranes; oxidation degrades membranes and makes them less fluid
Antioxidants are primarily compounds which react with free radicals (often by
forming a more stable free radical) and remove them from the site before damage
occurs.
Many substituted phenols are antioxidants because they form a stable phenoxyl
radical:
OH + R O + RH
Fats and cholesterol (in the form of fatty acid esters) are carried through the
bloodstream and distributed to and from the tissues and organs by lipoproteins
LDL: Low density lipoproteins carry cholesterol from liver to rest of body
High LDLs tend to deposit more lipid in blood vessels
Lipids are subject to oxidation (see previous page)
High LDL levels raise risk of atherosclerosis and heart disease
Saturated fats:
raise both LDL and HDL
1. Omega-3s are generally highly unsaturated, so they lower LDLs, raise HDLs
Since most dirt is oil-based, it is attracted to the center of the micelle and the soap
micelles therefore break up dirt particles (but remain soluble due to charged outer
layer)
Phospholipids, sphingolipids and the structure of cell membranes
Fatty acid ester composition varies; the more unsaturated the groups, the more
fluid and flexible the cell membrane.
Occurrence: Sphingolipids are found mainly in nerve and brain cell membranes.
Sphingomyelins make up the myelin sheath surrounding nerves
Cerebrosides (glycolipids) are found in brain tissue
Several human genetic diseases result from faulty metabolism or abnormal
accumulation of sphingolipids in the body:
A sphingolipid structure:
Normally, sphingolipids are metabolized to
their components: sphingosine, fatty
acids, sugars, phosphocholine, etc.
Precursors:
Functions:
Opposite of thromboxanes