Chemistry and digestion of

lipids

Tiget. A
 BIOMEDICAL IMPORTANCE

The lipids are a heterogeneous group of

compounds, including fats, oils, steroids, waxes

They have the common property of being:

Relatively insoluble in water and
Soluble in non-polar solvents such as ether and
chloroform.
Importance :
1. They are important dietary constituents because of:
a. Their high energy value
b. The fat-soluble vitamins and the essential fatty acids
contained in the fat of natural foods
.2. Fat is stored in adipose tissue, where it also serves as a
thermal insulator in the subcutaneous tissues and around certain
organs
.3. Non-polar lipids act as electrical insulators, allowing rapid
propagation of depolarization waves along myelinated nerves.
4.Combinations of lipid and protein (lipoproteins) are important
cellular constituent, occurring both in the cell membrane and in
the mitochondria, and serving also as the means of
Transporting lipids in the blood

5 Knowledge of lipid biochemistry is necessary in understanding

many important biomedical areas, eg, obesity, diabetes

mellitus, atherosclerosis, and the role of various

polyunsaturated fatty acids in nutrition and health.
 LIPIDS ARE CLASSIFIED AS

Simple lipids

Complex lipids:
 LIPIDS ARE CLASSIFIED AS:
SIMPLE OR COMPLEX

Simple lipids: Esters of fatty acids with various alcohols.

Fats: Esters of fatty acids with glycerol.
Oils and Waxes:

Complex lipids: Esters of fatty acids containing groups in addition

to an alcohol and a fatty acid.

I.Phospholipids: Lipids containing, in addition to fatty acids

and an alcohol, a phosphoric acid residue. eg, in
glycerophospholipids the alcohol is glycerol and in
sphingophospholipids the alcohol is sphingosine.
II. Glycolipids (glycosphingolipids):

Lipids containing a fatty acid, sphingosine, and carbohydrate.

Other complex lipids:

Lipids such as sulfolipids and aminolipids. Lipoproteins may
also be placed in this category.
 Fatty acids
Fatty acids are building block of most lipids,
Having one polar carboxyl group (head) and a non-polar
hydrocarbon chain (tail).
Fatty acids occur mainly as esters in natural fats and oils
but do occur in the un -esterified form as free fatty acids, a
transport form found in the plasma.
Fatty acids that occur in natural fats has even number of
carbon atoms.
The chain may be saturated (no double bonds) or
unsaturated ( one or more double bonds).
Thus, Saturated acids end in -anoic, eg, octanoic acid,

and Unsaturated acids with double bonds end in -enoic,

eg, octadecenoic acid (oleic acid).

 Carbon atoms are numbered from the carboxyl carbon (carbon

No. 1). the terminal methyl carbon is known as the ω or n-carbon.
 Various conventions use Δ for indicating the number
and position of the double bonds .
e.g. Δ9 indicates a double bond between carbons 9
and 10 of the fatty acid;
ω9 indicates a double bond on the ninth carbon
counting from the ω- carbon.

 In animals, additional double bonds are introduced

only between the existing double bond (e.g., ω9, ω6, or
ω3)
Unsaturated Fatty Acids Contain One or More
Double Bonds

Fatty acids may be further subdivided as follows:

Monounsaturated containing one double bond.
Polyunsaturated containing two or more double bonds.
Eicosanoid: (20-carbon) polyenoic fatty acids, comprise
the Prostanoids, leukotrienes (LTs), lipoxins (LXs).
Prostanoids include prostaglandins (PGs), prostacyclins
(PGIs), and thromboxanes (TXs).
Most Naturally Occurring Have cis Double Bonds.
If on the same side of the bond, it is cis-, as in oleic acid
if on opposite sides, it is trans-, as in “elaidic acid,”
the trans isomer of oleic acid.

Geometric isomerism of Δ9, 18:1

fatty acids (oleic and Elaidic
acids).
STEROIDS PLAY MANY PHYSIOLOGICALLY IMPORTANT ROLES

Cholesterol is probably the best known steroid because of

its association with atherosclerosis.

However, biochemically it is also of significance because it

is the precursor of a large number of equally important
steroids that include
=Bile acids,
=Adrenocortical hormones,
=Sex hormones,
=D vitamins, cardiac glycosides, sitosterols of the plant
kingdom, and some alkaloids.
 Cholesterol Is a Significant Constituent of Many Tissues
Cholesterol is widely distributed in all cells of the body but
particularly in nervous tissue.
It is a major constituent of the plasma membrane and of plasma
lipoproteins.
It is often found as cholesteryl ester, where the hydroxyl
group on position 3 is esterified with a long-chain fatty acid.
It occurs in animals but not in plants.

HO
 Cholesterol is important in many ways:

For the synthesis of bile salts that are important in

lipid digestion and absorption.
For the synthesis of steroid hormones that are
biologically important like the sex hormones estrogen
and progesterone.
For the synthesis of vitamin D3
As a structural material in biological membranes.
As a component of lipoproteins as transport forms of
lipid based energy.
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Metabolism of dietary lipids
Digestion, and Absorption
 1 Processing In Stomach
st

In infants :
 Digestion begins in stomach catalyzed by the acid-
stable lingual lipase from glands at the back of the
tongue.
 It digests short or medium chain fatty acids such as
those found in milk fat
 However, the rate of hydrolysis is slow because the
lipid is not yet emulsified.
 These TAG molecules can be degraded by a separate
gastric acid lipase. This enzyme is active only at neutral PH
Therefore, of little use in the adult stomach where, the ph is
low, but is active In neonates whose stomach PH is nearer to
neutrality and whose diets contain mainly milk lipids.

 Overall in adults dietary lipids are not digested to any

extent in the mouth or the stomach but rather progress more

or less intact to the small intestine.

 2nd Emulsification in the small intestine
 Emulsification of dietary lipids in the small intestine
(duodenum)

 Emulsification increases the surface area of the

hydrophobic lipid droplets so that the digestive act
effectively.

 Emulsification is accomplished by two mechanisms

namely:
 The use of the detergent ( amphipathic ) surface
active properties of bile salts synthesized in the liver
and stored in the gall bladder and
 3rd Degradation by pancreatic enzymes
By Several Pancreatic Lipases,
 TAG hydrolyzed by Pancreatic Lipase at 1 and 3 C.
 Into two types of product: free fatty acids (FFAs) and
2-monoacylglycerols.

 The drug orlistat inhibits lipases and thereby prevents

uptake of many fats as a means of treating obesity in
conjunction with a low-calorie diet.

 Phospholipids are hydrolyzed by phospholipases,

which remove a fatty acid from carbon 2, and which
may be further processed or absorbed.
Overview of lipid digestion
 Hormonal Control of lipid digestion

Cholecystokinin
 site of release : from jejunum and lower duodenum
In response to lipids and partially digested proteins
entering small intestines.

 Actions ;
-Gall bladder-- contraction and release of bile
- Pancreatic cells -- release of digestive enzymes
- Decreases Gastric motility
Secretin
 site –released from other intestinal cells

- In response to low pH of chyme

 Actions;

- Release of a watery solution by pancreas

and liver high in bicarbonate --appropriate

pH for action of pancreatic enzymes.

Hormonal control of lipid digestion
 6th Lipid malabsorption (Steatorrhea):

 Is the loss of > 6g of fat together with fat

soluble vitamins (A,D,E,K) and essential fatty
acids.
 Causes of steatorrea:
 Defective Digestion due to deficiency of pancreatic
lipase
as a result of chronic pancreatits,obstruction of
pancreatic
duct by tumors .
Fecal fat is mostly undigested TAGs.
Possible causes of steatorrea
 Fate Of Free-fatty Acids
 Directly enter adjacent muscle cells or adipocytes.
 Alternatively, free fatty acids may be transported by
albumin ,until they are taken by cells.
 Most cells can oxidize fatty acids to obtain energy.
 However, the brain and other nervous tissues,

erythrocytes and the adrenal medulla Can not

 Adipocytes can also re-esterify free-fatty acids to
produce triacylglycerols molecules, which are stored
until the fatty acids are needed .
 Fate Of Glycerol
 Glycerol to glycerol-3- phosphate by the liver for
Glycolysis.
 Fate of Chylomicron remnants are taken up by the liver
where , they are hydrolyzed to their component parts due to
Apolipoprotein E
 Deficiency of Apolipoprotein E, leads to familial
type
III hyperlipoproteinemia which leads to Defective
removal of Chylomicron -remnants from the plasma,
 Short answer Questions
1.Triacylglycerols are
A. soluble in water B. partially soluble in water
C. Insoluble in water D. None
2.What are the components of a triacylglycerols?
3.What are the sources of fatty acids?
4.At which position is the fatty acid attached to the cholesterol ring,?
5.which   fatty acid should have the least melting point out of the followings?
Steric acid[0db] Arachidonic acid[4db], Timnodonic acid  [5db]          
6.Name a fatty acid with 18 carbon atoms and a single double bond in trans configuration          
                                    
.7. Number carbons of cholesterol is -------------------
 Solution
1.Insoluble in water
2.Glycerol+3fatty acid
3.Diet, Endogenous synthesis and derived from adipose tissue by adipolysis.
4.3rd position
5.Timnodonic acid, since it has five double bonds; more the degree of
unsaturation, lesser is the melting point.
6.Elaidic acid
7.27C