Chapter 15 Lipids

15.1 Lipids

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Lipids
Lipids are Biomolecules that contain fatty acids or a steroid nucleus. Soluble in organic solvents but not in water. Named for the Greek word lipos, which means fat. Extracted from cells using organic solvents.

Types of Lipids
The types of lipids containing fatty acids are Waxes. Fats and oils (triacylglycerols). Glycerophospholipids. Prostaglandins. Not steroids, as they do not contain fatty acids.

Structures of Lipids

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15.2 Fatty Acids

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Fatty Acids
Fatty acids Are long-chain carboxylic acids. Typically contain 12-18 carbon atoms. Are insoluble in water. Can be saturated or unsaturated.

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Fatty Acid Formulas

The formulas for fatty acids are written as Condensed formulas. Line-bond formulas. For example caprylic acid with 8 carbon atoms. CH3(CH2)6COOH
CH3CH2CH2CH2CH2CH2CH2COOH
O OH
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Saturated Fatty Acids

Saturated fatty acids have Single CC bonds. Molecules that fit closely together in a regular pattern. Strong attractions between fatty acid chains. High melting points that make them solids at room temperature.

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Some Saturated Fatty Acids

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Unsaturated Fatty Acids

Unsaturated fatty acids Have one or more double C=C bond Typically contain cis double bonds.

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Properties of Unsaturated Fatty Acids

Unsaturated fatty acids Have kinks in the fatty acid chains. Do not pack closely. Have few attractions between chains. Have low melting points. Are liquids at room temperature.
kinks in chain

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Unsaturated Fatty Acids

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Comparing Melting Points of Some Fatty Acids

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Learning Check
Assign the melting points of 17C, 13C, and 69C to the correct fatty acid. Explain. stearic acid (18 C) saturated oleic acid (18 C) one double bond linoleic acid (18 C) two double bonds

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Solution
Stearic acid is saturated and would have a higher melting point than the unsaturated fatty acids. Because linoleic has two double bonds, it would have a lower mp than oleic acid, which has one double bond. stearic acid mp 69C saturated oleic acid mp 13C linoleic acid mp -17C most unsaturated

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Prostaglandins
Prostaglandins have 20 carbon atoms in their fatty acid chains. An OH on carbon 11 and 15. A trans double bond at carbon 13.

C 11 C 13 C 15
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Prostaglandins in the Body

Prostaglandins are Produced by injured tissues. Involved in pain, fever, and inflammation. Not produced when anti-inflammatory drugs such as aspirin inhibit their synthesis.
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Omega-6 and Omega 3- Fatty Acids

Fatty acids In vegetable oils are mostly omega-6 with the first C=C at C6. linoleic acid
CH3(CH2)4CH=CHCH2CH=CH(CH2)7COOH
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In fish oils are mostly omega-3 with the first C=C at C3. linolenic acid
CH3CH2(CH=CHCH2)3(CH2)6COOH
3
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Some Omega-6 and Omega-3 Fatty Acids

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Learning Check
Write a fatty acid with 10 carbon atoms that is: A. saturated B. monounsaturated omega-3 C. monounsaturated omega-6

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Solution
Write a fatty acid with 10 carbon atoms that is: A. saturated
CH3CH2CH2CH2CH2CH2CH2CH2CH2COOH

B. monounsaturated omega-3
CH3CH2CH=CHCH2CH2CH2CH2CH2COOH

C. monounsaturated omega-6
CH3CH2CH2CH2CH2CH=CHCH2CH2COOH
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Waxes, Fats, and Oils

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Waxes
Waxes are Esters of saturated fatty acids and long-chain alcohols. Coatings that prevent loss of water by leaves of plants.
TABLE 17.2

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Fats and Oils: Triacylglycerols

Fats and oils are Also called triacylglycerols. Esters of glycerol. Produced by esterification. Formed when the hydroxyl groups of glycerol react with the carboxyl groups of fatty acids.

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Triacylglycerols
In a triacylglycerol, Glycerol forms ester bonds with three fatty acids.

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Formation of a Triacylglycerol
glycerol + three fatty acids
O CH2 CH CH2 OH OH + OH HO C O HO C O HO C (CH2)14CH3 (CH2)14CH3

triacylglycerol

O (CH2)14CH3 (CH2)14CH3 + 3H2O

(CH2)14CH3 CH2 O C

O CH O C O CH2 O C (CH2)14CH3
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Olive Oil
Olive oil Contains a high percentage of oleic acid, which is a monounsaturated fatty acid with one cis double bond.

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Learning Check
What are the fatty acids in the following triacylglycerol?
O CH2 CH CH2 O O O C O C (CH2)7CH CH(CH2)7CH3 O C (CH2)12CH3 (CH2)16CH3

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Solution
O CH2 CH CH2 O O O C O C (CH2)7CH CH(CH2)7CH3 O C (CH2)12CH3 (CH2)16CH3

Stearic acid

Oleic acid

Myristic acid

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Melting Points of Fats and Oils

A triacylglycerol that is a fat Is solid at room temperature. Is prevalent in meats, whole milk, butter, and cheese.

A triacylglycerol that is an oil Is liquid at room temperature. Is prevalent in plants such as olive and safflower.

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Oils with Unsaturated Fatty Acids

Oils

Have more unsaturated fats. Have cis double bonds that cause kinks in the fatty acid chains. Cannot pack triacylglycerol molecules as close together as in fats. Have lower melting points than saturated fats. Are liquids at room temperature.

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Diagram of Triacylglycerol with Unsaturated Fatty Acids

Unsaturated fatty acid chains have kinks that do not allow close packing.
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Saturated and Unsaturated Fatty Acids In Fats and Oils

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Chemical Properties of Triacylglycerols

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Chemical Properties of Triacylglycerols

The chemical reactions of triacylglycerols are similar to those of alkenes and esters. In hydrogenation, double bonds in unsaturated fatty acids react with H2 in the presence of a Ni or Pt catalyst. In hydrolysis, ester bonds are split by water in the presence of an acid, a base, or an enzyme.

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Hydrogenation of Oils
The hydrogenation of oils Adds hydrogen (H2) to the carbon atoms of double bonds. Converts double bonds to single bonds. Increases the melting point. Produces solids such as margarine and shortening.

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Hydrogenation
O CH2 CH CH2 O O O C O C (CH2)5CH CH(CH2)7CH3 O C (CH2)5CH CH(CH2)7CH3 CH2 (CH2)5CH CH(CH2)7CH3

Ni + 3H2
O O O O C O (CH2)14CH3

glyceryl tripalmitoleate (tripalmitolean)

CH CH2

C (CH2)14CH3 O C (CH2)14CH3
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glyceryl tripalmitate (tripalmitin)

Learning Check
What product(s) is obtained from the complete hydrogenation of glyceryl trioleate?

1. Glycerol and 3 oleic acids 2. Glyceryltristearate 3. Glycerol and 3 stearic acids

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Solution
What product(s) is obtained from the complete hydrogenation of glyceryl trioleate? 2. Glyceryltristearate

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Olestra, A Fat Substitute

Olestra is Used in foods as an artificial fat. Sucrose linked by ester bonds to several long-chain fatty chains. Not broken down in the intestinal tract.

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Cis and Trans Fatty Acids

Unsaturated fatty acids can be Cis with bulky groups on same side of C=C. CH3 (CH2)5 (CH2)7 COOH cis C=C

Trans have bulky groups on opposite sides of C=C. CH3 (CH2)5 H

C=C
H (CH2)7 COOH

trans

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Trans Fatty Acids and Hydrogenation

Trans fatty acids

Are formed during hydrogenation when cis double bonds are converted to trans double bonds.
In the body behave like saturated fatty acids.

Are estimated to make up 2-4% of our total Calories.

Are reported in several studies reported to raise LDL-cholesterol and lower HDL-cholesterol.

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Learning Check
(1) True or (2) False A. There are more unsaturated fats in vegetable oils.

B. Vegetable oils have higher melting points than fats.

C. Hydrogenation of oils converts some cis-double bonds to trans- double bonds.

D. Animal fats have more saturated fats.

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Solution
(1) True or (2) False A. T There are more unsaturated fats in vegetable oils. B. F Vegetable oils have higher melting points than fats. C. T Hydrogenation of oils converts some cis-double bonds to trans- double bonds. D. T Animal fats have more saturated fats.

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Hydrolysis
In hydrolysis, Triacylglycerols split into glycerol and three fatty acids. An acid or enzyme catalyst is required.
O CH2 CH CH2 O O O C O (CH2)14CH3 H+ CH2 OH CH OH

C (CH2)14CH3 +3H2O O C (CH2)14CH3

+ 3 HO C

(CH2)14CH3

CH2 OH
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Saponification and Soap

Saponification Is the reaction of a fat with a strong base. Splits triacylglycerols into glycerol and the salts of fatty acids. Is the process of forming soaps (salts of fatty acids). With KOH gives softer soaps.

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Saponification
O CH2 O C O CH O C O CH2 O C (CH2)14CH3 (CH2)14CH3 + 3NaOH (CH2)14CH3

CH2 OH CH OH

+ 3 Na+ -O C (CH2)14CH3 soap CH2 OH

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Learning Check
What products are obtained from the complete hydrolysis of glyceryl trioleate? 1. Glycerol and 3 oleic acids 2. Glyceryl tristearate 3. Glycerol and 3 stearic acids

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Solution
What products are obtained from the complete hydrolysis of glyceryl trioleate? 1. Glycerol and 3 oleic acids

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Learning Check
Write the product of the following reaction.

O CH2 CH CH2 O C O O O (CH2)5CH CH(CH2)7CH3 CH(CH2)7CH3 + 3 H2 CH(CH2)7CH3 Ni

C (CH2)5CH O C (CH2)5CH

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Solution
O CH2 CH CH2 O O O C O (CH2)14CH3

C (CH2)14CH3 O C (CH2)14CH3

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Glycerophospholipids
Glycerophospholipids are The most abundant lipids in cell membranes. Composed of glycerol, two fatty acids, phosphate and an amino alcohol.

Fatty acid Glycerol

Fatty acid

PO4

Amino alcohol
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Glycerophospholipids Are Polar

A glycerophospholipid has Two nonpolar fatty acid chains. A phosphate group and a polar amino alcohol. CH3 + + HOCH2CH2NCH3 HOCH2CH2NH3 choline CH3 ethanolamine
+

NH3 HOCH2CHCOO
serine

Amino alcohols
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Structure and Polarity of A Glycerophospholipid

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Lecithin and Cephalin

Lecithin and cephalin are glycerophospholipids Abundant in brain and nerve tissues. Found in egg yolk, wheat germ, and yeast.

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Learning Check
Identify each as a A. fatty acid C. amino alcohol B. triacylglycerol D. glycerophospholipid

1. glyceryl trioleate 2. cephalin 3. choline 4. palmitic acid

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Solution
Identify each as a A. fatty acid C. amino alcohol B. triacylglycerol D. glycerophospholipid

1. glyceryl trioleate 2. cephalin 3. choline 4. palmitic acid

B. triacylglycerol D. glycerophospholipid C. amino alcohol A. fatty acid

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Learning Check
Identify the components and type of glycerophospholipid O CH2O C (CH2)16 CH3 O CH2O C (CH2)16 CH3
+

O NH3 CH2O P O CH2CHCOO O58

Solution
Identify the components and type of glycerophospholipid O CH2O C (CH2)16 CH3 O CH2O C (CH2)16 CH3
+

2 stearic acids

O NH3 CH2O P O CH2CHCOO serine Ophosphate amino alcohol

type = cephalin

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Sphingolipids

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Sphingolipids
Sphingolipids Are similar to phospholipids. Contain sphingosine (a long-chain amino alcohol), a fatty acid, phosphate, and a small amino alcohol. Have polar and nonpolar regions.
fatty acid

sphingosine amino alcohol

PO4

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Sphingosine
Sphingosine is a long-chain unsaturated amino alcohol.
CH3(CH2)12 CH=CHCHOH CHNH2 CH2OH sphingosine
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Sphingolipids
In sphingomyelin, a sphingolipid found in nerve cells There is an amide bond between a fatty acid and sphingosine, an 18-carbon alcohol.

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Glycosphingolipids
Glycosphingolipids contain monosaccharides bonded to the OH of sphingosine by a glycosidic bond.

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Glycosphingolipids and Cerebrosides

Glycosphingolipids Are sphingolipids that contain monosaccharides. Can be a cerebroside with galactose.

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Gangliosides
Gangliosides Are similar to cerebrosides, but contain two or more monosaccharides. Are important in neurons. Act as receptor for hormones and viruses. Can accumulate and cause genetic diseases.

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Gangliosides
GM2 is a ganglioside That accumulates in Tay-Sachs disease.

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Lipid Diseases (Lipidoses)

In many lipid diseases, the deficiency of an enzyme causes the accumulation of glycolipids.
TABLE 17.3

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Learning Check
Identify each as a 1) Fatty acid 2) Triacylglycerol 3) Amino alcohol 4) Glycerophospholipid 5) Glycosphingolipid A. Glyceryl trioleate B. Cephalin C. Choline D. Galactocerebroside E. Palmitic acid

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Solution
A. Glyceryl trioleate B. Cephalin C. Choline D. Galactocerebroside E. Palmitic acid 2) Triacylglycerol 4) Glycerophospholipid 3) Amino alcohol 5) Glycosphingolipid 1) Fatty acid

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Steroids: Cholesterol, Bile Salts, and Steroid Hormones

CH3 CH3 CH3 CH3 CH3

HO
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Steroid Nucleus
A steroid nucleus consists of

3 cyclohexane rings. 1 cyclopentane ring. No fatty acids.

steroid nucleus

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Cholesterol
Cholesterol Is the most abundant steroid in the body. Has methyl CH3- groups, alkyl chain, and -OH attached to the steroid nucleus.
CH3 CH3 CH3 CH3 CH3

HO
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Cholesterol in the Body

Cholesterol in the body Is obtained from meats, milk, and eggs. Is synthesized in the liver. Is needed for cell membranes, brain and nerve tissue, steroid hormones, and Vitamin D. Clogs arteries when high levels form plaque.
A normal, open artery.

An artery clogged by cholesterol plaque

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Cholesterol in Foods
Cholesterol is Synthesized in the liver. Obtained from foods. Considered elevated if plasma cholesterol exceeds 200 mg/dL.
TABLE 17.4

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Learning Check
Match the components of the cholesterol molecule with the following: ___ carbon chain ___hydroxyl group ___ steroid nucleus ___methyl group
D

CH3 CH3

CH3 CH3

CH3
A C

HO

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Solution
Match the components of the cholesterol molecule with the following: D carbon chain A hydroxyl group C steroid nucleus B methyl group
D

CH3 CH3

CH3 CH3

CH3
A C

HO

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Bile Salts
Bile salts

Are synthesized in the liver from cholesterol.

Are stored in the gallbladder. Are secreted into the small intestine. Have a polar and a nonpolar region Mix with fats to break them part. Emulsify fat particles to provide large surface area.

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Bile Salts
cholic acid, a bile acid CH3 OH CH3 CH3 O C N H glycine, an amino acid CH2

COO- Na+

Polar region

HO
Nonpolar region

OH

sodium glycocholate, a bile salt

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Lipoproteins
Lipoproteins Combine lipids with proteins and phospholipids. Are soluble in water because the surface consists of polar lipids.

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Types of Lipoproteins
Lipoproteins Differ in density, composition, and function. Include low-density lipoprotein (LDLs) and highdensity lipoprotein (HDLs).
TABLE 17.5

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Transport of Lipoproteins in the Body

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Steroid Hormones
Steroid hormones Are chemical messengers in cells. Are produced from cholesterol. Include sex hormones such as androgens (testosterone) in males and estrogens (estradiol) in females.

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Adrenal Corticosteroids
Adrenal corticosteroids are steroid hormones that

Are produced by the adrenal glands located on the top of each kidney. Include aldosterone, which regulates electrolytes and water balance by the kidneys. Include cortisone, a glucocorticoid, which increases blood glucose level and stimulates the synthesis of glycogen in the liver.

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Adrenal Corticosteroids

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Anabolic Steroids
Anabolic steroids Are derivatives of testosterone. Are used illegally to increase muscle mass. Have side effects including fluid retention, hair growth, sleep disturbance, and liver damage.

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Learning Check
Identify each as a 1. fatty acid 2. steroid 3. triacylglycerol 4. phospholipid 5. sphingolipid A. cholesterol B. glycerol, 2 fatty acids, phosphate, and choline C. glyceryl tristearate D. sphingosine, fatty acid, phosphate, and choline E. estradiol F. bile salts G. lipids in plasma membranes
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Solution
A. B. C. D. E. F. G. cholesterol 2 steroid glycerol, 2 fatty acids, phosphate, and choline 4 phospholipid glyceryl tristearate 3 triacylglycerol sphingosine, fatty acid, phosphate, and choline 5 sphingolipid estradiol 2 steroid bile salts 2 steroid lipids in plasma membranes 4 phospholipid, 5 sphingolipid

.
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Cell Membranes

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Cell Membranes
Cell membranes Separate cellular contents from the external environment. Consist of a lipid bilayer made of two rows of phospholipids. Have an inner portion made of the nonpolar tails of phospholipids with the polar heads at the outer and inner surfaces.

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Fluid Mosaic Model of Cell Membranes

The lipid bilayer Contains proteins, carbohydrates, and cholesterol. Has unsaturated fatty acids that make cell membranes fluid-like rather than rigid. Has proteins and carbohydrates on the surface that communicate with hormones and neurotransmitters.

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Fluid Mosaic Model

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Transport Through Cell Membranes

The transport of substances through cell Membranes involves Diffusion (passive transport), which moves particles from a higher to a lower concentration.

Facilitated transport, which uses protein channels to increase the rate of diffusion.
Active transport, which moves ions against a concentration gradient.

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Transport Pathways Through Cell Membranes

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Learning Check
The transport of particles across a cell membrane from high concentration to low concentration is called 1. Facilitated transport 2. Diffusion 3. Active transport

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Solution
The transport of particles across a cell membrane from high concentration to low concentration is called 2. Diffusion

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