Chemistry of biomolecules

Lecturer 6
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 Chemistry of Lipids
1. Introduction.
2. Classification of lipids.
A. Simple lipids
B. Compound lipids
C. Derived lipids
Fatty alcohol
Fatty acids
3. Chemical reactions of lipids
4. Rancidity
5. Analysis and Identification of fats and oils (Fats
Constants) 2
 Introduction:
 Lipids are a heterogenous group of organic compounds formed mainly
from alcohol and fatty acids combined together by ester linkage.
 Lipids are insoluble in water, but soluble in fat or organic solvents
(ether, chloroform, benzene, acetone, etc.).
 Lipids include fats, oils, waxes and related compounds. They are
widely distributed in nature both in plants and or in animals.

O
H2O O
R CH2 OH + HO C R
Esterase (lipase)
R CH2 O C R
Fatty alcohol Fatty acid ester (lipid)

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 Lipids include fats, oils, terpenoids,
phosphatides, waxes and related compounds.
They are widely distributed in nature both in
plants and or in animals.
 Examples:-

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 C H 2 -O -C O -R OH

C H -O -C O -R
OH
C H -O -C O -R

F a t o r O il M e ntho l V ita m in A
(trig lyc e rid e ) (T e rp e ne ) (T e rp e no id )

C H 2 -O -C O -R

C H -O -C O -R
O
+
C H 2 -O -P -O -C H 2 C H 2 N (C H 3 ) 2
- HO
O
L e c ithin C h o le ste ro l
(p ho sp h a tid e ) (ste ro id ) 5
 Importance of Lipids:

Lipids are important dietary

constituents, because:
 1. Render food more palatable ‫مستساغ‬.
 2. They have a high-energy value (20 - 25%
of the body needs) and they provide more
energy per gram than carbohydrates and
proteins but carbohydrates are the preferable
source of energy.

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 3- Supply the essential fatty acids that
cannot be synthesized in the body.
 4- Supply the body with fat-soluble vitamins
(A, D, E and K).
 5- They are important constituents of the
nervous tissues.

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 6- A stored lipid “depot ‫ مخزن‬fat” is stored in all
human cells. It is mainly triglycerides in nature
and acts as:

a) A store of energy.
b) A pad ‫بطانة‬for the internal organs to protect
them from outside shocks.
c) A subcutaneous thermal insulator against loss
of body heat (environmental heat changes).
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 7- Tissue fat “constant fat” is an essential
constituent of cell membrane and nervous
system. It is mainly phospholipids in nature
that are not affected by starvation ‫الجوع‬.

 8- Lipoproteins are important cellular

constituents that are present both in the
cellular and subcellular membranes.

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 9- Cholesterol enters in membrane structure
and is used for synthesis of adrenal cortical
hormones, sex hormones vitamin D3 and bile
acids.

 10- Understanding biochemistry of lipids

provides bases for dealing with diseases such
as obesity ‫السمنة‬, atherosclerosis, lipid-storage
diseases, essential fatty acid deficiency,
respiratory distress syndrome,.. etc.
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 ‫أهمية الدهون‪:‬‬ ‫‪‬‬

‫تعتبر الدهون من المكونات الغذائية الهامة‪ ،‬وذلك لألسباب التالية‪:‬‬ ‫‪‬‬

‫‪ .1‬يجعل الطعام أكثر قبوال‪.‬‬ ‫‪‬‬

‫‪ .2‬تحتوي على قيمة طاقة عالية (‪ %25 - 20‬من احتياجات الجسم) وتوفر طاقة لكل جرام أكثر من‬ ‫‪‬‬

‫الكربوهيدرات والبروتينات ولكن الكربوهيدرات هي المصدر المفضل للطاقة‪.‬‬

‫‪ .3‬إمداد الجسم باألحماض الدهنية األساسية التي ال يمكن تصنيعها‪.‬‬ ‫‪‬‬

‫‪ .4‬إمداد الجسم بالفيتامينات التي تذوب في الدهون (‪.)A، D، E، K‬‬ ‫‪‬‬

‫‪ 5.‬وهي مكونات هامة لألنسجة العصبية‪.‬‬ ‫‪‬‬

‫‪11‬‬
‫‪ . 6‬يتم تخزين الدهون المخزنة في جميع الخاليا البشرية‪ .‬وهو بشكل رئيسي ثالثي الجليسريد في الطبيعة‬ ‫‪‬‬

‫ويعمل على النحو التالي‪:‬‬

‫أ‪ .‬مخزن للطاقة‪.‬‬ ‫‪‬‬

‫ب‪ .‬وسادة لألعضاء الداخلية لحمايتها من الصدمات الخارجية‪.‬‬ ‫‪‬‬

‫ج‪ .‬عازل حراري تحت الجلد ضد فقدان حرارة الجسم (التغيرات الحرارية البيئية)‪.‬‬ ‫‪‬‬

‫‪ . 7‬دهون األنسجة "الدهون الثابتة" هي مكون أساسي لغشاء الخلية والجهاز العصبي‪ .‬وهي في األساس‬ ‫‪‬‬

‫فوسفوليبيدات في الطبيعة ال تتأثر بالجوع‪.‬‬

‫‪ . 8‬البروتينات الدهنية هي مكونات خلوية مهمة موجودة في األغشية الخلوية وتحت الخلوية‪.‬‬ ‫‪‬‬

‫‪ . 9‬يدخل الكوليسترول في بنية الغشاء ويستخدم في تصنيع هرمونات قشر الكظر الكظرية والهرمونات‬ ‫‪‬‬

‫الجنسية فيتامين د ‪ 3‬واألحماض الصفراوية‪.‬‬

‫‪ . 10‬إن فهم الكيمياء الحيوية للدهون يوفر أسس التعامل مع أمراض مثل السمنة‪ ،‬وتصلب الشرايين‪،‬‬ ‫‪‬‬

‫وأمراض تخزين الدهون‪ ،‬ونقص األحماض الدهنية األساسية‪ ،‬ومتالزمة الضائقة التنفسية‪ .. ،‬الخ‪.‬‬

‫‪12‬‬
 CLASSIFICATION OF LIPIDS

Simple lipid Complex lipid Derived lipids

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 SIMPLE LIPIDS
They are esters of FA with various alcohols

D/U the type of alcohols these are subclassified as

Neutral fats or oils Waxes

Alcohol is Alcohol is other

GLYCEROL than glycerol

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 NEUTRAL FATS OR OILS

Esters of FA with alcohol

GLYCEROL

Uncharged

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1. Simple lipids:
They are esters of fatty acids with fatty alcohol. They
are called neutral lipids and can be classified into:

Neutral fats: Tri-esters of fatty acids with glycerol
O
or triglycerides. CH2 O C R
O
CH O C R
O
CH2 O C R

Ester (Lipid) R = Long Chain FA

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17
WAXES

Esters of FA
with higher
molecular EXAMPLES
weight  Lanolin
 Beeswax
monohydric  Whale sperm
alcohols oil

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 Waxes:
 Esters of fatty acids with long-chain alcohols other
than glycerol that are mostly monohydric.
 True waxes are esters of cetyl alcohol (C16H33OH)
or a higher alcohol.
 Cholesterol esters with any fatty acid are waxes.
 Esters of vitamin A and vitamin D with fatty acid,
e.g., palmitic or stearic acid are waxes, too.

O
R-(CH2)n O C (CH2)n-R
Ester (Lipid) R = Long Chain FA and FAl
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 COMPLEX LIPIDS
These are esters of FA with alcohol containing additional
[prosthetic] groups.

Subclassified according to the type of prosthetic group

Phospholipids Glycolipids Lipoproteins

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2. Complex lipids:
They are lipids characterized by the
presence of a non-fat product (other than
fatty acids and alcohol) in the molecule.
 According to the nature of that non-fat
moiety they include the following types:

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A. Phospholipids (phosphatides): Compound
lipids containing fatty acids, alcohol,
phosphoric acid and often a nitrogenous base.

B. Glycolipids: Compound lipids containing fatty

acids, carbohydrate and sphingosine, but not
phosphoric acid nor glycerol.

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C. Lipoproteins: Compound lipids composed of a
lipid part associating by secondary bonds with
proteins as plasma and membranous
lipoproteins.
D. Other compound lipids: include:
• Sulfolipids: containing sulfur.
• Aminolipids: containing amino acids.

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A- PHOSPHOLIPIDS

FA + ALCOHOL + PHOSPHORIC
ACID

They
frequently
have
nitrogen
containing
bases

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 PHOSPHOLIPIDS

Phospholipids
may be
classified on
the basis of
the type of
alcohol
present

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A. Glycerophospholipids B. Spingophospholipids

ALCOHOL IS GLYCEROL ALCOHOL IS SPINGOSINE

 Phosphatidylcholine
 Phosphatidyl
ethanolamine
 Phosphatidyl serine  Spingomyelins
 Phosphatidyl inositol
 Plasmalogens
 Cardiolipins

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27
SPHINGOPHOSPHOLIPID

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 Functions of phospholipids

 In association with proteins phospholipids form the structural

components of membranes and regulate membrane permeability.
 Phospholipids participate in the absorption of fat from the
intestine.
 Essential for the synthesis of different lipoproteins, and thus
participate in the transport of lipids.
 Accumulation of fat in liver (fatty liver) can be prevented by
phospholipids, hence they are regarded as lipotropic factors.
 Arachidonic acid, an unsaturated fatty acid liberated from
phospholipids, serves as a precursor for the synthesis of
eicosanoids (prostaglandins, prostacyclins, thromboxanes etc.).

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 ‫باالشتراك مع البروتينات‪ ،‬تشكل الدهون الفوسفاتية المكونات الهيكلية لألغشية وتنظم‬ ‫•‬
‫نفاذية الغشاء‪.‬‬
‫تشارك الفوسفوليبيدات في امتصاص الدهون من األمعاء‪.‬‬ ‫•‬
‫ضروري لتخليق البروتينات الدهنية المختلفة‪ ،‬وبالتالي المشاركة في نقل الدهون‪.‬‬ ‫•‬
‫يمكن منع تراكم الدهون في الكبد (الكبد الدهني) عن طريق الدهون الفوسفاتية‪ ،‬وبالتالي‬ ‫•‬
‫تعتبر من العوامل المؤثرة على الدهون‪.‬‬
‫حمض األراكيدونيك‪ ،‬وهو حمض دهني غير مشبع متحرر من الدهون الفوسفاتية‪،‬‬ ‫•‬
‫يعمل بمثابة مقدمة لتخليق اإليكوسانويدات (البروستاجالندين‪ ،‬البروستاسيكلين‪،‬‬ ‫•‬
‫الثرومبوكسان‪ ،‬إلخ)‪.‬‬

‫‪30‬‬
Functions of phospholipids

 Phospholipids participate in the reverse cholesterol transport

and thus help in the
removal of cholesterol from the body.

 Phospholipids act as surfactants (agent lowering surface

tension).

 Cephalins,an important group of phospholipids participatin

blood clotting.

 Phospholipids( phosphatidyl inositoal ) involved in signal

transmission across membranes.

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‫تش‪AAA‬ارك الفوس‪AAA‬فوليبيدات في النق‪AAA‬ل العكس‪AAA‬ي للكوليس‪AAA‬ترول وبالت‪AAA‬الي تس‪AAA‬اعد في إزال‪AAA‬ة‬ ‫•‬
‫الكولسترول من الجسم‪.‬‬
‫تعمل الدهون الفوسفاتية كمواد خافضة للتوتر السطحي (عامل يخفض التوتر السطحي)‪.‬‬ ‫•‬
‫السيفالينات‪ ،‬وهي مجموعة مهمة من الدهون الفوسفاتية التي تشارك في تخثر الدم‪.‬‬ ‫•‬
‫تشارك الفوسفوليبيدات (فوسفاتيديل إينوسيتوال) في نقل اإلشارات عبر األغشية‪.‬‬ ‫•‬

‫‪32‬‬
 B- GLYCOLIPIDS

FA + ALCOHOL[SPINGOSINE]
+CARBOHYDRATE WITH NITROGEN BASE

 They do not contain phosphate group

Example
Cerebrosides
Gangliosides

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 C- LIPOPROTEINS

Chylomicrons
Lipid with
Very low density lipoprotein
prosthetic (VLDL)
group Low density lipoprotein (LDL)
PROTEIN High density lipoprotein (HDL)

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 3- DERIVED LIPIDS

These are the derivatives obtained on the hydrolysis of group 1

and group 2 lipids which possess the characteristics of lipids.

Example

Vitamin A
Fatty acids Steroids Cholesterol
and D

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3. Derived Lipids:
 They are the hydrolysis products of
simple and compound lipids and/or
their derivatives that still possess the
general characteristics of lipids and
include:

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 Fatty acids, monoglycerides and aldehydes.
 Fatty alcohols including glycerol cetyl alcohol,
myricyl alcohol and sphingosine.
 Sterols, steroids and hormonal derivatives of
vitamin D.
 Eicosanoids (prostaglandins, leukotrienes and
thromboxanes).

Ketone bodies.

37
 Fatty alcohols

Glycerol:
 It is a trihydric alcohol (containing three
OH groups) and has the popular name
glycerin. It is synthesized in the body from
glucose. It has the following properties:

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1. Colorless viscous oily liquid with sweet taste.
2. Miscible with water, hygroscopic and immiscible
with fat-solvents.
3. On heating with sulfuric acid gives acrolein (acryl
aldehyde) that has a bad odor. This reaction is
used for detection of free glycerol or any
compound containing glycerol.

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 CH2 OH H2SO4 CHO
HO CH CH
heat, - 2 H2O
CH2 OH CH2
Glycerol Acrolein

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4. It combines with three molecules of nitric acid to
form trinitroglycerin that is used as explosive and
vasodilator.

CH2 OH HNO3 CH2 ONO2

HO CH O2NO CH
heat
CH2 OH CH2 ONO2
Glycerol Trinitroglycerine

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5. On esterification with fatty acids it gives:
• Monoglyceride (one fatty acid + glycerol).
• Diglycerides (two fatty acids + glycerol).
• Triglyceride (three fatty acids + glycerol).

6. It has a nutritive value by conversion into

glucose and enters in structure of
phospholipids.

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7. Uses of Glycerol:
A. Glycerol enters in pharmaceutical and cosmetic
preparations (hygroscopic).
B. Reduces brain edema ‫ االستسقاء‬in cerebrovascular
disease.

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C. Nitroglycerin (glyceryl trinitrate) is used as
vasodilator especially for the coronary arteries,
thus it is used in treatment of angina pectoris
‫الذبحة الصدرية‬. Also, enters in explosives
manufacturing.
D. Glycerol is used in treatment of glaucoma ‫المياة‬
‫( البيضاء‬increased intraocular pressure) due to its
ability to dehydrate the tissue from its water
content.

44
Chemistry of biomolecules

Lecturer 7
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