Structure & Function of

Biomolecule

LIPIDS & CELL

MEMBRANE

By

Dewi Yuliani

Chemistry Department
UIN Maulana Malik Ibrahim
Malang
 Point in this Chapter

1. Lipid overview
2. Fatty Acids
3. Triacylglycerol
4. Waxes
5. Membrane Lipid
6. Properties of membrane Lipid

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 • Biological Lipid are a chemically diverse group of compounds, the
common and defining feature of which is their insolubility in water.

• Unlike others macromolecules, lipids are not polymers.

• Lipid carry out multiple functions

– Storage energy – Fats and oils
– Lipid membrane – phospholipids and sterol
– Enzyme cofactor – vitamin K , vitamin E
– Electron carrier – ubiquinone, plastoquinone
– Hormone (signal) – arachidonic acid, prostaglandin
– Intracellular messagers – phospatidylinositol triphosphate
– Pigment – carotene, chlorophyll

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 Overview - Fatty Acids

• The simplest lipids are the fatty acids.

• Fatty acid are hydrocarbon derivate, carbon

chain with a methyl group at one end of the
molecule and a carboxyl group at the other
end.

• Fatty acids are carboxylic acids with

hydrocarbon chains ranging from 4 to 36
carbons long (C4 to C36).

• Fatty acids in biological system usually contain

an even number of carbon atoms, typically
between 14 and 24.

• The 16- and 18-carbon fatty acids are most

common.

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 Overview - Fatty Acids

• Fatty acids are ionized at physiological pH.

• Fatty acids are weak acid, with pKa value

averaging about 4.5, RCOOH = RCOO- + H+

• The charge on the carboxyl group make it

extremely hydrophilic, and the long hydrocarbon
tail are very hydrophobic

• So, fatty acids behave a typical amphipathic

substance when we attempt to dissolved the in
water.

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 Fatty Acids - Structure of ionized form

Rigid bend (~30°) in hydrocarbon chain of oleic acid/oleate ion due to presence of cis
double bond.

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Fatty Acids – Long Hydrocarbon
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 Fatty Acids – Branches and cycle structure
• Although the hydrocarbon chain are linear in most fatty acids, some fatty
acid (found primarily in bacteria) contain branches or even cycle structure.

Tuberculostearic

Lactobacillic

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 Fatty Acids - Systematic Nomenclature

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 Fatty Acids - Systematic Nomenclature
• The systematic name for a fatty acid is derived from the name of its parent
hydrocarbon with addition –oic for the final e.

• Example: C18 saturated fatty acid (Octadecanoic acid), the parent of

hydrocarbon is octadecane.

• If C18 fatty acid with one double bond is called octadecenoic acid, two
double bonds is called octadecadienoic acid, and three double bonds is
called octadecatrienoic acid.

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 Fatty Acids - Systematic Nomenclature
• Fatty acid C atom are numbered starting at the carboxyl terminus.

• Carbon atoms 2 and 3 are often refereed to as α and β, respectively.

• The methyl carbon atom at the distal end of the chain is called the ω-carbon
atom.

• The notation 18:0 denotes a C18 fatty acid with no double bond.

• The position of a double bond is represented by the symbol ∆ followed by a

superscript number.

• For example, cis-∆9 means that there is a cis double bond between carbon
atoms 9 and 10.

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 Fatty Acids - Saturated and Unsaturated

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 Fatty Acids – Polyunsaturated fatty acids (PUFA)

EPA = Eicosapentaenoic acid AA = Arachidonic acid DHA = Docosahexaenoic acid

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 Fatty Acids - Saturated and Unsaturated Properties
• The properties of fatty acid and of lipids derived from them are markedly
dependent on chain length and degree of saturation.

• Cis orientation has an important effect on molecular structure, for each cis
double bond insert a bend into the hydrocarbon chain.

• Keep in mind, however, the molecule as rigid structured, there is freedom

of rotation about each single bond in the hydrocarbon chain. Thus, many
configuration are possible.

• Melting point and solubility is influenced by saturated and unsaturated

properties (length and degree of saturation of hydrocarbon chain).

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 Fatty Acids – Melting Point of Fatty Acids

• Unsaturated fatty acid have lower melting points than saturated fatty
acid of the same length.

• For example, the melting point of stearic acid is 69.6°C, whereas that of
oleic acid is 13.4°C.

Stearic acid / n-octadecanoic acid / 18:0

Oleic acid / n-octadecenoic acid / 18:1(∆9)

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 Fatty Acids – Melting Point of Fatty Acids

• At room temp. (25°C), the saturated

fatty acids from 12:0 to 24:0 have a
waxy consistency, whereas
unsaturated fatty acids of theses
lengths are oily liquids.

• The difference in melting points is

due to different degrees of packing
of the acid molecules.

• The melting points of PUFA of the

C18 series are even lower.

• Short chain length and unsaturation

enhance the fluidity of fatty acids
and of their derivatives.

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 Fatty Acids – Packaging

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 Fatty Acids – Packaging (Explanation)
• In the fully saturated compounds, free rotation around each C-C bond gives the
hydrocarbon chain great flexibility; the most stable conformation is the fully
extended form, in which the steric hindrance of neighboring atoms is
minimized.

• These molecule can pack together tightly in nearly crystalline arrays, with atoms
all along their lengths in van der Waals contact with the atoms of neighboring
molecules.

• In unsaturated fatty acid, a cis double bond force a kink in the hydrocarbon
chain.

• Fatty acids with one or several such kinks cannot pack together as tightly as
fully saturated fatty acids, an their interactions with each other are therefore
weaker.

• Because it takes less thermal energy to disorder these poorly ordered arrays of
unsaturated fatty acids, they have markedly lower melting points than saturated
fatty acids of the same chain length.

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 Fatty Acids – Solubility

• The nonpolar hydrocarbon chain accounts for the poor solubility of fatty
acids in water.

• Lauric acid (12:0, Mr 200) has a solubility in water of 0.063 mg/g. It is much
less than that of glucose (Mr 180) which is 1.100 mg/g.

• The longer the fatty acyl chain and the fewer the double bonds, the lower is
the solubility in water.

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 Fatty Acids – Trans configuration
• Trans fatty acids are produced by fermentation in the rumen of dairy
animal and obtained from technological processing, ex. during
hydrogenation of fish or vegetable oils.

• Trans isomer are not found in natural vegetable oil, whereas they occur in
small quantities in animal fats (in milk fat human 2-8%, and from 2-5% in
beef).

• Trans fatty acids correlate with increased blood levels of LDL and decreased
HDL. It is generally recommended that one avoid large amounts of trans
fatty acids.

• French fries, dough-nuts, and cookies tend to be high in trans fatty acids.

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 Fatty Acids - Overview
• In vertebrates, free fatty acids circulate in the blood bound noncovalently to
a protein carrier, such as serum albumin.

• However, fatty acid are present in blood plasma mostly as carboxylic acid
derivatives such as esters or amides.

• Lacking the charge carboxylate group, these fatty acid derivatives are
generally even less soluble in water than are the free fatty acid.

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 Triacylglycerols - Overview

• Other name: triglycerides, fats, or neutral fats.

• The simplest lipids constructed from fatty acids with nonpolar properties

• It is composed of 3 fatty acids each in ester linkage with a single glycerol.

• Simple triacylglycerols, for example, are tristearin, tripalmitin, triolein.

• Most naturally occurring triacylglycerols are mixed; they contain two or

more different fatty acid.

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 Triacylglycerols - Overview

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 Triacylglycerols – Simple Structure

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 Triacylglycerols – Mixed Structure

① Palmitic acid, ② Oleic acid, ③ Linolenic acid

Mixed triacylglycerol: 1-palmitoyl, 2-oleoyl, - 3-lyinolenoyl glycerol

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 Triacylglycerols – Energy Storage

• Lipids are much more efficient stores than carbohydrate.

• Advantages to using triacylglycerol as stored fuels

– Carbon atoms are more reduced
– Triacylglycerols are hydrophobic and unhydrated.

• Storage of fatty acids in organism is largely in the form of triacylglycerols or

fats.

• Oily droplets in the aqueous cytosol of most eukaryotic cells serve as depots
of metabolic fuel.
– Vertebrates : adipocytes (fat cells)
– Plants : germinating seeds

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 Triacylglycerols – Energy Storage

(a)
Adipocytes in vertebrates

(b)
Cotyledon cell from a seed of the plant Arabidopsis

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 Triacylglycerols – Energy Storage – Adipocytes

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 Triacylglycerols – Insulation

• In some animals, triacylglycerols stored under the skin sever not

only as energy stores but as insulation against low temperature.

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 Triacylglycerols – In some Food

• Most natural fats are complex

mixtures of simple and mixed
triacylglycerols, with a variety of
fatty acids differing in chain length
and degree of saturation.

• Vegetable oils (as corn and olive

oil) are composed unsaturated
fatty acid, liquid in room temp.

• Animal fats are composed by

saturated fatty acids, greasy solid
in room temp.

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 Triacylglycerols – In some Food

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 Waxes – Overview

• Biological waxes are esters of long-chain (C14 to C36) of fatty acids

with long-chain (C16 to C30) alcohols.

• Melting points (60-100°C) are generally higher than those of

triacylglycerols.

• In plankton, it is fuel storage while in vertebrates, it is used for

protecting hair and skin, a lubricant, and water-repellent.

• Biology waxes also find a variety of applications in the

pharmaceutical, cosmetic, and other industries

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 Waxes – Overview
Triacontanoylpalmitate, the major component of beeswax, is an ester of
palmitic acid with the alcohol triacontanol.

Lucas Busta
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 Type of Lipids in the Membrane Cell - Overview

• The central architectural feature of biological membranes is a double

layers of lipids, which act as a barrier to the passage of polar
molecules and ions.

• Membrane lipids are amphipathic.

• Their hydrophobic interactions with each other and their

hydrophilic interactions with water direct their packing into sheets
called membrane bilayers.

• In this sub section we describe five general types of membrane

lipids.

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 Type of Lipids in the Membrane Cell - Overview

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 Type of Lipids in the Membrane Cell

• Glycerophospolipids • Archaebacterial tetraether Lipid

• Galactolipids and Sulfolipids in • Spingolipids

Chloroplast
• Sterols

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 (1) Glycerophospholipid/Phosphoglyceride

The backbone of phospholipid

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 (2) Galactolipids and Sulfolipids

• This lipid is predominate in plant cells.

• Galactolipids is formed by one or two

galactose residues are connected by a
glycosidic linkage.

• Galactolipids are localized in the

thylakoid membrane of chloroplast and
make up 70-80% of the total membrane
lipids of a vascular plant.

• They are probably the most abundant

membrane lipids in the biosphere.

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 (2) Galactolipid and Sulfolipid

• Plant membrane also contain sulfolipids, in which a sulfonated glucose

residue is joined to a diacylglycerol in glycosidic linkage.

• In sulfolipids, the sulfonate on the head group bears a fixed negative

charge like that of the phosphate group in phospholipid

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 (3) Archaebacteria “extremophile” lipids

• The membrane of archaea differ in

composition from those of eukaryotes
or bacteria.

• The archaebacteria  bacteria live in

ecological niches with extreme
conditions – high temp., low pH, high
ionic strength.

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 (3) Archaebacteria “extremophile” lipids

Glycerol dialkyl glycerol tetraethers (GDGTs)

• Long-chain (C32) branched hydrocarbon and the length is twice of phospholipid and
sphingolipids.

• (1) The linkages are through ether rather than ester bonds, (2) the alkyl chains are
branched rather than linear, (3) the stereochemistry of the central glycerol is inverted.

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 (4) Sphingolipids are derivate of sphingosine

• Ceramide : structural parent of all sphingolipids.

• Sphingolipids are composed of one molecule of the long-chain amino

alcohol sphingosine (4-sphingenine) or one of its derivatives, one
molecule of long-chain fatty acid, and a polar head group is joined by a
glycosidic linkage in some cases and by a phosphodiester in other.

• Three subclasses of sphingolipids

– Sphingomyelins
– Glycosphingolipids
– Gangliosides

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 (4) Sphingolipids are derivate of sphingosine

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 (5) Sterols have four fused carbon rings

• Sterols are structural lipids

present in the membranes of most
eukaryotic cells.

• Steroid nucleus: 4 fused rings,

three with six carbons and on with
five.

• Steroid nucleus is almost and is

relatively rigid; the fused rings do
not allow rotation about C-C
bonds.

• For example, cholesterol

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 Lipid in the Membrane Cell
• Lipids are quite small molecule that have tendency to associate through non
covalent force.

• From a biological point of view, the most important of these consequence is

the tendency of lipids to form micelles and membrane bilayer.

• In aqueous environment, they tend to clump together for two fundamental

reason.
– As non polar group in protein associate via an entropy-driven hydrophobic
effect, so do the nonpolar tails of lipid.
– Stabilizing force come from the van der Waals interaction between the
hydrocarbon regions of the molecules.

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 Cell Membrane
• A membrane lipid is an amphipathic molecule containing a hydrophilic and
a hydrophobic moiety.

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 Cell Membrane – Micelle & Lipid Bilayer

• Membrane formation is a consequence

of the amphipathic nature of the
molecules.

• One way is to form a globular structure

called a micelle. Alternative is to form
lipid bilayer.

• The favored structure for most

phospholipid and glycolipid in
aqueous media is a bimolecular sheet
rather than micelle.

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 Cell Membrane – Micelle & Lipid Bilayer
• Two fatty acid chains of phospholipid or a glycolipid are too bulky to
fit into the interior micelle.

• The formation of bilayer instead of micelles by phospholipids is of

critical biological importance.

• A micelle is a limited structure, usually less than 20 nm, while a

biomolecular sheet can extended to macroscopic dimension, 106 nm
(mm).

• Lipid bilayers form spontaneously by a self-assembly process. It is

growth rapidly and spontaneously in water.

• Hydrophobic interaction are the major driving force for the formation
of lipid bilayers.

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 Cell Membrane – Lipid Bilayer

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 Cell Membrane – Lipid Bilayer

• Van der Waals interactive force between the hydrocarbon tails favor close
packing of the tails.

• Electrostatic and hydrogen bonding attractions between the polar head

groups and water molecules.

• These hydrophobic interaction have three significant biological

consequence:
– Lipid bilayers have an inherent tendency to be extensive.
– Lipid bilayers will tend to close on themselves so that there are no edges with
exposed hydrocarbon chains, and so they form compartment.
– Lipid bilayer are self-sealing because a hole in a bilayer is energetically
unfavorable.

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 Lipid vesicles can be formed from phospholipid
• Lipids vesicles (liposomes) are aqueous compartments enclosed by a
lipid bilayer.

• These structures can be used to study membrane permeability or to

deliver chemical to cells.

• Ion or molecules can be trapped in the aqueous compartments of lipid

vesicles by forming the vesicles in the presence of a substances, for
example glycine.

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 Cell Membrane – Lipid Bilayer
• Lipid bilayer membrane have a vary low permeability for ions and most
polar molecules.

• Water transverse such membranes relatively easily because of its small size,
high concentration, and lack of a complete charge.

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 Cell Membrane – Lipid Bilayer
• The permeability of small molecules is correlated with their solubility in a
nonpolar solvent relative to their solubility in water.

• An ion such Na+ traverses membranes very slowly because the replacement
of its coordination shell of polar water molecule by nonpolar interaction
with the membrane interior is highly unfavorable energetically.

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 The Structure & Properties of Membranes
The Fluid Mosaic Model

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 The Structure & Properties of Membranes
The Fluid Mosaic Model

• It is proposed by S.J. Singer and

G. L. Nicholson in 1972.

• Fluid – the phospholipid bilayer

is viscous and individual
phospholipid can move
position.

• Mosaic – the phospholipid

bilayer is embedded with
protein, resulting in a mosaic of
component.

Article Link: https://www.sciencedirect.com/science/article/pii/B9780122072505500087

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 The Structure & Properties of Membranes
Motion in Membranes
• A functioning biological membrane is not rigid. In fact, the lipid and protein
component are in constant motion.
• Under physiological conditions, the average time required for a
phospholipid molecule to wonder completely around a cell in the order of
seconds to minutes, membrane protein also move, but more slowly.

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 The Structure & Properties of Membranes
Motion in Synthetic & Biological Membranes

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 The Structure & Properties of Membranes
The Asymmetric of Membranes

• Asymmetric distribution of
phospholipids between the inner and
outer monolayer of the erythrocyte
plasma membrane.

• Two leaflets in bilayer are not identical.

• Some has to do with orientation of lipid-

synthesizing enzyme.

• Some has to do with “translocases” or

“flippases”.

• Function of membranes is more than

just a “cell sack”.

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 Common Features Underlie the Diversity of Biological
Membrane (Summary)

• Membranes are sheet-like structure that form closed boundaries

between different compartment. The thickness is between 6-10 nm.

• Membrane consist mainly of lipids and protein. The mass ration of

lipids to proteins ranges from 1:4 to 4:1. Membranes also contain
carbohydrates linking to lipids and proteins.

• Membrane lipids are small molecules that have hydrophilic and

phobic moieties.

• Specific protein mediate distinctive functions of membranes.

Proteins serve as pumps, channels, receptors, etc. Membrane
proteins are embedded in lipid bilayer.

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 Common Features Underlie the Diversity of Biological
Membrane (Summary)

• Membranes are noncovalent assemblies. The constituent protein and

lipid molecules are held together by many noncovalent interaction.

• Membranes are asymmetric. The two faces of biological membranes

always differ from each other.

• Membrane are fluid structure. Lipid molecules diffuse rapidly in the

plane of the membrane, as do proteins, unless they are anchored by
specific interaction. In contrast, lipid and protein do not readily rotate
across the membrane. Membrane can be regarded as two-dimensional
solution of oriented proteins and lipids.

• Most cell membrane are electrically polarized, such that the inside is
negative (typically – 60 mV). Membrane potential plays a key role in
transport, energy conversion, and excitability

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 The Structure & Properties of Membranes
Transport across membrane

Molecule or ion across membrane cell with different ways:

• Passive Transport - diffusion
• Passive facilitated – facilitated diffusion
• Active transport

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 Passive Transport – Facilitated Diffusion
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 Active Transport

• Active transport – movement of molecules across a semi-permeable

membrane against a concentration gradient with a protein.

• This transport needed energy, ATP.

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 Lipid Carry Messages

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 Lipid - Hormone

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 Lipid as a Vitamin

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 Lipid as a Hormone

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 Lipid as a Pigment

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