Biomembran

Chapter 2

Elmi . C. J. Pandelaki
“Struktur dan Sifat
(24030118420001)
Membran Lipid ”
 Lipid Crystals

Lipid-Water Mixtures

Topic
The Thermodynamics of
Lipid Polymorphism

Model Membrane Systems

 Lipid Crystals

Chemical nature of phospholipids-

Phosphatidylcholine
Different kinds of phospholipids-
 Lipid-Water Mixtures

1. Lamellar This form is

This form, the lipids are Liquid representing the bulk
organized in the form of Crystalline
Phase (𝐿𝛼 ) of the lipid
cylinders with the polar
groups on the inside, there
is a column of water.

4. The Major 2.
Hexagonal organized Lamellar
forms of lipid
II Phase – water Gel Phase
(𝐻𝐼𝐼 ) systems (𝐿𝛽 )

This is formed at low

This form, the lipids are 3. temperatures , and the
organized in the form of Hexagonal molecules are packed more
cylinders with the polar I Phase thightly.
groups on the outside, in (𝐻𝐼 )
contact with water.
1. Lamellar Liquid Crystalline Phase (𝐿𝛼 ) 2. Lamellar Gel Phase (𝐿𝛽 )

3. Hexagonal I Phase (𝐻𝐼 ) 4. Hexagonal II Phase (𝐻𝐼𝐼 )

Figure 1: Phase diagram of hydrated Figure 2: The hydrocarbon chain packing
dimyristoyl phosphatidylcholine (DMPC) is a hexagonal array for the (𝑃𝛽 ) phase
bilayers, together with representations and a ’distorted’ hexagonal lattice of the
of the (𝐿𝛼 ), (𝑃𝛽 ) and (𝐿𝛽 ) phases. (𝐿𝛽 ) phase

• The fluid phase is conventionally designated 𝐿𝛼 or ld (liquid-disordered) phase and the

gel phase is designated 𝐿𝛽 or so (solid-ordered) phase. In addition, an intermediate
phase 𝑃𝛽 , in which the bilayer is rippled, is found in the gel phase of certain
phospholipids.
Lipids assemble spontaneously into sheets, liposomes and micelles-
Lipids self-associate without covalent bonding; their tails cooperate to exclude water

A lipid’s chemistry determines its geometric shape

(e.g. cones, cylinder, etc.)

• one tail → micelle

• two tails → bilayer
The Thermodynamics of Lipid Polymorphism

1. The Hydrophobic Force

2. Micelle Formation

3.Micelle Shapes: Why Does a Bilayer Form?

4. Lipid Shapes
 1. The Hydrophobic Force

The major thermodynamic driving force stabilizing hydrated lipid aggregates is the hydrophobic
force. Other stabilizing factors are :

1. Van der Waals forces 2. Hydrogen bonding

• Short, weak attractive forces • Between polar headgroups

between adjacent of some lipid molecules
hydrocarbon chains. such as
• The attraction results from phosphatidylethanolamine
interactions between • Intermolecular bridging by
polarizable electron divalent cations can also be
(induced dipoles) important in some
circumstances with anionic
lipids
2. Micelle Formation
 3. Micelle Shapes: Why Does a Bilayer Form?
In order to understand the stability of the bilayer and the possible role of “non-bilayer-forming”
membrane component, it is necessary to develop further the thermodynamics of these systems
and to discuss the concept of lipid shapes in relation to the constraints of packing lipids together
in micelles.

In considering the problem of how amphiphilic molecules pack into a particular micelle
geometry, it is convenient to consider the packing requirements of the molecule in two parts.

first second
The nonpolar portion of the molecule has a
The optimal surface area required by the polar
fixed molecular volume (v) and a maximal
headgroup (𝑆𝑂 )
length

Without any other considerations, this will For biological phospholipids, the area per
determine the maximal radius of a spherical molecule in a hypothetical spherical micelle is
micelle, as well as the number of molecules that much larger than the optimal value for
can fit into the micelle headgroup packing
 Micelle Geometry And The Critical Packing Parameter

Three molecular parameters must be considered in determining the most stable micelle
geometry :

𝑆𝑜 ,the optimal surface area occupied by the molecule at the

hydrocarbon interface. Dependent on the solution conditions,
especially ionic strengh in the case of charged molecules.

L, the maximum length of the alkyl chain for simple single-chain

amphiphiles and for phospholipids. This will determine the upper
limit on micelle size, such as the radius of a spherical micelle or
thickness of a bilayer

V, the molecular volume of the hydrocarbon portion of the amphiphile.

The surface area available per unit volume is purely a function of micelle geometry and it is this
which basically determines what kind of micelle is formed by different amphiphiles. Some
possible micelle forms :

1. Spherical : Given the dimensional consentraints imposed by the length of the lipid chain, the
sphere has the highest area/volume ratio of any form and is favored by lipids with a large
value of 𝑆𝑜 , such as dodecyl sulfate in water.

2. Distorted spheres : Have a lower surface/volume ratio than spheres:

(a) Ellipsoids: considered to be unlikely because packing would be highly unfavorable in many
places
(b) Globular: bi-lobed, like two spheres merged.

3. Rods and Cylinders : Even lower surface/volume ratio. The ends would likely be
hemispherical so as to exclude water form the nonpolar portions yet maintain reasonable
packing.

4. Bilayer: Smallest surface/volume ratio, favored by lipids with a large molecular volume, such
as lipids with two alkyl chains.
 1.
Spherical

Some
2.
4. possible
Distorted
Bilayer micellar
spheres
forms:

3. Rods
and
Cylinders
 4. Lipid Shapes

The molecular shape of an

amphiphile (a surfactant or a
lipid) infuences the molecular
packing in self-assemblies. This
leads to different structural
and physical properties of drug
carriers hence drug
entrapment efficiencies and
release mechanisms. For
describing the effective
molecular shape, the critical
packing parameter (CPP) of
the amphiphile is de ned as v/
a0lc. Here, v is the volume of
the lipophilic chain, a0 is the
interfacial area occupied by
the hydrophilic head group,
and lc is the length of the
lipophilic chain.
Figure 3. Molecular shapes and critical packing parameters of
surfactants and lipids and the structures formed. This figure
has been redrawn from
 Liposomes

The term “liposome” can be defined as any lipid bilayer structure which encloses a volume.
Many phospholipids when dispersed in water spontaneously form a heterogeneous mixture
of vesicular structure which contain multiple bilayers forming a series of concentric shells

Fig. 1. Schematic diagram of different types of liposomal vesicles: SUV (small unilamellar
vesicles), LUV (large unilamellar vesicles), MLV (multilamellar vesicles), and MVL
(multivesicular liposomes). Each circle represents a lipid bilayer structure
DAFTAR PUSTAKA

Gennis, R.B. Nagarajan, R. 2003. Theory of Micelle Formation Quantitative Approach to

Predicting Micellar Properties from Surfactant Molecular Structure. The Pennsylvania
State University, University Park, Pennsylvania, U.S.A. Hal 4.
Salim, M., Sugimura, A., and Hashim, R. 2014. Amphiphilic designer nano-carriers for
controlled release: From drug delivery to diagnostics