Surfactants

Introduction to Liquid Crystals

Kausar Ahmad
Kulliyyah of Pharmacy

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 Contents
 Properties of liquid  Lyotropic
crystals  structures
 Types of liquid crystals  application

 Thermotropic  NIOSOMES

 nematic
 smectic
 cholesteric

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 Synergistic Effects of Surfactants
 Observed when surfactants having relatively similar
structure or ionic property are mixed
 Resulted in the formation of liquid crystal structures or
complexes at the interface by intermolecular
interactions between surfactants
 Examples
 Anionic and nonionic in synthetic latex emulsion
polymerisation,
 Mixture of a dispersant and a hydrating agent to
increase dispersion stability in agricultural chemicals
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 STATES OF MATTER

 Common states:
 solid
 liquid
 gas
 Matter can exist in
other states

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 LIQUID CRYSTALS
 A state that occurs between a solid & a liquid
 Possess properties characteristics of both
liquids & crystalline solids
 Also possess properties not found in either
liquids or solids
 May response to external perturbations &
some changes colour with temperature

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 Crystals vs Liquid Crystals
 A crystal is a highly ordered structure which
possesses long-range positional & orientational
order
 For many substances these two types of order are
destroyed simultaneously when the crystal melts to
form a liquid
 For some substances, these orders are
destroyed in stages. These are liquid crystals.
E.g. Slide 17

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 Properties of liquid crystals
 Liquid crystal can flow like a liquid, due to loss of positional order
 Liquid crystal is optically birefringent, due to its orientational order
 Transition from crystalline solids to liquid crystals caused by a
change of temperature – gives rise to THERMOTROPIC liquid
crystals
 substances that are most likely to form a liquid crystal phase at
a certain temperature are molecules that are ELONGATED &
have some degree of RIGIDITY. Try slide 29

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Typical chemical structures
 cholesterol ester
 phenyl benzoates
 surfactants such as
polyethylene-oxides,
alkali soaps, ammonium
salts, lecithin
 paraffins
 glycolipids
 cellulose derivatives
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 Typical applications
 LCD displays
 dyes (cholesterics)
 advanced materials (Kevlar)
 membranes
 temperature measurement (by changing colours)
 solvents for GC, NMR, reactions, etc.
 Drug delivery
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 Types of liquid crystals
Thermotropic
 Phase transition depends on temperature
 Nematic
 Smectic
 Cholesteric

Lyotropic
 Phase transition depends on temperature &
concentration

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 As temperature increases…..
 The first liquid crystal phase is the smectic A, where there
is layer-like arrangement as well as translational and
rotational motion of the molecules.
 A further increase in temperature leads to the nematic
phase, where the molecules rapidly diffuse out of the initial
lattice structure and from the layer-like arrangement as well.
 At the highest temperatures, the material becomes an
isotropic liquid where the motion of the molecules changes
yet again.

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 Nematic
 Simplest form is a
nematic liquid crystal
i.e. long-range
orientational order
but no positional
order
 The preferred direction
is known as director

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 Nematic…
 Despite the high degree of orientational order, nematic phase
as a whole is in disorder i.e. NO MACROSCOPIC ORDER
(orientation within a group is similar but not from one group to
another)
 Structure of nematic phase can be altered in a number of ways.
E.g. electric or magnetic field or treatment of surfaces of the
sample container
 Thus, possible to have microscopic order & macroscopic order
 Nematic liquid crystals are widely used in electro-optic display
devices

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 Cholesteric
 The first liquid crystal that was observed through a polarising microscope is
cholesteryl benzoate. Thus, CHOLESTERIC liquid crystal OR chiral nematic
liquid crystal

 E.g. cholesteryl benzoate: LC @ 147C, isotropic @ 186C

 Cholesteric liquid crystals have great potential uses as

- sensors

- Thermometer

- fashion fabrics that change colour with temperature

- display devices

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- In CHOLESTERIC phase, there
is orientational order & no
positional order, BUT, director is
in HELICAL ORDER.
 The structure of cholesteric
depends on the PITCH, the
distance over which the director
makes one complete turn
 One pitch - several hundred
nanometers
 Pitch is affected by:-
 Temperature
 Pressure
 Electric & magnetic fields

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 Smectic
 SMECTIC phase occurs at temperature below
nematic or cholesteric

 Molecules align themselves approx. parallel &

tend to arrange in layers
 Not all positional order is destroyed when a
crystal melts to form a smectic liquid crystal
 Chiral smectic C liquid crystals are useful in LCDS

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 LIQUID CRYSTAL POLYMERS
 Can form nematic, cholesteric, smectic
 When liquid crystal polymers solidify, the liquid
crystal structure ‘freeze in’
 This results in materials of high tensile strength
& in some cases unusual electro-optical
behaviour
 E.g. Kevlar aramid fibre – bullet-proof vest &
airplane bodies (aromatic polyamide)
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 Examples of phase changes
Cholesteryl myristate

71C 79C 85C

solid smectic A cholesteric isotropic

4, 4’-di-heptyloxyazoxybenxene
74C 94C 124C
solid smectic C nematic isotropic
 Thermotropic vs Lyotropic
THERMOTROPIC LYOTROPIC
 Absence of solvent  In solvent
 Rigid organic molecules  Surfactants
 Depends on Temperature
 Depends on Temperature,
 Structures:
Concentration, salt, alcohol
 Smectic
 Nematic
 Structures:
 Cholesteric  Lamellar
 Hexagonal etc

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 Structure formation in surfactant solution

monolayer
rod hexagonal
micelle

Oil/alcohol REVERSE
HEXAGONAL

Reverse micelle
Formation of MICROEMULSION bilayer

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Effect of temperature and concentration on the
structure of lyotropic liquid crystals

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 SURFACTANT VESICLES
[A] Phospholipids (e.g. lecithin) + H2O ---->
phospholipid vesicles or liposomes

[B] Liposomes + (long chain) stearylamine

------->
tve charge liposome (carriers for DNA)

[C] Liposomes + dicetyl phosphate -----

- ve charge liposome
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 Vesicles
 Bilayers that fold into a 3D structure
 Vesicles form because they get rid of
the edges of bilayers, protecting the
hydrophobic chains from the water, but
they still allow for relatively small
layers.
 Lipids found in biological membranes
spontaneously form vesicles in
solution.
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 Application of Liposomes
 can encapsulate:
 drugs,
 proteins,
 enzymes
 administered intravenously, orally or intramuscularly
 decrease toxicity
 increase specificity of drug uptake
 enable slow release

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 Problems with phospholipids

 phospholipids undergo oxidative

degradation
 handling & storage must be under nitrogen
 expensive

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 Formation of liquid crystals using surfactants
[A] Anionic
e.g. alkane sulfonates
[B] Cationic
e.g. hexadecyl trimethyl ammonium bromide
[C] Amphoteric
e.g. alkyl betaines

 Due to toxicity of ionic surfactants, the vesicles are not used for drug delivery
[D] Non-ionic
e.g. alcohol ethoxylates R-O-(CH2CH2O) m H m: 2-20, R :
mixed; alkyl group C8C18

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 Niosomes
 Non-ionic + cholesterol -> NIOSOMES
 These vesicles prolong the circulation of entrapped
drug
 Properties depend on
1. Composition of bilayer
2. Method of production
e.g. cholesterol & single alkyl-chain non-ionic
surfactant with a glyceril head group
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 Examples of niosome applications
 Ketoconazole niosomes were prepared by using surfactant
(Tween 40 or 80), cholesterol and drug
Satturwar PM; Fulzele SV; Nande VS; Khandare, JN Indian Journal of
Pharmaceutical Sciences. 2002 Mar-Apr; 64(2): 155-8

 Use for topical immunisation - Bovine serum albumin (BSA)loaded

niosomes composed of sorbitan monostearate/sorbitan trioleate
(Span 60/Span 85), cholesterol and stearylamine as constitutive
lipids
Sanyog Jain1, S. P. Vyas2, Journal of Pharmacy and Pharmacology Vol.
57, No. 9, pages 1177 (2005)

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 References
1. http://www.lci.kent.edu/lc.html#Description
2. http://liqcryst.chemie.uni-hamburg.de/lc_lc.php
3. http://www.glycoprojects.kimia.um.edu.my/website/Glyco/
(carbohydrate liquid crystal)
4. http://www.gla.ac.uk/~jmb17n/conacher.pdf (niosomes)
5. http://plc.cwru.edu/tutorial/enhanced/files/lc/phase/phase.ht
m
6. J Kreuter (ed.), Colloidal Drug Delivery Systems, Marcel
Dekker, New York (1994) Chapter 3&4

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http://plc.cwru.edu

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