LYOTROPIC STUDIES ON PALM KERNEL OIL BASED ON GLUCOSIDE

NORSYAZWANI BINTI YAHYA

FACULTY OF CHEMICAL ENGINEERING

UNIVERSITI TEKNOLOGI MARA
SHAH ALAM

2016

LYOTROPIC STUDIES ON PALM KERNEL OIL BASED ON GLUCOSIDE

NORSYAZWANI BINTI YAHYA

This report is submitted in partial fulfillment of the requirements needed for the
award of Bachelor in Chemical Engineering (Hons)

FACULTY OF CHEMICAL ENGINEERING

UNIVERSITI TEKNOLOGI MARA
SHAH ALAM

DECLARATION

I hereby declare that this report is the result of my own work except for quotes and
summaries which had been duly acknowledged.

Name: Norsyazwani Binti Yahya

ID No: 2012894206

Date : 30th June 2016

SUPERVISORS DECLARATION

I hereby declare that I have read this thesis and in my opinion this project report is
sufficient in terms of scope and quality for the award of Bachelor in Chemical
Engineering (Hons).

Signature

Name

: Dr. Nurul Fadhilah Kamalul Aripin

Date

: 30th June 2016

Accepted:

Signature

: ........................

Date

:
Head of Programme
Dr. Syed Shatir A. Syed Hassan
Faculty of Chemical Engineering
Universiti Teknologi MARA,
Shah Alam

Signature

: ..

Date

: .

Coordinator
Dr.Safari Bin Zainal
Faculty of Chemical Engineering
Universiti Teknologi MARA,
Shah Alam

5
ACKNOWLEDGEMENTS

Alhamdulillah, thanks to Allah S.W.T. for his merciful and guidance from him in
completing the research project. I would like to thank all those people who made this
research paper possible and an unforgettable experience for me encountered the hardship
and obstacles.
First of all, I would like to express my deepest sense of Gratitude to my
supervisor, Dr. Nurul Fadhilah Kamalul Aripin who offered her continuous advice and
encouragement throughout the course of this research project. Biggest appreciation to
her for the systematic guidance, ideas from initial project until the end of the preparation
report.
I also would like to thank to Master student under supervision Dr. Nurul Fadhilah
Kamalul Aripin, Miss Marina Yusoff for assisting me in the laboratory to finish the
Research project. Last but not least, I want to give this token appreciate to lecturers,
family and friends and to those who had been directly or indirectly involved in the
preparation and accomplishment of this Research Project Project.

6
ABSTRACT

The main study of this topic is about to determine the Lyotropic liquid crystal
phase of alkyl glucoside based on palm kernel oil. Alkyl glycoside is one type of nonionic surfactant that is from renewable sources. As world is concern about the
environmental issues that spread all over news, specialist are tend to find alternative
ways to replace the non-renewable sources to renewable sources. This is because the
surfactants based on renewable sources are bio-degradable and much safer. In this
experiment the material that are under studied and observed is a compound known as /
-Gluc-PKO (C12). The compound is one of types of Alkyl Glycosides group.
Lyotropic behaviour is studied from this compound and using method of contact
penetration of water using Optical Polarizing Microscope. Before the compound are
studied and observed more, the compound is synthesis by undergo three major routes;
acetylation, glycosylation and deacetylation. The result of penetration of water based on
the compound showed Lyotropic phases that exist are micelles(L 1),cubic phase and
hexagonal phase.

7
TABLE OF CONTENTS
PAGE
ACKNOWLEDGEMENTS
TABLE OF CONTENTS

v
vii -ix

LIST OF TABLE

LIST OF FIGURES

xi-xii

LIST OF ABBREVIATION

xiii

ABSTRACT

vi

CHAPTER 1 INTRODUCTION
1
2
3
4

Research Background
Problem Statement
Objective of Study
Scope of Study

1
2
4
4

CHAPTER 2 LITERATURE REVIEW

2.1

Surfactants

2.2

Classification of Surfactants

2.2.1 Anionic surfactant

2.2.2 Cationic surfactant
2.2.3 Zwitterionic surfactant
2.2.4 Non-ionic surfactant

7
7
8

Surfactants resources
2.3.1 Palm Kernel oil
Glycosides

9
9
11

2.4.1 Alkyl Glycosides

12

2.5

Liquid crystal

13

2.5.1

2.5.1 Thermotropic mesophase

14

2.5.2 Lyotropic mesophase

2.5.2.1 Lamellar phase

15
15

2.3
2.4

8
2.5.2.2 Hexagonal phase

17

2.5.2.3 Cubic phase

18

CHAPTER 3 METHODOLOGY
3.1
3.2

Experimental Work Overview

Methodology Flow Chart

21
22

3.3

Sample Preparation
3.3.1 Sample material

23
23

3.4

Method of experiment

23

3.4.1 Optical Polarizing Microscope

3.4.2 Contact Penetration Method

23
25

CHAPTER 4 RESULTS AND DISSCUSSION

4.1
4.2

Results of Lyotropic phase

Comparison Lyotropic phases between previous study and current

26
28

compound

CHAPTER 5 CONCLUSION AND RECOMMENDATIONS

5.1

Results of Lyotropic phase

34

5.2

Limitations and Recommendation

35

REFERENCES

36

APPENDICES

40

LIST OF TABLES

TABLE

TITLE

PAGE

10
4.1

Summary of Lyotropic behaviour during the water of

penetration

27

4.2

Summary comparison of several glycolipids based on

glucosides that exhibited Lyotropic phases.

30

4.3

Summary comparison phase exhibited based on the Glucoside

(head group mixture from palm oil and palm kernel oil) with
the other pure Maltoside.

32

LIST OF FIGURES

FIGURE

TITLE

PAGE

11

1.1

Comparison production between synthetic versus natural

surfactants

2.1

The Structure of Surfactant

2.2

Classification of Surfactant

2.3

Anionic Surfactant

2.4

Cationic Surfactant

2.5

Zwitterion Surfactant

2.6

Total Worldwide Production in 2012 included Oil and Fat

10

2.7

Cross-section of palm fruit

11

2.8

Structure of Alkyl Glucoside

12

2.9

Fischer Reaction

13

2.10

Koenigs-Knorr Method

13

2.11

Structure of Lamellar phase

16

2.12

Length of each bilayer of lamellar

16

2.13

Structure of Hexagonal phase(H1)

17

2.14

Structure of Reversed Hexagonal phasa(H2)

18

2.15

Structure of Bicontinous cubic phase

19

2.16

Structure of Normal Cubic mesophase

19

3.2

Flow of experiment

22

3.3

Schematic Principle of Polarizing Light of OPM

24

4.1

Lyotropic sequences show micelles followed by cubic,

hexagonal phase and crystal + water

28

4.2

The chemical structure of Glc(C12)

29

4.3

The structure of 2-hexyldecyl- (/) D-glucoside

29

12
4.4

Lyotropic phase behaviour of glycolipid MalC12N3 - (A)

water, (B) HI, (C) VI, (D) pure compound (SmA).

31

4.5

The activity of water penetration of MalOC3OC12 cause a

sequences of (A) water from the left, followed by (B) cubic
phase (C) columnar phase (D) columnar phase (E) cubic
phase and (F) pure compound (SmA)

32

4.6

The lamellar phase exhibited in (a) Malto-Palm-S and (b)

Malto-PKO

33

LIST OF ABBREVIATIONS

ABBREVIATION

DESCRIPTION

13
AG

Alkyl Glucosides

CMC

Critical Micelle Concentration

et

et al; and others

H1

Normal Hexagonal phase

H11

Reversed Hexagonal phase

Discontinuous Cubic

i.e

id est; that is

L1

Micellar phase

Lamellar phase

Malto

Maltoside

OPM

Optical polarizing microscope

PEG

Polyethylene Glycol

PKO

Palm kernel oil

PO

Palm oil

Cubic phase

Bicontinous cubic

CHAPTER 1

INTRODUCTION

1.1

RESEARCH BACKGROUND

After the environmental issue started to arise, advanced studies have been explored
on a new type of surfactant (Foley, Kermanshahi pour, Beach, & Zimmerman, 2012).
The specialists are more focused on finding a ways to used renewable resources as to
reduce the impact greenhouse (Patel, 2003). As the studies of surfactant become
extensively in ten years back, some of the studies have proposed of producing a biodegradable surfactant (ShamsiJazeyi, Kaiser, Wylde, & Mahmoudkhani). The biosurfactant having an impressive demand because it is less toxic compared to nonrenewable sources, less expensive and the material is biodegradable(Rojas,
Stubenrauch, Lucia, & Habibi). Bio-surfactants basically can be classified into five
major classes. They are lipopeptides, glycolipids, phospholipids, neutral lipids, and
polymeric compounds (Desai & Banat, 1997).

Surfactant is an amphiphlic molecule that has two main structures which are
hydrophilic head and hydrophobic tail. When dissolved in an aqueous solution such
as water, hydrophilic head make contact with water while hydrophobic tails avoid
from making contact with water. The consequence behavior of hydrophobic tail in

the water will create driving force for the surfactant to self-assembly and aggregates
to form micelles.

Surfactant can be divided into four types;anionic, cationic, zwitterionic

andnonionic surfactant. Each of these surfactants has different charge inside the head
of hydrophilic. Anionic surfactant contains negative charge, cationic charge contains
positive charge, zwitterionic contain both charge;positive and negatives charge and
nonionic surfactant does not contain any charge. Amongst types of surfactants,
anionic and nonionic surfactants show highest demand.

But today, nonionic surfactant has dominating demands due to

biodegradable properties and eco-friendly. Generally, synthesis of nonionic surfactant
made from natural resources and petroleum. Example of nonionic surfactants from
natural resource is alkyl glycoside and example of nonionic surfactants from
petroleum is polyethylene glycol (PEG). Since, PEG is made from petroleum
derived; the demand is more focusing on alkyl glycoside.

Surfactants have ability to lower surface tension. As the concentration of

surfactants increase in the solvent, it will self-assembly, aggregate and formed
micelles. The most interesting part is if the concentration of surfactant tends to
increase and exceed critical micelles concentration (CMC), the micelles will start
form variety phase of behavior which known as liquid crystal behavior.

1.2 Problem statements

Any of surfactants taken from natural resources are known as natural surfactants.
Natural surfactants can be taken from plant or animal sources. The process of getting

3
the sample of natural surfactants can be done by several steps which include
extraction, precipitation or distillation (Holmberg, 2001).

The application of natural surfactants becomes widely used and many

researchers are focusing on it. This is because natural surfactant has several
properties that considered as environmental friendly as it is less toxic, easily
biodegradable and thus it is less harmful to the environment. But, there are several
problems if the sample is natural surfactants.

One of the major problems when producing a natural surfactant is that the
cost for sample processing could be quite expensive in which it could exceed the cost
of producing synthetic surfactants. Furthermore, the end product of natural surfactant
processes could only be obtained in small amount. Other than that, the separation
process has to be done in a long period (Holmberg, 2001).

Another problems when using natural surfactants, the behavior of liquid

crystal is hard to be observed. So, the another alternatives is done to solve all these
problems by replacing the natural surfactants to synthetic surfactants(Hashim,
Hassan, Hamzah, Vill, & Wulf, 2003). Example of synthetic surfactant is alkyl
glycosides. Figures 1.1 shows comparison production between synthetic and natural
surfactants.

Figure 1.1: Comparison production between synthetic versus natural surfactants

4
Sources: Farn,2006
5

Objectives

In this study, the objective are focusing on the effect of concentration of water to
determine the Lyotropic phase behavior

1.4 Scope of study

In this study, the scope are divided into three major things which are what types of
surfactant used, lyotropic mesophase behavior and effect of addition of solvent.
Synthetic surfactant is applied to study the behaviour of liquid crystal. The specific
name for the synthetic surfactant is alkyl glucosides. The structure of alkyl glucoside
are consists of glucose as the hydrophilic head and fatty alcohol as the hydrophobic
tail. The derivation of alcohol and fatty acid from plant will synthesis hydrophobic
tail of alkyl glucosides. Type of fatty acid extract from palm kernel oil is saturated
fatty acid. The composition of saturated fatty acid is highest compare to others oils
and make raw material from palm kernel oil to synthesis alkyl chain of alkyl
glucosides acceptable

Alkyl glucosides will act as the surfactant in this study. The surfactant will
dissolve in a solvent. The solvent used in this experiment is water. Then, the
surfactant will exhibited phases. The phases are based on lyotropic mesophase.
Lyotropic mesophase is one type of liquid crystal. Basically, liquid crystal has
another two type which are thermotropic and amphotropic. But both type of liquid
crystal did not covered in this study.

The phase behavior of lyotropic is studied by controlled the temperature

(cooling or heating) but the study is more focused about concentration of solvent.
Contact penetration method is applied to determine the multiphase of Lyotropic
might appear on that Alkyl glucosides.

CHAPTER 2

LITERATURE REVIEW

2.1

Surfactants

Surfactants are known as amphiphlic molecules. The molecules are composed with
two parts which are hydrophilic head, the part that contact with water and another
part is hydrophobic tail, the part that avoid from contact with water but more
interested to make contact with non-polar condition such as oil. Figure 2.1 shows
structure of surfactant. As the hydrophobic tail avoids making contact with water, it
will create a driving force for the molecules to aggregate in water(Uppgrd, 2002).
The surfactants are already existed in cell membrane of living things (Kovensky,
2005) and have widely application in cosmetics, detergent, lubricant, etc.

Figure 2.1: Structure of surfactant

6
2.2 Classification of surfactant
According to (Salager, 2002), surfactants are usually classified into types based on its
use. But when the classification have made according to its uses, it create
misperceptions because surfactants have more than one uses. In more correct word,
surfactants have their own classification which is basically based on their detachment
in water. Surfactants can be classified to anionic, cationic, zwitterionic and nonionic
surfactants. Figure 2.2 shows classification of surfactants.

Figure 2.2: Classification of surfactants

Source: Essays, UK. (November 2013)

2.2.1 Anionic surfactant

Anionic surfactants are known as a surfactant which carries a negative charge at the
head of hydrophilic (Cullum, 1994). Example of anionic surfactant is alkylbenzene
sulfonates (detergents), fatty acid (soaps), lauryl sulfate (foaming agent), di-alkyl
sulfosuccinate (wetting agent), lignosulfonates (dispersants) etc. The productions of
anionic surfactants are about half of the world and the usage of surfactants have
highest demand co7iimpared to other surfactants(Salager, 2002)

Sodium Dodecylsulfate

Figure 2.3: Anionic surfactant

Source: Santos, Medronho, Santos & Antunes, 2013

2.2.2 Cationic surfactant

Cationic surfactants are known as a surfactant which carries a positive charge at the
head of hydrophilic (Cullum, 1994). Examples of cationic surfactants are fatty amine
salts and alkyltrimethylammonium salts. The cost of productions of cationic
surfactants is more expensive compared to anionic surfactants. This is because
process of production cationic surfactants required high pressure and the reaction
took place in hydrogenation. The application of cationic surfactant can be as an
inhibitor of corrosion(Salager, 2002)

Dodecyltrimethylammonium Bromide

Figure 2.4: Cationic surfactant

Source: Santos, Medronho, Santos & Antunes, 2013

2.2.3 Zwitterionic Surfactants

The surfactants are also as amphoteric surfactant. This surfactant has a positive
charge and negative charge at the head of hydrophilic (Cullum, 1994). The examples
of Zwitterionic Surfactants are betaines or sulfobetaines and natural substances such
as aminoacids and phospholipids. A part of zwitterionic surfactants are unresponsive
when tested using pH. This is because of the structure of this surfactant have charges,
cation and anion. The consequences of having both charges will make the cation
show low pH while anion shows high pH and eventually zwitterionic surfactant
exhibited at intermediate pH. The usage of zwitterionic surfactants is more focusing
on cosmetic. The surfactants are less toxic(Salager, 2002)

Betaine

Figure 2.5: Zwitterionic Surfactants

Source: Santos, Medronho, Santos & Antunes, 2013

2.2.4 Nonionic Surfactants

Nonionic surfactants have no charge at the head of hydrophilic (Cullum, 1994).

(Rojas et al.). Today, nonionic surfactant demand has dominated against anionic
surfactants and other surfactants due to its low environmental impact as a
biodegradable surfactants(Lavergne, Zhu, Molinier, & Aubry, 2012). Examples of
nonionic surfactants are polyethylene glycol (PEG) and glucoside (sugar based)
(Salager, 2002). Polyethylene glycol (PEG) is a nonionic surfactant based on
petroleum. Since the surfactant is based on petroleum derived, the production of

9
nonionic surfactant is quite expensive and also contribute to environmental and
toxicity issues. Later, the specialist has decide to find other alternative to replace
nonionic surfactants based petroleum to nonionic surfactant based natural-derived
(Rojas et al.)

2.3 Surfactant resources

The raw material to synthesis surfactant can produce from non-renewable sources
and renewable sources. Since non-renewable source have problem regarding to
environmental issues, the specialist tend to find other alternatives by increase the
production surfactant made from renewable sources which is vegetable fats and oils.
They found out that surfactant made from renewable sources are environmental
friendly and bio-degradable(Hill, 2000). Example of common surfactant made from
renewable source is alkyl glycosides. The alkyl chain which is fatty acid of
glycosides is synthesis from kernel oil of palm fruit.

Fatty acid act as alkyl chain is extracted from vegetable oils. Fatty acid can be
divided into two groups which are saturated fatty acid and unsaturated fatty acid.
Saturated fatty acid contains carbon single bond while unsaturated fatty acid contains
carbon double bond. The presence of carbon double bond in the compound will make
the compound unstable.

2.3.1 Palm kernel oil

The

production

oil

from

palm

fruit

is

dominating

by

Malaysia

and

Indonesia(Ashihara, Crozier, & Komamine, 2010). Both of the country covered

about 85% production of oil in the world. In 2012 (Figure 2.6), the palm oil and palm
kernel oil shows highest production compare to other resources oil.

10

Figure 2.6: Total worldwide production oil in 2012 also included oils and fats
Source: Oil World, 2013

Palm fruit oil has two components; mesocarph and kernel (Figure 2.7). Both
of the components produce oil that useful in variety application such as margarine,
cosmetics and others. Even though they produce oil from the same fruit, the contents
of fatty acid are difference. Oil from kernel contains higher contents of saturated
fatty acid compared palm oil.
Palm kernel oil can be obtained from the extraction oil from the kernel of
palm fruit. The extraction oil from the kernel is usually done in the milling process of
palm fruits(Tang & Teoh, 1985). About 50% of kernel oil can be extracted in the
milling process. Basically, there are two ways to extract the kernel oil. They are
mechanical expression and solvent extraction.

11

Figure 2.7: Cross-section of palm fruit

Source: Sime Darby Plantations, 2014

2.4 Glycosides
Glycosides also can be known as glycolipids. Glycosides are nonionic surfactants.
Glycosides have several significant functions such as membrane formation,
mediators of cell-cell-recognitions and others particular functions. These surfactants
have special properties like biodegradability and chemical stability. Glycosides are
synthesized from oligosaccharides and fatty alcohols(Hato, Minamikawa, Tamada,
Baba, & Tanabe, 1999). They can be found in cell membrane of the plant, animal and
other living things(Faivre & Rosilio, 2010).

2.4.1Alkylglycoside
Alkyl glycosides (AGs) are come from a family of nonionic surfactants. They have
interesting properties such as eco-friendly, easily to biodegrade and also in protein
extraction(Lin, Riedel, & Kinne, 1979). As today, environmental issue become a big
concern, these surfactants are become demand in market share. These surfactants are
widely applied in personal care products.

12
The head of alky glycosides contain carbohydrate and do not carry any
charge(Milkereit, Garamus, Veermans, Willumeit, & Vill, 2005). Figure 2.8 shows
structure of alkyl glycoside.

Figure 2.8: Structure of alkyl glucoside

2.4.2 Synthesis of alkyl glycosides

The materials to synthesis alkyl glycosides are starch and alcohols(Larsson,
Svensson, & Adlercreutz, 2005). There are several common chemical method used to
synthesis alkyl glycoside such as Koenigs-Knorr method, the Fischer glycosylation
and others. Chemical synthesis method basically has to involve several protection,
deprotection and activation steps(Rather & Mishra, 2013).
Fischer glycosylation is simple reaction. The cost of work-up is less
expensive(Rather & Mishra, 2013). But the presence of alcohol and the reaction of
acidic condition can cause the problem at the purification process at the end of
products (Roy et al, 2007). Figure show Fischer reaction is applied to synthesis
perfluoroalkylglucosides from glucose and alcohols.

13
Figure 2.9 : Fischer Reaction
Source: Nowicki, Mokrzycki & Sulikowski,2015

Other chemical method to synthesis alkyl glycoside is known as KoenigsKnorr method. This method is quite common to synthesis alkyl glycoside but
restricting to produce in large scale because of heavy metal salts such as cadmium
carbonate is used as promoters during the reaction(Wimmer, Pechov, & Saman,
2004).Figure 2.10 show Koenigs-Knorr reaction.

Figure 2.10 : Synthetic way reaction of Koenigs-Knorr method

Source : Chatterjee,Pong & Sen,2015

Another method beside chemical synthesis method is enzymetic-synthesis.

There are two main reaction involved in this method which are transglycosidation
and reverse hydrolysis.(BilaNioV, MaStihuBa, & MaStihuBoV, 2010).
Glycosidases is used as the enzyme in this method (Mladenoska, Winkelhausen, &
Kuzmanova, 2008). Both of these reactions are influence by its nature of the glycosyl
donor. In transglycosylation, glycoside is applied as glycosyl donor (disaccharide)
while in reverse hydrolysis, the reaction is achieved by using monosaccharide
(glucose) (Ismail, Soultani, & Ghoul, 1999).

2.5 Liquid crystal

14
Basically, state of matter consists of solid, liquid and gas. Solid is where the particles
are arranged in closed pack due to intermolecular forces interact between them.
Liquid is where the particles are arranged in closed pack but there is still a gap
existing between them. Lastly, gas is where the particles are arranged but the forces
are not strong to hold the particle in closed pack and thus the particle are moving
around. Even, three basic states of matter are already known but the researchers have
found there is also existing of intermediate state of matter between the liquid and
crystal (Andrienko, 2006). The intermediate state is known as liquid crystal. Liquid
crystal is formed when the surfactant are dissolve in an aqueous solution. The
surfactant will self-assemble and exhibited sequence of structure which are
hexagonal, lamellar, reversed hexagonal and cubic(Tiddy, 1980).

Liquid crystal behavior can be found at glycolipids cell wall(M. K. Singh &
Jayaraman, 2012). Glycolipids formed a liquid crystal because of the hydrophilic part
contain carbohydrate. Liquid crystal behavior cannot be seen by visual observation.
There are methods used in the experiment such as polarized light microscopy, X-ray
scattering and RMN spectroscopy so that the phase of transition can be observed and
studied extensively.

There are three types of liquid crystal behavior which consists of

thermotropic and lyotropic. Thermotropic behavior depends on effect of
temperatures. The second type of liquid crystal is lyotropic behavior which depends
on effect of concentrations and also temperature. And another type of liquid crystal is
amphotropic. Amphoteric liquid crystal exhibited both behavior of thermotropic and
lyotropic.

2.5.1 Thermotropic mesophase

Thermotropic mesophase is influenced by the effect of temperature which either by
cooling or heating. The structure of thermotropic was studied extensively by Friedel

15
in 1926. He concluded that structure of thermotropic can be classified into three
types which consist of nematic, smetic and cholesteric

2.5.2 Lyotropic mesophase

Lyotropic mesophase is one type of liquid crystal behavior. This mesophase has been
discovered first by and later thermotropic was discovered. Lyotropic behavior is
quite complicated and the researcher tends to focus to thermotropic behavior. The
lyotropic behavior has been studied by Friedel in 1926. Then after many years, they
have found lyotropic significance. Major factors that determine lyotropic phase
structures are electrostatic interactions, surfactant head group hydration and steric
repulsions, and alkyl chain conformations(Tiddy, 1980). Lyotropic mesophase
exhibited phase transition after the concentration of solvent is added and temperature
started to variable (cooling or heating). Generally, phase transition of lytropic
consists of lamellar phase, cubic phase and hexagonal phase. But mostly, lamellar
and hexagonal phase show establish phase.

2.5.3 Lamellar phase

Lyotropic mesophase formation is depends on the concentration of solvent and effect
of temperature. The increase of concentration of solvent will cause the concentration
of surfactant to be increase. The surfactant will self-assembly and aggregate in an
aqueous solution. The aggregation of surfactant in an aqueous solution is known as
micelles formation. Micelles basically formed after the concentration of surfactant
exceed the Critical micelle concentration (CMC) in isotropic micellar solution (IS).
The lyrotropic structures still not appear after the concentration of surfactant exceed
the CMC. But, after the continuously addition of solvent, the lyotropic begin to show
in orderly manner and even more obvious in 3D microscope vision (Burducea,
2004).
The phase state after the micelles formation is lamellar phase which also
called as Neat soap. The structure of lamellar can be described having multiple
bilayer of molecules organized in which the hydrophilic head will contact with

16
solvents while hydrophobic tail will avoid from contact with water. The solvent
position will be in between of each bilayer. Figure shows the structure of lamellar.
The structure of lamellar is quite similar with smetic of thermotropic mesophase. The
property of lamellar phase is fewer viscous compare to hexagonal phase (Burducea,
2004). Lamellar phase also can be identified from its symbol, , 2, 3 (Figure 2.12)
which denotes how much length between each bilayer (Hyde, 2001).

Figure 2.11: Structure of lamellar phase, L

Source: Seddon & Templer,1995

Figure 2.12: Length of each bilayer of Lamellar phase

Source: Hyde, 2001

17
2.5.4 Hexagonal phase

Hexagonal phase also known as middle soap is phase after cubic phase. Hexagonal
phase will appear after the addition of solvent in the cubic phase (Burducea, 2004).
The structure of hexagonal phase can described as rod shapes. Basically, hexagonal
phase can be classified into two types; the hexagonal phase (H1) and the reversed
hexagonal phase (H2). In H1 phase (Figure 2.13), the hydrophilic head is pointed
outward to the solvent while in H2 phase (Figure 2.14) the hydrophobic tail is
pointed outward. Both of these phases can be observed by OPM. The viscosity of
hexagonal phase is higher compared to lamellar phase.

Figure 2.13: The structure of hexagonal phase, H1

Source: Collings & Hird,1997

18

Figure 2.14 : Structure of reversed hexagonal phase (H2)

Source: Source: Collings & Hird,1997

2.5.5 Cubic phase

Cubic phase is known as viscous isotropic. The phase has been given name as cubic
because of the arrangenment of micelles in cubic pattern. Cubic phase have two
types of phase;I and V phase. I phase is formed from the micelles aggereates into
spherical structure. Some of them mentioned cylindrical and elipisodal. V phase is
formed from micelle aggreates into sort of rod shape which link in 3D pattern. I
phase can be classifed into two types which are normal phase, I 1 and reversed
micelles, I2. For V phase also can be classifed into two types which are normal
phase,V1 and reversed micelles, V2. The V phase (Figure 2.15) also can be known as
bicontinous cubic (Burducea, 2004).
Cubic phase is different compared to lamellar and hexagonal phase. Lamellar
and hexagonal are anisotropic and both phases can observed under OPM. But for
cubic phase, the structure cannot observed under OPM. This is because the properties
of cubis is isotropic. So, normally cubic phase can be identified from its position. I
phase can identified in between the isotropic

19
micellar solution and hexagonal one, while the V phase can be identified is between
the hexagonal phase and the lamellar one (Burducea, 2004). Besides that, cubic
phase does not have enough of shear plane to slide and thus it exhibited higher
viscosity compared to lamellar and hexagonal phase (Collings & Hird,1997).

Figure 2.15: Structure of bicontinous cubic phase

Source: Burducea, 2004

20
Figure 2.16: Structure of normal cubic mesophase ,I1
Source: Collings & Hird,1997

21

CHAPTER 3

RESEARCH METHODOLOGY

3.1 Experimental Work Overview

All of the experimental works were done in the facultys laboratory located at
University Malaya. The experiment is done to identify the phase behavior of liquid
crystal present in Alkyl glycosides (AG) at different temperature by using water as a
solvent. Water was used as an aqueous media in the process of transition phase of
liquid crystal. The method of dissolving water into Alkyl glycosides is called contact
or phase penetration experiment where the amphiphilic molecules are brought into
water or an aqueous surface (Sein, van Breemen, & Engberts, 1995). But later phase
of behavior will be observed and identified by Optical Polarising Microscope. The
rate of the heating process takes place at 5C/min.

22
3.2 Methodology Flow chart

Sample of AG is taken
in a small quantity

Later, the sample was

put on the slide of
microscope and
pressed under a cover
slide
The sample of AG was
heated to its melting
point at rate of
5C/min and then
cooled to room

The water used as

solvent, in a very
careful way was
contact with the
sample

Then, the phase

behavior was observed
and identified by OPM.

Figure 3.2: Flow chart of experiment

23
3.3 Sample Preparation
The flow chart of experiment showed briefly the procedure of experiment. Basically,
the experiment is studied about the behavior of liquid crystal appear at different
range of temperature by using water as a solvent. The sample is initial at room
temperature, T=25C. But then the sample will continuing heated until it reached
clearing temperature. Clearing temperature is where the phase transition temperature
of liquid crystal to its isotropic.

3.3.1 Sample Material

In this experiment the material that are under studied and observed is a compound
known as / -Gluc-PKO (C12). The material is prepared by Glycolipids Jabatan
Kimia, University Malaya by undergo three major routes; acetylation, glycosylation
and deacetylation

3.4 Method of experiment

3.4.1 Optical polarising microscopy (OPM)
Usage of OPM will applied after the contact of penetration of the sample is done.
The phase behavior of AG can only be seen by using OPM. The optical microscope
becomes a tool to observe transparent objects until it becomes visible. Thus, OPM
contribute a lot of benefit in microscope field. OPM is differing from other
microscope that is widely used nowadays in a laboratory. Microscope which
common used is known as compound microscope. Compound microscope view an
image of material by objective lens and then the image is magnified by eyepiece.

24

OPM can even differentiate between isotropic and anisotropic materials.

Liquid crystal of material will possibility portrays a difference of structure such as
hexagonal, lamellar phase and cubic phase. Hexagonal and lamellar phases are
anisotropic while cubic phase is isotropic which ends up do not portray any structure.
Then, the phase of liquid crystal can be observed and identified by a magnification of
100 OPM.

The principle of OPM is using a polarized light. A light with a specific and
polarizing direction can only pass through a polarizer. Basically there are two
polarizer used in OPM. The position of both polarizers is in cross polar, oriented at
right angle to each other. For the first polarizer, the polarizing direction is positioned
vertically to the incident beam, and only allows waves with vertical direction permit
through it. But for the second polarizer, the vertical waves that permit the first
polarizer cannot permit through it. This is because the second polarizer is positioned
horizontally.

Figure 3.3 Schematic Principle of Polarizing Light of OPM

Source: Nikon Corporation

25
3.4.2 Contact Penetration Method
Liquid crystal of AP can be formed by using contact preparation method (Van Doren
and Wingert, 1994). The technique suggested can create a slope of concentration
water which dissolved inside the sample of AG. The consequences of this will tend to
display all phases started from the pure state without water to the fully hydrated
sample of AG. As the sample dissolved with water, the water can have possibility to
evaporate so the sample has to be covered by glass.

The water act as a solvent in this experiment to enhance the arrangement of

surfactant and formed variety phases in the water. The concentration of water will
increase the concentration of solution .Thus it will create vigorous activity of
surfactant to aggregate and form micelles. The probability of surfactants to form
micelles or not are measured by Krafft Point (T K). In order to form micelles, the
surfactants have to pass the temperature of Krafft Point. If the surfactants do not pass
the Krafft Point, they will stay as insoluble surfactants in the water(S. Singh &
Dunmur, 2002).

After the surfactants succeed to pass Krafft Point and increase addition of
water, the surfactants have a potential to form lyotropic mesophase. Lyotropic
mesophase are consists of several phase transitions such as lamellar, hexagonal and
bicontinous cubic.

26

CHAPTER 4

RESULT AND DISCUSSION

4.1 Result of Lyotropic Phases from OPM

The self-assembly within this sample, alkyl glucosides are observed by using optical
polarized microscopy (OPM). The contact penetration method is applied to identify
the phase that might appear under the OPM. The optical textures are observed and
used as result to identify the Lyotropic behaviour. The experiment is more focussing
on qualitative result rather than a quantitative. Final result should result by using
SAXS.

Water penetrations were observed at 1 minute interval. At high water

concentration, micelles formation was observed along with cubic phase. Micelles and
cubic textures are optically black under observation OPM and can differentiate
between by them by examined the shape of bubbles trapped in the phase (Chung and
Jeffrey 1989). Then, water keep penetrate through the sample and about time at 2
minutes, the phase observed is hexagonal phase.

The hexagonal phases are

confirmed exist on that compound as it portrayed birefringent texture (Chung and

Jeffrey 1989).

27
After that, the water continuing to penetrate the sample but other phase has been
discovered at time=4 minutes. The other phase is hydrated crystal phase. Then, water
keep penetrate through the sample but the flow of water started to become slower as
the water approached to the centre of the sample.

Table 4.1: Summary of Lyotropic behaviour during the water of penetration

Time for water penetration(min)

Lyotropic phase

L1

L1, Q

L1, Q, H1

L1, Q, H1, Hydrated

crystal

28

HEXAGON
AL PHASE

MICELLES
FOLLOWED
BY CUBIC

WATER
REGION

WATER
BOUNDAR
Y

HYDRATE
D
CRYSTAL

Figure 4.1: Lyotropic sequences show micelles followed by cubic, hexagonal phase
and crystal + water

4.2 Comparison Lyotropic phases between previous study and current

compound

29
There are other compounds based on glucoside that have been extensively study
about Lyotropic(concentration and temperature). Guerbet branched-chain -Dglucosides(i.e. -Glc-C10C6) is a compound based glucosides are known as one of
the previously that study about Lyotropic phases(Brooks, Hamid et al. 2011). Based
on the study, the high purity compound mimic to glycoglycerolipids which ranging
from C8 to C24 is observed on their Lyotropic phases. From the results of the study,
-D-glucosides(C20) compound exhibited in the HII phase only.

Another lyotropic phase behaviour is observed in Figure 4.2 Glc(C 12)2

(Hato, Minamikawa et al. 1999). This structure is quite similar to 2hexyldecyl- (/) D-glucoside (Ramsch, Ahmad et al.) and was observed
with rich phase behaviour in both liquid crystal phases, thermotropic and
lyotropic respectively. The first phase exhibited isotropic phases (high
probability cubic phase) and the phase replaced by H II phase. Table 4.2
summaries the comparison of several glycolipids based on glucosides that
exhibited Lyotropic phases.

Figure 4.2: The chemical structure of Glc(C12)2 (Hato, Minamikawa et al. 1999)

30
Figure 4.3: The structure of 2-hexyldecyl- (/) D-glucoside

Table 4.2:Summary comparison of several glycolipids based on glucosides that

exhibited Lyotropic phases.
Compound

Lyotropic phases

Glc(C12)2 (Hato, Minamikawa et al.

Cub, HII

1999)
-D-glucosides(C20) (Brooks, Hamid et

HII

al. 2011)
/ -Gluc-PKO (C12)

L1 , Q, HI, Hydrated crystal

The mesophases behaviour can be related to few factors. The chain effect is
one of the factors that can exhibit multiple different Lyotropic phases. According to
Zahid, N., et al., branched chains compound can exhibited reverse non-lamellar
phases due to large chain of hydrophobicity effect. -Dglucosides (C20) formed as
branched-chain compound exhibited an inverse hexagonal phase (Brooks, Hamid et
al. 2011) which shows more complicated difference phase compare to single chain
of current compound, / -Gluc-PKO (C12)

that exhibited normal hexagonal

phase. Another branched-chain compound, Glc(C12)2 (Hato, Minamikawa et al.

1999) shows similar Cubic phase to single chain of current compound at initial
penetration of water. But at the end of penetration of water, Glc(C12)2 shows
inversed hexagonal phase while
normal hexagonal phase.

single chain of current compound exhibited

31
Few comparisons of Lyotropic phases based on maltoside from previous study with
current study based on glucosides are made. Even both structure of compound are
not same but there are some similarity Lyotropic phases can found. Pure compound
of maltose, MalC12N3 (Garidel, Kaconis et al. 2015) have similar hexagonal phase
and cubic phase to / -Gluc-PKO (C12). But micelles do not appeared on MalC12N3.
Another compound of maltoside, MalOC3OC12 from (Garidel, Kaconis et al. 2015)
shows slightly two dissimilarities and one similar of Lyotropic phases. The
compound exhibited complicated cubic phase and hexagonal phase which are
discontinuous cubic phase (I1), a broad hexagonal phase (HII) at the initial of
peneratration of water while single chain of current compound exhibited micelles
phase and normal hexagonal phase. The similar part is both compound exhibited
similar bicontinous phase(V) but at different concentration of surfactant/water.

Figure 4.4: Lyotropic phase behaviour of glycolipid MalC12N3 - (A) water, (B) HI,
(C) VI, (D) pure compound (SmA).

32

Figure 4.5 The activity of water penetration of MalOC3OC12 cause a sequences of

(A) water from the left, followed by (B) cubic phase (C) columnar phase (D)
columnar phase (E) cubic phase and (F) pure compound (SmA). Image above and
below are from (Garidel, Kaconis et al. 2015)

Table 4.3: Summary comparison phase exhibited based on the Glucoside (head group
mixture from palm oil and palm kernel oil) with the other pure Maltoside.
Compound

Lyotropic phases

MalC12N3 (Garidel, Kaconis et al.

HI, VI

2015)
MalOC3OC12 (Garidel, Kaconis et al.

Cub,Col,Col,Cub

2015)
Malto-PKO (N.F.K. Aripin., 2009)

Malto-Palm-S (N.F.K. Aripin., 2009)

/ -Gluc-PKO (C12)

L1 , Q, HI, Hydrated crystal

33

(a) Malto-Palm-S

(b)

Malto-PKO

Figure 4.5: The lamellar phase exhibited in (a) Malto-Palm-S and (b) Malto-PKO
(Image from N.F.K. Aripin., 2009)

The pure maltoside with different alkyl chain synthesis from palm kernel and
palm oil (N.F.K. Aripin., 2009) also exhibited the Lyotropic phase. The results from
the penetration of water into Malto-PKO exhibited lamellar phase and reveals the
same result with Malto-Palm-S even though there is differences between their
average chain lengths. / -Gluc-PKO and Malto-PKO (N.F.K. Aripin., 2009) is
synthesis from the same source which is Palm kernel oil but the mimic to natural
compound ,/ -Gluc-PKO possesses additional phases, HI..

The head group of glycolipid gives effect to the isotropic texture. Headgroup
based on glucoside is a monosaccharide so it makes the structure contain less OH.

34
Less contain of OH will cause less solubility of water and cause a viscous surface.
Hexagonal phase is more viscous texture compare to lamellar (Rosen 2004). And that
makes the head group of sugar that contain less OH, prone to gives high viscous of
texture.

35

CHAPTER 5

CONCLUSION AND RECOMMENDATIONS

5.1 Conclusion
Alkyl glycoside is a non-ionic surfactant based from palm kernel oil. The application
for this surfactant is widely used in cosmetic products, drug delivery system and
many more. In this study, the compound used is a synthetic compound. The palm
kernel oil extracted from palm fruit is acted as the hydrophobic tail and glucose is
selected became the headgroup due to economical aspect.

Based on the experiment, head group sugar and other factor such as chain
effect plays roles that can determine different Lyotropic phases. Head group of
Maltoside preferred exhibited normally lamellar and hexagonal phases compared to
head group of glucosides which can exhibited viscous isotropic figure, cubic phases.
For the chain effect, the branch-chain compound of glucosides preferred exhibited
more complicated figure, inverted hexagonal phase compared to single chain which
only exhibited normal hexagonal phase.

36

Besides that, similarity of Lyotropic phases can be found from the

single chain of current compound to other different chemical structure of
compound. Pure maltoside, MalC12N3 and single chain of current compound based
glucosides, both exhibited normal hexagonal phases and bicontinous phases.
Another compound of maltoside, MalOC3OC12 shows one similarity of Lyotropic
phases which is bicontinous cubic phase.

5.2 Limitation and Recommendation

The limitation for this study is previous research involved pure alkyl glucosides
(C12) is still less (Boyd, Drummond et al. 2000). Several comparisons of previous
study involved pure compounds with synthesis compound are hard to make as the
information regarding pure straight chain of glucosides (C12) have limitations. The
anomeric effect do not cover because the anomer effects are preferred a short chain
compared to long chain. Lastly, Lyotropic phases that exists during the penetration of
water have to be confirmed by using SAXS method so that the confirmation of
phases exists can be verified for the compound.

37
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APPENDICES

Heating stage

Image formed during water penetrate into surfactant