R AT I O N A L

DESIGN OF
NOVEL
S U R FA C TA N T S

By Nickolas Rampaul
Supervisor: Dr. Lorale Lalgee
 Introduction

What is a surfactant?

• This is an amphiphilic molecule containing hydrophilic (strong affinity for

dissolving in water) and hydrophobic (water repelling or fearing) fragments.

• Surfactant systems are especially researched as a result of their applications

in industries such as households and solubilizing agents.

• For this project alkyl polyglycosides (particularly Pentose and 6-deoxy

hexose) surfactants are studied, particularly their acyclic conformations.

 Pentose Surfactants

RS SR RS SR RS SR

H OH HO H H OH

H OH H OH HO H

H OH H OH H OH

CH2OR' CH2OR' CH2OR'

D-Ribose Derivative D-Arabinose Derivative D-Xylose Derivative

6-Deoxy-hexose Surfactants

RS SR RS SR RS SR

H OH HO H H OH

H OH H OH HO H

HO H H OH HO H

HO H HO H H OH

CH3 CH3 CH3

L-Rhamose Derivative L-Fucose Derivative D-Fucose Derivative

a) SR
b) c)
SR SR

H SR H SR H SR

(CHOH)n (CHOH)n (CHOH)n

CH2OH CH2O R' CH3

Figures a) and b) represent the surfactant derivatives of the pentoses to be tested

while figure c) represents the surfactant derivatives of the 6-deoxy-hexoses
to be tested

Red represents the hydrophobic portion of the surfactants

where R = C2H5, C3H7, C12H25 and Ph
and R' = CH3, C2H5, (CH3)3, C6H5 and C11H23

Blue represents the hydrophilic portion of surfactants

 Introduction
What is Critical Micelle Concentration (CMC)?

• There two rules that one must follow regarding a surfactant’s surfactivity.

• Firstly, the CMC needs to be determined, which is the surfactant’s concentration when
the surfactant undergoes saturation adsorption at the solution’s surface and micelles
first start to appear.

• Secondly, the surface tension (γ0) that corresponds at the CMC (this is the smallest
surface tension that surfactants can most likely reach).
 Introduction
What is Critical Micelle Concentration?

• Below the CMC is where the surface tension would decrease with respect to an
increase in the surfactant’s concentration since the number of surfactants at the
solution interface would increase.

• In contrast, beyond the CMC is where the solution’s surface tension becomes
constant due to the interfacial concentration of the surfactant not changing further.
 Introduction
What is Quantitative Property Structure Relationships (QSPR) and Multiple Linear
Regression (MLR)?

• QSPRs are models that mathematically correlate features derived from the structures
of a compound to their physiochemical or biological activity. QSPR works on the basis
that structurally akin compounds have similar activities.
 Introduction
What is Quantitative Property Structure Relationships (QSPR) and Multiple Linear Regression
(MLR)?

• In his 2007 study of non-ionic surfactants, Mahmoud Gad developed a model (an equation resembling
MLR) for predicting CMC in HyperChem using Molecular weight (Mw), Hydrophobic-Hydrophilic
fragments molecular weight ratio (χ), Polarizability (α), Partition coefficient (log P) and Energy of
Hydration (EH).

• Log (CMC) = -0.0911 + 0.0157 Mw – 0.3246 χ – 0.2551 α – 0.2992 log (P) – 0.3130 EH
 Rationale for this project

• To construct environmentally friendly novel non-ionic surfactants with the help of QSPR.

• To compute log (CMC) values for surfactants using each parent sugar.

• To compare log (CMC) values within each parent sugar while identifying trends.

• To compare log (CMC) values across parent sugars while identifying trends.

• To compare log (CMC) values of the created novel surfactants to the range of log (CMC)

values for non-ionic surfactants which would determine if the surfactant is an acceptable

surfactant.

• To order the acceptable surfactants of decreasing surfactivity.

 All 24 combinations for the D-Ribose Derivative were drawn and their molecular weight and hydrophobic-
hydrophilic molecular weight ratio were recorded.

Next, the D-Ribose Derivatives were copied and pasted into Chem Draw 3D and were promptly saved
M as .mol files.
ET
H
Following that, each D-Ribose surfactant were individually merged into Hyper Chem, the semi-empirical
O
AM1 method was selected and under QSAR properties, Polarizability, Log P and Energy of Hydration were
D
obtained.
O
L
O
G After all necessary data was obtained, an excel sheet was formed and the log (CMC) values for each
Y surfactant was obtained using Mahmoud Gad’s equation.

The procedure was repeated for the derivatives of D-Arabinose, D-Xylose, L-Rhamnose, L-Fucose and D-
Fucose where only 4 drawings were obtained for the 6-deoxy-hexose surfactants due to only having R
groups.
Results
Results
Results
Results
Results
Results
Results
Results
Results
 Discussion of Results
• Within the derivatives; R’ group constant & changing R group and increasing the alkyl

chain length , the log (CMC) decreased.

• The log (CMC) values decreased due to increasing steric strain via R & R’ groups, causing

micelle formation at lower concentrations.

• Since is the bulkiest group with the largest steric strain, the low log (CMC) values were

noted whereby its decreased from Ph to The same trend is seen for keeping R constant

and changing R’.

• Out of all the Pentose and the 6-deoxy-hexose Surfactants; the surfactants with highest log

(CMC) values and lowest Hydration Energy, were the D-Xylose & D-Fucose surfactants.
 Advantages and Disadvantages

• 39 surfactant models were found to have fallen in this range, 11 D-Xylose, 12 for D-
Ribose and D-Arabinose and 2 for L-Rhamnose and L-Fucose.

• One advantage of using these surfactant models is that they were easy to make in
HyperChem and Chem Draw due to those programs having the necessary tools and
databases to make them.

• One disadvantage of using these surfactant molecules was that as the R and R’ groups
got bulkier, the model took longer to generate results.
 Conclusion
• From this project, it was noted that alkyl chain length influenced the log (CMC) value of a
non-ionic surfactant. Where the greater the alkyl chain length, the lower the log (CMC)
value is.

• In the Log (CMC) range (-1 to -5.76), of the 84 created novel surfactants, 39 were deemed
acceptable.

• Surfactant 26 with highest log (CMC) at -1.121 & Surfactant 6 with lowest at -5.751.

• 12 were D-Arabinose derivatives and D-Ribose Derivative.

• This means D-Ribose and D-Arabinose would be the best parent sugars to model Alkyl
Polyglycoside surfactants after.
 References

• Mahmoud Gad, E. A. QSPR for Nonionic Surfactants. Journal of Dispersion Science and
Technology 2007, 28, 231–237. https://doi.org/10.1080/01932690601058810.

• Karlheinz Hill. Alkyl Polyglycosides; Weinheim New York Basel Cambridge Tokyo Vch,
1996.

• Turchi, M.; Karcz, A. P.; Andersson, M. P. First-Principles Prediction of Critical Micellar

Concentrations for Ionic and Nonionic Surfactants. Journal of Colloid and Interface
Science 2022, 606, 618–627. https://doi.org/10.1016/j.jcis.2021.08.044.
 Acknowledgements

I would like to thank Dr. Lalgee for being my supervisor for this project and for allowing me to
partake in this study. As well as my project members for their cooperation.
Thank you for watching