synthesis and analysis of surfactant chelating precursors on copper ions

1. PRESENTED BY SHAILEND SINGH SUMMAH
*

2. * General Introduction To Surfactant
Chemistry
*Surfactants form a unique class of chemical
compounds. Their nature and physical
properties of surfactants, emphasizing their
ability to radically alter surface and interfacial
properties and to self-associate and solubilize
themselves in micelles.

3. *Surfactants are amphiphilic molecules, which have both a
hydrophobic and a hydrophilic group, on opposite ends. They
work by arranging themselves in such a manner that a polar
solvent (such as water) will only be in contact with the
hydrophilic group or vice versa.
Figure 1.1.1: Structure of a surfactant monomers

4. *1.Surfactants is soluble in water
*2.Detergency
*3. Foaming

5. *Non ionic
*Cationic
*Anionic
*Amphoteric
1.1.5.2Surfactant classifications
Class Examples structures
Anionic Na Stearate
Na dodecyl sulfate
Na dodecyl benezene sulfonate
CH3(CH2)16COO
-
Na
+
CH3(CH2)11SO4
-
Na
+
CH3(CH2)11C6H4SO3
-
Na
+
Cationic Laurylamine hydrochloride
Trimethyl dodecylammonium
chloride
Cetyl trimethylammonium chloride
CH3(CH2)11NH
+
3Cl
-
C12H25N
+
(CH3)3Cl
-
CH3(CH2)15N
+
(CH3)
3
Br
-
Non-ionic Polyoxyethylene alcohol
Alkylphenol ethoxylate
CnH2n+1(OCH2 CH2)MOH
C9H19-C6H4-(OCH2CH2)NOH
Zwitterionic Dodecyl betaine
Lauramidopropylbetaine
C12H25N
+
(CH3)2CH2COO
-
C12H23CONH(CH2)3N
+
(CH3)2CH
2COO
-
Table 1.1:.surfactant classifications.

6. * A micelle is an aggregate of surfactant molecules dispersed in a
liquid colloid. A typical micelle in aqueous solution forms an
aggregate with the hydrophilic "head" regions in contact with
surrounding solvent, sequestering the hydrophobic single-tail
regions in the micelle centre.
* How micelles is formed in water?
* • In aqueous solutions of this type of surfactant tend to
formed ordered aggregates such as micelles and bilayers.
* • Here the polar groups are exposed to the water and the
hydrocarbon portions are "buried" within the core, away from
the water.
* Figure 1.5:- Structure of micelles in aqueous solution.

7. *The process of forming micelles is known as
micellisation and forms part of the Phase behaviour of
many lipids according to their polymorphism.
*Micelles are non-stable components formed by the
aggregation of individual surfactant monomers,
capable of exhibiting different types of structures.
The possibility of structures can be spherical,
cylindrical and planar. The shape and size of micelle
depends of factors such as the surfactant molecule
chemical structure, varying environmental conditions
such as temperature, concentration, surfactant
property, ionic strength, and pH.

8. *Types of micelles
*1. Reverse micelles
*2. Direct micelles

9. *
*Definition Of Critical Micelle Concentration
*Factors affecting the critical micelle concentration
and micellar size
*There are several factors affecting the CMC of a
surfactant. These include the amphiphile chain
length, dissolved salts, the structure of the head
group, temperature, the structure of the alkyl chain
and polar additives. The effects of chain length, salts
and alcohol on the critical micelle concentration
have been widely studied.
*The krafft point
*The cloud point

10. *Role of copper in the human body.
*Copper toxicity
*Chelation therapy

11. * INTRODUCTION
*Strategies of synthesizing phenylalaninol
* Figure 2.00: Conversion of L-phenylalanine to L-phenylalaninol

12. *Reduction of L-phenylalanine
Figure 2.3: Reduction of phenylalanine.

13. Figure 2.1: 1H NMR spectrum of compound L-phenylalanine.
Type of
proton
Chemical shift
(ppm)
benzene
7.12-7.55
CH (methine) 4.0
CH2 (methylene) 3.0-3.19
NH2 (amine) 3.25-3.35
Table 2.0Characterisation of the 1H NMR spectra of phenylalaninol
Figure 2.4: 1H NMR spectrum of compound L-phenylalaninol.

14. The results obtained is shown below:-
*Conversion of glycine to glycinol
Before synthesizing glycinol the starting compound glycine was analysed using 1
H
NMR and infrared spectroscopy.

15. *
Type of proton Chemical shift
(ppm)
Relative number
of protons
Splitting pattern
CH2 (methylene) 3.59 3.554 singlet
Figure 2.7: 1H NMR spectrum of compound glycine.
Table 2.3 Characterisation of the 1H NMR spectra of glycine.

16. Figure 2.8: IR spectrum of compound glycine.

17. Figure 2.9: Conversion of glycine to glycinol
Figure 2.10: 1H NMR spectrum of compound glycinol

18. Second attempt of synthesising glycinol
H2N
O
OH
glycine
SOCl2
CH3OH
18hrs
step 1
OCH3
H2N
O
Glycine methyl ester
H2N
OH
glycinol
distilled THF
LIAlH4
Heating
under
reflux
70o
C
20hrs
step 2
Step 1: Methylation of glycine.
Step 2 :the reduction of glycine methyl ester to
glycinol.

19. Figure 2.14: 1H NMR spectrum of glycinol second attempt
Type of proton Chemical shift
(ppm)
CH2 (methylene) 3.5-3.7 9
NH2 (amine) 2.20-2.50
OH 1.0-1.5
Table 2.5 Characterisation of the1H NMR spectra of glycinol second attempt

20. Strategies of synthesizing alaninol
1.Conversion of alanine to alaninol
2.The starting compound DL-alanine as the starting material was analysed
using 1H NMR and infrared spectroscopy. The results obtained is shown
below:-
Figure 2.16: 1H NMR spectrum of alanine
Type of proton Chemical shift
(ppm)
CH3 (methyl) 1.40-1.55
CH(methine) 3.70-3.90
Table 2.6: Characterisation of the1H NMR spectra of alanine

21. Figure 2.17: 1H NMR spectrum of alaninol
Figure 2.18: 1H NMR spectrum of alaninol first time purification

22. Second attempt of synthesizing alaninol.
In this case the synthesis of alaninol consists of two steps.
Step 1:- methylation of alanine
Step 2:- involve the reduction of alanine methyl ester to alanine the final product.
Figure 2.19: Conversion of alanine to alanine methyl ester to alaninol
The formation of alanine methyl ester was confirmed by 1H NMR and infrared spectroscopy as shown
below.
Figure 2.20: 1H NMR spectrum of alanine
methyl ester

23. Second attempt of synthesizing alaninol
Figure 2.21: 1H NMR spectrum of alaninol

24. PROCEDURE TO DETERMINE THE NUMBER OF LIGANDS CHELATING WITH COPPER (II)
and COPPER (I) IONS
1.Stoichiometric determination of copper ion complexes
The stoichiometric ratio of the complexes were determined on:-
1. A calibrated conductivity meter
2. A calibrated pH meter
3. A calibrater voltage meter
4. A calibrated ion analyser to investigate activity
2.All techniques have the same procedure of experimentation
3.Examples of how stoichiometric ratios of copper complexes is
determined
Graph of activity of ions for M1 complexing with L1.

25. Volume of L1/
cm3 Number of
moles
M1 L1 Mole ratio
4.07 1.25x 10-4 4.07x10-5 3:1
11.0 1.25x 10-4 1.1x10-4 1:1
39.0 1.25x 10-4 3.9x10-4 1:3
Table2.8: Stoichiometric ratio of M1L1 complex
Transition state of M1L1 (1:1) complex to M1L1 (1:3)

26. Determinationofbindingconstantsbyspectrophotometrytechniques
General procedures for determining binding constant of metal
complexes
1. The maximum absorbance are recorder within the range
of 400nm to 600nm for the UV spectrophotometer and within the
range of 400nm to 800nm for the colourimeter.
2. The concentration of metal ions denoted as [GUEST] is
calculated for each volume added.
3. The free extinction coefficient is calculated and subtracted
to the extinction coefficient obtained after addition of metal
ligands.
4. A graph of [Guest]/( Ea-Ef) versus [GUEST] is plotted and
binding constant calculated as explained below
5. Finally all these procedures are repeated for all UV and
colourimetric analysis for the quest of finding the binding constant
of all metal complexes.

27. SUMMARY OF BINDING CONSTANT AND STOICHIOMETRIC RATIOS.
Type of
complex
Stoichiometric
ratios obtained in
conductivity analysis
Stoichiometric ratios
obtained in
potentiometric
analysis
Stoichiometric
ratios obtained in
voltammetry
analysis
Stoichiometric
ratios obtained in
activity
analysis
Binding
constant
In UV analysis
Binding constant
In colourimetric
Analysis
M1L1 3:1
1:1
1:3
1:2 1:3 1:4 2.062X10-1 6.66X101
M1L2 1:1
1:2
3.08X103 1.81X102
M1L3 1:3
1:3
1:4 1:1
1:1
1:3
8.33X101 6.9X101
M1L4 2:1 1:3
1:3
1:2
1:2
3.78X102 1.16X102
M1L5 1:2
1:2
1:2 7:1
3:1
1.68X102 7.30X102
M1L6 1:4 1:2 1:2
1:4
1:3
1:2
2.75X102 6.68X101
M2L1 1:1
1:4
1:2 1:2 6.5X101 1.83X102
M2L2 1:1
1:3
7.4 5.86X101
M2L3 1:3 1.6X101 1.86X103
M2L4 1:1
1:4
2:1 1:3 1.70X101 8.92X101
M2L5 1:2
1:3
8.00X101 1.50X101
M2L6 1:2
1:3
1:3 2.90X102 3.18X101
.. Table2.9: Summary of stoichiometric ratios and binding constant.

28. Possible structures and transition phase of copper
(II)complexes
Figure 2.28: Copper (II) ethylenediamine (M1L1) mole ratio 1:4
OHH2N
Cu+2
OH2H2O
M1L2 mole ratio 1:1
transition
phase
OHH2N
Cu
OHH2N
+2
M1L2 mole ratio 1:2

Figure 2.29: possible transition phase diagram of M1L2 (1:1) to M1L2
(1:2)
Figure 2.30: Copper (II) ammonia (M1L3)
mole ratio 1:3
Figure 2:31: Copper (II) ammonia
M1L3 mole ratio 1:4
Figure 2.32: Transition phase of M1L3 (1:1) TO
M1L3 (1:3)

29. Figure 2.33: Copper (II) phenylalaninol M1L4 mole
ratio 2:1
Figure 2.34: Copper (II) phenylalaninol M1L4
mole ratio 1:2
Figure 2.35: Copper (II) phenylalaninol M1L4 mole ratio 1:3
Figure 2.36: Copper (II)
glycinol M1L5 Figure 2.38: Transition state of M1L6 (1:2)
TO M1L6 (1:4)

30. Possible structures and transition phase of copper
(I)complexes
NHHN
Cu
M2L1 mole ratio1:1
Cu
H2NH2N
NH2NH2H2NH2N
NH2 NH3
M2L1 mole ratio 1:4
transition
phase

Figure 2.40 Transition phase of M2L1 (1:1) to M2L1
(1:4)
Figure 2.42: Transition phase
of M2L2 (1:1) TO M2L2 (1:3)
Figure 2.43: Copper (I)
ammonia M2L3 (1:3)
Figure 2.44:- Transition phase of M2L4
(1:1) to M2L4 (1:4)
Figure 2.47:- Transition phase of
M2L5 (1:2) to M2L5 (1:3)
Figure 2.48:- transition phase of M2L6 (1:2)
to M2L6 (1:3)

31. Comparison of binding strength of metal complexes
obtained from UV analysis
1.From table 2.16 the decreasing order of binding
strength is obtained
M1L1<M1L3<M1L5<M1L6<M1L4<M1L2
M2L2<M2L3<M2L4<M2L1<M2L5<M2L6
2.Conclusion and comparison of binding strength for copper (II)
complexes
3.Conclusion and comparison of binding strength for copper (I)
complexes
4.Comparison of binding strength of metal complexes
obtained from colourimetric analysis
From table 2.16 the decreasing order of binding strength is
obtained for colourimetric analysis
M1L3<M1L4<M1L2<M1L1<M1L6<M1L5
M2L5<M2L6<M2L4<M2L1<M2L2<M2L3

32. CONCLUSION AND COMPARISON OF RESULTS AND TECHNIQUES FOR THE
INVESTIGATION OF STOICHIOMETRIC RATIOS OF METAL COMPLEXES
1.Conclusion
In summary, our investigation showed that ethanolamine and phenylalaninol can basically act as ligands
capable of coordinating to copper (II) ions in aqueous solution because their stoichiometric of metal
ions to ligands are 1:2 and 1:3.
In summary, our investigation showed that phenylalaninol can basically act as ligands capable of
coordinating to copper (I) ions in aqueous solution because the stoichiometry of the metal ions to
ligands are 1:4.