All the above characterizations show that the Schiff base amphiphiles of interest were

synthesized.

3.4 DSC

After characterization, DSC was taken for the samples. The resulted

thermograms are displayed in figures 3.28, 3.29, 3.30, 3.31, 3.32 and 3.33. The melting

transition temperatures of the samples are presented in table 3.6

It can be noted that there is only less variation in the transition when the length of

the carbon chain is increased, whereas in case of the two aromatic systems (2A, 2B, 2C

and 2D) there is sudden hike in temperature. This may be due to the increase in

stiffness in those compounds induced by the additional aromatic ring.

Sample Transition Temperature

in °C
1a 54.01
2a 89.90
3a 60.35
1b 58.25
2b 94.08
3b 64.04
1c 67.77
2c 80.68
3c 72.16
1d 31.17
2d 72.44
3d 40.91

Table 3.6 Melting Transition temperature of the samples

a)

b)

igu

re

3.28 DSC curves of a) 1A and b) 2A

a)

b)

Figure 3.29 DSC curves of a) 3A and b) 1B

a)

b)

Figure 3.30 DSC curves of a) 2B and b)3B

a)

b)

Figure 3.31 DSC curves of a) 1C and b) 2C

a)

b)

Figure 3.32 DSC curves of a) 3B and b) 1D

a)

b)

Figure 3.33 DSC curves of a) 2D and b) 3D

3.5 UV- Visible spectra

The figures 3.34, 3.35, 3.36 and 3.37 show the UV-Visible spectra of the

compounds. The electronic transitions may be due to azomethine group and aromatic

ring present in the compounds. The maximum absorbance, λmax are shown in table 3.7.

Sample Maximum Absorbance, λ max Intensity

in nm in a.u.

1a 286.4 0.2405
2a 274.8 0.1899
3a 287.7 0.1925
1b 308.2 0.3448
395.6 0.0431
2b 317.0 0.1821
408.0 0.0061
3b 308.2 0.2569
395.6 0.0219
1c 258.8 0.2999
2c 260.2 0.4851
3c 260.2 0.3336
1d 283.5 0.2340
2d 257.0 0.2550
3d 248.5 0.2890

Table 3.7 Maximum Absorbance of the samples

It can be seen that only one peak was noticed for all compounds except 1B, 2B

and 3B.The spectra of these compounds shows two absorption peaks. The additional

peak may be due to the n-Π* transition of –N(CH3)2 group. As for as other spectra the

area under the peak for some compounds is broad compared to others. This implies

that the absorption is dependent on variation of substituents. On changing the

substituent from nitro to N, N dimethyl group, bathochromic shift is noticed, whereas for

substitution with cyano and fluoro groups show hypsochromic shifts.

0 .2 5 1A
I n t e n s it y ( a . u ) 2A
0 .2 0
3A

0 .1 5

0 .1 0

0 .0 5

0 .0 0
200 300 400 500 600
W a v e le n g t h ( n m )

Figure 3.34 UV- Visible spectra of 1A, 2A and 3A

1B
0.35

0.30
3B
0.25
Intensity (a.u.)

0.20
2B
0.15

0.10

0.05

0.00
200 300 400 500 600
Wavelength (nm)
 Figure 3.35 UV- Visible spectra of 1B, 2B and 3B

0 .5
I n t e n s it y ( a . u . ) 2C
0 .4
3C

0 .3
1C

0 .2

0 .1

0 .0
200 300 400 500 600
W a v e le n g t h ( n m )

Figure 3.36 UV- Visible spectra of 1C, 2C and 3C

0 .3 0 3D
2D
0 .2 5 1D
I n t e n s it y ( a . u . )

0 .2 0

0 .1 5

0 .1 0

0 .0 5

0 .0 0
200 300 400 500 600

W a v e le n g t h ( n m )
 Figure 3.37 UV- Visible spectra of 1D, 2D and 3D

3.6 Fluorescence spectra

All samples fluoresce when given an excitation wavelength of 230nm. The

fluorescence spectra of the samples as bulk are presented in figures 3.38, 3.39, 3.40

and 3.41. The spectra show hyperfine lines but were not well resolved. This implies that

some absorption not seen in UV-Visible spectra also given fluorescence.

a) b)
4
3.0
1A 2A
2.5
3 Intensity (a.u.)
2.0
Intensity (a.u.)

2 1.5

1.0
1
0.5

0 0.0
250 300 350 400 450 500 550 600 250 300 350 400 450 500 550 600

Wavelength (nm) Wavelength (nm)

c) 4

3A
3
Intensity (a.u.)

0
250 300 350 400 450 500 550 600

Wavelength (nm)
 Figure 3.38 Fluorescence spectra of a) 1A, b) 2A and c) 3A

a) 4

1B
3
Intensity (a.u.)

0
250 300 350 400 450 500 550 600
Wavelength (nm)

b)
4

2B
3
Intensity (a.u.)

0
250 300 350 400 450 500 550 600
3.5
Wavelength (nm)
3.0
3B
2.5
c)
Intensity (a.u.)

2.0

1.5

1.0

0.5

0.0
250 300 350 400 450 500 550 600

Wavelength (nm)
 Figure 3.39 Fluorescence spectra of a) 1B, b) 2B and c) 3B

a)
4

1C
3
Intensity (a.u.)

0
250 300 350 400 450 500 550 600
Wavelength (nm)

3.5
b)
3.0 2C

2.5
Intensity (a.u.)

2.0

1.5

1.0

0.5

0.0
4250 300 350 400 450 500 550 600
Wavelength (nm)
3
3C
Intensity (a.u.)

c)
2

0
250 300 350 400 450 500 550 600
Wavelength (nm)
 Figure 3.40 Fluorescence spectra of a) 1C, b) 2C and c) 3C

a) 3.5

3.0
1D
2.5
Intensity (a.u.)

2.0

1.5

1.0

0.5

0.0
250 300 350 400 450 500 550 600

3.5
Wavelength (nm)
b) 3.0
2D
2.5
Intensity (a.u.)

2.0

1.5

1.0

0.5

0.0
250 300 350 400 450 500 550 600

Wavelength (nm)
3.5

3.0
c) 2.5
3D
Intensity (a.u.)

2.0

1.5

1.0

0.5

0.0
250 300 350 400 450 500 550 600
Wavelength (nm)
 Figure 3.41 Fluorescence Spectra of a) 1D, b) 2D and c) 3D

3.7 Molecular Modeling

Molecular modeling studies were performed on to know the kind of packing

arrangement. Recently, an X-ray crystallographic method for ascertaining the molecular

packing of self-assemblies has been reported [31]. First, the molecular length of three

amphiphiles was calculated by using Corey–Pauling–Koltun (CPK) modeling based on

single crystal data for oleic, linoleic, and linolenic acid [32]. The models showed similar

values despite a bending effect. Second, X-ray diffraction patterns were measured. The

‘d‘ spacing values of crystalline compounds are shown in Table 3.8.

Sample ‘d’spacing Distance obtained

obtained from XRD from molecular structure
1A 30.19 27.93
2A 47.65 35.14
3A 31.54 30.59
1B 13.99 29.15
2B 18.09 34.69
3B 43.19 31.92
1C 47.28 28.72
2C 57.26 35.35
3C 45.69 31.22
1D 29.95 27.36
2D 39.26 34.12
3D 46.16 29.95

Table 3.8. ‘d’ spacing of the crystalline samples at 100% relative intensity
 The compounds 1A, 3A, 1C, 2C, 3C and 3D all show ‘d ‘ spacing longer than the

length of a single molecule obtained from the CPK model suggesting that this is longer

than the length of a single amphiphile but smaller than twice the length (as in a bilayer

arrangement). These results strongly suggest that self-assembled structures of these

molecules form a bilayer structure with a relatively small region interdigitated by

hydrophobic interaction, as shown in figures 3.42, 3.43, 3.44 and 3.45.

The ‘d’ spacing values for compounds 1B and 2B are less than that obtained

from the CPK model. This may be due to poor orientation of these compounds in the

crystalline state. For comparison purpose, ‘d’ spacing values of 27.89 and 50.29 A°

which correspond to relative intensity less than 100% are taken for 1B and 2B

respectively and the molecular models based on these values are built.

a) b) c)
 b) c)
a) Figure 3.42
Models
representing molecular packing
in a) 1A, b) 2A and c) 3A

a) b) c)
Figure 3.43

Models representing molecular

packing in a) 1B b) 2B and c) 3B
a) b) c)
Figure
3.44 Models representing
molecular packing in a) 1C, b)
2C and c) 3C

Figure 3.45 Model representing molecular packing in a) 1D, b) 2D and c) 3D