Study of Aggregation Behavior of Predesigned Azobenzene-Cholesteryl Derivatives in Deep Eutectic Solvents
Author(s) : Rathinam Balamurugan 1 , Liu Bo-Tau 1 and Murugesan Vajjiravel 2
1 Department of Chemical and Materials Engineering, , National Yunlin University of Science and Technology , Taiwan
2 Department of Chemistry , B. S. Abdur Rahman Crescent Institute of Science And Technology , India
Glob J Chem Sci
Article Type : Research Article
Characterization of Ia-Ie
The synthetic route for the preparation of azobenzene and cholesteryl-based conjugates (azo-1 to azo-5) is shown in (Figure 1). The photosensitive azo benzene derivatives (Ia-e) were obtained by reacting sodium phenoxide with respective p-substituted aniline in the presence of nitrous acid (diazonium salt). All the azo derivatives were purified by repeated recrystallization in hot ethanol.
FT-IR (KBr, ?max/cm-1)?3463 (-OH), 1517, 1580 (C-C in Ar), 1728 (C=O). 1H-NMR (CDCl3,
500 MHz, ? in ppm)?8.4 (d, 2H, Ar-C-COO), 8.19 (d, 2H, Ar-H), 7.9-8.0 (m,
4H, Ar-C-N), 7.0 (d, 2H, Ar-C-OH), 5.79 (broad, s, -OH), 4.38 (q, 2H, O-CH2),
1.39 (t, 3H, O-CH2-CH3).
Figure 1: Synthetic routes and structures of
azobenzene-cholesteryl derivatives and materials for DES.
Characterization of Azo-1 to Azo-5
The above-synthesized azo derivatives (Ia-e) were
further subjected to react with cholesteryl chloroformate in presence of
triethylamine in chloroform or dichloromethane to get eutectic gelators (azo-1
to azo-5) with a yield of 59-79%. All the compounds were purified by
recrystallization in ethanol. All the compounds were found to be soluble in
DMF, CHCl3, CH2Cl2, acetone, and insoluble in ethanol, methanol, and toluene. The
structures of all the azo compounds were confirmed by 1H and 13C-NMR analysis.
Azo-1: Yield: 79%; FT-IR (KBr, ?max/cm-1):2868,
2947 (CH2), 1764 (C=O), 1500, 1586 (C-C in Ar), 1247 (COC). 1H-NMR
(CDCl3, 500 MHz, ? in ppm) : 7.97 – 7.90 (m, 4H), 7.53-7.47 (d, 2H),
7.36 – 7.34 (m, 2H), 7.26 (t, 1H), 5.44 (d, 1H), 4.66 (m, 1H), 2.51–1.33 (m,
28H), 1.09 (s, 3H), 0.93 (d, 3H), 0.87 (d,6H), 0.69 (s, 3H). 13C NMR (500 MHz,
CDCl3) ? 152.91, 150.21, 139.05, 131.07, 129.07, 124.05, 123.28,
121.65, 79.13, 77.25, 56.66, 56.12, 49.97, 42.30, 39.69, 39.50, 37.92, 36.82,
36.54, 36.17, 35.78, 31.90, 31.83, 28.21, 28.00, 27.63, 24.27, 23.82, 22.81,
22.55, 21.04, 19.27, 18.71, 11.85.
Azo-2: Yield: 73%; FT-IR (KBr, ?max/cm-1)?2869, 2942 (CH2), 1762 (C=O), 1503, 1593 (C-C in Ar), 1247
(COC).1H NMR (500 MHz, CDCl3) ? 7.92 – 7.89 (m, 4H), 7.33-7.26 (d,
2H), 7.02 – 7.00 (m, 2H), 5.43 (d, 1H), 4.69 (m, 1H), 3.88 (s, 3H), 2.51–1.33
(m, 28H), 1.08 (s, 3H), 0.93 (d, 3H), 0.87 (d,6H), 0.68 (s, 3H). 13C NMR (500
MHz, CDCl3) ? 162.11, 152.58, 150.34, 146.88, 139.06, 124.76,
123.69, 121.56, 114.19, 79.05, 77.25, 56.65, 56.11, 55.54, 49.95, 42.29, 39.68,
39.50, 37.91, 36.81, 36.53, 36.16, 35.17, 31.88, 31.82, 28.20, 27.99, 27.62,
24.26, 23.82, 22.80, 22.55, 21.03, 19.26, 18.70, 11.84
Azo-3: Yield: 76%; FT-IR (KBr, ?max/cm-1)?2867, 2949 (CH2), 1763 (C=O), 1718 (C=O), 1497, 1602 (C-C in
Ar), 1255 (COC).1H NMR (500 MHz, CDCl3) ? 8.20-8.19 (d,
2H), 8.18 (d, 2H), 7.99 – 7.92 (m, 4H), 7.37 – 7.36 (m, 2H), 7.26 (t, 1H), 5.43
(d, 1H), 4.43-4.39 (m, 1H), 2.50–1.33 (m, 28H), 1.17 (s, 3H), 0.99 (d, 3H),
0.87 (d,6H), 0.68 (s, 3H). 13C NMR (500 MHz, CDCl3) ? 165.99,
154.92, 153.48, 150.10, 139.01, 132.24, 130.55, 124.38, 123.30, 122.60, 121.74,
79.21, 77.25, 61.25, 56.65, 56.12, 49.96, 42.29, 39.68, 39.49, 37.90, 36.81,
36.53, 36.16, 35.77, 31.89, 28.20, 27.99, 27.61, 24.26, 23.81, 22.80, 22.54,
21.03, 19.26, 18.70, 11.84.
Azo 4: Yield: 69 %; FT-IR (KBr, ?max/cm-1)?2874, 2947 (CH2), 1759 (C=O), 1721 (C=O), 1490, 1606 (C-C in
Ar), 1251 (COC).1H NMR (500 MHz, CDCl3) ? 8.36 (d, 2H), 7.94-8.34
(m, 4H), 7.01 – 7.26 (d, 2H), 5.39 (d, 1H), 4.04 - 4.12 (d, 2H), 2.39–1.85 (m,
28H), 1.11 (s, 3H), 0.97 (d, 3H), 0.87 (d,6H), 0.66 (s, 3H). 13C NMR (500 MHz,
CDCl3, ? in ppm) 162.94, 156.06, 154.68, 148.18, 146.17, 139.40,
125.60, 124.68, 123.07, 122.88, 114.91, 77.62, 77.25, 77.00, 76.74, 68.51, 67.84,
56.67, 56.12, 49.98, 42.29, 39.50, 38.05, 36.85, 36.53, 36.16, 35.77, 31.88,
31.83, 28.20, 28.00, 27.70, 25.96, 25.70, 24.26, 23.81, 22.80, 22.54, 21.02,
19.24.
Azo-5: Yield: 59 %; FT-IR (KBr, ?max/cm-1)?2862, 2949 (CH2), 1756 (C=O), 1726 (C=O), 1484, 1607 (C-C in
Ar), 1254 (COC).1H NMR (500 MHz, CDCl3) ? 8.30 (d, 2H),
7.99-8.79 (m, 4H), 7.14 – 7.32 (d, 2H), 5.37 (d, 1H), 4.06 - 4.13 (d, 2H),
2.39–1.85 (m, 28H), 1.14 (s, 3H), 0.99 (d, 3H), 0.88 (d,6H), 0.63 (s, 3H). 13C
NMR (500 MHz, CDCl3, ? in ppm): 156.41, 154.48, 148.32, 146.14,
139.14, 125.63, 124.49, 123.27, 122.79, 114.77, 77.59, 77.35, 77.09, 76.44,
68.61, 67.69, 56.71, 56.11, 49.89, 42.29, 39.54, 36.99, 36.61, 36.14, 35.66,
31.80, 31.76, 28.19, 28.02, 27.54, 25.79, 25.65, 24.29, 23.71, 22.78, 22.49,
21.00, 19.16.
All the spectral values are in accordance with the
assigned structures. For example, the 1H-NMR spectrum of compound
azo-4 is shown in (Figure 2). The
presence of aromatic protons between 7.01-8.36 ppm and the presence of alkene
proton (C=CH) at 5.39 ppm confirm the presence of azobenzene and cholesteryl unit
in the structure. All other alkane protons in the cholesteryl units are
resonated between 0.5-2.0 ppm. The 13C-NMR for compound azo-4 was depicted in (Figure 3). The presence of peaks
around 154 ppm and 122 ppm corresponding to carbonyl (C=O) and -C=CH- carbon
(in cholesteryl unit) confirmed the successful formation of azo-4. All the
spectral values are in accordance with the structure of the molecule.
Figure 2: 1H-NMR spectrum of Azo-4.
Figure 3: 13C-NMR spectrum of Azo-4.
Gelation ability of predesigned azo derivatives in DES
The gelation ability of all the azo compounds (Azo-1 to Azo-5) is shown in (Table 1).
Compoumd/DES |
Azo-1 |
Azo-2 |
Azo-3 |
Azo-4 |
Azo-5 |
Zn:EG |
Insoluble |
Insoluble |
Insoluble |
Insoluble |
Gel |
Ch:EG |
Soluble |
Gel |
Insoluble |
Insoluble |
Insoluble |
Ch:Urea |
Gel |
Insoluble |
Gel |
Gel |
Insoluble |
Ch:Gly |
Insoluble |
Insoluble |
Insoluble |
Gel |
Insoluble |
Table 1: Gelation ability of Azo-1 to Azo-5 in DES.
From the table, it was observed that all the
derivatives form a gel in at least one of the DES studied. For example, azo-1 and
azo-2 form gel in Ch: Urea and Ch: EG respectively. Whereas, azo-3 and azo-4 were
form gel in Ch: Urea and Ch: Gly. Azo-5 form gel in Zn:EG. All the derivatives
are structurally isomeric with varying substitutions such as hydrogen, ether,
ester, nitro, etc at the terminals of azobenzene. This indicates that the
substituents at the terminals of azobenzene play a crucial role in gelation ability
in DES.
The gel color varied from light orange to dark red color depended on the color of the synthesized compound as well as the type of DES. The gelators molecules formed semi-transparent gels (Figure 4) and demonstrated thermos-reversibility, which means the compounds could be brought into solution by heating and the hot solution could be converted back to the gels upon cooling to room temperature.
Figure 4: Representative pictures of eutectic gels.
Morphological studies
To gain visual insights regarding the morphologies of the molecular aggregation modes, all the eutectic gelators were subjected to SEM analysis and the results are depicted in (Figure 5). The gelators exhibited as self-assembled flower-like, microplates/sheets, and bundle fiber-like aggregates with several lengths to breadth ratio as shown in the figure. Azo-1 exhibits a more crystalline-like structure than azo-2. In the case of azo-4 both in Ch: urea and Ch: EG exhibit similar flower-like aggregates with porous structure. However, unlike Ch: urea, entangled fibrous textures were seen on Ch: EG-based gels. These morphologies indicate that the nature of the eutectic solvent is crucial in the aggregation of the gelators.
Figure 5: The SEM morphology of gels from (a) azo-1 in Ch:Urea, (b) azo-2 in Ch:EG, (c) azo-3 in Ch:urea, (d) azo-4 in Ch:urea, (e) azo-4 in Ch:Gly and (f) azo-5 in Zn:EG
Potential applications
In general, the organo/hydro gelators can be used as a
template or support for the synthesis of nanoparticles such as silver
nanoparticles (AgNP), gold nanoparticles (AuNPs), and iron nanoparticles
(FeNPs). Since the gelators possesses a 3D network structure, a large number of
functional groups can provide space for the nucleation and growth of the noble
metal nanoparticles [24-26]. Therefore, we attempt to use our eutectic gelators
as template/structure-directing agents for the synthesis of copper chloride
nanoparticles (CuCl NPs). For that, the gelator azo-4 in Ch:Urea was chosen and
applied as a template for the synthesis of CuCl NPs as shown in the
experimental section.
Thus obtained copper chlorides from both neat and azo-4 based eutectic gels were subjected to morphological analysis by SEM and the results were merged in (Figures 6a-d).
Figure 6: The SEM morphology of gels from (a and b) CuCl2 in Ch:Urea, (c and d) CuCl2 in Azo-4 eutectic gel.
From the morphology, it can be observed that the neat
eutectic solvent exhibited self- assembled CuCl nanoparticles (Figure 6a and 6b),
whereas eutectic gel exhibited aggregated nano-rods-like textures (Figure 6c
and 6d).
The morphology of CuCl nanoparticles from the neat is almost similar to the reported textures by Ying Huang et al, in which the author used PVP [27]. But in our case, sodium bisulfite was used. However, the size of the particles is found to be too high (<500 nm) when compared to the reported one. This may be due to the fact that the addition of PVP which preventing the aggregation and controlled the size of the nanoparticles, whereas in our case we didn’t add any size controlling reagent. In the case of eutectic gelators-based synthesis, nanoparticles were expected. But, interestingly, aggregated rods with lengths of several micrometers and diameters of approximately 200-400 nm were observed. This may be due to the fact that the complexation of copper with the nitrogen of pyridine units of the azo-4 gel may assist or direct nanoparticles aggregated into form nanorods. However, the exact mechanism of the formation of nano-rods is unclear. These results revealed that the azo-4 eutectic gelators can act as a template for the synthesis of nano-rods. However, these preliminary studies need to go a long way in order to optimize the conditions and reagents if need to be added to form nanorods of <100 nm, and the mechanism of formation of nano-rods by various analytical techniques such as XRD and XPS analysis are under progress.
Photolysis
The effects of photo-irradiation of all the compounds were studied by irradiating under UV-vis light and the changes were recorded. The representative results of photoirradiation of azo-4 in DES were shown in (Figure 7). From the figure, it was observed that azo-4 eutectic gel exhibited an absorbance at 331 nm. Since azobenzene undergoes trans-to-cis isomerization under UV light, the gel-to-solution transition was expected similar to the corresponding organ gels.
Figure 7: Changes in UV spectral characteristics during photolysis of Azo-4 gel in a eutectic solvent.
However, in azo-4 eutectic gels did not undergo gel to sol transition; moreover, the corresponding absorption profiles also revealed that there was no change after irradiation of azo-eutectic gel by UV light for 2 min. After 10 min of irradiation showed no obvious or little changes in the absorption profile. However, there is no change in the nature of the gel even after irradiated over 30 min under UV light, indicating that azo-4 the eutectic gel didn’t undergo isomerization under UV light. It may be due to the formation of strong/hard gel as well as high viscosity of the eutectic solvent in which the azo molecule remains in the stable transform.
The cholesteryl appended azobenzene derivatives with varying terminal
substituents were synthesized and their gelation ability in deep eutectic
solvents was studied. All the gels are hard, semi-transparent, and thermally
reversible. The morphology of eutectic gels by SEM analysis revealed dense
fibrous, flower-like, and sheet-like textures, depending on the type of deep
eutectic solvents used. Unlike azobenzene organogelators, these azobenzene
eutectic gels did not undergo gel-to-sol transition during photolysis, which
may be due to the hardness of the gel which restricts the transformation of
trans-to-cis form, which was further supported by their absorption profiles
before and after photolysis. Finally, an attempt has been taken to use this
eutectic gel as a template for the synthesis of copper chloride nanorods. These
primary studies investigated the designing of novel eutectic gels and their
applications for nanomaterial synthesis.
This study
was supported financially by the Ministry of Science and Technology, the
Republic of China (MOST 108-2221-E-224-026-MY3).
The authors
declare no competing interests.
*Corresponding Author: Rathinam Balamurugan, Department of Chemical and Materials Engineering, National Yunlin University of Science and Technology, Taiwan, Republic of China
Copyright: © 2021 All copyrights are reserved by Rathinam Balamurugan, published by Coalesce Research Group. This This work is licensed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution and reproduction in any medium, provided the original author and source are credited.