S

ynthesis and characterization of 1-(2-pyridylazo)-2-naphthol

modified -cyclodextrin polymer

Cyclodextrins (CDs) are water soluble cyclic, non reducing oligosaccharides consisting of D(+)-gluocopyranose units linked through -1,4-glycosidic linkages. The major and most
common three cyclodextrins, -cyclodextrin, -cyclodextrin and -cyclodextrin consists of
six, seven and eight D-(+)-gluocopyranose units, respectively. In CDs every gluocopyranose
unit has three free OH groups, two of which (C-2 and C-3) are secondary and one (C-6) is
primary. As each of these free hydroxyl group can be modified, it makes selective
modification extremely difficult. Cyclodextrins are modified for a wide variety of reasons. In
CD derivative family, CD polymers reserve a special position. In recent years attention has
been expanding from supramolecular chemistry of cyclodextrins to supramolecular chemistry
of cyclodextrins based polymers because more sophisticated structures and advanced
functions have been achieved by the formation of supramolecular cyclodextrin polymers.
Compounds consisting of covalently linked cyclodextrin rings are called cyclodextrin
polymers. The cyclodextrins fixed into polymeric structures behave differently from their
monomeric derivatives. CD polymers not only have the inclusion ability, the controlled
release ability, like their parent CDs, but also have fine mechanical intensity and excellent
stability. Therefore, CD polymers have been studied for a long time and received much
attention in pharmaceutical industry, biomedical areas and environmental chemistry. The first
review of the potential application of cyclodextrin polymers in pharmaceutical industry was
given by Fenivesy [344] and Szeman et al. [345]. Renard et al. proposed that the molecular
weight of the water soluble -cyclodextrin polymer depends on the base concentration and
the reaction time [346]. They proposed that higher base concentration leads to modification
on both the faces of -cyclodextrin, whilst lower base concentration leads to substitution only
on face of cyclodextrin.

Why CD modification is needed?

Cyclodextrins (CDs) are water soluble; therefore they cannot be used as an adsorbent in the
uptake of the metal ions and various organic pollutants. The only possible way is to cross link
the cyclodextrin either by using a suitable cross-linking agent or by covalently binding the
cyclodextrin to the backbone of the existing polymers.

Modification of Cyclodextrins
-Cyclodextrin can be modified by one of the two possible methods:
(i)
(ii)

Direct method
Indirect method.

Direct method involves the direct modification of cyclodextrin using a coupling agent or a
cross-linker that results in the formation of a three dimensional structure (Fig. 3.1.1). The
properties of the cross-linked cyclodextrin are determined by the following factors:
type of cyclodextrin viz., -, - and -CD,
type of cross-linker and
molar ratio of the cyclodextrin and the cross-linker.
Variation in all these factors leads to the formation of cyclodextrin polymers with different
sorption behaviour, porosity, chemical properties and density.
Indirect method
Indirect method involves the covalent binding of the cyclodextrin molecule to the already
existing polymeric structure alternatively the surface of the fibers can be modified using
cross-linked cyclodextrin polymers and subsequently used for the filtration, delivery or
debittering purposes.
Because of non-toxic, biodegradable and bioabsorbable properties of CDs, cyclodextrins
fixed into polymeric structures have found a range of applications in various fields such as
food industry, pharmaceuticals and in environmental remediation. These applications have
been reviewed as follows:
Liu et. al., (2005) Synthesized a novel reagent by reaction of -Cyclodextrin polymer (CDP) with 2-DHPH(2,4-dihydroxyacetophenone phenylhydrazone) and exploited its use in
the determination of Cd(II) in different water samples [347].
-Cyclodextrin polyurethanes have been exploited for the removal of organic contaminants
by S.D. Mhlanga et. al., (2007) [348].
L. Ding et al., (2010) Studied the -Cyclodextrin-Zn(II) inclusion complex [349].
R. Mirzajani et al., (2013) exploited -Cyclodextrin based polyurethane (-CDPU) polymers
as a solid media for adsorption and determination of Pb(II) ion in dust and water samples
[350].
J. Rima and K. Assaker (2013) Exploited the use of -Cyclodextrin polymer modified with
beet root fibers for the determination of Zn(II), Pb(II) and Cu(II) [351].

Shirasawa et al., (2013) -CD polymer cross-linked with 4,4 -methylenebisphenylene

diisocyante (MPDI) was synthesized and used in the solid phase extraction of patulin from
apple juice [352].
Raoov et al., (2013) -Cyclodextrin ionic liquid (-CDIL) cross-linked with toluene
diisocyante (TDI) was used to adsorb As(V) and phenols [353].
Sikder et al., (2014) presented a novel remediation method for the removal of Cu(II) from
different water samples using -cyclodextrin cross-linked with epichlorohydrin. They found
that the uptake of Cu(II) followed pseudo second order kinetics and justified the Langmuir
adsorption isotherm [354].
Kawano et al., (2014) -CD cross-linked with dibasic acid was synthesized and used as an
adsorbent for the removal of polychlorinated biphenyls (PCBs) from oil samples [355].
Kayaci et al., (2014) carried out a comparative study using electrospun nanofibres modified
with -, - and -cyclodextrin cross-linked with citric acid for the removal of phenanthrene
and concluded that modification of the fibre followed the order: -CDP > -CDP > -CDP
[356].
For exploiting the utility of CD polymers in preconcentration/separation of metal ions,
pristine polymer is modified with a suitable chelating agent. Chelating group can be loaded
into the sorbent by three different means:
i
ii

the synthesis of new sorbents containing chelate group (new sorbents);

the chemical bonding of such groups on existing sorbents (functionalized

iii

sorbents);
the physical binding of the groups on the sorbent by impregnating the solid matrix
with a solution containing the chelating ligand (impregnation, coated or loaded
sorbents).

The latter remains the most simple to be used in practice.

Chapter 3 deals with the synthesis of -Cyclodextrin polymer using 1,4-butanediol diglycidyl
ether as the cross-linker. The synthesized polymer is then further modified using the chelating
reagent, 1-(2-pyridylazo)-2-naphthol (PAN). The chelating reagent was physically loaded on
to -CD polymer (-CDP). The reagent being hydrophobic in nature gets included in the
hydrophobic cavity of the CD polymer resulting in formation of -CDP-PAN inclusion
complex. Inclusion complex is stabilized by the hydrophobic interactions and Vander Waals
interaction. No chemical bond is involved during inclusion complex formation

3.1 Synthesis of -Cyclodextrin Polymer (-CDP) modified 1-(2pyridylazo)-2-naphthol (PAN)

3.1.1 Materials
3.1.1.1 Equipment
A thermostatic shaking water bath (Perfit India Ltd.) was used to carry out all the inclusive
procedures.

3.1.1.2 Reagents
All reagents used were of analytical reagent grade (Sigma Aldrich/Merck). Double distilled
water was used throughout the experiment.
4 10-6 M solution of the PAN reagent was prepared by dissolving an appropriate amount of
PAN (Fluka Chemical Company) in N,N-dimethylformamide (DMF) solvent.
1,4-Butanediol diglycidyl ether was obtained from sigma Aldrich chemical company
(U.S.A.).
-Cyclodextrin was obtained from SD fine chemical India private limited (Mumbai).
Calibrated glass apparatus (Borosil) were used for volumetric purposes. Glass wares were
washed with chromic acid and soaked in 5% nitric acid and rinsed with double distilled water.

3.1.2 Procedure
3.1.2.1 Synthesis of the -Cyclodextrin polymer (-CDP)
-CDP was synthesized by known method [357]. A brief procedure for the synthesis is
described here. 20gm of -CD was dissolved in 50mL of 20% NaOH. To this was added
20mL of 1,4-butanediol diglycidyl ether drop wise. The polymer was formed in 1.5h and
dried at 900C. The polymer was ground, sieved and washed with double distilled water 5-6
times. Then, the polymer was dried again at 900C and kept at room temperature (250C) in a
dessicator.

Fig. 3.1.1 Represents generalized form showing cavity, toroidal form, primary
and secondary faces of -Cyclodextrin (-CD) & -Cyclodextrin polymer (CDP).

Fig. 3.1.2 Schematic representation of the synthesis cyclodextrin polymer

3.1.2.2 Mechanism of the synthesis of -Cyclodextrin polymer (-CDP)

The Synthesis of -Cyclodextrin polymer (-CDP) from -CD (-Cyclodextrin) and cross
linker 1,4-Butanediol diglycidyl ether involves the abstraction of hydrogen ion from free
primary and secondary hydroxyl groups to form oxy anions (I). The resulting oxy anion then
attacks on to the epoxide ring of the cross-linker resulting in the generation of a new oxy
anion (II) which then abstracts the hydrogen ion (H +) from the medium and results in the
formation of (III). This reaction goes on and results in the formation of cross-linked cyclodextrin polymer.

Fig. 3.1.3 Mechanism of the synthesis of -Cyclodextrin polymer (-CDP)

3.1.2.2 Inclusion of the reagent PAN to form PAN modified -CDP polymer
The regent PAN was included into cavity of the -CD polymer following the literature
method [358]. 5.0gm of the synthesized polymer, -CDP was taken in a 250 mL Stoppard
conical flask. To this was added 10mL of 9.5 pH buffer solution and polymer was allowed to
swell for 15 minutes. A fixed volume of 4 10 -6 M solution of the PAN was added to the
treated polymer and made 50 mL with distilled water. It was shaken for two hours. The
colored polymer so obtained was washed with distilled water and dried at 100 0C. The
modified polymer was stored in a dessicator at room temperature for future use.

3.1.3 Structure of the PAN modified -CDP polymer

Fig. 3.1.4 1-(2-pyridylazo)-2-naphthol (PAN) Included in the cavity of Cyclodextrin Polymer (-CDP) to form PAN- -CDP Host-guest inclusion
complex

3.1.4 Characterization of -CDP

The synthesized polymer was subjected to different techniques for characterization purpose
(i)
(ii)
(iii)
(iv)
(v)

FT-IR Analysis,
SEM Analysis,
TGA/DTA Analysis &
XRD Analysis
Elemental Analysis.

3.1.4.1 Fourier Transform Infra-red (FT-IR) Analysis

The reactant -Cyclodextrin (-CD), the synthesized -Cyclodextrin polymer (-CDP) and
PAN modified -CDP (-CDP-PAN) were subjected to IR analysis on a Pro resolution FTIR
system as KBr pellets in the range 4000-400 cm-1region. From FT-IR (KBr) of -CD, -CDP
and -CDP-PAN it can be seen that: for -CD, 3600- 3000 (OH), 2900 (CH); while for CDP a sharp band at 3400 (OH) is obtained which indicates free OH group as shown in the
structure above. A prominent band at 1120 (COC) ether linkage which is present in the
linker and its absence in -CD spectra clearly indicates the polymerization process.

Fig. 3.1.5 FT-IR Spectrum of native -Cyclodextrin

Fig. 3.1.6 FT-IR Spectrum of cross-linked -Cyclodextrin polymer (-CDP)

Fig. 3.1.7 FT-IR spectrum of PAN modified -CD polymer (-CDP-PAN)

3.1.4.2 Scanning Electron Microscope (SEM) Analysis

The synthesized polymers were subjected to SEM analysis to study their morphological
aspects. SEM Scans of the polymers were carried out at Sophisticated Instrumentation centre
(SIC), Punjabi University, Patiala on JEOL (Tokyo, JAPAN) JSM-6510/LV-SEM Instrument.
For the above experiment 1mg. of the sample was mounted on a glass slide and subjected to
scan at an acceleration voltage of 10Kv. The SEM images were taken at five different
magnifications from X200, X1000, X2500, X3000 and X5000. From the SEM micrographs it
is obvious that the structure of -CD is rock like and -CDP is relatively fibrous which shows
that cross-linking has taken place.

Fig. 3.1.8 SEM scan of -CD at X200

Fig. 3.1.9 SEM scan of -CD at X1000

Fig. 3.1.10 SEM Scan of -CD at X2500 Fig. 3.1.11 SEM Scan of -CD at
X3000

Fig. 3.1.12 SEM Scan of -CD at X5000

Fig. 3.1.13 SEM Scan of -CDP at X200 Fig. 3.1.14 SEM Scan of -CDP at
X1000

Fig. 3.1.15 SEM Scan of -CDP at X2500 Fig. 3.1.16 SEM Scan of -CDP at
X3000

Fig 3.1.17 SEM Scan of -CDP at X5000

Fig. 3.1.18 SEM Scan of -CDP-PAN

at X200

Fig. 3.1.19 SEM Scan of -CDP-PAN

at X1000

Fig. 3.1.20 SEM Scan of -CDP-PAN

X2500

Fig. 3.1.21 SEM Scan of -CDP

PAN at X3000

Fig. 3.1.22 SEM Scan of -CDP-PAN at X5000

3.1.4.3 Thermo gravimetric and Differential thermo gravimetric (TGA/DTA)

Analysis
The synthesized polymers were subjected to TGA/DTA analysis on a TA instruments Q-500
to investigate the thermal and stability properties of the polymers. The analysis was carried
out at SMITA Lab, Dept. of Textile Tech., IIT, Delhi. The thermo gravimetric analyses were
carried out in air up to temperature of 600 0C. at a heating rate of 10 0C/min. on a 15-20 mg.
of samples.
The following changes have been observed during:
(i)
(ii)

The weight loss at 100 0C is primarily due to charring of glucose molecules.

The enhanced stability of -CD polymer is attributed to the cross-linked nature.

(iii)

Since it is well known that cross linking leads to thermal stability.

The presence of two exothermic peaks are due to linkage of cross linker

Fig. 3.1.23 TGA/DTA curve of cross-linked -Cyclodextrin polymer (-CDP)

Fig. 3.1.24 TGA/DTA curve of PAN modified -Cyclodextrin polymer (-CDPPAN)

3.1.4.4 XRD Analysis

Further evidence for the formation of the -CD polymer was obtained through the X-ray
powder diffraction (XRD) as demonstrated in the coming slides. The XRD analysis of the
polymers was carried out at XRD analysis centre at IIT Ropar, Ropar (Punjab). From the
XRD scan, it can be observed, the diffraction pattern of -CDP showed several sharp peaks
and is less diffused which corresponds to relatively crystalline nature of -CDP. But XRD
pattern of PAN--CDP is more diffused and peaks are not as sharp as that of parent polymer,
which simply accounts for amorphous nature of PAN modified -CD polymer.

Fig. 3.1.25 XRD Spectra of cross linked -Cyclodextrin polymer (-CDP)

Fig. 3.1.26 XRD spectra of PAN modified cyclodextrin polymer (-CDP-PAN)

3.1.4.5 Elemental analysis

The synthesized polymers were subjected to elemental analysis at Instrumentation Centre
Department of Chemistry, Punjabi University, Patiala on a CHNS Elementar Analysen
Systeme, Vario Micro Cube, Hanau (Frankfurt) Germany Instrument. The experimental
results obtained from elemental analysis of synthesized polymers were found to be same as
that of calculated one.

Fig. 3.1.27 Elemental analysis spectrum of -Cyclodextrin polymer (-CDP)

Fig. 3.1.28 Elemental analysis spectrum of PAN modified -Cyclodextrin

polymer (-CDP-PAN)

Fig. 3.1.29 Elemental analysis spectrum of PAN modified -Cyclodextrin

polymer (-CDP-PAN)