Professional Documents
Culture Documents
Technical University of d,
Faculty of Process and Environmental Engineering,
ul. Wlczaska 213, 90-924 d, Poland,
zmodrzej@wipos.p.lodz.pl
1Sea Fisheries Institute in Gdynia,
ul. Kotaja 1, 81-332 Gdynia, Poland
Abstract
The method IR and NMR have been used to study the structure of chitosan
microgranules chelated by Ag+ ions. The change of the structure was confirmed
by XRD diffractograms which illustrated the crystalline structure. Analysis of the
IR and NMR spectra confirmed major participation of NH2 and OH groups in
attachment of Ag+ ions to a chitosan molecule which indicates in the same time
changes occurring at glycosidic bonds during the process. After adsorption of
Ag+ ions, the crystalline structure changes. Certain ordering of the structure in
the amorphous part is observed.
Progress on Chemistry and Application of Chitin and Its ..., Volume XIV, 2009 49
Z. Modrzejewska, M. Dorabialska, R. Zarzycki, A. Wojtasz-Pajk
1. Introduction
Chitosan is a polymer which is characterized by good adsorption ability mainly
toward transition metal ions, as it can form chelate compounds. The complex-forming
abilities and stability of a metal-chitosan complex depend mostly on polymer parameters,
i.e. deacetylation degree (DD), polymer chain length and crystallinity. Important are also
the physical form of an adsorbent and adsorptive properties such as composition, pH and
ionic strength. Most studies on the mechanism of formation of chitosan-chelate compounds
refer to copper ions.
From the above mentioned schemes appear that amino and hydroxyl groups are
involved primarily in the process of metal ions binding by chitosan.
50 Progress on Chemistry and Application of Chitin and Its ..., Volume XIV, 2009
The Mechanism of Sorption of Ag+ Ions on Chitosan Microgranules: IR and NMR Studies
In the case of chitosan, the IR spectra are used to compare types (different
deacetylation degrees) and forms of chitosans (chitosan salt, granules, thermosensitive gels)
[1 - 9]. On this basis it is also possible to determine the deacetylation degree, beside molecular
weight which is the major parameter characterizing the polymer [10 - 13]. The IR studies are
carried out also to specify structural changes occurring in a glucosamine molecule, mainly
after modification [14 - 16], cross-linking with an aldehyde, epichlorohydrin, genipine
[16 - 21] and metal ions [22 - 30], degradation [33 - 34] in chitosan+another polymer system
(e.g. PVA, collagen, acrylic acid) [35 - 45] or using additional pharmacological means [46 - 49].
Below, basing on literature data, the most frequently identified bonds which
correspond to a given wave number (cm-1) in the IR spectra are presented:
n 3450, 3500 this band provides an evidence of the presence of OH groups (they are
at carbon C3OH and C6-CH2OH) and strong interrelations between and inside the
molecules. Shifting of this band maximum toward higher frequencies can indicate a
growing ordering of the structure,
n 3360 the band coming from NH groups (broad bands derived from OH and NH groups
overlay each other),
n 2920, 2880 characteristic of CH2 groups are related to the symmetric and asymmetric
bonds in a sacchharide ring,
n 1660 oscillations of C=O in amino groups provide an evidence of the presence of
acetylamino groups, i.e. a partly deacetylated form of chitin,
n 1630 protonated amino groups, the peak is characteristic of chitosan groups,
n 1560 the frequency is related to oscillation of NH groups in amide groups,
n 1590 the peak is characteristic of NH2 amino groups,
n 1425 the frequency corresponds to CH2 group which changes the primary system at
least in the amorphous region into a more advantageous one by hydrogen bonds with the
OH group,
n 1420, 1320 oscillations of OH and CH groups,
n 1380 CH bond, C-CH3 deformations in amide groups,
n 1150-1040 C-O-C in glycosidic bonds,
n 850, 840 CH3COH groups.
Progress on Chemistry and Application of Chitin and Its ..., Volume XIV, 2009 51
Z. Modrzejewska, M. Dorabialska, R. Zarzycki, A. Wojtasz-Pajk
OH C5 +
NH 3
C4 C6 C3 C2 C1
O O HO O
C1
HO C2
O O
C3 NH C4 C6 C5
C7 OH
O
C8
CH 3
52 Progress on Chemistry and Application of Chitin and Its ..., Volume XIV, 2009
The Mechanism of Sorption of Ag+ Ions on Chitosan Microgranules: IR and NMR Studies
Figure 3. The image of the structure before powdering from an electron microscope.
Microgranules used in the tests were formed from chitosan with deacetylation degree 83.4%
and molecular weight 380 kDa. Their characteristic is as follows:
n inner surface about 200 m2/g [66],
n crystallinity as for the initial chitosan (WAXS diffractograms, Figure 4),
n crystallinity index 30% [67],
n there is unbound water in the structure (a characteristic spectrum as for water, maximum
at the temperature around 110 C, enthalpy 300-370 J/g) (DSC spectrum, Figure 5).
90
68
45
23
Progress on Chemistry and Application of Chitin and Its ..., Volume XIV, 2009 53
Z. Modrzejewska, M. Dorabialska, R. Zarzycki, A. Wojtasz-Pajk
3. Results
In the present study, the structural changes following Ag+ ion sorption on chitosan
microgranules are discussed.
2.0
1.5
qc [mmol/g]
1.0
0.5
0.0
54 Progress on Chemistry and Application of Chitin and Its ..., Volume XIV, 2009
The Mechanism of Sorption of Ag+ Ions on Chitosan Microgranules: IR and NMR Studies
The best fitting was obtained when equilibrium was described by the Dubinin-
Radushkevich and Toth isotherms. The obtained results show that adsorption can be
interpreted by the theory of volumetric filling of micropores and that adsorption surface
has a heterogeneous character. A good description of the equilibrium obtained by the Toth
isotherm indicates that the adsorption energy distribution has a rather asymmetric quasi-
Gaussian character extended toward low energies.
chitosan microgranules
70 1.13 mmol Ag/g
0.125 mmol Ag/g
60
50
T [% ]
40
30
20
10
0
4500 4000 3500 3000 2500 2000 1500 1000 500
-1
[cm ]
Progress on Chemistry and Application of Chitin and Its ..., Volume XIV, 2009 55
Z. Modrzejewska, M. Dorabialska, R. Zarzycki, A. Wojtasz-Pajk
70
chitosan microgranules
60 1.13 mmol Ag/g
0.125 mmol Ag/g
50
T [% ]
40
30
20
10
0
1800 1600 1400 1200 1000 800 600 400
-1
[cm ]
In the IR spectrum, a broad band 3600 - 3100 cm-1 is observed. Its shape changes
toward lower frequencies it becomes more asymmetric which indicates the presence of
OH and NH2 groups.
Changes occur also at the frequencies 2900 and 2880 cm-1; peaks corresponding
to CH2 groups tend to equalization, the height of a peak which occurs for a smaller wave
number decreases.
Changes in the range I and II of the amide band indicate that there are amino
groups in the formed compound of chitosan + Ag (I). The peak which corresponds to amino
groups 1590 cm-1 is lowered proportionally to an increase in the number of adsorbed ions.
In the adsorption process amino groups become protonated there is a peak at the wave
number 1530 cm-1 to which the observed increase of pH of the adsorptive corresponds.
The presence of CH2OH groups is very probable, as the peak for the frequency
1420 cm-1 disappears. A decrease of this peak is proportional to the increase of adsorbed
Ag (I) ions.
It seams that the sacharide structure changes after adsorption of Ag (I) ions the
peak 1050 cm-1 becomes more visible.
Changes are also reported in the range of low frequencies from 650 to 400 cm-1. These
changes may be a result of the reducing action of chitosan and precipitation of metallic silver.
56 Progress on Chemistry and Application of Chitin and Its ..., Volume XIV, 2009
The Mechanism of Sorption of Ag+ Ions on Chitosan Microgranules: IR and NMR Studies
Progress on Chemistry and Application of Chitin and Its ..., Volume XIV, 2009 57
Z. Modrzejewska, M. Dorabialska, R. Zarzycki, A. Wojtasz-Pajk
Table 1 shows maxima recorded for the NMR spectra for pure chitosan granules
and for granules which were used in the adsorption of Ag (I) ions.
Chitosan
104.6 57.3 74.8 81.6/83 173.435 22.933
a-0.22 mmol Ag/g
Chitosan
104.1 57.4 74.97 80/82.5 172.621 22.846
a-0.9 mmol Ag/g
Chitosan included in
104.1 57.9 74.7 173.243 23.01
a-1.98 mmol Ag/g C3 C5
Once the silver ions have been adsorbed on carbon C1, the changes are rather
small. After adsorption of 0.22 to 0.9 mmol/g, a slight shift of the peak to the right is
observed, however without any change in its shape. At the adsorption around 2 mmol/g, the
peak becomes less acute, its height decreases and the peak broadens. Moreover, such peaks
appear whose maxima occur at 97 and 107 ppm.
58 Progress on Chemistry and Application of Chitin and Its ..., Volume XIV, 2009
The Mechanism of Sorption of Ag+ Ions on Chitosan Microgranules: IR and NMR Studies
Major changes in the spectrum after adsorption of Ag (I) ions are observed at
carbon C4. In the case of pure chitosan, the peak related to C4 is overlapped by two whose
maxima occur at about 81 and 83 ppm, however, intensity of the peak for 83 ppm is much
higher. After adsorbing 0.25 mmol/g, the peaks are equalized. From analysis of the change
of the peak after adsorption of 0.88 mmol/g, it follows that there is a change in the peak
observed at a lower ppm.
After the adsorption of Ag (I) ions, changes on carbon C1 are rather small. Upon
adsorption of 0.22 and 0.9 mmol Ag/g CS, we can observe a slight shift of the peak to the
right, however without changes in its shape. At a maximum sorption volume 2 mmol/g, the
peak is less acute, its height decreases and it becomes broader. Additionally, such peaks
appear whose maxima occur at 97 and 107 ppm.
From analysis of the NMR spectra it follows that after the sorption of Ag+ ions,
major changes in a chitosan molecule occur at carbons C2, C6 and C4.
50 40
40
30
30
20
20
10
10
18.0 32.0 46.0 60.0 [2*teta] 18.0 32.0 46.0 60.0 [2*teta]
Figure 10. Diffractograms of the microgranule structure after adsorption of Ag+ ions.
In diffraction patterns of pure chitosan granules there are mainly two peaks
2q =10 and 20, which according to literature might indicate crystalline form II.
After the adsorption of Ag+ ions, the crystalline structure changes. From the X-ray
analysis it follows that after adsorption of both metal ions the degree of ordering of the
tested sample is reduced. This can provide an evidence of a dependence of the ordering
degree, i.e. supramolecular structure of chitosan on the adsorption of both metal ions. We
Progress on Chemistry and Application of Chitin and Its ..., Volume XIV, 2009 59
Z. Modrzejewska, M. Dorabialska, R. Zarzycki, A. Wojtasz-Pajk
can observe disappearance of the peak at the angle 2q = 20, broad bands appear at the angle
2q = 35, which indicates that the structure is ordered in the amorphous part.
It follows from the analysis of IR spectra that in the case of adsorption of Ag (I)
ions the basic role in the formation of chelate chitosan compounds with the mentioned
ions is played by amino and hydroxyl groups, which confirms the theory presented in the
literature. These spectra provide also an evidence for the protonation of amino groups
during adsorption process.
Analysis of the NMR spectra confirmed major participation of NH2 and OH groups
in attachment of Ag (I) ions to a chitosan molecule which indicates in the same time changes
occurring at glycosidic bonds during the process.
After adsorption of Ag+ ions, the crystalline structure changes. Certain ordering of
the structure in the amorphous part is observed.
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