Spectrochimica Acta Part A 75 (2010) 1304–1307
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Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa
Adsorption of isoniazid onto sepiolite–palygorskite group of clays: An IR study
Sevim Akyuz
a,∗
, Tanil Akyuz
a
, Elif Akalin
b
a
Istanbul Kultur University, Science and Letters Faculty, Department of Physics, Atakoy Campus, 34156 Istanbul, Turkey
b
Istanbul University, Science Faculty, Department of Physics, Vezneciler, 34134 Istanbul, Turkey
article info
Article history:
Received 19 November 2009
Accepted 31 December 2009
Keywords:
Adsorption
Clays
IR spectroscopy
Isoniazid
Loughlinite
Palygorskite
Sepiolite
abstract
The adsorption of isoniazid (INH) on sepiolite, loughlinite (natural Na-sepiolite) and palygorskite from
Anatolia was investigated by FT-IR spectroscopy. Experimental results indicated that INH molecules,
adsorbed on sepiolite–palygorskite group of clays, are coordinated to surface hydroxyls by H-bonding
interaction through the pyridine ring nitrogen lone pairs. Moreover, some of the adsorbed INH molecules
may enter the interior channels of the sepiolite–palygorskite structure and involve H-bonding interaction
with zeolitic water. Some intensity and frequency changes in the OH stretching band of surface hydroxyls
(Si–OH) of the INH-treated sepiolite and loughlinite were observed. However, this band is found to be less
affected by the adsorption of isoniazid in the case of palygorskite, probably because the surface Si–OH
groups in palygorskite appear to be less abundant than in sepiolite or loughlinite.
© 2010 Elsevier B.V. All rights reserved.
1. Introduction
Isoniazid (C
6
H
7
N
3
O, abbreviated as INH) is an important drug
for the chemotherapy of tuberculosis. It also seems to be effective in
the treatment of extrapulmonary illnesses such as meningitis and
genito-urinary infections [1,2].
Sepiolite, loughlinite, and palygorskite form an important
group of the (palygorskite–sepiolite) phyllosilicate class of clay
minerals which has many industrial, catalytic and environ-
mental applications [3–6]. Loughlinite is known as natural
Na-sepiolite and is virtually identical in appearance to sepiolite,
both in a hand specimen and microscopically [5,7]. However,
field observations and mineralogical determinations indicate that
loughlinite and sepiolite are formed authigenically and indepen-
dently in different physicochemical environments rather than
being the product of a transformation of one to the other
[7]. The chemical formulas of loughlinite, sepiolite, and paly-
gorskite are Na
2
Mg
3
Si
6
O
16
·8H
2
O, Mg
4
Si
6
O
15
(OH)
2
·6H
2
O, and
(Mg,Al)
5
(Si,Al)
8
O
20
(OH)
2
·8H
2
O, respectively [4–6]. Structurally,
they consist of blocks and channels extending in the c-axis direction
[8]. The width of the channels is different in sepiolite and paly-
gorskite [8,9]. It is known that surface silanol (Si–OH) groups play
an important role in the selective sorption on the external surfaces
of the sepiolite group of clays [8].
∗
Corresponding author. Tel.: +90 2124984401; fax: +90 2124658310.
E-mail address: s.akyuz@iku.edu.tr (S. Akyuz).
In our previous work we reported the spectroscopic results
of the adsorption of isoniazid on natural montmorillonite and
saponite [10]. As a continuation of our studies on clay–drug inter-
actions, in this study the adsorption of isoniazid on sepiolite,
loughlinite and palygorskite from Anatolia were investigated by
FT-IR spectroscopy.
2. Experimental
In the present work, natural sepiolite, loughlinite, and paly-
gorskite samples from the Mihalliccik-Eskisehir region of Anatolia
(Turkey) were employed. The clays were ground to a fine powder of
<0.5 m particle size, and then were analyzed for purity by X-ray
diffraction, differential thermal, and IR spectroscopic techniques.
The results indicate that loughlinite is associated with analcime
(approx. 8%) and Al
2
O
3
(approx. 6%), and has a detectable calcite
impurity (IR; 1435 cm
-1
). The chemical compositions of starting
clays were given in a previous paper [11].
Solid INH was reagent grade (Sigma) and was used as received.
INH-treated clays were prepared by methods analogous to those
given in literature [10] or by solid–solid reactions [12,13].
Solid–solid reactions are known as useful ways to introduce organic
guest species into the interlayer species of clays [12,13]. The
products were washed with solution to remove excess organic
molecules and then dried. The FT-IR spectra of KBr discs of sam-
ples were recorded on a Jasco 300E FT-IR spectrometer (2 cm
-1
resolution) based on averaging 200 sample and 40 background
scans. Spectral manipulations such as baseline adjustment, band
fitting, and obtaining the second derivative were performed using
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doi:10.1016/j.saa.2009.12.069