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ESSENC
CE - Interna
ational Jourrnal for Envvironmentaal Rehabilitaation and Conservation
n
Volume VI: No. 2 2015 [28
[ – 34] [ISS
SN 0975 - 62722]
[ww
ww.essence-jouurnal.com]
Abstractt
In thhis comm munication, synthessis, actiivity against C. albicanss. The antim
microbial
characterrization an nd electrocchemistry of actiivity was coompared witth a standarrd drug,
Dimethyl-dibenzo[b,,h]tetraphenyyl - 2, 3, 8, 9- Genntamycin.
tetraazacyclododeca - 1, 3, 7,, 9 - tetraeene Keyywords: Macrocyclicc compleexes |
macrocycclic complexes of Fe(IIII) and Co((II) elecctronic specttral studies | cyclic voltaammetry
complexees have been n carried ouut. The specttral | anttibacterial acctivity.
studies are in good agreem ment with the t Intrroduction
octahedraal geometry y of thesee macrocycclic In Recent advances inn chemistryy have
complexees. Cyclic voltammetric
v c studies were provvided the abbility to dessign and syynthesise
carried out
o on Pt dissh (0.031 cm m2) electrodee in mimmics of natuural macrocyyclic systems and to
DMSO. Cyclic vo oltammetric studies haave preddict their properties. Chemistts have
shown onne electron riversible reedox processes surmmounted delicate
d moolecular sttructures
for thesee macrocycliic complexees on the baasis throough the deevelopment of novel synthetic
s
of their peak
p seperattion and peakk current rattio. metthods (Costees, 1987; Baldwin et al., a 1975
The hetterogeneous electron transfer rate r andd Reddy et al.,
a 2012). Thhere has beeen much
0
constant (K ) was also determ mined with thet inteerest in thet field of mixed--valence
help of Nicholson and Kochi’s method and a maccrocyclic compounds,, especiallly the
found inn the orderr K0Co(II) > K0Fe(III). The T appearance of thhe classificaation system devised
macrocycclic com
mplexes a
also show
wed by scientists and
a theoretical treatise on the
antimicroobial activities againstt E. coli, P. elecctronic confiiguration. Prrussian blue, a three
aeruginoosa, B. cereu us, S. aureus and antifunggal dim
mensional arrray of Fe (IIII) center bridged
For corresspondence: by [Fe(CN)6]4-- units, hass been useed as a
Departmennt of Chemistry
y, Gurukula Kaangri pigm ment in ink and dyes beecause of itss intense
Vishwaviddyalaya, Haridw
war, India
bluee colour whiich arises duue to metal-tto-metal
E-mail: prashant_tevatia@yahoo.co.in
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Tevatia et al. /Vol. VI [2] 2015/28 – 34
charge transfer (MMCT) transition (Malik et electronic and IR spectra of these macrocyclic
al., 1983; Ma et al., 2006 and Verani et al., complexes were recorded on Double Beam
2000) whereby an electron is transferred from Spectrophotometer (Shimadzu 2450
an Fe (II) to Fe(III) center. The MMCT spectrophotometer) in methanol and
transition is not possible in the oxidized Fe (II) Schimadzu-8400S double beam
- Fe (III) or reduced Fe (II) - Fe (I) states spectrophotometer by KBr DRS method
resulting in loss of the blue coloration making respectively. The electrochemical studies of
this compound brown and white respectively. these macrocyclic complexes were carried on
The significant roles played in living systems the Platinum electrode (0.031 cm2) using Auto
by metal ions depend on their confinement lab Metrohm 663 VA Stand Instrument. Tetra
within approximately planar tetradentate ethyl ammoniumperchlorate (TEAP) used as
totally enclosed macrocyclic systems which are supporting electrolytes. The pre-treatment of Pt
themselves, highly conjugated species. Much electrode was carried out before every
of the mystique associated with the binding of experiment.
molecular oxygen by naturally occurring heme, Preparation of the Macrocyclic complexes
has been removed by successful challenge to The macrocyclic complexes have been
this field (Lonibala et al., 2006; Soderberg,
synthesized according to the literature method
2008; Nunez et al., 2010 and Chen et al.,
using 2 moles of 3,4 - diaminotoluene (0.244
2012). The ability of synthetic macrocyclic
complexes to mimic the properties of naturally g), 2 moles of benzyl (0.420 g) and 1 mole of
occurring macrocyclic systems is now well iron (III) chloride (0.162 g) (Tevatia et al.,
recognized. Keeping all views, in this 2014 and Singh et al., 2002).
communication, synthesis, characterization and Ph Ph
Cl
to the cleavage of CH3 and Cl units (Chandra 0.20 V. This redox process is the
et al., 2013). quasirreversible as also indicated by the peak
Electrochemical studies current ratio ipa/ipc. The redox process,
Cyclic voltammetry of these macrocyclic Co+2/Co+1 of this macrocyclic complex is also
found the quasirreversible redox process,
complexes have been carried out in DMSO
supported by corresponding peak separation
containing 0.1M TEAP as supporting
electrolyte. Cyclic voltammograms of these ∆E and the peak current ratio. Further, the
macrocyclic complexes are shown in fig. 2. In plots of ip against v1/2 were found to be linear,
indicating that the redox process was
this communication, the diffusion coefficient
controlled by diffusion, following the Randles-
(D0) and heterogeneous electron transfer rate
constant (K0) for these macrocyclic complexes Sevcik equation for reversible electrochemical
reactions.
have been calculated with the help of
Nicholson and Kochi methodologies (Anuj et i = -2.69 × 105 n3/2AD1/2cv1/2
al., 2015 and Nicholson and Shain, 1964). The Where n is the number of electrons transferred,
cyclic voltammogram (Fig. 2a) of Fe(III) A is the area of the electrode, D is the diffusion
macrocyclic complex at 200 mVs-1 scan rate coefficient, c is the analyte concentration and v
exhibited two anodic peaks corresponding to is the scan rate.
the cathodic peak and one anodic peak without The diffusion coefficient (D0) and
corresponding cathodic peak. The first redox heterogeneous electron transfer rate constant
process of Fe (III) macrocyclic complex is a (K0), as calculated are in the order D0Co(II)
reversible redox couple Fe+2/Fe+1 corresponds (2.11× 10-5 cm2/s) > D0Fe(III) (1.7 × 10-5 cm2/s)
to peak separation ∆E = -0.07 V and formal and K0Co(II) (5.41 × 10-3 cm/s) > K0Fe(III) (3.41 ×
potential E1/2 = -0.95 V while the second redox 10-3 cm/s).
process is a quasi-reversible with the
corresponding to peak separation ∆E = 0.15 V
and formal potential E1/2 = 0.65 V for the
couple, which is also supported by the peak
current ratio (ipa/ipc) that is close to unity. The
cyclic voltammogram (Fig. 2b) of [Co(II)L]
complex showed a reversible redox couple
L/L-1 corresponding to peak separation ∆E = -
0.13 V and formal potential E1/2 from -1.01 V
at 200 mV s-1 scan rate. The reversibility of
this couple is also supported by the ratio ipa/ipc
that is close to unity while the second redox
couple for Co+2/Co+3 is found at formal .
potential +0.80 V with peak separation ∆E = (a)
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Tevatia et al. /Vol. VI [2] 2015/28 – 34
15
2005). Solvent medium was used as a negative Fe(III)
10 Co(II)
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Tevatia et al. /Vol. VI [2] 2015/28 – 34
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Tevatia et al. /Vol. VI [2] 2015/28 – 34
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