Experimental

Apparatus

Potentiometric measurements were made using a double junction Ag/AgCl reference electrode
Thermo Orion 720 A Model pH-ion meter. Thermo Orion 812600 combined glass
electrode,which is with internal solution of potassium chloride (900002) saturated with silver
chloride and external filling solution potassium nitrate (900003), and as reference electrode
thiocyanate-selective carbon paste electrode as indicator electrode was used. The CPE body used
was boughtobtained from Bioanalytical Systems, Inc. (BASI MF-2010). Deionized distilled water
with a conductivity of 18.2 MΩ obtained from the ELGA Purelab Classic Ultra Pure Water
System device was used in the preparation of all solutions. Impedance measurements and
chronopotentiometric measurement plots (E-t) were taken with the BASi C3 cell stand combined
with the CHi 660D Model Analysis system. For this, a triple electrode system consisting of
reference electrode (Ag/AgCl, (3M NaCl), auxillary electrode (Pt wire BASi MW-1032) and
nanomaterial based thiocyanate-selective carbon paste indicator electrode was used. The SEM
image of the electrodes was taken from the LEO-EVO 40 model SEM device. The potentiometric
titration experiments on samples containing thiocyanate of the electrode were performed with an
Orion Model 940 automatic titrator.

Reagents and preparation of solutions

In this study, the dichlorobis(methyldiphenyl-phosphine)palladium(II) complex used as an

ionophore in the production of thiocyanate-selective electrodes and all chemicals used in the
preparation of the solutions were obtained from Sigma-Aldrich with the highest purity.
Plasticizers such as BEHA, BEHP, BEHS, o-NPOE and lipophilic additives such as THATPB,
TBATPB, THPTPB were used by procuring nanoparticles from Sigma-Aldrich in selectophore
purity.

Anion solutions were prepared in pH 4.0 buffer solution (acetic acid/acetate). In addition, MES
buffer (pH 5.0; pH 6.0) and TRIS buffer (pH 7.0) solutions containing 0.1 molm -3 NaCl were also
used in this study. Sodium thiocyanate calibration solutions were freshly prepared before each
experiment.

Construction of nanomaterial modified carbon paste electrodes

In this study, nanomaterial modified thiocyanate selective carbon paste electrodes were
obtained by adding appropriate amount of ionophore, plasticizer, graphite powder,
lipophilic additive and MONPs at varying rates as shown in Table 1. A homogeneous cake
was prepared by mixing these ingredients for 30-40 minutes with the help of a spatula. The
cavity of the resulting commercially available CPE body (BASi MF-2010) was completely
filled with the resulting composite mixture to fabricate thiocyanate- selective CPE based on
nanomaterial. Then, the surface was smoothed with circular movements on wax paper. The
electrodes were conditioned with 1.0×10-4 molm-3 NaSCN solution before measurements.

Electrochemical measurements

All electrochemical measurements were taken with the electrochemical cell set up as below at
23.0±2.0 oC with the given electrochemical cell setup below.

DJ Ag/AgCl RE || analyte solution | CPE E-t graphs modified with nanomaterial were obtained
by adding thiocyanate ion to solutions containing 0.1 molm -3 NaCl (pH:4.0) in a way to provide a
10-fold concentration change.

EIS studies were carried out in alternating current impedance technique by using 0.2 V open
circuit devices with a frequency range of 101-106 Hz with 0.005 V amplitude as a surgical
parameters. Nyquist plots were obtained for solutions containing thiocyanate in different methods
at pH 4.0.

Sample preparation for analytical application

For analytical sample application, Erythromycin thiocyanate by Medicavet was prepared.the

declared value in solution powder 0.0284g thiocyanate / equivalent to 1.0000g Erythromycin
thiocyanate.

It was kept in an ultrasonic bath for about 3 hours to ensure complete dissolution of the drug in
50 cm3 of ethyl alcohol. Then, 50 cm 3 of deionized water was added to the bottle to make it up to
100 cm3, and the mixture was stirred for one hour again. Appropriate amounts of this solution
were taken and 50.0 cm3 samples were prepared for analysis by adjusting their pH to 4.0.