Sun light assisted synthesis of silver nanoparticles in zeolite matrix and study
of its application on electrochemical detection of dopamine and uric acid in
urine samples
S. Meenakshi, S. Devi, K. Pandian, R. Devendiran, M. Selvaraj
PII:
DOI:
Reference:

S0928-4931(16)30606-3
doi: 10.1016/j.msec.2016.06.037
MSC 6651

To appear in:

Materials Science & Engineering C

Received date:
Revised date:
Accepted date:

13 February 2016
2 June 2016
9 June 2016

Please cite this article as: S. Meenakshi, S. Devi, K. Pandian, R. Devendiran, M. Selvaraj,
Sun light assisted synthesis of silver nanoparticles in zeolite matrix and study of its
application on electrochemical detection of dopamine and uric acid in urine samples,
Materials Science & Engineering C (2016), doi: 10.1016/j.msec.2016.06.037

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Sun Light Assisted Synthesis of Silver Nanoparticles in Zeolite
Matrix and Study of Its Application on Electrochemical Detection of

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Dopamine and Uric Acid in Urine Samples

Department of Inorganic Chemistry, University of Madras,

Guindy Campus, Chennai - 600 025
Department of Chemistry, Guru Nanak College,
Velachery, Chennai 600 042

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S. Meenakshi1, S. Devi1, K. Pandian1, *, R. Devendiran2, M. Selvaraj2

To whom address correspondence should be made

Dr. K. Pandian, Associate Professor
Department of Inorganic Chemistry
University of Madras

Chennai- 600025, India.

Email: jeevapandian@yahoo.co.uk
Tel.: +91-44-22202795

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Abstract

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Sunlight assisted reduction of silver ions were accomplished for the synthesis of silver

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nanoparticles incorporated within the mesoporous silicate framework of zeolite Y. The zeolite-Y

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and AgNP/Zeo-Y were characterized by field emission scanning electron microscopy,

transmission electron microscopy, N2 adsorption-desorption BET isotherm and Xray diffraction

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techniques. The incorporation of silver nanoparticles within the porous framework was further
confirmed by cyclic voltammetry and electrochemical impedance spectroscopy. An enhanced

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electrocatalytic oxidation of biologically important molecules like dopamine and uric acid using
AgNP/Zeo-Y modified glassy carbon electrode has been developed. A simultaneous oxidation of

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DA and UA peaks were obtained at + 0.31 V and + 0.43 V (vs. Ag/AgCl) using AgNP/ZeoY/GCE under the optimum experimental condition. A well-resolved peak potential window (~

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120 mV) for the oxidation of both DA and UA were observed at AgNP/Zeo-Y/GCE system. The
calibration curves for DA and UA were obtained within the dynamic linear range of 0.02 x 10
to 0.18 x 10

-6

M (R2 = 0.9899) and 0.5 x 10

-6

to 0.7 x 10

-6

-6

M (R2 = 0.9996) and the detection

limits were found to be 1.6 x 10-8 M and 2.51 x 10-8 M by using differential pulse voltammetry
method. The proposed method was successfully applied for the determination of both DA and
UA in human urine samples with a related standard deviation was less than 3 %, and n = 5 using
the standard addition method.
Key words:

Sun light assisted synthesis, Silver nanoparticles, Zeolite Y, Dopamine, Urine

Samples.

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1. Introduction
Zeolite is a mesoporous alumina silicate based solid materials and its contain well

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defined open-pore structure, with often the tunable pore size and they are very attractive host

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materials for developing nanocomposites because of their ability to selectively exchange and

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integrate transition metal cations within their cages and interconnecting channels [1]. The metal
modified porous materials have been used for the widest range of applications like catalysis [2,

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3], anti-bacterial materials [4], fuels [5], water treatment [6, 7], and biosensors [8-12]. Recently,
zeolite modified electrodes (ZMEs) have continued to be a major concern because of its surface

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area, porous nature, surface functionalization and chemical inertness [13-15]. ZMEs are widely
used in ion-exchange [16], electrocatalysis and electroanalytical devices with better sensitivity

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[17], high thermal and chemical stability [18]. Nowadays, the ZMEs were accomplished in
various routes through copper doped zeolite expanded graphite epoxy electrode [19], iron-ion

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doped natrolite zeolite- MWCNT modified GCE [20], Ag-doped zeolite expanded graphiteepoxy composite electrode [21], methylviologen supported on zeolite Y modified electrode [22],
graphite-zeolite modified electrode [23], mesoporous carbon [24], cytochrome c immobilized on
NaY zeolite [25], methylene blue incorporated into mordenite zeolite [26] bismuth modified
zeolite doped CPE [27], NiCo2/O4/nano-ZSM-5 nanocomposite [28] and Ru-red incorporated
zeolite modified CPE [29].
Dopamine (DA) is usually coexisting with uric acid (UA) in biological fluids which are
playing an important role in human metabolism [30]. The abnormal concentration level of these
molecules will lead to certain diseases such as schizophrenia, Parkinsons disease,
hyperuricemia, gout and pneumonia [31, 32]. Therefore, the development of selective and
sensitive method is important to determine the concentration level of DA and UA accurately.

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The electrochemical methods are accessible for sensing and quantification of DA and UA due to
simple, more accurate with lower detection limits, high electrocatlytic activity and large potential

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window [33]. However, the oxidation of DA and UA are occurring in the same potential region

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at conventional electrodes. To overcome this problem, various kinds of chemically modified

electrodes were utilized to resolve well-defined peak separation between DA and UA system.
example,

copper

nanoparticles

incorporated

polypyrrole

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For

film

[34]

and

gold

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nanoparticles/choline modified electrodes [35] were used for the assay of DA and UA. Lin et al.,
demonstrated the PtNPs deposited polydopamine coating on MWCNT for simultaneous

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detection of DA and UA [36]. Recently self-assembled monolayer of cysteamine functionalized

MWCNT on gold have shown for the enhanced simultaneous detection of both DA and UA [37].

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Silver nanoparticles have been concerned worldwide research interest due to their unique
physical and chemical properties which lead to plentiful potential applications like catalysis [38],

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optics [39], biosensors [40], electronics [41] and antimicrobial agents [42] etc. Several methods
for synthesis silver nanoparticles for instant thermal method [43], photochemical [44],
microwave irradiation [45], green synthesis [46] and microemulsion [47]. In this present work,
we proposed a sunlight assisted reduction method to incorporate silver nanoparticles into the
mesoporous zeolite matrix. Various analytical methods were used for characterization of silver
nanoparticles incorporated zeolite to understand the optical and electrochemical behavior of the
system. The electrocatalytic oxidation behavior of AgNP/Zeo-Y modified glassy carbon
electrode (GCE) was tested against the electrochemical oxidation of DA and UA in phosphate
buffer solution (PBS) medium. Enhanced oxidation peak current values were observed at
modified electrodes in both analytes with greater sensitivity. Thus, the present method can be

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considered as an efficient for simultaneous detection of DA and UA in human urine samples.
The electrode stability and interference of other biological important molecules were also tested.

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2. Experimental Methods

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2.1 Chemicals

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Dopamine hydrochloride, uric acid and silver nitrate (AgNO3) were received from Sigma
Aldrich (Bio Corporals, Chennai, India). Zeolite Y was obtained from Hi-Media (Sri Hari

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Chemicals Pvt. Ltd., Chennai, India). Potassium hydrogen phosphate (K2HPO4), potassium

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dihydrogen phosphate (KH2PO4) and potassium chloride (KCl) were received from SRL Pvt.
Ltd. (Vijaya Scientific, Chennai, India). All other chemicals obtained from commercial sources

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preparation of all stock solutions.

without any further purification processes. Double distilled (DD) water was used for the

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2.2. Synthesis of silver nanoparticles using zeolite Y as a template

0.1 M of silver nitrate was dissolved in 20 mL of distilled water. Then 1% ammonium
hydroxide solution was added drop wise, until the color of the solution change from greenish
gray to colorless. 1 g of zeolite Y was added into the above reaction mixture and then stirred
under sunlight for 1 h. Finally, the product was collected and washed several times with distilled
water, centrifuged and then dried.
2.3 Instrumental Methods
Morphological and structural investigations are carried out using field emission scanning
electron microscopy (FE-SEM, SU6600, Hitachi, Japan) and transmission electron microscopy
(TEM, JEM 2100, 200KeV, JEOL, USA). UV-Visible diffuse reflectance spectrophotometer was
carried out using a Perkin-Elmer Lambda 650. Nitrogen adsorption measurements were
performed at 77.3 K by a Quantachrome Instruments, Autosorb-IQ volumetric adsorption
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analyzer. The sample was out gassed 300 K for 3 h in the degas port of the adsorption apparatus.
The specific surface area of each zeolite was calculated from the adsorption data points obtained

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at P/P0 using the Brunauer-Emmett-Teller (BET) equation. The pore diameter was estimated
using Barret-Joyner-Halenda (BJH) method. The XRD patterns of the powdered samples were

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recorded using X PERT-PRO diffractometer with a Cu K Radiation (=1.5406 ).

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Electrochemical experiments were carried out using Gamry, USA model 330 including PV220

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software and a CHI 660A electrochemical instrument, USA. A three electrode system consisting
of GCE of 3 mm of the geometrical surface area was purchased from BAS, Pvt. Ltd, USA. The

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Ag/AgCl with 3 M KCl was used as a reference electrode and platinum wire as a counter
electrode. Bioanalytical system (BAS, USA) polishing kit was used to polish GCE surface. The

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surface of GCE was cleaned first mechanically by polishing with 500 micron alumina powder,
washing with DD water and then sonicated for 5 min. GCE substrate was modified with

temperature.

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AgNP/Zeo-Y solution (5L) by a drop casting method using micro-syringe and dried under room

Electrochemical impedance spectroscopy (EIS) measurements were performed with the use
of the CHI-660A electrochemical instrument. The electrolyte was prepared by using 0.1 M KCl
containing a 10 mM [Fe(CN)6]3/4 redox probe. All solutions were purged with high purity
nitrogen gas for about 10 min before performing all electrochemical experiments. All
experiments were carried out at room temperature.
A buffer solution of pH 7.0 was prepared by mixing of 0.1 M KCl, 0.1 M KH2PO4 and 0.1
M K2HPO4 in 250 ml standard flask using DD water. The pH of the solution was checked using
an Elico-pH meter at room temperature. The stock solution of dopamine (0.1 M) and uric acid
(0.1 M) were prepared freshly with deoxygenated DD water and stored in a dark room at 5 oC.

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3. Results and Discussion
3.1 Synthesis and characterization of AgNP incorporated with zeolite-Y

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The sunlight assisted photochemical reduction method was adapted to synthesis AgNP

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incorporated on zeolite Y system. The photochemical conversion of silver ion into silver

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nanoparticles is characterized using various instrumental methods like the FE-SEM, TEM, XRD,
BET and DRS UV. Figure 1 depicts the FE-SEM images of zeolite Y (Fig.1 A) and AgNP/Zeo-

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Y (Fig.1 B). By comparing the FE-SEM images of zeolite Y, silver nanoparticles incorporated
zeolite Y shows some white spots. These white spots are due to the presence of silver

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nanoparticles on the surface of mesoporous zeolite and also regular shaped silver nanoparticles
are shown without any external binding agents. The size of the silver nanoparticles was further

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confirmed by TEM images (Fig. 2). The uniform distribution of Ag nanoparticles within the
zeolite matrix and its average size of the nanoparticles is 10 nm. A similar observation was

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shown in a recently reported result using 3-aminopropyltriethoxysilane modified zeolite to

stabilize silver nanoparticles [48]. Elemental composition of Zeo-Y and AgNP/Zeo-Y were
confirmed by energy dispersive X-ray analysis (EDAX) as shown in Fig.S1. Thus, the present
method can be utilized for the effective loading of silver nanoparticles without adding any
external binding agents. Zeolite and the loading of silver nanoparticles within the zeolite matrix
(ie., within and cages) were confirmed by DRS UV-Visible spectral studies (Fig. 3). A
characteristic of silver plasmon band appears at 410 nm, indicating the formation of metallic
silver within the zeolite matrix.
The porous nature and pore size distribution of before and after loading of AgNP with
zeolite matrix have been measured by N2 adsorption-desorption isotherms. A typical type II
isotherm confirms a narrow hysteresis loop of Zeo-Y and AgNP/Zeo-Y as shown in Fig. 4A.
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From the comparison plot, Zeo-Y shows a high surface area and AgNP/Zeo-Y exhibits a quite
decrease because of silver nanoparticles incorporated on zeolite-Y matrix and its BET surface

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area of Zeo-Y and AgNP/Zeo-Y were found to be 520 m2 g-1 and 323 m2 g-1 respectively. The

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porousity of Zeo-Y and AgNP/Zeo-Y were calculated from the pore size distribution plot as
shown in Fig. 4B. The mesoporous of Zeo-Y shows a pore size distribution in the range of 4-10

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nm, whereas AgNP/Zeo-Y reveals a narrow pore size distribution (2 - 4 nm). These results

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indicate that the BET surface area and porous size of AgNP/Zeo-Y are found to be less when
compared to Zeo-Y and decreasing the surface area is due to incorporation of silver nanoparticles

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within the zeolite matrix.

The XRD pattern of pure zeolite Y (a), silver ion modified zeolite Y (b) and

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photochemically treated silver nanoparticles modified zeolite Y (c) are shown in Fig. 5. As can
be seen, the XRD peak intensities of ion-exchanged or reduced samples are decreased relatively

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when compared with pure zeolite Y. It may be due to some changes of charge distribution and
electrostatic fields are occurring when replacement of sodium ions by silver ions. In AgNP/ZeoY, the four major peaks at 2 of 36.55, 44.32, 64.71 and 72.87, which are assigned to the
111, 200, 220, and 311 crystallographic planes of the face-centered cubic (fcc) silver
nanoparticles present within the zeolite matrix [49].
Based on the above synthesis and characterization, we propose a possible mechanism for
the formation of silver ions into silver nanoparticles under sunlight. In the beginning, silver
nitrate reacts with ammonium hydroxide to form a solution of [Ag(NH3)2]+ under stirring
condition as shown in below [50];
..
(1)
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During the addition of negatively charged zeolite in above mixture, the positively
charged silver ions are easily incorporated into mesoporous alumina silicate followed by ion-

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exchange mechanism. It occurs the deprotonation of hydroxyl groups on zeolite surface ie., metal

.. (2)

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ion exchanges with H+ ions [51].

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When this mixture was kept under sunlight irradiation or g-radiolysis, it produces a

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following species [52-54];

.. (3)

The solvated electrons and free radical are acting as a strong reducing agent, so it reduces

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the silver ions into silver nanoparticles or silver atoms and the oxidizing radical is one of

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additional product during the radiolysis.

.... (4)

3.2 Electrochemical behavior of AgNP/Zeo-Y/GCE

The electrochemical behavior of a) bare GCE, b) Zeo-Y and c) AgNP/Zeo-Y modified
GCE was investigated using 0.1 M KCl as supporting electrolyte at a scan rate of 50 mVs -1 as
shown in Fig. 6. The bare GCE and Zeo-Y exhibits a flat and drab voltammetric response,
whereas AgNP/Zeo-Y modified GCE shows a set of redox peaks due to oxidation and reduction
of silver nanoparticles present within the zeolite matrix. A sharp anodic peak and a shallow
reduction peak were appearing at a peak potential of + 0.06 V and 0.09 V (vs. Ag/AgCl)
respectively. These peak potential values are closely related to previously reported results [55].
The influence of scan rate on anodic oxidation peak current values of AgNP/Zeo-Y/GCE was
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investigated. The peak current responses were increased when increasing the peak potential scan
rate from 20 - 100 mV/s, as seen in Fig. 7. A linear relationship was obtained while increasing

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the potential scan rates and a linear regression equation of anodic peak current is found to be Ipa

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(A) = 0.6735 (/mV/s) + 3.8390 (R2 = 0.9934), indicates that the redox process is adsorption

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controlled electron transfer process.

The electrochemical behavior of AgNP/Zeo-Y/GCE was tested in various electrolyte

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medium like KCl, KNO3 and K2SO4. Figure S2 represents the comparative cyclic voltammogram

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of AgNP/Zeo-Y/GCE in three different electrolyte medium. Among these three electrolytes, KCl
medium exhibits a well-defined redox peaks with enhanced peak current response at + 0.06 V

and 0.09 V (vs. Ag/AgCl) corresponds to Ag (0) to Ag (I) redox couple. On the other hand, the

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remaining two electrolyte medium exhibits an anodic peak potential shifted to positive potential

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with a lower current response as compared to KCl medium. This sharp increase in anodic peak
current is due to the formation of silver halide during the redox reaction [56-58]. Therefore, we
have chosen KCl as suitable supporting electrolyte for the further studies.
3.3 Electrochemical impedance studies (EIS) of AgNP/Zeo-Y/GCE
Electrochemical impedance spectroscopic measurement (EIS) was carried out to
understand the electron transfer at electrode-electrolyte interface on modified electrode surface
[40]. The curve of EIS includes a semicircular part and a linear part. The semicircular part at
higher frequencies correspond to electron-transfer-limited process and its diameter is equal to the
electron transfer resistance (Rct) which controls the electron transfer kinetics of redox probe at
electrode interface. Meanwhile, the linear part at lower frequencies corresponds to diffusion
process. Figure 8 shows EIS was carried out in 0.1 M KCl containing 10 mM K3[Fe(CN)6]3-/4- as
a redox probe with a frequency range from 0.1 Hz to 105 Hz (Amplitude 5 mV). At bare GCE
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exhibited an almost straight line indicates a diffusion limited electrochemical process. For ZeoY/GCE shows a semicircular part (higher frequency) indicates a high electron transfer resistance,

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whereas the AgNP/Zeo-Y/GCE reveals a semicircular as well as linear portion, indicating a

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charger electron transfer and diffusion controlled electron transfer reaction. These results
indicate that the AgNP/Zeo-Y/GCE system has both diffusion and charge transfer limitation

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electrochemical process.

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3.4 Electrochemical oxidation of DA using AgNP/Zeo-Y/GCE

The electrochemical oxidation of DA was investigated on a) and b) bare GCE (absence and

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presence) and c) AgNP/Zeo-Y modified GCE in the presence of DA in 0.1 M KCl containing
PBS (pH 7.0) by cyclic voltammetric (CV) method at a scan rate of 50 mV/s as shown in Fig. S3.

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At bare GCE, a poor redox behavior was observed for the oxidation of DA with an anodic peak
potential at + 0.037 V (vs. Ag/AgCl). In the case of AgNP/Zeo-Y/GCEs, the oxidation peak

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current was increased remarkably and the oxidation peak potential was shifted less positively
(less than 102 mV) and the peak current response is four times higher than bare GCE due to the
electrocatalytic oxidation of DA on the surface of silver nanoparticles. The AgNP/Zeo-Y
modified electrode displays an enhanced electrochemical performance towards the oxidation of
DA. The oxidation peak current has increased with each addition of 0.1 M dopamine solution
and its linear ranges from 0.08 x 10-4 to 0.96 x 10-4 M with the calibration plot as shown in Fig.
9A. Cyclic voltammogram was clearly depicted that the oxidation peak current is increased
linearly while increasing the potential scan rates from 20100 mV/s (Fig. 9B). The observed
peak current has linear relationship with square root of the scan rate with linear regression
equation of Ip (A) = 0.4891 (1/2/mV1/2/s1/2) 0.4834 (R2 = 0.9936). These results reveal that

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the electrochemical oxidation of DA at modified electrode is a diffusion-controlled electron
transfer process.

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3.5 Electrochemical oxidation of UA using AgNP/Zeo-Y/GCE

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The electrochemical oxidation of UA was investigated on a) and b) bare GCE (presence

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and absence) and c) AgNP/Zeo-Y/GCE in the presence of 0.1 mM of UA in 0.1 M KCl

containing PBS (pH 7.0) by the CV method at a scan rate of 50 mV/s (Fig. S4). In bare GCE, a

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broad anodic oxidation peak potential was observed at + 0.410 V (vs. Ag/AgCl) whereas the
anodic oxidation peak potential of AgNP/Zeo-Y/GCE is shifted negatively and the observed

AgNP/Zeo-Y/GCE

exhibits

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peak current response increased three times higher than bare GCE. From this study, the
enhanced

electrochemical

performance

towards

the

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electrochemical oxidation of UA. A linear calibration plot is obtained by plotting the oxidation
peak current against the concentration of UA and its ranges from 0.5 x 10-3 M to 4.0 x 10-3 M as

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shown in Fig. 10A. Cyclic voltammogram was obviously shows that the oxidation peak current
is increased linearly while increasing the potential scan rates from 20100 mV/s (Fig. 10B). A
linear relationship was observed by plotting peak current against square root of the potential scan
rates with a linear regression equation of Ip (A) = 0.4514 (1/2/mV1/2/s1/2) + 1.4581 (R2 =
0.9854). These results reveal that the electrochemical oxidation of UA at modified electrode is a
diffusion-controlled electron transfer process.
3.6 Electrochemical oxidation of DA and UA using AgNP/Zeo-Y/GCE
The cyclic voltammograms of 0.2 mM of DA and 0.3 mM of UA at a) and b) bare GCE
(absence and presence) and c) AgNP/Zeo-Y/GCE in the presence of 0.1 M KCl containing PBS
(pH 7.0) were analyzed. Figure S5 shows the simultaneous oxidation of DA and UA at bare
GCE, the anodic oxidation peak potential of DA and UA is obviously merged together and

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appeared as a single broad peak with peak potential of + 0.33 V (vs. Ag/AgCl) which due to the
poor selectivity, sluggish redox behavior and UA directly interferes with DA, so the bare GCE

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fails to display the individual electrochemical oxidation peaks for DA and UA. Interestingly, the

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AgNP/Zeo-Y/GCE exhibits a well-resolved peak potential window (~ 120 mV) and a higher
oxidative peak current at + 0.31 V and + 0.43 V (vs. Ag/AgCl) for the oxidation of DA and UA,

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respectively. In addition, the strong electrostatic interaction between the positively charged DA

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and negatively charged silver nanoparticles embedded zeolite Y which facilitates the electron
transfer process is favorable and the oxidation peak potential of DA is resolved against UA. It

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suggests that the AgNP/Zeo-Y/GCE has excellent electrocatalytic activity towards the oxidation
of DA than UA with a significant peak to peak separation and exert no interference in selective

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determination of DA and UA. Thus, the present method can be exploited for the simultaneous
determination of both analytes in biological samples without any overlapping of the oxidation

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peak potentials.

3.7 Influence of pH on oxidation of DA and UA using AgNP/Zeo-Y/GCE

The influence of pH of the medium on electrochemical oxidation of peak current and
potential were investigated for DA and UA using AgNP/Zeo-Y/GCE in presence of 0.1 M KCl
containing PBS at different pHs (1-11) as shown in (Fig. S6). While increasing the pH of the
solution, both the oxidative peak potential of DA and UA are shifted towards the less negative
values as shown in Fig. S6A and S6B. In contrast, the peak current value increases gradually
with increasing the pH of the medium upto pH 7 and then decreases in basic medium. Figure
S6C and S6D shows the variation of anodic peak current of DA and UA versus variation of pH
of the medium. From the graph, it can be clearly observed that the peak potential and current
were closely related to pH value (pH 7.0) of supporting electrolyte. The linear regression
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equation of DA and UA were Epa (V) = 0.08110 + 0.05429 pH (R2 = 0.9930) and Epa (V) = 0.4057 + 0.05757 pH (R2 = 0.9915), respectively. The slopes of the plot (Ep vs. pH) for DA and

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UA were calculated as 54.9 mV/pH and 57.57 mV/pH, respectively, which are close to the

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Nernstian value (59 mV/pH) for a two electrons/two protons redox process. According to the
following equation;

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dEp/dpH (slope) = 2.303 mRT/nF

(1)

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where m and n are number of proton and electron transferred, respectively. The number of

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proton and electron transferred during the electrochemical process are same. Since the maximum
peak current response and separation of peak potentials were observed at pH 7. Therefore, in

order to obtain high sensitivity under physiological environment, pH 7 was fixed at an optimum

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pH value for the determination of DA and UA in all the experiments

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The following mechanism was proposed for the oxidation of DA and UA based on the
electrocatalytic redox behavior of these analytes [59].

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3.8 Individual/Simultaneous determination of DA and UA using AgNP/Zeo-Y/GCE
The differential pulse voltammetry (DPV) technique was exploited for the selective and

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sensitive detection of DA and UA at the AgNP-Zeo-Y modified GCE because of its high current

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sensitivity and better peak resolution. The determination of DA and UA in mixtures was

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performed at the AgNP/Zeo-Y/GCE by DPV which eliminates the residual charging current
values and the pure faraday current values only measured. The concentration of DA was varied,

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while keeping the UA concentration constant. The oxidation peak potentials were observed with

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adequate peak to peak separation values at + 0.075 V and + 0.375 V (vs. Ag/AgCl) for DA and
UA respectively (Fig. 11A). By varying the concentration of DA from 0.02 x 10-6 M 0.18 x 10M, while keeping the concentration UA as constant, the linear increase of peak current values

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were noted and there are no obvious changes in peak current of UA. The linear regression
equation was expressed as Ipa (A) = 0.3369 + 12.050 C (M) with a correlation coefficient of

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0.9899. The limit of detection (LOD) was found to be 1.60 x 10-8 M for DA using 3/slope,
where is the standard deviation of the mean value for five independent voltammogram of
blank solution. This result implies that the oxidation of DA and UA at AgNP/Zeo-Y/GCE is
relatively independent.

Similarly, the electrochemical oxidation of UA was also investigated by varying the UA

concentration while keeping the DA concentration as constant (30 M) at the AgNP/Zeo-Y/GCE
in presence of 0.1 M KCl containing PBS (pH 7.0). As can be seen from Fig. 11B, the oxidation
peak potential for DA and UA were found to be + 0.075 V and + 0.375 (V vs. Ag/AgCl)
respectively at the AgNP/Zeo-Y/GCE. By varying the concentration of UA from 0.5 x 10-6 M
0.7 x 10-6 M, the anodic peak of DA is almost stable without any obvious changes observed in
the peak current of DA. The linear regression equation was expressed as Ipa (A) = 0.5319 +
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19.2975 C (M) with a correlation coefficient of 0.9996 as shown in Inset Fig. 11B. The limit of
detection value (3/slope, where is the standard deviation) was found to be 2.51 x 10-8 M for

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UA. The detection limit of the proposed method is comparable with previously reported values

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as shown in Table 1.

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Simultaneous determination of DA and UA at the AgNP/Zeo-Y/GCE were studied by

using DPV method. The simultaneous study was carried out in the potential range from 0.1 V

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to + 0.7 V (Fig. 12A). The concurrent determination of DA and UA using AgNP/Zeo-Y/GCE

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shows a well resolved separation between two anodic peak potentials corresponding to their
oxidation peak current. The peak separation between DA and UA were found to be 220 mV. The

simultaneous determination of DA and UA in a mixture was carried out at AgNP/Zeo-Y/GCE

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when concentrations of two species were changed. From the Fig. 12B, the peak current of DA
and UA were linearly proportional to the same concentration of DA and UA (0.2 107 M to 1.2

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106 M). The linear relationship is obtained with the regression equation of Ipa (A) = 3.0385 C
(M) + 1.6113 (R2 = 0.9936) and Ipa (A) = 4.1514 C (M) + 1.8673 (R2 = 0.9858) for DA and
UA respectively. The detection limit value (3/slope, where is the standard deviation) was
found to be 0.02 x 10-7 M and 0.036 x 10-7 M for DA and UA respectively. These results strongly
suggest that the individual and simultaneous determination of DA and UA on AgNP/Zeo-Y/GCE
can be achieved with a high selectivity and sensitivity.
3.9 Stability, reproducibility and interference studies
The long term stability of the prepared electrode (AgNP/Zeo-Y/GCE) was tested and
storing them at 4 C for about two weeks. After two weeks, the CV response has retained about
98.3 % current response than the freshly prepared one. Further stability of the electrode was

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tested after 25 cycles recording by CV experiment in 0.1 M KCl containing PBS (pH 7.0) about
97.2 % current was retained and its indicates that the AgNP/Zeo-Y/GCE shows a good stability

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and reproducibility. At different time intervals, DPV studies were carried out for the

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determination of DA and UA in 0.1 M KCl containing PBS (pH 7.0). The peak current was
preserved the same with the relative standard deviation of 2.9 % for five determinations. This

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result suggests that the good reproducibility of the AgNP/Zeo-Y/GCE. Ascorbic acid (AA) was

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the major interference coexists with DA and UA in body fluids. We have investigated the
influence of AA in the detection of DA and UA by adding 200-fold excess of ascorbic acid

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compared to DA and UA concentrations. There is small interference was obtained for AA and
also other interferences such as cysteine, citric acid, glucose, caffeine, aspartic acid, L-dopa,

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aspirin, tartaric acid, NaCl, KCl, epinephrine (EP), tyrosine and tryptophan did not interfere with
the peak of DA and UA as shown in Fig S7. The proposed AgNP/Zeo-Y modified electrode was

method.

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applied for the determination of DA and UA in human urine samples using standard addition

3.10 Real sample analysis

3.10.1 Determination of DA in urine samples

The utilization of proposed method in real samples analysis was also investigated by direct
analysis of DA in human urine samples. The urine samples were diluted 500 times with PBS (pH
7.0) before measurement. No other pretreatment process was performed. The recovery rate was
listed in Table 2 with the recovery range of 93.20 % - 108.1 %. The R.S.D. (n = 5) value was less
than 3.0%, indicating that the assay could be potentially used for determination of DA in real
biological samples.

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3.10.2 Determination of UA in human urine samples
The determination of UA in human urine samples was also investigated by using DPV

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method. Before the measurement, all urine samples were diluted 200 times with PBS (pH 7.0) in

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order to fit into the linear range of real samples. No other pretreatment process was performed.
The standard addition method was used for testing recovery rates. In Table 3, the recovery rates

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of the spiked samples ranged between 97.15 % and 104.5 % (R.S.D. < 1.9 %, n = 5) and a linear

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relationship between the relative recovery and concentration of UA (high and low concentration)
as shown in Fig. S8. These results indicating the suggested method are good accuracy,

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repeatability and free from interferences of the urine sample matrix.

4. Conclusion

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In conclusion, an AgNP/Zeo-Y nanocomposite was successfully synthesized via a simple

ion exchange method followed by sunlight assisted approach to reduce silver ion into silver

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nanoparticles. The size and shape of silver nanoparticles can be studied by FE-SEM and TEM
analysis. A sensitive and selective electrochemical sensor with AgNP/Zeo-Y nanocomposites
modified electrode was developed for the determination of DA in the presence of UA and UA in
the presence of DA. The AgNP/Zeo-Y/GCE shows a significantly improved peak current
towards the oxidation of DA and UA. The present electrochemical sensor displayed an excellent
electrocatalytic activity and electron transfer rate towards the oxidation of DA and UA.
Moreover, the sensor electrode shows a good sensitivity, selectivity, reproducibility and low
detection limit in the simultaneous detection of DA and UA at AgNP/Zeo-Y/GCE. The
developed sensor was successfully applied for electrochemical determination of DA and UA in
human urine samples.

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Acknowledgement: The authors (Dr. K. P and S. M) would like to thank National Centre for
Nanoscience and Nanotechnology, University of Madras for providing instrumental facilities.

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The authors would like to thank Prof. B. Viswanathan (emeritus), National Center for Catalysis,

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Indian Institute of Technology Madras, Chennai for providing TEM facility and Dr. A.
Pandurangan, Associate Professor, Department of Chemistry, Anna University for providing

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BET analysis.

M.G. Valdes, A.I.P. Cordoves, M.E.D. Gracia, Zeolite and zeolite-based materials in

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[1]

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FIGURE CAPTIONS

Figure 2 TEM images of Zeolite-Y (A) and AgNP/Zeo-Y (B).

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Figure 1 FE-SEM images for Zeolite-Y (A) and AgNP/Zeo-Y (B).

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Figure 3 DRS-UV Visible spectrum of a) Zeo-Y and b) AgNP/Zeo-Y.

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Figure 4 N2- adsorption isotherms (A) and pore size distribution of Zeolite-Y and AgNP/ZeoY nanocomposites (B).

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Figure 5 XRD analyses of a) Zeo-Y and b) AgNP/Zeo-Y

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Figure 6 Cyclic voltammogram of a) bare, b) Zeo-Y and c) AgNP/Zeo-Y/GCE in the presence

of 0.1 M KCl containing PBS (pH 7.0) at a scan rate of 50 mV/s. Error bars

designates the standard deviation for five independent measurements.

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Figure 7 (A) Cyclic voltammogram of AgNP/Zeo-Y/GCE in the presence of 0.1 M KCl

containing PBS (pH 7.0) at different scan rates ranging from 20 100 mV/s. (B)

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Linear plot of peak current (Ip) vs. scan rate (). Error bars designates the standard
deviation for five independent measurements.
Figure 8 Nyquist plots of bare GCE, Zeo-Y/GCE and AgNP/Zeo-Y/GCE in the presence of 0.1
M KCl containing 10 mM K3[Fe(CN)6]3-/4- over a frequency range from 0.1 Hz to 105
Hz; Amplitude 5 mV.
Figure 9 (A) Cyclic voltammograms of AgNP/Zeo-Y/GCE in the presence of 0.1 M KCl
containing PBS (pH 7.0) for different concentrations (0.08 x 10-4 M to 0.96 x 10-4 M)
of DA at a scan rate 50 mV/s. Inset: Calibration plot of electrocatalytic peak currents
vs. DA concentrations. (B) Cyclic voltammograms of DA at various scan rates a) 20
b) 40 c) 60 d) 80 and e) 100 mV/s. Inset: Plot of electrocatalytic peak currents vs.

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scan rates (mV/s). Error bars designates the standard deviation for five independent
measurements.

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Figure 10 (A) Cyclic voltammograms of AgNP/Zeo-Y/GCE in the presence of 0.1 M KCl

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containing PBS (pH 7.0) for different concentrations (0.05 x 10-4 M to 0.4 x 10-4 M)
of UA at a scan rate 50 mV/s. Inset: Calibration plot of electrocatalytic peak currents

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vs. UA concentrations. (B) Cyclic voltammograms of UA at various scan rates a) 20

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b) 40 c) 60 d) 80 and e) 100 mV/s. Inset: Plot of electrocatalytic peak currents vs.

scan rates (mV/s). Error bars designates the standard deviation for five independent

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measurements.

Figure 11 (A) Differential pulse voltammograms of DA at AgNP/Zeo-Y/GCE in 0.1 M KCl

containing PBS (pH 7.0) in the presence of 20 M UA. The DA concentrations are

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0.02, 0.04, 0.06, 0.08, 0.10, 0.12, 0.14, 0.16 and 0.18 M (from a-i). (B) UA at

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AgNP/Zeo-Y/GCE in 0.1 M KCl containing PBS (pH 7.0) in 30 M DA. The UA

concentrations are 0.5, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60,
0.65 and 0.70 M (from a-n). Error bars designates the standard deviation for five
independent measurements.
Figure 12 (A) Simultaneous determination of DA and UA using AgNP/Zeo-Y/GCE in the
presence of 0.1 M KCl containing PBS (pH 7.0). (B and C) Calibration plots of
electrocatalytic peak currents vs. DA and UA concentrations. Concentrations of the
two compounds: DA (0.2 x 10-7 M to 1.2 x 10-6 M) and UA (0.2 x 10-7 M to 1.2 x 10-6
M). Error bars designates the standard deviation for five independent measurements.
Scan rate: 20 mV/s, Pulse width: 50 mV, Pulse Amplitude: 25 mV.

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TE

MA

NU

SC

RI

PT

Figure 10

40

ACCEPTED MANUSCRIPT

AC
CE
P

TE

MA

NU

SC

RI

PT

Figure 11

41

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Figure 12

PT

UA

AC
CE
P

TE

MA

NU

SC

RI

DA

42

ACCEPTED MANUSCRIPT
Comparison table of the different electrodes.

Table 2

Determination of DA in human urine samples (n = 5)

Table 3

Determination of UA in human urine samples (n = 5)

AC
CE
P

TE

MA

NU

SC

RI

PT

Table 1

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R2

Conc. range (M)

Method
DA

UA

DA

Detection
Limit (M)

UA

DA

UA

Ref.

DPV

0.2-80

1.2-100

0.9982

0.9994

0.12

0.60

[60]

PAAMWNTs/GCE

LSV

0.04-3

0.3-10

0.02

0.10

[61]

EBNBH/CNPE

DPV

0.1-900

20-600

0.9981

0.9989

0.08

15.0

[62]

PANI-AuNP

DPV

7 - 148

29-720

3.0

20.0

[63]

LaPO4/CPE

DPV

0.4-11

2.7-24

0.9995

0.9991

0.13

0.9

[64]

Au-CA-MWNT

DPV

0.2-100

1-100

0.02

0.1

[35]

PPGE

DPV

0.15-15

0.3-150

0.9991

0.9988

0.03

0.12

[65]

2 - 30

9-100

0.9995

0.9991

0.50

2.30

[66]

DPV

0.25-20

0.3-13

0.9990

0.9990

0.08

0.12

[36]

PAM/rGO/ GCE

CV

0.3-50

1 - 50

0.9967

0.9984

0.1

0.5

[67]

AgNP/Zeo-Y/GCE

DPV

0.9899

0.9969

0.016

0.025

This
work

NU

MA

TE

DPV

AC
CE
P

MCMS/
Thionine/GCE
MWCNT @
PDOP@PtNP/
GCE

SC

GNP/Ch/GCE

RI

Electrode

PT

Table 1

0.02-0.18 0.04-0.52

*GNP - Gold Nanoparticles

GCE - Glassy Carbon Electrode
PAA Poly (Acrylic acid),
DPV Differential Pulse Voltammetry
MWNTs - Multiwalled Nanotubes
MCMS Magnetic Chitosan Microsphere
LSV - Linear Sweep Voltammerty
PPGE Pretreated Pencil Graphite Electrode
PDOP @ PtNP Polydopamine @ Platinum Nanoparticles
PAM/rGO Polyacrylamide/reduced Graphene oxide

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Table 2

1
2
3
4
5

5
10
15
20
25

4.87
9.32
16.22
20.34
24.67

2.32
1.33
2.54
1.43
0.99

Relative
Recovery
(%)
97.4
93.2
108.1
101.7
98.68

PT

R.S.D.
(%)

RI

Found
(M)

SC

Added
(M)

AC
CE
P

TE

MA

NU

Urine
Samples

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Table 3

Found
(M)

R.S.D
(%)

22.25

20

41.41

1.8

98.01

18.73

20

37.63

2.5

97.15

23.09

20

45.05

2.3

104.5

19.56

20

39.77

1.2

100.53

20.41

20

40.11

1.7

99.25

NU

AC
CE
P

TE

MA

PT

Added
(M)

SC

Detected
(M)

RI

Relative
Recovery
(%)

Urine
Samples

46

AC
CE
P

TE

MA

NU

SC

RI

PT

ACCEPTED MANUSCRIPT

47

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Highlights

PT

Sun light assisted synthesis of silver nanoparticles modified zeolite Y via ion exchange
method.

RI

Enhanced electrocatalytic oxidation peak current values for dopamine and uric acid with
a well separated peak to peak position.

SC

AgNP/Zeo-Y modified glassy carbon electrode for the simultaneous detection of

dopamine and uric acid by differential pulse voltammetry method.

NU

Detection limit was found to be 1.60 10-8 and 2.51 10-8 M for uric acid and dopamine
respectively.

AC
CE
P

TE

MA

Differential pulse voltammetry technique was effectively realistic to detect dopamine and
uric acid in urine samples.

48