Hydrothermal Synthesis of Boron Nitride Quantum Dots/Poly(Luminol) Nanocomposite for Selective Detection of Ascorbic Acid - IOPscience
←
→
Page content transcription
If your browser does not render page correctly, please read the page content below
Journal of The Electrochemical
Society
OPEN ACCESS
Hydrothermal Synthesis of Boron Nitride Quantum Dots/Poly(Luminol)
Nanocomposite for Selective Detection of Ascorbic Acid
To cite this article: R. Jerome and Ashok K. Sundramoorthy 2019 J. Electrochem. Soc. 166 B3017
View the article online for updates and enhancements.
This content was downloaded from IP address 46.4.80.155 on 25/08/2021 at 05:16
Journal of The Electrochemical Society, 166 (9) B3017-B3024 (2019) B3017
JES FOCUS ISSUE ON 4D MATERIALS AND SYSTEMS
Hydrothermal Synthesis of Boron Nitride Quantum
Dots/Poly(Luminol) Nanocomposite for Selective Detection of
Ascorbic Acid
R. Jerome1 and Ashok K. Sundramoorthy 1,2,z
1 Department of Chemistry, SRM Institute of Science and Technology, Kattankulathur-603 203, Tamil Nadu, India
2 SRM Research Institute, SRM Institute of Science and Technology, Kattankulathur-603 203, Tamil Nadu, India
Boron nitride quantum dots (BNQDs) were synthesized hydrothermally using boric acid and urea. High-resolution transmission
electron microscopy (HR-TEM) analysis confirmed the formation of BN quantum dots with the lattice size of 0.227 nm. Fourier-
transform infrared (FT-IR) and Ultraviolet–visible (UV-Vis) spectroscopies revealed the B-N, O-H and N-H bond formation in
the BNQDs and the maximum absorption wavelength at 269 nm. BNQDs exhibited strong fluorescence emission at a wavelength
of 330 nm. Furthermore, BNQDs were coated onto a glassy carbon electrode (GCE). Followed by, poly(luminol) (Plu) was
electrochemically deposited onto BNQDs/GCE from 0.1 M H2 SO4 containing 0.5 mM luminol in order to prepare nanocomposite
(hybrid film) coated electrode with improved stability and electrochemical activity. Due to unique nature and synergetic effect
between BNQDs and Poly(luminol), as-prepared hybrid Plu/BNQDs film coated GCE showed improved electrocatalytic activity for
vitamin C (ascorbic acid, AA) oxidation at 0.2 V. The calibration graph was obtained from 10 to 100 μM AA by amperometry and
limit of detection (LOD) was found to be 1.107 μM. The interference effects were also carried out in the presence of uric acid (UA),
dopamine (DA) and glucose (Glu). Interestingly, UA, DA and Glu did not produce significant responses on the Plu/BNQDs/GCE
which indicated good selectivity of the sensor for AA. Moreover, Plu/BNQDs/GCE based sensor showed reproducible and repeatable
analytical performances. We propose that the Plu/BNQDs based hybrid film can be used as a selective sensor probe for the detection of
the AA.
© The Author(s) 2019. Published by ECS. This is an open access article distributed under the terms of the Creative Commons
Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any
medium, provided the original work is properly cited. [DOI: 10.1149/2.0041909jes]
Manuscript submitted November 12, 2018; revised manuscript received January 14, 2019. Published January 24, 2019. This paper
is part of the JES Focus Issue on 4D Materials and Systems.
Boron nitride (BN) is an extraordinary material which is similar to these important functions in human system, the determination of
to graphite.1 Researchers have shown much interest toward this ma- AA concentration in aqueous solution is of great importance.28,29 Var-
terial for fabricating nanodevices due to its exclusive properties such ious AA determination methods have been reported such as potassium
as high thermal conductivity, low dielectric constant, large intrin- iodate,34 Fluorimetric,35 UV-Vis,36 spectrophotometrically based on
sic bandgap (5.7 eV), excellent mechanical characteristics, chemical its reaction with hexacyanoferrate (III)37 (5 to 100 μM AA) and ox-
stability, electrical insulation properties, lack of toxicity, chemical in- idation using the Cu(II)-neocuproine complex38 (5 to 80 μM AA).
ertness, tunable bandgap etc.1–6 The exfoliated hexagonal structure of But, these methods have their own limitations. For example, they
boron nitride (h-BN) is a two-dimensional material which has hon- might require sample pre-concentration step, longer analysis time,
eycomb structure based on sp2 covalent bonds similar to graphene, skilled person, expensive equipment’s etc. For these reasons, modi-
with atomically smooth surface.7,8 Among various structural forms, fied electrodes are more attractive. Electrochemical sensors made of
h-BN was very stable and has been exploited in various fields such as nanomaterials relatively preferable for the detection of AA since it
optoelectronics, catalysts and semiconductor devices.9–12 offers simple analytical procedure, highly selective, rapid analysis, no
Quantum dots (QDs) are zero-dimensional nanomaterial which interferences and cost-effective.30,39–48
shows unique physical and chemical properties when they are made In this work, BNQDs were synthesized by hydrothermal method
atomically thin. One of the best example is graphene quantum dots using boric acid and urea as starting materials. Urea (as a nitrogen
(GQDs) which displays amazing photoluminescence when it size get source to synthesize BNQDs) has several advantages over melamine13
reduced.13,14 Due to their extraordinary optical and physical proper- because it is an environmentally friendly material, highly water sol-
ties, QDs has been largely used in various field of research including uble, colorless and non-toxic.49 As synthesized BNQDs were char-
bio-imaging, biological labeling, drug delivery, photocatalyst, electri- acterized and confirmed using FT-IR, fluorescence emission spec-
cal devices and sensors.15,16 Researchers have attempted to synthesis tra, TEM, UV-Vis, and zeta potential measurements. The obtained
QDs by various approaches. As a result, QDs have been synthe- BNQDs exhibited florescence (blue) emission at 330 nm excitation
sized for various applications from phosphorus, indium phosphide, wavelength. FT-IR characterization corroborated the formation of BN-
graphene, carbon and BN (BNQDs).17–24 Recently, synthesis of BN- QDs as indicated by functional groups such as B-N, N-H and O-H.
QDs from bulk h-BN by liquid phase exfoliation using various solvents Then electrochemical polymerization of luminol (Scheme 1) was car-
were reported15,25–27 and used in the analysis of biomolecules. ried out onto the BNQDs film. The electrochemical and catalytic
Ascorbic acid (Vitamin C, AA) is one of the effective water-soluble
antioxidants in human plasma and highly available radical scavengers
in many cell types.28–30 AA is very important for the biological cycle
and it can be used to cure the disease scurvy by taking dietary supple-
ments. Sometimes, the reduction in the vitamin C supplement could
cause a low risk of cancer, and cardiovascular diseases. AA is one
of the important nutrients for repairing tissue were immune system
works properly with the help of this.31–33 AA also helps in the proper
function and production of enzymes for certain neurotransmitters. Due
z Scheme 1. Chemical structural formula of luminol.
E-mail: ashokkumar.sun@ktr.srmuniv.ac.in
B3018 Journal of The Electrochemical Society, 166 (9) B3017-B3024 (2019)
Scheme 2. Schematic representation of synthesis of BNQDs.
properties of Plu/BNQDs hybrid film were studied which showed Synthesis of BNQDs.—BNQDs were synthesized by a single step
high catalytic activity for AA in physiological condition.30,39–47 hydrothermal method. In a typical procedure, the boric acid (0.5 g)
was dissolved in ethanol (10 mL) and deionized water (5 mL). Af-
ter that urea (0.97 g) was dissolved in 10% of liquid ammonia (10
mL) and added to the boric acid/ethanol mixture. This mixture was
Experimental heated hydrothermally in a Teflon-equipped stainless-steel autoclave
Materials and reagents.—Boric acid, ammonia solution (25%), at 200◦ C for 12 h. After that, the mixture solution was cooled to room
urea, sulfuric acid, luminol, AA were purchased from Sigma-Aldrich, temperature (25◦ C ± 2). Finally, BNQDs dispersion was vacuum fil-
India and used without further purification. Vitamin C (Limcee) tablets tered using a filter paper with a pore sizes of 0.22 μm and centrifuged
were purchased from a local drug store in Tamilnadu. Distilled water at 6500 rpm for 30 mins. After centrifugation, top supernatant liq-
was obtained from a Millipore ultrapure water system (18.2 M.cm uid (∼70%) was collected and stored for further characterization and
@ 25±2◦ C). Solutions and buffers were prepared according to the electrochemical measurements (Scheme 2).
usual laboratory procedures. Before each electrochemical experiment,
solutions were deoxygenated by purging with a pre-purified nitrogen Preparation of Plu/BNQDs sensor.—Glassy carbon electrode
gas. (GCE) was polished on a polishing cloth using alumina powder
(Al2 O3 , particle size ∼0.05 μm) in order to get a mirror like surface
and bath sonicated for 5 min in distilled water. To get a hydrophilic
Apparatus.—Electrochemical measurements such as cyclic surface, GCE was electrochemically activated in 0.1 M H2 SO4 so-
voltammetry and amperometry were carried out by using the elec- lution by potential cycling between −0.5 and 1.0 V for 10 cycles
trochemical workstation (CHI Instrument; Model: CHI-760E, USA). at a scan rate of 0.05 Vs−1 . Afterwards, 10 μL BNQDs dispersion
Bare GCE or modified GCE (Plu/BNQDs/GCE) were used as a work- was coated on the pretreated GCE and dried for 3 h in the absence
ing electrodes. Ag/AgCl (3 M KCl) and platinum wire were used as of light. The BNQDs/GCE was rinsed using deionized water. Then,
a reference and counter electrode, respectively. The absorption spec- polymerized luminol film was coated onto BNQDs/GCE by electro-
tra of the BNQDs were recorded by using UV-Vis spectrophotome- chemical polymerization method. For this, BNQDs/GCE was poten-
ter (Perkin Elmer). Fourier-transform Infrared spectrometer (FT-IR; tial swept (between −0.5 and 1.0 V for 10 cycles at a scan rate 0.05
NICOLET3 80) was used to analyze the functional groups using KBr Vs−1 ) in 0.1 M H2 SO4 containing 0.5 mM luminol (lu). As obtained,
pellet technique. BNQDs dispersion was directly mixed with KBr to Plu/BNQDs/GCE was thoroughly rinsed with double-distilled water
make a pellet for FT-IR spectrum measurements. The morphology and and then dried at room temperature for an hour in the absences of
crystal structure of BNQDs were characterized by transmission elec- light. It was noted as Plu/BNQDs/GCE and then used for further stud-
tron microscope (TEM) (FEI-Tecnai F20 microscope) and HR-TEM ies. For comparison measurements, BNQDs/GCE and Plu/GCE were
(JEM-2100 Plus Electron Microscope, Japan). For HR-TEM analy- prepared similarly and used for further investigations. (Scheme 3).
sis, the sample was prepared by coating of “Cu” grid using 10 μL of
purified BNQDs dispersion and dried in the room temperature. Zeta
Results and Discussion
potential measurements were done using Nanotrac Wave II; Microtrac
Inc, USA. All fluorescence measurements were recorded by using a FT-IR, HR-TEM, UV-Vis and PL studies.—The FT-IR could con-
fluorescence spectrophotometer (Hitachi, Japan) with excitation slit firm the nature of functional groups and chemical bonds present on
set at 2 nm under ambient conditions. BNQDs dispersion was directly the sample. The FT-IR spectrum of as-synthesized BNQDs showed
used to measure fluorescence without further dilutions. absorption bands at 1329,1450,1638 cm−1 due to the B-N stretching
Journal of The Electrochemical Society, 166 (9) B3017-B3024 (2019) B3019
Scheme 3. Schematic representation of electrode modification to detect AA.
modes (Fig. 1).50 The stretching mode of the O-H and N-H groups charged functional groups present on the surface of the BNQDs50
were also observed at 3270 cm−1 with a broad absorption peak. These which formed a stable dispersion.
observations confirmed the presences of B-N, O-H and N-H groups
on the synthesized BNQDs. HR-TEM analysis was carried out to Preparation of Plu/BNQDs/GCE.—Fig. 4 shows the electropoly-
ascertain the details about the morphology and the topography of merization of luminol on BNQDs/GCE. The first anodic oxidation
the BNQDs. The prepared BNQDs were placed in the TEM grid for peak was observed for oxidation of the primary amino group of lu-
its morphological analysis. From HR-TEM images, it was understood minol monomer at +0.84 V (Pa1 ). In the reverse scan, a cathodic
that the circular/spherical particles were represented the quantum dots peak observed at +0.44 V (Pc1 ). With further successive potential
of BN (Figs. 2a, 2b). BNQDs had uniform distribution and good crys- scans, a new anodic peak was observed at +0.55 V (Pa2 ). This re-
tallinity with a lattice of 0.227 nm. Lattice parameter was in good versible redox peak (Pa2 /Pc1 ) begins to grow on the subsequent cycles
agreement with reported value of 0.21 nm.15,25,51 The BNQDs particle which was due to the growth of poly(lu) film on the BNQDs/GCE.30
size distribution is shown in the histogram of Fig. 2c. As we could Polymer film growth was faster for the first eighteen cycles. After
see, BNQDs were appeared as spherical particles in the range (size) the 20th cycle, polymer film growth got stopped which showed the
of 1.5 to 5.4 ± 1 nm (Fig. 2c). saturation.30 For further studies, we deposited Plu film by controlling
UV-Vis and PL excitation (PLE)/emission spectra gave brief de- electro-polymerization up to 20 cycles. However, Plu deposition was
tails about optical properties of the BNQDs. From UV-vis spectrum, carried out up to 50th cycle, but the redox peak current of Plu did not
the maximum absorption wavelength of BNQDs was found to be change significantly, so we used only 20 cycles (for polymerization)
269 nm as shown in Fig. 3a.50,52,53 The inset of Fig. 3a showed blue in order to control the Plu film thickness on BNQDs/GCE. The anodic
fluorescence under the illumination of 365 nm UV light. The PLE data and cathodic peak potentials of Poly(lu) (Plu) were in good agreement
of BNQDs under different excitation wavelengths were also recorded with the reported redox potential for Plu. The chemical composition,
(Fig. 3b). The emission intensities of BNQDs were first increased and and redox mechanism of Plu might be similar to polyaniline as re-
then started to decrease with excitation wavelengths.50 The maximum ported elsewhere30,53,56–59 (Scheme 4).
fluorescence emission was recorded at 330 nm excitation wavelength.
It was suggested that edges and point defects of BNQDs (BO2 − , Electrochemical impedance spectroscopy (EIS) studies.—Fig. 5
zigzag carbene edges and 1,3-B centers) were responsible for the ob- shows EIS plots of the various modified electrodes. EIS could give
served luminescence effects.54,55 In addition, the surface charge of information about the solid-liquid interface system of the modified
the BNQDs was investigated by measuring the respective Zeta poten- electrodes. In the impedance spectrum, the semicircle portion repre-
tial, which was found to be −19.3 mV. This indicated that negatively sents the electron transfer limited process at the higher frequency and
the linear plot represent the diffusion process at the lower frequency.
The semicircle diameter at the higher frequency represents the charge
transfer resistance (Rct ) of the electrode.51,60 Fig. 5 shows Nyquist
plots obtained for Plu/BNQDs/GCE (curve a), Plu/GCE (curve b), BN-
QDs/GCE (curve c) and bare GCE (curve d) in 5 mM [Fe(CN)6 ]3−/4−
+ 0.1 M KCl solution.
A small semicircle plot and tail may indicate the diffusion con-
trolled process.61 The Nyquist impedance spectra of Plu/GCE (196.3
) (curve b), bare GCE (275.1 ) (curve d) and the modified BN-
QDs/GCE (671.5) (curve c) were compared with each other and
found that there was increase in Rct values after deposition of BNQDs
compared to bare GCE (curve d). This may be due to point defects of
BNQDs (dielectric interface) structure which could result in a wide
bandgap with insulating behavior.55,62 However, after Plu deposition
on the BNQDs/GCE surface, linear plot at the higher frequency in-
dicated a faster redox reaction due to the presence of conducting Plu
film. For Plu/BNQDs/GCE, Rct was decreased to 103.6 , this may
be due to the high conductive nature of the hybrid Plu/BNQDs film
as an effective proton transfer medium.51,60,63
Electrocatalytic oxidation of AA.—Fig. 6 represents the CVs of
Plu/BNQDs/GCE (curve a), Plu/GCE (curve b), BNQDs/GCE (curve
c) and bare GCE (curve d) in 0.1 M PBS (pH 7.4) with 1 mM AA. In
contrast to other coated electrodes, Plu/BNQDs/GCE showed higher
oxidation current (∼2.5 times higher than BNQDs/GCE) for 1 mM AA
Figure 1. FT-IR spectrum of synthesized BNQDs. at reduced overpotential of 0.2 V which confirmed that the hybrid film
B3020 Journal of The Electrochemical Society, 166 (9) B3017-B3024 (2019) Figure 2. (a and b) HR-TEM images of synthesized BNQDs and (c) particle size distribution histograms of BNQDs. Figure 3. (a) UV-Vis spectrum of BNQDs (Inset: visual images of BNQDs under normal and UV light). b) Fluorescence emission spectra of BNQDs at different excitation wavelengths from 300 to 400 nm.
Journal of The Electrochemical Society, 166 (9) B3017-B3024 (2019) B3021
Scheme 4. Redox reaction of Poly-luminol (Plu).
Figure 4. CVs of the Plu film growth on BNQDs/GCE from the 0.1 M H2 SO4 Figure 6. CVs of Plu/BNQDs/GCE (curve a), Plu/GCE (curve b), BN-
containing 0.5 mM luminol monomers. Scan rate = 0.05 V/s. QDs/GCE (curve c) and bare GCE (curve d) in (pH 7.4) 0.1 M PBS containing
1 mM AA and (curve e) is represending the CV of Plu/BNQDs/GCE in the
absence of AA (Scan rate = 10 mV/s).
has electrocatalytic properties (curve a). AA oxidation was appeared
at 0.25 V with lower current on bare GCE and BNQDs/GCE (curves
d and c). In addition, if we observe closely, AA oxidation current
was higher for BNQDs/GCE than bare GCE (curves c and d). This
proved that as-synthesized BNQDs has electrocatalytic activity. This
improved electrocatalytic acitivity was due to that AA diffuses to the
Plu/BNQDs/GCE surface effectively and in turn, it produced higher
oxidation current for AA compared to bare and BNQDs/GCE. It was
suggested that due to synergistic effect between Plu and BNQDs,
this new hybrid film showed higher catalytic current for AA oxidation
(curve a). AA electro-oxidation reaction at the Plu/BNQDs/GCE could
be explained as given in the Equation 2 (Scheme 5).64–66
Effect of scan rate on AA oxidation.—The effect of scan rates
on the oxidation peak current (Ipa ) of AA at Plu/BNQDs/GCE was
studied in 0.1 M PBS from 10 to 100 mV/s as shown in Fig. 7a. The Ipa
Figure 5. EIS data for Plu/BNQDs/GCE (curve a), Plu/GCE (curve b), BN- of AA was increased with square roots of scan rate (ν1/2 ). According
QDs/GCE (curve c) and bare GCE (curve d) in 5 mM [Fe(CN)6 ]3−/ 4− + 0.1 M to Ipa -ν1/2 curve, the oxidation peak current increased linearly (r2 =
KCl solutions by applying an AC voltage with 5 mV amplitude in a frequency 0.99) with the scan rates. This indicated a diffusion controlled electron
range from 100 MHz to 100 kHz. transfer process of AA oxidation on Plu/BNQDs/GCE (Fig. 7b).61
Scheme 5. Electro-catalytic oxidation of AA on Plu/BNQDs film.
B3022 Journal of The Electrochemical Society, 166 (9) B3017-B3024 (2019)
Figure 7. a) CVs of the effect of scan rates on 100 μM AA oxidaation at Plu/BNQDs/GCE. b) Linear plot of AA oxidation current vs. squre root of scan rates.
Amperometric detection of AA.—Fig. 8a shows the amperometric Interference and repeatability studies.—Since, dopamine (DA),
response of Plu/BNQDs/GCE for oxidation of AA (different concen- uric acid (UA) and glucose (Glu) have similar oxidation potentials
trations) at an applied potential of 0.1 V. In this experiment, 10 mL compared to AA. They may interfere on the oxidation of AA in
of 0.1 M PBS was used as an electrolyte (pH 7.4). After each addi- physiological pH. The addition of these biomolecules such as 5 μM
tion of AA, Plu/BNQDs/GCE responded linearly in current steps. A DA, 5 μM UA and 5 μM Glu were investigated in 0.1 M PBS using
calibration plot was made against concentration of AA vs. oxidation Plu/BNQDs/GCE as a sensor at an applied potential of 0.1 V in amper-
current which revealed that there was a linear relationship from 10 ometry. These interfering molecules did not produce any observable
to 100 μM with a correlation coefficient (R2 ) of 0.985 (Fig. 8b). The current at this condition. This indicated that the Plu/BNQDs/GCE
response time was 1.8 s, (Fig. 8a). The limit of detection (LOD) for have good selectivity for AA (Fig. 9a). There is no significant current
AA was estimated as 1.107 μM using the following equation:67 change observed in CV studies as shown in Fig. 9b which also proves
that, there is no interference of DA, UA and Glu. This selectivity to-
3S D ward AA may come from the specific interaction between Plu/BNQDs
LOD =
S hybrid film and AA in nutral media. As reported, luminol exist as fully
protonated (redued) form in neutral medium,68 so it gets attracted to
The slope of the calibration graph was (S) 5.846 × 10−11 A μM−1 negatively charged AA molecules.69
and the standard deviation (SD) of blank was 2.15 × 10−11 A. The Moreover, the repeatability was also tested by recording CVs in
calculated LOD (1.107 μM) was lowest compared to other reported the presence of 100 μM AA in PBS using Plu/BNQDs/GCE. CV
methods (Table I). The improved electrocatalytic activity of the hybrid responses were repeated in fresh PBS with 100 μM AA using same
film (Plu/BNQDs) may be due to the fast electron transfer between Plu/BNQDs/GCE at 60 min time intervals. The relative standard de-
the analyte and the electrode surface. viation (RSD) of the current measurements was 2.2%. This proved
Figure 8. a) The amperometric responses recorded using Plu/BNQDs/GCE at an applied potential of 0.1 V vs. Ag/AgCl to successive addition of 10 to 100 μM
AA in 0.1 M PBS (pH 7.4), rotation rate = 1000 rpm. b) Calibration graph of AA.
Journal of The Electrochemical Society, 166 (9) B3017-B3024 (2019) B3023
Table I. Comparison of analytical performance of Plu/BNQDs/GCE sensor with other reported AA sensors.
Electrochemical detection methods Transducer Linear response LOD References
Potentiometry Two ion sensitive field effect transistors 0.25–2.0 mM – 71
(ISFET)
Potentiometry MnO2 modified nanoparticles ion sensitive 0.02–1.27 mM 0.01 mM 72
field effect transistor (ISFET)
Cyclic Voltammetry Platinum electrode 0.31–20 mM 0.075 mM 73
Cyclic Voltammetry Carbon paste electrode 0.07–20 mM 0.062 mM 73
Cyclic Voltammetry and Differential Gold nanoparticles/overoxidized 210–1010 μM 2.0 μM 74
Pulse Voltammetry polyimidazole composite modified GCE
Differential Pulse Voltammetry Gold nanoparticles modified GCE 0.3–1.4 mM 90 μM 75
Amperometry Clark oxygen electrode 0.10–0.55 mM 0.023 mM 76
Amperometry and cyclic Modified GCE with Palladium Nanoparticles 0.02–2.28 mM – 77
voltammetry supported on GO
Amperometry Plu/BNQDs/GCE 10-100 μM 1.107 μM This work
Figure 9. a) Typical amperograms obtained with a Plu/BNQDs/GCE in 0.1 M PBS (pH 7.4) at an applied potential of 0.1 V, stirring rate = 1000 rpm. Successive
additions of 10 μM AA (first two additions), 5 μM UA, 5 μM DA, 5 μM Glu and 10 μM AA (last three additions). b) CV responses of Plu/BNQDs/GCE to the
addition of AA (100 μM) and different interfering species: DA (50 μM), UA (50 μM), and Glu (50 μM) in 0.1 M PBS (pH 7.4). Scan rate: 10 mV/s.
that Plu/BNQDs/GCE had high stability which retained 97.8% elec- calculated using vitamin C tablet samples on Plu/BNQDs/GCE (see
trode response after storage of 6 h in the absence of light at room Table II). The estimated AA concentrations were in the range of ac-
temperature. ceptable levels. The AA recovery varied from 98.8 to 102% in Vitamin
C tablet samples (Table II).
Real sample analysis.—The real application of Plu/BNQDs/GCE
was tested with 10 mg of vitamin C tablet using amperometric tech-
Conclusions
nique by standard addition method. The vitamin C tablet was finely
powdered, from that 10 mg of the substance was dissolved in 10 mL In summary, we have synthesized BNQDs via a simple hydrother-
of 0.1 M PBS solution.30,70 The diluted tablet samples were analyzed mal treatment method using boric acid and urea. As-synthesized
by using Plu/BNQDs/GCE with various spiked concentration of AA. BNQDs have been characterized using FT-IR, fluorescence emission
In this analysis, amperograms were recorded in 0.1 M PBS with the spectra, HR-TEM, UV-Vis, and Zeta potential measurements. These
addition of different concentrations of AA tablet samples after series studies confirmed the formation of BNQDs. The BNQDs showed a
of dilutions with and without spiked AA which indicated that other strong blue fluorescence under UV light. In addition, the electrochem-
components/additives present in tablets did not affect the electrode ical properties of Plu/BNQD were tested after coating on the GCE.
response. The analyzed AA samples and their recovery values were Plu/BNQDs/GCE exhibited improved electro-catalytic performance
Table II. The detection of AA in vitamin C tablet samples using Plu/BNQDs/GCE as a sensor.
S.No. Samples Content (μM) AA added (μM) Total AA founda (μM) RSDa % Recoveries %
Sample 1 AA tablet solution 10 - 9.88 1.24 98.8
Sample 2 AA tablet solution with spiked AA 10 50 61.17 1.22 101.95
Sample 3 AA tablet solution with spiked AA 10 60 69.9 1.31 99.8
a Mean value of three replicates.
B3024 Journal of The Electrochemical Society, 166 (9) B3017-B3024 (2019)
toward AA, with linear range of detection from 10 to 100 μM. The 28. X.-H. Pham, E. Hahm, T. H. Kim, H.-M. Kim, S. H. Lee, Y.-S. Lee, D. H. Jeong, and
LOD was estimated to be 1.107 μM. This Plu/BNQDs/GCE exhibited B.-H. Jun, Scientific Reports, 8, 6290 (2018).
29. C.-H. Su, C.-L. Sun, and Y.-C. Liao, ACS Omega, 2, 4245 (2017).
rapid response (1.8 sec) time for AA, and highly selective in the pres- 30. S. Ashok Kumar, H.-W. Cheng, and S.-M. Chen, Reactive and Functional Polymers,
ence of DA, UA and Glu. Real sample analysis was also performed 69, 364 (2009).
to detect AA in vitamin C tablet samples with good recovery. We 31. A. Barberis, Y. Spissu, G. Bazzu, A. Fadda, E. Azara, D. Sanna, M. Schirra, and
believe that this new hybrid sensor based on BNQDs and Plu could be P. A. Serra, Analytical Chemistry, 86, 8727 (2014).
32. S. Huang, F. Zhu, Q. Xiao, W. Su, J. Sheng, C. Huang, and B. Hu, RSC Advances, 4,
a valuable tool for the detection of AA in biological and food samples. 46751 (2014).
33. S. Vermeir, B. M. Nicolaı̈, P. Verboven, P. Van Gerwen, B. Baeten, L. Hoflack,
V. Vulsteke, and J. Lammertyn, Analytical Chemistry, 79, 6119 (2007).
Acknowledgments 34. G. Deshmukh and M. Bapat, Fresenius’ Zeitschrift für analytische Chemie, 145, 254
(1955).
We appreciate the Science and Engineering Research Board 35. S. Arya, M. Mahajan, and P. Jain, Analytica Chimica Acta, 417, 1 (2000).
(SERB), India (Ref. No.: ECR/2016/001446) for financial support. 36. S. Vermeir, M. Hertog, A. Schenk, K. Beullens, B. Nicolai, and J. Lammertyn,
We acknowledge the SRM Institute of Science and Technology for Analytica chimica acta, 618, 94 (2008).
providing ‘‘HR-TEM facility’’ and the Government of India for fi- 37. J. A. Nóbrega and G. S. Lopes, Talanta, 43, 971 (1996).
38. K. Güçlü, K. Sözgen, E. Tütem, M. Özyürek, and R. Apak, Talanta, 65, 1226 (2005).
nancial support (MNRE Project No.31/03/2014-15/PVSE-R&D). R.J 39. C. Duan, H. Cui, Z. Zhang, B. Liu, J. Guo, and W. Wang, The Journal of Physical
thanks SRM IST for Ph.D. student fellowship. Chemistry C, 111, 4561 (2007).
40. K. L. Lin, T. Yang, F. F. Zhang, G. Lei, H. Y. Zou, Y. F. Li, and C. Z. Huang, Journal
of Materials Chemistry B, 5, 7335 (2017).
ORCID 41. Y.-J. Tong, L.-D. Yu, L.-L. Wu, S.-P. Cao, Y.-L. Guo, R.-P. Liang, and J.-D. Qiu, ACS
Sustainable Chemistry & Engineering, 6, 9333 (2018).
Ashok K. Sundramoorthy https://orcid.org/0000-0002-8512-9393 42. Z. Wang, D. Chen, X. Gao, and Z. Song, Journal of Agricultural and Food Chemistry,
57, 3464 (2009).
43. N. Yan, Z. Zhu, D. He, L. Jin, H. Zheng, and S. Hu, Scientific Reports, 6, 24577
References (2016).
44. Z.-F. Zhang, H. Cui, C.-Z. Lai, and L.-J. Liu, Analytical Chemistry, 77, 3324 (2005).
1. D. Y. Hwang, K. H. Choi, J. E. Park, and D. H. Suh, Physical Chemistry Chemical 45. L. He, Z. W. Peng, Z. W. Jiang, X. Q. Tang, C. Z. Huang, and Y. F. Li, ACS Applied
Physics, 19, 4048 (2017). Materials & Interfaces, 9, 31834 (2017).
2. C. Anichini, W. Czepa, D. Pakulski, A. Aliprandi, A. Ciesielski, and P. Samorı̀, 46. D. Jia, J. Dai, H. Yuan, L. Lei, and D. Xiao, Talanta, 85, 2344 (2011).
Chemical Society Reviews, 47, 4860 (2018). 47. S. A. Kumar, H.-W. Cheng, and S.-M. Chen, Electroanalysis, 21, 2281 (2009).
3. V. Kumar, K. Nikhil, P. Roy, D. Lahiri, and I. Lahiri, RSC Advances, 6, 48025 (2016). 48. T. V. Kumar, S. K. Yadav, and A. K. Sundramoorthy, Journal of The Electrochemical
4. C.-H. Lin, H.-C. Fu, B. Cheng, M.-L. Tsai, W. Luo, L. Zhou, S.-H. Jang, L. Hu, and Society, 165, B848 (2018).
J.-H. He, npj 2D Materials and Applications, 2, 23 (2018). 49. M. C. Matsudo, R. P. Bezerra, S. Sato, P. Perego, A. Converti, and J. C. M. Carvalho,
5. H. Zhao, J. Ding, and H. Yu, New Journal of Chemistry, 42, 14433 (2018). Biochemical Engineering Journal, 43, 52 (2009).
6. Y. Zheng, D. Zhang, S. N. A. Shah, H. Li, and J.-M. Lin, Chemical Communications, 50. B. Liu, S. Yan, Z. Song, M. Liu, X. Ji, W. Yang, and J. Liu, Chemistry – A European
53, 5657 (2017). Journal, 22, 18899 (2016).
7. N. Chejanovsky, Y. Kim, A. Zappe, B. Stuhlhofer, T. Taniguchi, K. Watanabe, 51. J. Lin, C. He, L. Zhang, and S. Zhang, Analytical biochemistry, 384, 130 (2009).
D. Dasari, A. Finkler, J. H. Smet, and J. Wrachtrup, Scientific Reports, 7, 14758 52. M. Liu, Y. Xu, Y. Wang, X. Chen, X. Ji, F. Niu, Z. Song, and J. Liu, Advanced Optical
(2017). Materials, 5, 1600661 (2016).
8. A. Merlo, V. R. S. S. Mokkapati, S. Pandit, and I. Mijakovic, Biomaterials Science, 53. J. Wu and L. Yin, ACS Applied Materials & Interfaces, 3, 4354 (2011).
6, 2298 (2018). 54. C. Tang, Y. Bando, C. Zhi, and D. Golberg, Chemical Communications, 4599 (2007).
9. B. Singh, G. Kaur, P. Singh, K. Singh, B. Kumar, A. Vij, M. Kumar, R. Bala, 55. L. Lin, Y. Xu, S. Zhang, I. M. Ross, A. C. Ong, and D. A. Allwood, Small, 10, 60
R. Meena, A. Singh, A. Thakur, and A. Kumar, Scientific Reports, 6, 35535 (2016). (2014).
10. L. Takahashi and K. Takahashi, Dalton Transactions, 46, 4259 (2017). 56. V. Ferreira, A. C. Cascalheira, and L. M. Abrantes, Electrochimica Acta, 53, 3803
11. X. Tian, Y. Li, Z. Chen, Q. Li, L. Hou, J. Wu, Y. Tang, and Y. Li, Scientific Reports, (2008).
7, 17794 (2017). 57. S. A. Kumar and S.-M. Chen, Sensors and Actuators B: Chemical, 123, 964 (2007).
12. Y.-W. Yeh, Y. Raitses, B. E. Koel, and N. Yao, Scientific Reports, 7, 3075 (2017). 58. S. A. Kumar, C.-F. Tang, and S.-M. Chen, Talanta, 74, 860 (2008).
13. B. Huo, B. Liu, T. Chen, L. Cui, G. Xu, M. Liu, and J. Liu, Langmuir, 33, 10673 59. G. Li, X. Zheng, and L. Song, Electroanalysis, 21, 845 (2009).
(2017). 60. S. A. Kumar, L. Po-Hsun, and C. Shen-Ming, Nanotechnology, 19, 255501 (2008).
14. J.-H. Jung, M. Kotal, M.-H. Jang, J. Lee, Y.-H. Cho, W.-J. Kim, and I.-K. Oh, RSC 61. J. Tang and R. A. Marcus, Physical review letters, 95, 107401 (2005).
Advances, 6, 73939 (2016). 62. N. Atar and M. L. Yola, Journal of The Electrochemical Society, 165, H255 (2018).
15. Z. Lei, S. Xu, J. Wan, and P. Wu, Nanoscale, 7, 18902 (2015). 63. T. Bertók, J. Katrlı́k, P. Gemeiner, and J. Tkac, Mikrochimica acta, 180, 1 (2013).
16. D. Peng, L. Zhang, F.-F. Li, W.-R. Cui, R.-P. Liang, and J.-D. Qiu, ACS Applied 64. Y.-T. Chang, K.-C. Lin, and S.-M. Chen, Electrochimica Acta, 51, 450 (2005).
Materials & Interfaces, 10, 7315 (2018). 65. S.-M. Chen and K.-C. Lin, Journal of Electroanalytical Chemistry, 523, 93 (2002).
17. S. Bhowmick, A. K. Singh, and B. I. Yakobson, The Journal of Physical Chemistry 66. K.-C. Lin and S.-M. Chen, Journal of Electroanalytical Chemistry, 589, 52 (2006).
C, 115, 9889 (2011). 67. T. V. Kumar and A. K. Sundramoorthy, Journal of The Electrochemical Society, 165,
18. D. Krepel, L. Kalikhman-Razvozov, and O. Hod, The Journal of Physical Chemistry B3006 (2018).
C, 118, 21110 (2014). 68. U. Riaz, S. Jadoun, P. Kumar, M. Arish, A. Rub, and S. M. Ashraf, ACS Applied
19. S. S. Yamijala, A. Bandyopadhyay, and S. K. Pati, The Journal of Physical Chemistry Materials & Interfaces, 9, 33159 (2017).
C, 117, 23295 (2013). 69. X.-L. Wen, Y.-H. Jia, and Z.-L. Liu, Talanta, 50, 1027 (1999).
20. N. Murugan and A. K. Sundramoorthy, New Journal of Chemistry, 42, 13297 (2018). 70. N. Chauhan, J. Narang, and C. Pundir, Analyst, 136, 1938 (2011).
21. S. Angizi, A. Hatamie, H. Ghanbari, and A. Simchi, ACS Applied Materials & 71. V. Volotovsky and N. Kim, Sensors and Actuators B: Chemical, 49, 253 (1998).
Interfaces, 10, 28819 (2018). 72. X.-L. Luo, J.-J. Xu, W. Zhao, and H.-Y. Chen, Analytica Chimica Acta, 512, 57
22. A. Bandyopadhyay, S. S. R. K. C. Yamijala, and S. K. Pati, Physical Chemistry (2004).
Chemical Physics, 15, 13881 (2013). 73. A. M. Pisoschi, A. Pop, G. P. Negulescu, and A. Pisoschi, Molecules (Basel, Switzer-
23. A. Dehghani, S. Madadi Ardekani, P. Lesani, M. Hassan, and V. G. Gomes, ACS land), 16, 1349 (2011).
Applied Bio Materials, 2018. 74. C. Wang, R. Yuan, Y. Chai, S. Chen, F. Hu, and M. Zhang, Anal Chim Acta, 741, 15
24. Q. Xue, H. Zhang, M. Zhu, Z. Wang, Z. Pei, Y. Huang, Y. Huang, X. Song, H. Zeng, (2012).
and C. Zhi, RSC Advances, 6, 79090 (2016). 75. J. B. Raoof, A. Kiani, R. Ojani, R. Valiollahi, and S. Rashid-Nadimi, Journal of Solid
25. H. Li, R. Y. Tay, S. H. Tsang, X. Zhen, and E. H. T. Teo, Small, 11, 6491 (2015). State Electrochemistry, 14, 1171 (2010).
26. L. Lin, Y. Xu, S. Zhang, I. M. Ross, A. C. M. Ong, and D. A. Allwood, Small, 10, 60 76. G. Csiffáry, P. Fűtő, N. Adányi, and A. Kiss, Food Technology and Biotechnology,
(2014). 54, 31 (2016).
27. P. Thangasamy, M. Santhanam, and M. Sathish, ACS Applied Materials & Interfaces, 77. G.-H. Wu, Y.-F. Wu, X.-W. Liu, M.-C. Rong, X.-M. Chen, and X. Chen, Analytica
8, 18647 (2016). Chimica Acta, 745, 33 (2012).
You can also read
