Article

Cyclophosphazene Intrinsically Derived Heteroatom

(S, N, P, O)-Doped Carbon Nanoplates for Ultrasensitive
Monitoring of Dopamine from Chicken Samples
Yasir Abbas 1,†, Naeem Akhtar 2,†, Sania Ghaffar 3,†, Ahlam I. Al-Sulami 4, Muhammad Asad 5,
Muhammad Ehsan Mazhar 6, Farhan Zafar 7, Akhtar Hayat 8,* and Zhanpeng Wu 1,*

1 Laboratory of Carbon Fiber and Functional Polymers (Beijing University of Chemical Technology), Ministry
of Education, Beijing 100029, China
2 Institute of Chemical Sciences, Bahauddin Zakariya University (BZU), Multan 60800, Pakistan

3 Nishtar Medical University, Multan 60800, Pakistan

4 University of Jeddah, College of Science, Department of Chemistry, Jeddah 21589, Saudi Arabia

5 Department of Materials Science and Engineering, University of Science and Technology of China No. 96

Jinzhai Road, Hefei 230026, China

6 Department of Physics, Bahauddin Zakariya University (BZU), Multan 60800, Pakistan

7 Department of Chemistry, COMSATS University Islamabad, Lahore Campus, Lahore 54000, Pakistan

8 Interdisciplinary Research Centre in Biomedical Materials (IRCBM), COMSATS University Islamabad, La-

hore 54000, Pakistan

* Correspondence: akhtarhayat@cuilahore.edu.pk (A.K.); wuzp@mail.buct.edu.cn (Z.W.)
‡ These authors have contributed equally to this work.

Supplementary Materials:

1. Experimental Section

1.1 Characterization Analyses

Polymerization was confirmed via Fourier Transform Infrared (FTIR) by using a Bruker Vertex 70
FTIR spectrometer. The morphology of as prepared samples was investigated using Field
emission scanning electron microscopy (FE-SEM, S-4800, JEM-6701F). Energy dispersive X-ray
spectroscopy (EDX) coupled with FE-SEM was used to determine the elemental percentages.
Microstructures of graphitic materials were carried out on FEI Tecnai T-20 TEM. It provides
information about the morphology; dimensions and crystallinity as well as defects and crystal
orientations. To analyze the crystal structures, a diffractometer (XRD-6000) was used to
characterized for powder X-ray diffrac-tion (PXRD) at voltage of 40 kV using monochromated Cu
Kα radiation (λ = 1.54 Å, 40 kV, 30 mA) at scan rate of 10° min-1. Raman spectroscopy is a simple
but versatile technique used to identify rotational, vibrational, and other lower energy modes in
the materials. Using Raman (Renishaw invia microscope), we studied ratio of in-plane vibrations
of the sp2 carbon (G-band) and disorder-induced mode (D-band) at excitation wavelength of 633
nm. The N2 adsorption-desorption were measured via a Quantachrome Autosorb-1C-VP. Prior to
N2 adsorption-desorption, all the sample were subjected at 200 ̊ C under vacuum for 5 hours.
Specific surface area was determined via Brunauer−Emme −Teller method. X-rays photoelectron
spectroscopy (XPS) is surface sensitive spectroscopic techniques used to measure the chemical
states surface compositions, and electronic states. XPS was performed (using K-Alpha, Thermo
Fisher Scientific, USA) coupled to an ultrahigh vacuum system equipped with a monochromatic
Al Kα (1486.6 eV).

Biosensors 2022, 12, 1106. https://doi.org/10.3390/bios12121106 www.mdpi.com/journal/biosensors

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2. Results and discussion

Figure S1. Digital image of LPG system prepared for electrochemical measurements.

Figure S2. XRD analysis of PCD polymer.

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Figure S3. SEM image of PCD polymer revealing sphere like morphology.

Figure S4. Pore size distribution of all three electrodes.

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Figure S5. (A) Survey spectrum of SNPO-CPL-800. Deconvoluted high resolution XPS spectrum of
C (B), O (C), N (D), S (E) and P (F).
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Figure S6. (A) Mapping analysis of SNPO-CPL-800 with homogeneous distribution (A) of S (B), N
(C), P (D), O (E) and C (F).

2.1 The Electrochemical Activity of SNPO-CPL-(600, 800 and 1000)

The electrochemical activity of SNPO-CPL-(600, 800 and 1000) modified LPG was assessed through
cyclic voltammogram (CV) measurements in 0.1 M PBS electrolyte containing 5 mM [Fe(CN)6] with
in applied potential rang of 0.0 to 0.75 V. A pair of redox peak with varying peak current and po-
tential appeared at the surface of all four electrodes (Figure S7A). However, SNPO-CPL-800 shows
high peak current and small peak separation difference compared to SNP-CPL-600 and SNP-CPL-
1000. This high sensing efficacy of SNP-CPL-800 could be attributed to efficient charge density at
the delocalized surface because of maximum percentage doping of S, N, P, O, and graphitic C.

Additionally, charge transfer capability of the SNPO-CPL-(600, 800 and 1000) were also calculated
by impedance spectroscopy (EIS). Figure S7B shows the Nyquist plot of impedance spectrum with
two portions; semicircle at high frequency refers the electron transfer resistance (Res) and line part
at low frequencies reflects the diffusion process velocity. Results indicate that SNP-CPL-800 have
the smallest semicircle diameter compared to others, which indicate high electron transport effi-
ciency of the developed electrode.

Figure S7. Shows CV (A) and typical -Nyquist impedance spectra (B) for SNPO-CPL-600, SNPO-
CPL-800, and SNPO-CPL-1000 in 5 mM [Fe(CN)6] in 0.1 M PBS (pH:7).
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Table S1. Atomic percentages of the as synthesized electrocatalysts from XPS analysis.

Catalyst Atomic % Atomic % Atomic % Atomic % Atomic %

(S) (N) (P) (O) (C)

SNPO- 0.63 1.99 1.7 21.89 73.75

CPL-600

SNPO- 0.87 2.02 1.87 22.3 72.98

CPL-800

SNPO- 0.00 0.00 0.88 14.24 71.84

CPL-1000

Figure S8. (A) Peak potential versus pH and (B) plot of anodic current versus pH derived from
Figure 3B.
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Figure S9. (A) CV of SNPO-CPL-800 with varying scan rate from 20- 100 mV/s. (B) Peak current vs.
scan rate derived from figure S9-A.

Table S2. Sensitivity and limit of detection comparison of different carbon-based electrodes for DA.

Electrocatalysts Sensitivity Limit of detection References

(μA/mM) (nM)
Carbon nano- 5 60 [1]
rods
Graphene oxide 2.39 80 [2]
nanorib-
bons/GCE
S doped carbon 4.1 3 [3]
N-doped gra- 9.87 1 [4]
phene
N Gra- 0.113 250 [5]
phene/GCE
N doped gra- 2.22 630 [6]
phine
N doped gra- __ 930 [7]
phine
N, S doped car- __ 0.02 [8]
bon
P doped gra- __ 0.36 [9]
phene
N, P doped car- 7.94 600 [10]
bon
SNPO-CPL-800 0.38 0.009 This work

Limit of detection calculated by using equation S1.

LOD = F x SD/b……………………………………….. (S1)
Where
F: Factor of 3.3, SD: Standard deviation of the blank, standard deviation of the ordinate in-
tercept, or residual standard deviation of the linear regression, b: Slope of the regression line
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References
1. Demuru, S., et al., Scalable Nanostructured Carbon Electrode Arrays for Enhanced Dopamine Detection. ACS sensors, 2018. 3(4):
p. 799-805.
2. Sun, C.-L., et al., Microwave-assisted synthesis of a core–shell MWCNT/GONR heterostructure for the electrochemical detection of
ascorbic acid, dopamine, and uric acid. Acs Nano, 2011. 5(10): p. 7788-7795.
3. Emran, M.Y., et al., One-step selective screening of bioactive molecules in living cells using sulfur-doped microporous carbon. Bio-
sensors and Bioelectronics, 2018. 109: p. 237-245.
4. Feng, X., et al., Three-dimensional nitrogen-doped graphene as an ultrasensitive electrochemical sensor for the detection of dopamine.
Nanoscale, 2015. 7(6): p. 2427-2432.
5. Sheng, Z.-H., et al., Electrochemical sensor based on nitrogen doped graphene: Simultaneous determination of ascorbic acid, dopa-
mine and uric acid. Biosensors and Bioelectronics, 2012. 34(1): p. 125-131.
6. Wiench, P., et al., Beneficial impact of oxygen on the electrochemical performance of dopamine sensors based on N-doped reduced
graphene oxides. Sensors and Actuators B: Chemical, 2018. 257: p. 143-153.
7. Li, S.-M., et al., Controllable synthesis of nitrogen-doped graphene and its effect on the simultaneous electrochemical determination of
ascorbic acid, dopamine, and uric acid. Carbon, 2013. 59: p. 418-429.
8. Gao, W., et al., One-Step Pyrolytic Synthesis of Nitrogen and Sulfur Dual-Doped Porous Carbon with High Catalytic Activity and
Good Accessibility to Small Biomolecules. ACS Applied Materials & Interfaces, 2014. 6(21): p. 19109-19117.
9. Zhang, X., et al., Phosphorus-doped graphene-based electrochemical sensor for sensitive detection of acetaminophen. Analytica
Chimica Acta, 2018. 1036: p. 26-32.
10. Zhao, L., et al., Electropolymerization fabrication of three-dimensional N, P-co-doped carbon network as a flexible electrochemical
dopamine sensor. Sensors and Actuators B: Chemical, 2017. 253: p. 1113-1119.