Composites Communications 37 (2023) 101398

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Composites Communications
journal homepage: www.elsevier.com/locate/coco

Low-cost, disposable sensors based on polystyrene waste and V–TiO2

microneedle composites for diagnosis of renal malfunction and
muscle dystrophy
Tehzeeb Sawaira a, 1, Amna Jamil a, 1, Saba Aziz b, Adnan Mujahid a, Tajamal Hussain a,
Adeel Afzal a, *
a
School of Chemistry, University of the Punjab, Quaid-i-Azam Campus, Lahore, 54590, Pakistan
b
Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education, Northeast Normal University, Changchun, 130024, China

A R T I C L E I N F O A B S T R A C T

Keywords: A compact, cost-efficient, and disposable electrochemical creatinine sensor is designed using disposable screen-
Creatinine printed carbon electrodes coated with a composite receptor based on polystyrene foam (i.e., packaging material
Disease diagnostics waste) and anatase-phase V–TiO2 microneedles. The electrochemical sensor is capable of monitoring 1–25 μM
Electrochemical sensors
creatinine in a standard redox solution at 7.4 pH and room temperature. The electrochemical measurements are
Point-of-care
performed with a portable potentiostat using an android smartphone. Cyclic voltammetry and differential pulse
voltammetry characteristics are measured to monitor the concentration of creatinine. The sensor exhibits
excellent creatinine sensitivity of 30.95 ± 1.73 μA/cm2⸳μM and an extremely low threshold detection limit of
184 nM creatinine.

1. Introduction (POC) diagnosis of muscular dystrophy and renal malfunction.

The human body produces different biomarkers, whose concentra­
tion in biological fluids such as saliva, serum, and urine. may change
under certain physiological conditions. The critical concentration
changes usually serve as an indicator for various diseases. For instance,
creatinine, a nitrogenous compound formed by muscle tissues, is a
signature of renal malfunction, chronic kidney disease, and muscle
impairment [1]. Creatinine is present in the blood, saliva, and urine in
varying concentrations depending upon the age, sex, and well-being of
the individuals [1,2].
For instance, normal physiological levels of creatinine in the serum
of healthy male and female adults are 61.89–106.10 μM and
44.21–88.42 μM, respectively, while a normal physiological level of
creatinine in the saliva is 4.4–17.7 μM. A significantly decreased con­
centration of serum creatinine (male: <55 μM; and female: <39 μM) is
an indicator of extreme muscular dystrophy, whereas a considerable
increase in the serum creatinine levels (male: >113 μM; and female:
>95 μM) indicates renal malfunction and kidney failure [2,3]. Hence,
sensing creatinine in physiological fluids is essential for point-of-care
Azimirad and co-workers [4] reviewed different methods for the
determination of creatinine. However, clinical detection of creatinine is
performed via spectroscopic methods such as those based on the Jaffé
reaction [5,6]. Nonetheless, these methods are neither deliverable nor
affordable for continuous monitoring of creatinine in physiological
fluids due to the requirement of sophisticated instruments, trained
personnel, or insufficient sensitivity [4]. To overcome these limitations,
electrochemical sensors are being designed for the direct determination
of creatinine in solution and physiological fluids [7–11]. However, to
comply with the ASSURED principle that refers to affordable, sensitive,
selective, user-friendly, rapid and robust, easy-to-use, and deliverable
diagnostics [12], it is necessary to develop new POC diagnostics for
continuous creatinine analysis and determining the onset or early
diagnosis of any disease.
Herein, we report the design and synthesis of a composite receptor
layer made of V–TiO2 microneedles embedded into the polystyrene-
based waste packaging material (PS foam) to develop a portable elec­
trochemical sensor for smartphone-based rapid detection of creatinine
at room temperature and pH 7.4, as shown in Fig. 1(a). The proposed

* Corresponding author.
E-mail addresses: adeel.chem@pu.edu.pk, aa@aafzal.com (A. Afzal).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.coco.2022.101398
Received 23 September 2022; Received in revised form 28 October 2022; Accepted 2 November 2022
Available online 5 November 2022
2452-2139/© 2022 Published by Elsevier Ltd.
T. Sawaira et al.
Fig. 1. (a) An image of the electrochemical sensor setup showing an android smartphone-controlled Sensit Smart potentiostat along with (b) disposable, screen-
printed electrodes for the fabrication of creatinine sensors, and (c) a typical CV scan of creatinine (structure shown) in a standard redox solution at pH 7.4.
detection method is not only simple but highly sensitive and cost-
efficient. It uses inexpensive, commercially available screen-printed
carbon electrodes (cost: <2$) (Fig. 1(b)). Fig. 1(c) shows a typical CV
scan of creatinine in a standard redox solution. The experimental details
are given in the Supplementary Data (Materials and Methods). The
preliminary electrochemical measurements revealed excellent results
for the recognition of 1–25 μM creatinine in standard redox solutions.
The disposable electrochemical sensor exhibits great potential for
routine analysis of creatinine in physiological fluids.
2. Results and discussion
Fig. 2(a) shows the XRD pattern of V–TiO2 microneedles, which in­
dicates the formation of the anatase structure (JCPDS Card No.
21–1272) [13,14]. The characteristic peaks of V2O5 are not observed,
which implies that V5+ ions are successfully incorporated into the TiO2
lattice to form substitutionally doped V–TiO2 microneedles [15]. XRD
measurements indicate that anatase V–TiO2 is nanocrystalline material
since the calculations using the Debye-Scherrer formula for the main
peak (101) at 25.6◦ 2θ position (shown in Fig. 2(a) inset) show a crys­
tallite size of 6.6 nm for V–TiO2 microneedles. Fig. 2(b) shows the FTIR
spectra of V–TiO2 microneedles and PS/V–TiO2 coatings. The
sol-gel-derived V–TiO2 microneedles show a characteristic broad peak in
the range of 3100–3500 cm− 1 with a maximum at ~3350 cm− 1, which is
attributed to the hydroxyl (–OH) groups present on the surface of
V–TiO2 microneedles [16,17]. On the other hand, the FTIR spectrum of
composite PS/V–TiO2 sensing material predominantly exhibits the
characteristic peaks for PS or styrene [18,19], and it does not exhibit a
broad peak for hydroxyl groups. This is possibly due to the small amount
(565 μg/mL) of V–TiO2 microneedles embedded in the PS matrix. The
SEM image of pristine V–TiO2 is shown in Fig. 2(c), which depicts
V–TiO2 microneedles forming a flower-like clustered microstructure. On
the other hand, V–TiO2 microneedles are homogeneously dispersed into
the PS matrix forming a uniform PS/V–TiO2 composite sensor coating,
as shown in Fig. 2(d).
To start with the electrochemical sensor measurements, the effect of
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Composites Communications 37 (2023) 101398
scan rate on CV characteristics of 1 μM creatinine solution in PBS is
studied, as shown in Fig. 3(a). It is observed that an increase in scan rate
from 20 mV/s to 100 mV/s improves the current response of the PS/
V–TiO2 sensor. The oxidation peak observed at ~0.2 V anodic potential
is ascribed to the oxidation of creatinine [20]. Due to an increased
anodic peak current at 100 mV/s, the same scan rate was used in all
electrochemical sensor measurements. The electrochemical sensing
properties are measured by CV and DPV of PS/V–TiO2 modified
disposable sensor. The PS/V–TiO2 sensor is exposed to a few microliters
of the standard redox solution containing PBS buffer (pH 7.4) with 1–25
μM of creatinine and 2.5 mM K3[Fe(CN)6] and K4[Fe(CN)6]. Fig. 3(b)
shows the current response of the PS/V–TiO2 sensor to different con­
centrations of creatinine. It exhibits a significant increase in the peak
anodic current from 40.2 μA for 1 μM creatinine to 105.4 μA for 25 μM
creatinine at +0.214 V. Fig. 3(c) shows a magnified view of the anodic
peak current variations with different concentrations of creatinine. The
values of peak currents obtained from these measurements are plotted in
Fig. 3(d) as a function of the creatinine concentration. The plot exhibits a
straight line with a slope of 2.451 μA/μM and a correlation coefficient
(R2) of 0.936.
To demonstrate the sensitivity of the PS/V–TiO2 sensor and deter­
mine its threshold limit of detection (LOD) and limit of quantification
(LOQ), DPV studies were performed with various concentrations of
creatinine (1, 5, 10, 15, 20, and 25 μM) in a standard redox solution
within the potential range of − 0.1 V to +0.5 V, as shown in Fig. 4(a).
DPV measurements show a significant increase in the peak current from
268 μA to 322 μA at ~0.2 V due to an increase in the creatinine con­
centration from 1 μM to 25 μM. The resultant changes in current density
are determined from the DPV measurements and are plotted as a func­
tion of creatinine concentration in Fig. 4(b). The plot exhibits a linear
increase in current density with an R2 value of 0.988 in the creatinine
concentration range of 1–25 μM. The sensitivity of the PS/V–TiO2 sensor
is found to be 30.95 ± 1.73 μA/cm2⸳μM.
Both LOD and LOQ are determined from the slope of the straight line
and standard deviation according to the formulae described elsewhere
[21]. Thus, the calculated values of LOD and LOQ are 184 nM and 557
T. Sawaira et al.
Fig. 2. (a) XRD pattern of V–TiO2 microneedles (inset shows the main peak (101) at 25.6◦ 2θ position). (b) FTIR spectra of V–TiO2 microneedles and PS/V–TiO2
composite. SEM images of (c) pristine V–TiO2 microneedles, and (d) PS/V–TiO2 composite coating.
nM, respectively. The sensitivity and LOD of the PS/V–TiO2 sensor are
remarkably better than recently reported electrochemical creatinine
sensors. A comparison of the sensor’s performance with recently re­
ported electrochemical creatinine detection methods is provided in
Table S1. The disposable electrochemical sensor based on PS/V–TiO2
composite could be optimized for real-time, non-invasive detection of
creatinine in human saliva and would pave the way toward POC diag­
nostic applications.
3. Conclusions
A simple and inexpensive method for the detection of micromolar
concentrations of creatinine is developed, tested, and validated in this
work. To design ASSURED-compliant sensors that are mainly affordable,
sensitive, and deliverable, disposable screen-printed carbon electrodes
are modified with PS/V–TiO2 sensitive coating. PS was obtained from
the waste of packaging material and was activated by the incorporation
of V–TiO2 microneedles. Thus-fabricated PS/V–TiO2 electrochemical
sensors revealed excellent sensitivity (30.95 μA/cm2⸳μM) for creatinine
and linear detection range (1–25 μM). This detection range is clinically
significant for POC diagnosis of creatinine in human saliva samples,
where its concentration usually lies within the 4.4–17.7 μM range in
healthy beings. Hence, this work may lead to an affordable POC solution
for routine monitoring and clinical diagnosis of renal malfunction and
muscular dystrophy.
3
Composites Communications 37 (2023) 101398
Funding
This work was supported by the Royal Society of Chemistry (grant
number R21-9209614762).
CRediT authorship contribution statement
Tehzeeb Sawaira: Data curation, Investigation, Methodology,
Validation. Amna Jamil: Data curation, Investigation, Methodology,
Validation. Saba Aziz: Data curation, Investigation, Validation. Adnan
Mujahid: Resources, Visualization, Writing – review & editing. Tajamal
Hussain: Resources, Validation. Adeel Afzal: Conceptualization,
Formal analysis, Funding acquisition, Project administration, Resources,
Supervision, Visualization, Writing – original draft, Writing – review &
editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
T. Sawaira et al. Composites Communications 37 (2023) 101398

Fig. 3. (a) CV of 1 μM creatinine in standard redox solution at different scan rates. (b) CV scans of the disposable PS/V–TiO2 sensor when exposed to different
concentrations of creatinine in PBS. (c) A magnified view of CV scans showing the variations in peak anodic current as a function of the creatinine concentration. (d)
A calibration curve: anodic peak current at +0.214 V vs. the concentration of creatinine.

Fig. 4. (a) DPV characteristics of the disposable PS/V–TiO2 sensor when exposed to different concentrations of creatinine in PBS. (b) A calibration curve showing the
sensitivity of the PS/V–TiO2 sensor to creatinine in the linear detection range of 1–25 μM.

Acknowledgments References

Adeel Afzal is grateful to the Royal Society of Chemistry for the
Research Fund (R21-9209614762). The authors also thank Dr. Ather
Farooq Khan (COMSATS University Islamabad, Lahore Campus) and Dr.
Amir Habib (University of Hafr Al Batin, KSA) for providing XRD and
SEM characterizations, respectively.
Appendix B. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.coco.2022.101398.
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