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. 2022 May 10;14(10):1942.
doi: 10.3390/polym14101942.

New Potentiometric Screen-Printed Platforms Modified with Reduced Graphene Oxide and Based on Man-Made Imprinted Receptors for Caffeine Assessment

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New Potentiometric Screen-Printed Platforms Modified with Reduced Graphene Oxide and Based on Man-Made Imprinted Receptors for Caffeine Assessment

Hisham S M Abd-Rabboh et al. Polymers (Basel). .

Abstract

Caffeine is a psychoactive drug that is administered as a class II psychotropic substance. It is also considered a component of analgesics and cold medicines. Excessive intake of caffeine may lead to severe health damage or drug addiction problems. The assessment of normal caffeine consumption from abusive use is not conclusive, and the cut-off value for biological samples has not been established. Herein, new cost-effective and robust all-solid-state platforms based on potentiometric transduction were fabricated and successfully utilized for caffeine assessment. The platforms were modified with reduced graphene oxide (rGO). Tailored caffeine-imprinted polymeric beads (MIPs) based on methacrylic acid (MAA) and ethylene glycol dimethacrylate (EGDMA) were prepared, characterized, and used as recognition receptors in the presented potentiometric sensing devices. In 50 mM MES buffer, the sensors exhibited a slope response of 51.2 ± 0.9 mV/decade (n = 6, R2 = 0.997) over the linear range of 4.5 × 10−6−1.0 × 10−3 M with a detection limit of 3.0 × 10−6 M. They exhibited fast detection of caffeinium ions with less than 5 s response time (<5 s). The behavior of the presented sensors towards caffeinium ions over many common organic and inorganic cations was evaluated using the modified separate solution method (MSSM). Inter-day and intra-day precision for the presented analytical device was also evaluated. Successful applications of the presented caffeine sensors for caffeine determination in commercial tea and coffee and different pharmaceutical formulations were carried out. The data obtained were compared with those obtained by the standard liquid chromatographic approach. The presented analytical device can be considered an attractive tool for caffeine determination because of its affordability and vast availability, particularly when combined with potentiometric detection.

Keywords: caffeine; molecularly imprinted polymers (MIPs); potentiometry; screen printed; solid-contact ISEs.

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Conflict of interest statement

The authors declare that there are no conflicts of interest.

Figures

Figure 1
Figure 1
Schematic design of homemade screen-printed fabrication.
Figure 2
Figure 2
A schematic representation for the imprinting process.
Figure 3
Figure 3
SEM images of (A) MIPs and (B) NIPs.
Figure 4
Figure 4
Calibration plot for caffeine sensors in different membrane plasticizers.
Figure 5
Figure 5
Response mechanisms for the SC-ISEs. Electric-double-layer (EDL) capacitance-based SC-ISEs with MWCNT and rGO as solid-contact transducer.
Figure 6
Figure 6
The effect of pH on the potentiometric response of the MIP/oNPOE membrane-based sensor.
Figure 7
Figure 7
EIS measurements of (a) non-modified and (b) modified caffeine-ISEs.
Figure 8
Figure 8
Chronopotentiometry measurements of the applied sensor; (a) non-modified and (b) modified caffeine-ISEs.
Figure 9
Figure 9
Water-layer tests for (a) non-modified, and (b) modified caffeine-ISEs.

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