Voltammetric Detection of Caffeine in Beverages at Nafion/Graphite Nanoplatelets Layer-by-Layer Films

We report for the first time a procedure in which Nafion/Graphite nanoplatelets (GNPs) thin films are fabricated using a modified layer-by-layer (LbL) method. The method consists of dipping a substrate (quartz and/or glassy carbon electrodes) into a composite solution made of Nafion and GNPs dissolv...

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Main Authors: Sandra Hernandez-Aldave, Afshin Tarat, James D. McGettrick, Paolo Bertoncello
Format: Article
Language:English
Published: MDPI AG 2019-02-01
Series:Nanomaterials
Subjects:
Online Access:https://www.mdpi.com/2079-4991/9/2/221
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author Sandra Hernandez-Aldave
Afshin Tarat
James D. McGettrick
Paolo Bertoncello
author_facet Sandra Hernandez-Aldave
Afshin Tarat
James D. McGettrick
Paolo Bertoncello
author_sort Sandra Hernandez-Aldave
collection DOAJ
description We report for the first time a procedure in which Nafion/Graphite nanoplatelets (GNPs) thin films are fabricated using a modified layer-by-layer (LbL) method. The method consists of dipping a substrate (quartz and/or glassy carbon electrodes) into a composite solution made of Nafion and GNPs dissolved together in ethanol, followed by washing steps in water. This procedure allowed the fabrication of multilayer films of (Nafion/GNPs)<sub>n</sub> by means of hydrogen bonding and hydrophobic‒hydrophobic interactions between Nafion, GNPs, and the corresponding solid substrate. The average thickness of each layer evaluated using profilometer corresponds to ca. 50 nm. The as-prepared Nafion/GNPs LbL films were characterized using various spectroscopic techniques such as X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDS), FTIR, and optical microscopy. This characterization highlights the presence of oxygen functionalities that support a mechanism of self-assembly via hydrogen bonding interactions, along with hydrophobic interactions between the carbon groups of GNPs and the Teflon-like (carbon‒fluorine backbone) of Nafion. We showed that Nafion/GNPs LbL films can be deposited onto glassy carbon electrodes and utilized for the voltammetric detection of caffeine in beverages. The results showed that Nafion/GNPs LbL films can achieve a limit of detection for caffeine (LoD) of 0.032 &#956;M and linear range between 20‒250 &#956;M using differential pulse voltammetry, whereas, using cyclic voltammetry LoD and linear range were found to be 24 &#956;M and 50‒5000 &#956;M, respectively. Voltammetric detection of caffeine in beverages showed good agreement between the values found experimentally and those reported by the beverage producers. The values found are also in agreement with those obtained using a standard spectrophotometric method. The proposed method is appealing because it allows the fabrication of Nafion/GNPs thin films in a simple fashion using a single-step procedure, rather than using composite solutions with opposite electrostatic charge, and also allows the detection of caffeine in beverages without any pre-treatment or dilution of the real samples. The proposed method is characterized by a fast response time without apparent interference, and the results were competitive with those obtained with other materials reported in the literature.
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spelling doaj.art-15e0944d280f4e28a1a294ab740bdd852022-12-22T01:38:28ZengMDPI AGNanomaterials2079-49912019-02-019222110.3390/nano9020221nano9020221Voltammetric Detection of Caffeine in Beverages at Nafion/Graphite Nanoplatelets Layer-by-Layer FilmsSandra Hernandez-Aldave0Afshin Tarat1James D. McGettrick2Paolo Bertoncello3Systems and Process Engineering Centre, College of Engineering, Bay Campus, Swansea University, Crwmlyn Burrows, Swansea SA1 8EN, UKPerpetuus Advanced Materials, Unit B1, Olympus Court, Millstream Way, Swansea Vale, Llansamlet, SA7 0AQ, UKSPECIFIC, College of Engineering, Bay Campus, Swansea University, Swansea SA1 8EN, UKSystems and Process Engineering Centre, College of Engineering, Bay Campus, Swansea University, Crwmlyn Burrows, Swansea SA1 8EN, UKWe report for the first time a procedure in which Nafion/Graphite nanoplatelets (GNPs) thin films are fabricated using a modified layer-by-layer (LbL) method. The method consists of dipping a substrate (quartz and/or glassy carbon electrodes) into a composite solution made of Nafion and GNPs dissolved together in ethanol, followed by washing steps in water. This procedure allowed the fabrication of multilayer films of (Nafion/GNPs)<sub>n</sub> by means of hydrogen bonding and hydrophobic‒hydrophobic interactions between Nafion, GNPs, and the corresponding solid substrate. The average thickness of each layer evaluated using profilometer corresponds to ca. 50 nm. The as-prepared Nafion/GNPs LbL films were characterized using various spectroscopic techniques such as X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDS), FTIR, and optical microscopy. This characterization highlights the presence of oxygen functionalities that support a mechanism of self-assembly via hydrogen bonding interactions, along with hydrophobic interactions between the carbon groups of GNPs and the Teflon-like (carbon‒fluorine backbone) of Nafion. We showed that Nafion/GNPs LbL films can be deposited onto glassy carbon electrodes and utilized for the voltammetric detection of caffeine in beverages. The results showed that Nafion/GNPs LbL films can achieve a limit of detection for caffeine (LoD) of 0.032 &#956;M and linear range between 20‒250 &#956;M using differential pulse voltammetry, whereas, using cyclic voltammetry LoD and linear range were found to be 24 &#956;M and 50‒5000 &#956;M, respectively. Voltammetric detection of caffeine in beverages showed good agreement between the values found experimentally and those reported by the beverage producers. The values found are also in agreement with those obtained using a standard spectrophotometric method. The proposed method is appealing because it allows the fabrication of Nafion/GNPs thin films in a simple fashion using a single-step procedure, rather than using composite solutions with opposite electrostatic charge, and also allows the detection of caffeine in beverages without any pre-treatment or dilution of the real samples. The proposed method is characterized by a fast response time without apparent interference, and the results were competitive with those obtained with other materials reported in the literature.https://www.mdpi.com/2079-4991/9/2/221Nafiongraphite nanoplateletscaffeineelectrochemical sensors
spellingShingle Sandra Hernandez-Aldave
Afshin Tarat
James D. McGettrick
Paolo Bertoncello
Voltammetric Detection of Caffeine in Beverages at Nafion/Graphite Nanoplatelets Layer-by-Layer Films
Nanomaterials
Nafion
graphite nanoplatelets
caffeine
electrochemical sensors
title Voltammetric Detection of Caffeine in Beverages at Nafion/Graphite Nanoplatelets Layer-by-Layer Films
title_full Voltammetric Detection of Caffeine in Beverages at Nafion/Graphite Nanoplatelets Layer-by-Layer Films
title_fullStr Voltammetric Detection of Caffeine in Beverages at Nafion/Graphite Nanoplatelets Layer-by-Layer Films
title_full_unstemmed Voltammetric Detection of Caffeine in Beverages at Nafion/Graphite Nanoplatelets Layer-by-Layer Films
title_short Voltammetric Detection of Caffeine in Beverages at Nafion/Graphite Nanoplatelets Layer-by-Layer Films
title_sort voltammetric detection of caffeine in beverages at nafion graphite nanoplatelets layer by layer films
topic Nafion
graphite nanoplatelets
caffeine
electrochemical sensors
url https://www.mdpi.com/2079-4991/9/2/221
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AT afshintarat voltammetricdetectionofcaffeineinbeveragesatnafiongraphitenanoplateletslayerbylayerfilms
AT jamesdmcgettrick voltammetricdetectionofcaffeineinbeveragesatnafiongraphitenanoplateletslayerbylayerfilms
AT paolobertoncello voltammetricdetectionofcaffeineinbeveragesatnafiongraphitenanoplateletslayerbylayerfilms