Recent Advances in Quartz Crystal Microbalance-Based Sensor Applications

A special issue of Chemosensors (ISSN 2227-9040). This special issue belongs to the section "Applied Chemical Sensors".

Deadline for manuscript submissions: closed (30 August 2022) | Viewed by 28164

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Kalsruhe Institute of Technology, Institute of Functional Interfaces, Chemistry of oxydic and organic Interfaces, Hermann-von-Helmholtz-Platz 1, Geb. 330, R. 324, 76344 Eggenstein-Leopoldshafen, Germany
Interests: organic; inorganic; semiconducting thin film interfaces and their application to electronic devices, such as QCM based electronic nose/tongue applications using SURMOF sensor arrays in gas/liquid interfaces
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Dear Colleagues,

There has been a rapid increase in the number of publications related to QCM sensing applications during the last few decades. They have been extensively used in deposition rate monitoring for controlling thickness in many deposition techniques, such as thermal vapor deposition, sputtering, and electrochemical deposition. QCMs have recently been used in many other applications in various disciplines of science and technology for the detection of vapors, volatile organic compounds (VOCs), environmental pollutants, biomolecules, disease biomarkers, cells, and pathogens in many different environments, including vacuum.

Recent advances in high-frequency QCMs allow measuring the mass change in analytes adsorbed on modified QCM surfaces around pg/cm2 sensitivities. Among many other analytical techniques, QCM provides one of the most promising sensor technologies based on its low cost, rapid response, portability, nonhazardous label-free real-time procedure, and high sensitivity, which is ideal for the sensitive detection of analytes for next-generation sensors such as chemical sensing, including electronic nose, electronic tongue, microfluidic devices, lab-on-a-chip, single molecule sensing, nanosensors, medical analyzers, enzyme sensors, drugs, and medicodiagnostic testing.

This Special Issue of Chemosensors is dedicated to the discussion of the state of the art in QCM sensors with challenging material-coating techniques not only for gas/liquid phase and biosensing but also for primary industries such as agriculture and aquatic products in industry.

Prof. Dr. Salih Okur
Guest Editor

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Keywords

  • QCM-based gas sensors
  • Electrochemical quartz crystal microbalance (EQCM)
  • QCM-based sensors with biofunctional materials and food inspection
  • Application of QCM for medical diagnosis
  • Protein immobilization, cell attachment, cell adhesion
  • Drug discovery and complex biopolymeric/biomolecular systems
  • QCM-based biosensors modified with molecular imprinted polymers
  • Quartz crystal microbalance with dissipation monitoring analysis using QCM/QCM-D
  • Chiral recognition, odor classification, and composition analysis
  • Multichannel QCM array systems, QCM-based electronic nose, and electronic tongues

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Published Papers (8 papers)

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Research

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13 pages, 2720 KiB  
Article
A Study on Regenerative Quartz Crystal Microbalance
by Ioan Burda
Chemosensors 2022, 10(7), 262; https://doi.org/10.3390/chemosensors10070262 - 5 Jul 2022
Cited by 4 | Viewed by 1656
Abstract
The quartz crystal microbalance with dissipation (QCM-D) represented a substantial breakthrough in the use of the QCM sensor in diverse applications ranging from environmental monitoring to biomedical diagnostics. To obtain the required selectivity and sensitivity of a volatile organic compounds (VOC) sensor, it [...] Read more.
The quartz crystal microbalance with dissipation (QCM-D) represented a substantial breakthrough in the use of the QCM sensor in diverse applications ranging from environmental monitoring to biomedical diagnostics. To obtain the required selectivity and sensitivity of a volatile organic compounds (VOC) sensor, it is necessary to coat the QCM sensor with a sensing film. As the QCM sensor is coated with the sensing film, an increase in the dissipation factor occurs, resulting in a shorter and shorter ring-down time. This decrease in ring-down time makes it difficult to implement the QCM-D method in an economical and portable configuration from the perspective of large-scale applications. To compensate for this effect, a regenerative method is proposed by which the damping effect produced by the sensing film is eliminated. In this sense, a regenerative circuit as an extension to a virtual instrument is proposed to validate the experimental method. The simulation of the ring-down time for the QCM sensor in the air considering the effect of the added sensing film, followed by the basic theoretical concepts of the regenerative method and the experimental results obtained, are analyzed in detail in this paper. Full article
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12 pages, 2649 KiB  
Article
QCM-Based HCl Gas Detection on Dimethylamine-Functionalized Crosslinked Copolymer Films
by Jinchul Yang and Jinyoung Park
Chemosensors 2022, 10(2), 70; https://doi.org/10.3390/chemosensors10020070 - 10 Feb 2022
Viewed by 2182
Abstract
In this work, sensing behaviors and mechanisms of two crosslinked copolymers with dimethylamine and dimethylamide functional groups were compared and investigated for their ability to detect hydrogen chloride (HCl) gas. The crosslinked copolymer films were photopolymerized on quartz crystal electrodes using a micro-contact [...] Read more.
In this work, sensing behaviors and mechanisms of two crosslinked copolymers with dimethylamine and dimethylamide functional groups were compared and investigated for their ability to detect hydrogen chloride (HCl) gas. The crosslinked copolymer films were photopolymerized on quartz crystal electrodes using a micro-contact printing technique. The gas sensing behaviors were analyzed by measuring resonant frequency (Δf) of quartz crystal microbalance (QCM). The HCl binding capacity of photopolymerized films, with a mass between 4.6 and 5.9 μg, was optimized. Under optimized film mass conditions, the poly(2-dimethylaminoethyl methacrylate-co-ethylene glycol dimethacrylate) (DMAEMA-co-EGDMA), poly(DMAEMA-co-EGDMA), film, C2-DMA, showed a 13.9-fold higher binding capacity than the poly(N,N-dimethylacrylamide-co-ethylene glycol dimethacrylate, poly(DMAA-co-EGDMA), film, C0-DMA, during HCl gas adsorption. HCl gas was effectively adsorbed on the C2-DMA film because of the formation of tertiary amine salts through protonation and strong ionic bonding. Furthermore, the C2-DMA film exhibited excellent sensitivity, of 2.51 (ng/μg) (1/ppm), and selectivity coefficient (k* = 12.6 for formaldehyde and 13.5 for hydrogen fluoride) compared to the C0-DMA film. According to the experimental results, and due to its high functionality and stability, the C2-DMA film-coated QC electrode could be used as an HCl gas sensor, with low-cost and simple preparation, in future endeavors. Full article
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16 pages, 4346 KiB  
Article
Sniff Species: SURMOF-Based Sensor Array Discriminates Aromatic Plants beyond the Genus Level
by Salih Okur, Chun Li, Zejun Zhang, Sahi Vaidurya Pratap, Mohammed Sarheed, Adnan Kanbar, Leonard Franke, Felix Geislhöringer, Lars Heinke, Uli Lemmer, Peter Nick and Christof Wöll
Chemosensors 2021, 9(7), 171; https://doi.org/10.3390/chemosensors9070171 - 6 Jul 2021
Cited by 4 | Viewed by 2546
Abstract
Lamiaceae belong to the species-richest family of flowering plants and harbor many species that are used as herbs or in medicinal applications such as basils or mints. The evolution of this group has been driven by chemical speciation, mainly volatile organic compounds (VOCs). [...] Read more.
Lamiaceae belong to the species-richest family of flowering plants and harbor many species that are used as herbs or in medicinal applications such as basils or mints. The evolution of this group has been driven by chemical speciation, mainly volatile organic compounds (VOCs). The commercial use of these plants is characterized by adulteration and surrogation to a large extent. Authenticating and discerning this species is thus relevant for consumer safety but usually requires cumbersome analytics, such as gas chromatography, often coupled with mass spectroscopy. Here, we demonstrate that quartz-crystal microbalance (QCM)-based electronic noses provide a very cost-efficient alternative, allowing for fast, automated discrimination of scents emitted from the leaves of different plants. To explore the range of this strategy, we used leaf material from four genera of Lamiaceae along with lemongrass, which is similarly scented but from an unrelated outgroup. To differentiate the scents from different plants unambiguously, the output of the six different SURMOF/QCM sensors was analyzed using machine learning (ML) methods together with a thorough statistical analysis. The exposure and purging of data sets (four cycles) obtained from a QCM-based, low-cost homemade portable e-Nose were analyzed using a linear discriminant analysis (LDA) classification model. Prediction accuracy with repeated test measurements reached values of up to 0%. We show that it is possible not only to discern and identify plants at the genus level but also to discriminate closely related sister clades within a genus (basil), demonstrating that an e-Nose is a powerful device that can safeguard consumer safety against dangers posed by globalized trade. Full article
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15 pages, 2898 KiB  
Article
Quartz Crystal Microbalance (QCM) Based Biosensor Functionalized by HER2/neu Antibody for Breast Cancer Cell Detection
by Merve Yılmaz, Monireh Bakhshpour, Ilgım Göktürk, Ayşe Kevser Pişkin and Adil Denizli
Chemosensors 2021, 9(4), 80; https://doi.org/10.3390/chemosensors9040080 - 14 Apr 2021
Cited by 17 | Viewed by 3706
Abstract
The heterogeneity and metastatic features of cancer cells lead to a great number of casualties in the world. Additionally, its diagnosis as well as its treatment is highly expensive. Therefore, development of simple but effective diagnostic systems which detect the molecular markers of [...] Read more.
The heterogeneity and metastatic features of cancer cells lead to a great number of casualties in the world. Additionally, its diagnosis as well as its treatment is highly expensive. Therefore, development of simple but effective diagnostic systems which detect the molecular markers of cancer is of great importance. The molecular changes on cancer cell membranes serve as targets, such as HER2/neu receptor which is detected on the surface of highly metastatic breast cancer cells. We have aimed to develop a specific and simple quartz crystal microbalance (QCM)-based system to identify HER2/neu expressing breast cancer cells via a receptor-specific monoclonal antibody. First, the QCM chip was coated with polymeric nanoparticles composed of hydroxyethylmethacrylate (HEMA) and ethylene glycol dimethacrylate (EDMA). The nanoparticle coated QCM chip was then functionalized by binding of HER2/neu antibody. The breast cancer cells with/without HER2/neu receptor expression, namely, SKBR3, MDA-MB 231 and also mouse fibroblasts were passed over the chip at a rate of 10–500 cells/mL and the mass changes (Δm) on cell/cm2 unit surface of sensor were detected in real-time. The detection limit of the system was 10 cells/mL. Thus, this QCM-based HER2/neu receptor antibody functionalized system might be used effectively in the detection of HER2/neu expressing SKBR3 breast cancer cells. Full article
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10 pages, 2425 KiB  
Article
Improving Surface Imprinting Effect by Reducing Nonspecific Adsorption on Non-Imprinted Polymer Films for 2,4-D Herbicide Sensors
by Jin Chul Yang, Suck Won Hong and Jinyoung Park
Chemosensors 2021, 9(3), 43; https://doi.org/10.3390/chemosensors9030043 - 26 Feb 2021
Cited by 5 | Viewed by 2033
Abstract
Surface imprinting used for template recognition in nanocavities can be controlled and improved by surface morphological changes. Generally, the lithographic technique is used for surface patterning concerning sensing signal amplification in molecularly imprinted polymer (MIP) thin films. In this paper, we describe the [...] Read more.
Surface imprinting used for template recognition in nanocavities can be controlled and improved by surface morphological changes. Generally, the lithographic technique is used for surface patterning concerning sensing signal amplification in molecularly imprinted polymer (MIP) thin films. In this paper, we describe the effects of silanized silica molds on sensing the properties of MIP films. Porous imprinted poly(MAA–co–EGDMA) films were lithographically fabricated using silanized or non-treated normal silica replica molds to detect 2,4-dichlorophenoxyacetic acid (2,4-D) herbicide as the standard template. The silanized mold MIP film (st-MIP) (Δf = −1021 Hz) exhibited a better sensing response than the non-treated normal MIP (n-MIP) (Δf = −978 Hz) because the imprinting effects, which occurred via functional groups on the silica surface, could be reduced through silane modification. Particularly, two non-imprinted (NIP) films (st-NIP and n-NIP) exhibited significantly different sensing responses. The st-NIP (Δfst-NIP = −332 Hz) films exhibited lower Δf values than the n-NIP film (Δfn-NIP = −610 Hz) owing to the remarkably reduced functionality against nonspecific adsorption. This phenomenon led to different imprinting factor (IF) values for the two MIP films (IFst-MIP = 3.38 and IFn-MIP = 1.86), which was calculated from the adsorbed 2,4-D mass per poly(MAA–co–EGDMA) unit weight (i.e., QMIP/QNIP). Moreover, it was found that the st-MIP film had better selectivity than the n-MIP film based on the sensing response of analogous herbicide solutions. As a result, it was revealed that the patterned molds’ chemical surface modification, which controls the surface functionality of imprinted films during photopolymerization, plays a role in fabricating enhanced sensing properties in patterned MIP films. Full article
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Review

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21 pages, 4382 KiB  
Review
Recent Advances in Quartz Crystal Microbalance Biosensors Based on the Molecular Imprinting Technique for Disease-Related Biomarkers
by Semra Akgönüllü, Erdoğan Özgür and Adil Denizli
Chemosensors 2022, 10(3), 106; https://doi.org/10.3390/chemosensors10030106 - 10 Mar 2022
Cited by 17 | Viewed by 4617
Abstract
The molecular imprinting technique is a quickly developing field of interest regarding the synthesis of artificial recognition elements that enable the specific determination of target molecule/analyte from a matrix. Recently, these smart materials can be successfully applied to biomolecule detection in biomimetic biosensors. [...] Read more.
The molecular imprinting technique is a quickly developing field of interest regarding the synthesis of artificial recognition elements that enable the specific determination of target molecule/analyte from a matrix. Recently, these smart materials can be successfully applied to biomolecule detection in biomimetic biosensors. These biosensors contain a biorecognition element (a bioreceptor) and a transducer, like their biosensor analogs. Here, the basic difference is that molecular imprinting-based biosensors use a synthetic recognition element. Molecular imprinting polymers used as the artificial recognition elements in biosensor platforms are complementary in shape, size, specific binding sites, and functionality to their template analytes. Recent progress in biomolecular recognition has supplied extra diagnostic and treatment methods for various diseases. Cost-effective, more robust, and high-throughput assays are needed for monitoring biomarkers in clinical settings. Quartz crystal microbalance (QCM) biosensors are promising tools for the real-time and quick detection of biomolecules in the past two decades A quick, simple-to-use, and cheap biomarkers detection technology based on biosensors has been developed. This critical review presents current applications in molecular imprinting-based quartz crystal microbalance biosensors for the quantification of biomarkers for disease monitoring and diagnostic results. Full article
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20 pages, 3316 KiB  
Review
Ionic Liquid-Based Quartz Crystal Microbalance Sensors for Organic Vapors: A Tutorial Review
by Bishnu P. Regmi, Puspa L. Adhikari and Beni B. Dangi
Chemosensors 2021, 9(8), 194; https://doi.org/10.3390/chemosensors9080194 - 27 Jul 2021
Cited by 6 | Viewed by 5614
Abstract
Organic vapor sensors are used in diverse applications ranging from environmental monitoring to biomedical diagnostics. Among a number of these sensors, quartz crystal microbalance (QCM) sensors prepared by coating ionic liquids (ILs) or their composites are promising devices for the analysis of volatile [...] Read more.
Organic vapor sensors are used in diverse applications ranging from environmental monitoring to biomedical diagnostics. Among a number of these sensors, quartz crystal microbalance (QCM) sensors prepared by coating ionic liquids (ILs) or their composites are promising devices for the analysis of volatile organic compounds (VOCs) in complex chemical mixtures. Ionic liquids are remarkable materials, which exhibit tunable physico-chemical properties, chemical and thermal stability, multiple interactions with diverse group of molecules, and enormous structural variability. Moreover, ILs exhibit viscoelastic properties, and hence these materials are ideal for creation of QCM virtual sensor arrays. While the scientific literature on IL-coated QCM sensors is rapidly growing, there is still much to learn. This manuscript provides a comprehensive review on the development of IL-coated QCM sensors and multi-sensor arrays as well as their applications for the analysis of VOCs in complex mixtures. Furthermore, IL-coated QCM virtual sensor arrays and their applications are presented. A short overview of some of the QCM designs, future research areas, and recommendations are also discussed. This short review is a necessary first step towards standardization and further development of QCM for the analysis of VOCs. Full article
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24 pages, 2748 KiB  
Review
Coating-Based Quartz Crystal Microbalance Detection Methods of Environmentally Relevant Volatile Organic Compounds
by Rocío L. Pérez, Caitlan E. Ayala, Jong-Yoon Park, Jin-Woo Choi and Isiah M. Warner
Chemosensors 2021, 9(7), 153; https://doi.org/10.3390/chemosensors9070153 - 24 Jun 2021
Cited by 14 | Viewed by 4012
Abstract
Volatile organic compounds (VOCs) that evaporate under standard atmospheric conditions are of growing concern. This is because it is well established that VOCs represent major contamination risks since release of these compounds into the atmosphere can contribute to global warming, and thus, can [...] Read more.
Volatile organic compounds (VOCs) that evaporate under standard atmospheric conditions are of growing concern. This is because it is well established that VOCs represent major contamination risks since release of these compounds into the atmosphere can contribute to global warming, and thus, can also be detrimental to the overall health of worldwide populations including plants, animals, and humans. Consequently, the detection, discrimination, and quantification of VOCs have become highly relevant areas of research over the past few decades. One method that has been and continues to be creatively developed for analyses of VOCs is the Quartz Crystal Microbalance (QCM). In this review, we summarize and analyze applications of QCM devices for the development of sensor arrays aimed at the detection of environmentally relevant VOCs. Herein, we also summarize applications of a variety of coatings, e.g., polymers, macrocycles, and ionic liquids that have been used and reported in the literature for surface modification in order to enhance sensing and selective detection of VOCs using quartz crystal resonators (QCRs) and thus QCM. In this review, we also summarize novel electronic systems that have been developed for improved QCM measurements. Full article
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