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The key social issues of health, medicine, the environment, food and safety cannot be addressed without the support of chemical sensors and biosensors, whose performance is constantly improving in terms of reliability and cost, particularly in the production of autonomous devices connected to the Internet.
Obtaining high-intensity transduction signals arising from the interaction of an analyte and a sensor, enabling the identification and dosage of a given compound, requires the selection of suitable physical measurement methods and the creation of structures that react specifically to different types of analyte.
Nanotechnologies and Nanomaterials Applied to Chemical Sensors and Biosensors details recent advances in the field of sensor design using carbon-based nanomaterials (graphene, carbon nanotubes, carbon quantum dots, etc.) and inorganic nanomaterials (metallic nanoparticles, nanocrystals, transition metal dichalcogenides, etc.), as well as a variety of physical sensing methods (electrochemical, piezoelectric, electromagnetic, optic, optoelectronic, etc.).
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Cover
Table of Contents
Title Page
Copyright Page
Introduction
This book at a glance
Part 1: nanomaterials, separation, amplification, recognition and transduction
Part 2: environmental and biological sensors
PART 1: Nanomaterials, Amplification, Separation, Recognition and Transduction
1 Nanomaterials
1.1. Carbon nanomaterials
1.2. Inorganic nanomaterials
1.3. Conclusions
2 Separation and Amplification Techniques
2.1. Principle of the PCR technique applied to the concentration amplification of DNA traces
2.2. Sequencing techniques
2.3. Separation techniques for product mixtures
2.4. Conclusions
3 Recognition Principles
3.1. The different molecular or chemical identification techniques
3.2. Sensor networks and artificial intelligence
3.3. Conclusions
4 Physico-chemical Transduction Techniques
4.1. Electrochemical methods
4.2. Piezoelectricity for gravimetric analysis
4.3. Field effect transistors
4.4. Optical and optoelectrochemical detection methods
4.5. Conclusions
PART 2: Environmental and Biological Sensors
5 Ion and Gas Sensors
5.1. Membrane electrodes for potentiometric pH measurement
5.2. Ion selective electrodes (ISE)
5.3. Gas sensors
5.4. Conclusions
6 Biosensors for Health
6.1. Blood sugar, uremia and cholesterol
6.2. Biomarkers
6.3. Pathogens
6.4. Conclusions
Conclusion
References
Index
Other titles from iSTE in Nanoscience and Nanotechnology
End User License Agreement
Chapter 6
Table 6.1. Different cancer and cardiac biomarkers (excluding nucleic acids), ...
Introduction
Figure I.1. Working principle of a chemical sensor or biosensor Adapted from C...
Chapter 1
Figure 1.1. (a) Image of fullerene C60. Adapted from Balch et al. (1998). (b) ...
Figure 1.2. Structure of the two stereoisomeric carboxyfullerenes C3-C60 and D...
Figure 1.3. Fluorescence of ND nanocrystals with NV defects. (a) Structure of ...
Figure 1.4. Structure of carbon quantum dots (CQDs) showing the association be...
Figure 1.5. Luminescence of an aqueous solution of CQDs produced by laser abla...
Figure 1.6. Simplified schematic of the CVD device used to produce CNTs. Adapt...
Figure 1.7. Formation of an SWCNT defined by the rolling up of a graphene frag...
Figure 1.8. Examples of CNTs with different configurations. (a) Examples of tw...
Figure 1.9. Resistivity variations of graphene and 2D materials as a function ...
Figure 1.10. Graphene deposits on Ni and Cu and transferred onto a Si/SiO2 supp...
Figure 1.11. Different stages of the catalytic process of forming a graphene m...
Figure 1.12. Graphene paper (rGO) obtained after reducing graphene oxide (GO) ...
Figure 1.13. SEM images of graphene fibers. (a) Knot formation; (b) two-strand...
Figure 1.14. Implications of graphene derivatives in different fields.
Figure 1.15. Obtaining N-GQDs by pyrolysis of TATB. The TATB precursor is made...
Figure 1.16. Photoluminescence (PL) intensity curves of GQDs as a function of ...
Figure 1.17. Interpretation of the photoluminescence of GQDs according to thei...
Figure 1.18. Cumulative progression of the number of articles published on the...
Figure 1.19. Transmission electron microscopy (TEM) images of gold NPs of diff...
Figure 1.20. SEM images of NRs obtained from decahedral seeds. (a) Schematic d...
Figure 1.21. Comparative luminescence of gold NCs chelated by simple Au(I)-Thi...
Figure 1.22. Photoluminescence of some QDs showing that their color emission d...
Figure 1.23. Representation of the crystal structures of TMDs (MX2 structure)....
Figure 1.24. Principle of the method of obtaining Ti3C2OH sheets from Ti3AlC2....
Figure 1.25. Structural and energetic characteristics of phosphorene. (a) Pers...
Figure 1.26. Structure and topology of MOF-5. (a) Representation of the unit c...
Figure 1.27. Principle of synthesis by isoreticulation. The use of fumarate th...
Chapter 2
Figure 2.1. Structure of a DNA sequence, containing two strands linked togethe...
Figure 2.2. Representation of single-strand RNA and double-strand DNA helices....
Figure 2.3. The three steps of the first PCR cycle leading to the doubling of ...
Figure 2.4. Structures of nucleotides dNTP and ddNTP.
Figure 2.5. Diagram of the sequencing of a DNA strand using the Sanger method....
Figure 2.6. IonTorrent sequencer and chip. (a) IonTorrent sequencer HID Ion Ge...
Figure 2.7. Principle of nanopore sequencing. (a) Diagram of the device compri...
Figure 2.8. Basic principle of liquid chromatographic separation. Drawing adap...
Figure 2.9. Peptide mass fingerprint (PMF) identification principle of the mic...
Figure 2.10. Schematic representation of the immobilization mechanism of an am...
Figure 2.11. Principle of 2D electrophoresis. Adapted from a diagram Wikipedia...
Figure 2.12. Basic setup of a capillary electrophoresis device.
Figure 2.13. Schematic representation of the mobilities of neutral (0), cation...
Figure 2.14. Stacking mechanism of an anionic analyte at the BGE/analyte inter...
Figure 2.15. Principle of isotachophoretic analyte concentration. (a) Variatio...
Figure 2.16. Principle of analyte pre-concentration by dynamic pH junction. (a...
Figure 2.17. Electropherogram of a neutral analyte in a micellar medium. (a) S...
Figure 2.18. Comparative separation of a mixture of amino acids by CEC accordi...
Figure 2.19. CEC separation of enantiomer pairs with a monolithic stationary p...
Chapter 3
Figure 3.1. Examples of cation-specific ionophores. (a) Simple cations such as...
Figure 3.2. Examples of ionophores corresponding to cobalt complexes, specific...
Figure 3.3. The structure of an IgG antibody, with “heavy” and “light” chains,...
Figure 3.4. Structure of a camelid hcIgG antibody (heavy chain IgG, symmetrica...
Figure 3.5. Schematic representation of nanobodies (VHH, or single-domain anti...
Figure 3.6. General diagram of the aptamer-target association, according to a ...
Figure 3.7. General recognition process of molecularly imprinted polymers.
Figure 3.8. Illustration of a stamping method for printing macromolecular targ...
Figure 3.9. Enzymatic recognition of a target (S) and its chemical transformat...
Figure 3.10. MIPs functionalized by mimicking-peroxidase catalytic nanoparticl...
Figure 3.11. Mechanisms of oxygen interaction on n-type semiconductor NPs. (a)...
Figure 3.12. Role of the distribution of NP catalysts at grain boundaries. Rep...
Figure 3.13. Comparative designs of traditional and intelligent sensors. (a) T...
Figure 3.14. Machine learning detection and gas mixture analysis using a singl...
Chapter 4
Figure 4.1. Typical diagram of an electrochemical cell and a potentiometric an...
Figure 4.2. Cyclic voltammogram model of an Ox species in solution.
Figure 4.3. Differential pulse voltammetry (SWV). (a) Potential variation curv...
Figure 4.4. Nyquist diagram corresponding to an electrode reaction controlled ...
Figure 4.5. Diagram of a sensor with interdigitated electrodes. (a) Example of...
Figure 4.6. Principle of selective detection of an analyte by the quartz cryst...
Figure 4.7. Determination of air moisture levels using various functionalized ...
Figure 4.8. Representative diagram of a two-port SAW sensor. Adapted from Muja...
Figure 4.9. Field effect transistors. (a) Configuration of a field effect tran...
Figure 4.10. Schematic diagram of an n-type channel BioFET biosensor. We note ...
Figure 4.11. Variation in source-drain current IDS of an FET attenuated by the...
Figure 4.12. Attenuation by PEG of the electrostatic screen effect experienced...
Figure 4.13. Typical diagram of an OECT operating with a conductive polymer as...
Figure 4.14. Representative diagram of an EGOFET in the “Top-Gate” configurati...
Figure 4.15. Jablonski diagram indicating the energetic origin of fluorescence...
Figure 4.16. Detection of a nucleic acid (DNA) by OFF-ON fluorescence. Adapted...
Figure 4.17. Principle of the ECL produced by a QD and a co-reagent (C) in con...
Figure 4.18. Different development stages of the immunobiosensor ECL g-C3N4-Au...
Figure 4.19. ECL characteristics of the biosensor [AuNPs/g-C3N4/GCE] for detec...
Figure 4.20. Schematic of the dual emission ECL Immunosensor. (a) Representati...
Figure 4.21. Operating principle of the ratiometric immunosensor with two exci...
Figure 4.22. ECL characteristics of the ratiometric device (mp53-PtNP/Lu/CdS/G...
Figure 4.23. Schematic representation of the ratiometric electrochemiluminesce...
Figure 4.24. Schematic representation of the different stages of grafting on I...
Figure 4.25. Principle of a ratiometric ECL assay of PSA on BPE. (a) The catho...
Figure 4.26. Evolution of ECL emissions on the cathode (ECLcat) and anode (ECL...
Figure 4.27. Comparison of structures of EIS, ISFET and LAPS sensors. (a) EIS ...
Figure 4.28. Operating principle of a photoelectrochemical sensor to H+ ions. ...
Figure 4.29. Operating principle of a LAPS comprising a light source of consta...
Figure 4.30. Photocurrent imaging of a LAPS divided into four sectors (chamber...
Figure 4.31. Operating principle of a LAPS frequency up-conversion. (a) Energy...
Figure 4.32. Photoelectrochemical ratiometric sensor comprising a pair of phot...
Figure 4.33. Representative energy diagram of Raman scattering. (a) Origin of ...
Figure 4.34. Kretschmann SPR device for immunoassays. (a) The base of the pris...
Figure 4.35. Plasmon resonance of metal NPs. (a) Diagram of the resonance mech...
Figure 4.36. Plasmon resonance “hot spot” between two spherical metal NPs. (a)...
Figure 4.37. Micro-spectrophotometric device with dark field condenser for mea...
Figure 4.38. Change in color of a set of gold NPs due to physical stress or ch...
Figure 4.39. Principle of nanosphere lithography (NSL). (a) Production of a ma...
Figure 4.40. SERS spectrum of rhodamine 6-G (R6G) obtained on a microporous Zn...
Chapter 5
Figure 5.1. Structural diagram of a glass electrode (GE). (a) Structure of a g...
Figure 5.2. Representation of the ionic equilibria between a membrane selectiv...
Figure 5.3. Potentiometric curves of an ion IzI in the presence of an interfer...
Figure 5.4. Schematic representation of an electrochemical cell for potentiome...
Figure 5.5. Schematic representation of an EPAD with an ion-selective membrane...
Figure 5.6. Manufacturing diagram of an ISE type potentiometric paper sensor f...
Figure 5.7. Principle of an immunopotentiometric assay. (a) Addition of the an...
Figure 5.8. The use of aptamers for the potentiometric assay of thrombin. (a) ...
Figure 5.9. ZnO nanowire networks used for the conductometric determination of...
Figure 5.10. Operating principle of TiO2/PANI for NH3 sensors. (a) SEM (scanni...
Figure 5.11. NH3 titration curves with the TiO2/PANI sensor. (a) Current inten...
Figure 5.12. Resistive sensor based on the composite rGO/Co3O4 for detecting N...
Figure 5.13. Resistive rGO/Co3O4 sensor for detecting NO2. (a) FESEM (field em...
Figure 5.14. Time–sensitivity curves of an MoS2 (2L)-based FET-type sensor sub...
Figure 5.15. Working principle and response curve of a resistive sensor to NO2...
Figure 5.16. Comparison of response curves for NO2 with resistive sensors base...
Figure 5.17. Resistance variation of BP, Au/BP and Pt/BP sensors after injecti...
Figure 5.18. Operating principle of the Co3O4@PEI/Ti3C2Tx sensor. (a) Schemati...
Figure 5.19. Heat map of the 59 main characteristics (SF1 to SF59) recorded fo...
Figure 5.20. Spectrum of relative resistance variations (∆R/R0) between air an...
Figure 5.21. Variations ∆f of resonance frequencies obtained on SAW sensors co...
Figure 5.22. PCA diagrams for mixtures of combat gas “simulants” and interfere...
Figure 5.23. Operating principle of a network of colorimetric sensors interact...
Figure 5.24. Examples of chromogenic molecules belonging to different families...
Figure 5.25. Characteristic images of different volatile compounds interacting...
Figure 5.26. Colorimetric detection of TATP vapors for concentrations between ...
Chapter 6
Figure 6.1. Enzymatic electrochemical determination of glucose. Diagram illust...
Figure 6.2. Examples of marketed self-monitoring blood glucose devices. In all...
Figure 6.3. Examples of “electrochemical” strips used in Accu-Chek devices: (a...
Figure 6.4. Some continuous glucose measuring devices currently on the French ...
Figure 6.5. The Clarke error grid compares the blood glucose values given by a...
Figure 6.6. The GlucoWatch blood glucose monitor. (a) Principle of inverse ion...
Figure 6.7. Inverse opal surface colorings. (a) Photograph of thin-film alumin...
Figure 6.8. Application of an inverse opal to the colorimetric detection of ur...
Figure 6.9. OECT biosensor for urea measurement. (a) Photograph of a printed O...
Figure 6.10. Example of portable blood cholesterol testing devices.
Figure 6.11. Fluorescence quenching due to hybridization of a miRNA target. Tw...
Figure 6.12. Diagram of an ECL biosensor used to determine PSA. In its initial...
Figure 6.13. Schematic diagrams of an EGFET-type sensor used to detect the BRC...
Figure 6.14. Schematic diagram of the FONLISA (fiber optic nanogold-linked imm...
Figure 6.15. Test strip reading device. On the left is the optical strip reade...
Figure 6.16. i-STAT system developed by Abbott. (a) iSTAT cassette for cTnI pr...
Figure 6.17. Electrochemical detection of the NT-proBNP protein by sandwich as...
Figure 6.18. The expected concentration ranges of stress biomarkers and the bi...
Figure 6.19. Illustration of cortisol detection by competitive ELISA. Diagram ...
Figure 6.20. Illustration of the competitive cortisol assay process by ELISA o...
Figure 6.21. Diagram of a lateral flow detection device for cortisol (F) using...
Figure 6.22. Electrochemical device for detecting cortisol using molecular rec...
Figure 6.23. Recognition of cortisol in sweat by an aptamer and transduction v...
Figure 6.24. Cortisol response of electrolyte-gated and aptamer-functionalized...
Figure 6.25. Analytical results obtained on sRNA (COVID-19) from patient swabs...
Figure 6.26. Schematic representation of SARS-CoV-2 and the appearance of the ...
Figure 6.27. Graphene FET used for SARS-CoV-2 assay. Adapted from Seo et al. (...
Figure 6.28. FET-G-SAb response to COVID-19. (a) Relative variations in IDS cu...
Figure 6.29. FET-SWCNT for the SARS-CoV-2 assay. (a) Schematic of the device s...
Figure 6.30. Schematic of a silicon nanowire FET transistor for Dengue virus d...
Figure 6.31. Floating gate electrolyte-gated transistor developed for ricin de...
Figure 6.32. Results obtained for the detection of ricin on the floating gate ...
Cover Page
Table of Contents
Title Page
Copyright Page
Introduction
Begin Reading
Conclusion
References
Index
Other titles from iSTE in Nanoscience and Nanotechnology
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Series EditorJean-Charles Pomerol
Pierre Camille Lacaze
Benoît Piro
Jean-Christophe Lacroix
First published 2024 in Great Britain and the United States by ISTE Ltd and John Wiley & Sons, Inc.
Apart from any fair dealing for the purposes of research or private study, or criticism or review, as permitted under the Copyright, Designs and Patents Act 1988, this publication may only be reproduced, stored or transmitted, in any form or by any means, with the prior permission in writing of the publishers, or in the case of reprographic reproduction in accordance with the terms and licenses issued by the CLA. Enquiries concerning reproduction outside these terms should be sent to the publishers at the undermentioned address:
ISTE Ltd27-37 St George’s RoadLondon SW19 4EUUK
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John Wiley & Sons, Inc.111 River StreetHoboken, NJ 07030USA
www.wiley.com
© ISTE Ltd 2024The rights of Pierre Camille Lacaze, Benoît Piro and Jean-Christophe Lacroix to be identified as the authors of this work have been asserted by them in accordance with the Copyright, Designs and Patents Act 1988.
Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s), contributor(s) or editor(s) and do not necessarily reflect the views of ISTE Group.
Library of Congress Control Number: 2024941764
British Library Cataloguing-in-Publication DataA CIP record for this book is available from the British LibraryISBN 978-1-78630-660-9
The environment, health and the agri-food sector are areas that are subject to very strict regulatory standards with an increasing use of detection and analysis systems (sensors) to carry out the numerous controls and verifications. A sensor is thus a device that measures, continuously where possible, either a physical quantity (temperature, pressure, light intensity, object position, acceleration, etc.) or detects and accurately measures the concentration of a chemical or biological compound present in the surrounding environment.
Long before nanotechnologies emerged, the design of all kinds of chemical sensors was a hot topic in analytical chemistry. The operation of a chemical or biochemical sensor involves a cause and effect relationship between three entities: the compound to be analyzed (analyte)1, the receptor and a transduction device that transforms the interaction between the analyte and the receptor into a measurable signal, which, depending on the case, can be electrical, electrochemical, optical, thermal or gravimetric (Figure I.1).
One of the oldest commercialized systems is probably the electrochemical detection of glucose in the blood of the human body, initially proposed by Clark and Lyons in 1962 (Clark and Lyons 1962), which carries the greatest number of associated research studies and has seen the greatest technological evolution. This is how various enzymatic or non-enzymatic detection systems subsequently emerged, based on nanomaterials, and were miniaturized and designed as portable systems, making it possible to carry out precise continuous measurements of glucose in the blood (Wang 2008), with a semi-invasive approach (e.g. by insertion of a transcutaneous needle) or by new methods aiming toward non-invasive systems (Chen et al. 2017).
Figure I.1.Working principle of a chemical sensor or biosensor Adapted from Chambers et al. (2008).
Over the last few decades, numerous increasingly efficient chemical and biological sensors have been manufactured, including receptors made of carbon nanomaterials (carbon nanotubes [CNTs], graphene and carbon nanodots) as well as inorganic nanomaterials (various shaped metal nanoparticles, nanocrystals, nanowires, semiconductor quantum dots [QDs]). The advantages provided by these nanomaterials are significant, particularly when they are involved in the design of systems involving electrical or optical transduction. In the case of graphene and CNTs, their very high conductivity as well as their very high charge mobilities, which are susceptible to significant variations as soon as slight surface modifications occur, make them extremely sensitive receptors. Furthermore, the very high specific surface areas of these materials (~2,600 m2/g for graphene) mean that, in the form of an atomic monolayer, they are capable of adsorbing significant quantities of the compound to be measured and, therefore, of producing a high intensity transduction signal, much better than that obtained with other micron-sized carbonaceous materials.
In parallel with this research, significant efforts have been devoted to the “portability” of very high sensitivity sensors equipped with various transduction systems, with a signal amplification effect based on the development of the sensor in the form of a field-effect transistor (FET). The ultimate design objective is that these sensors have total autonomy in terms of operation based on the capture and transformation of surrounding energy into electrical energy (e.g. self-charging power systems) (Kausar et al. 2014; Pu et al. 2018a).
Our objective is to analyze the different challenges faced in the design of a sensor and to show what methods are used to, on the one hand, separate the analytes from a mixture and, on the other hand, choose a physical method that gives an intense transduction signal leading to selective detection. This book therefore has two parts: the first is a description of the most common nanomaterials used in the making of sensors and the physical methods to identify and separate these nanomaterials; the second is more applied and describes the different sensors used in the environmental and biomedical fields.
Chapter 1 describes the properties of some of the most important organic and inorganic nanomaterials. We highlight the main contribution of new carbon nanomaterials such as CNTs, graphene, carbon nanodots, conductive polymers in thin layers, but also various forms of inorganic nanomaterials (nanowires, nanotubes and nanosheets), which have allowed enormous progress in the design of portable detection and analysis systems (Kim et al. 2019).
Chapter 2 is devoted to separation methods of compound mixtures and concerns the different chromatography and electrophoresis techniques. Furthermore, DNA amplification techniques necessary for element identification and sequencing, often present only in trace amounts, are also briefly described.
Chapter 3 develops the main analyte–receptor recognition systems, which generally involve pairs of self-assembling molecules, with very high affinities for each other, as observed with the protein pairs avidin–biotin, antibody–antigen, as well as associations between complementary DNA strands.
Chapter 4 describes the characteristics of the main physical methods used to produce a transduction signal, based essentially on the use of electronic, electrochemical, piezoelectric or optoelectronic devices, illustrated using some examples.
Chapter 5 is devoted to chemical sensors specific for environmental issues. It mainly concerns the analysis of mineral salts and gases in terms of toxicology. This is a field that has seen significant developments in ion-selective (membrane and ionophore) electrodes (ISE), subsequently adapted to the production of all-solid portable devices with, in the latter case, a strong involvement of nanomaterials. The same evolution occurred for the analysis of gases, applied mainly to a few toxic gases.
Chapter 6 focuses primarily on biomedical analysis problems. Innovative solutions are proposed with the contribution of nanomaterials (Lin et al. 2018) being decisive. The real-time control of the primary molecules secreted by the body is a main focal point that we describe in the case of glucose, urea and cholesterol, three key chronic disease-causing molecules. Biomarkers of certain diseases (cancers, heart diseases, etc.), food pathogens, as well as viruses and bacteria are also areas covered, for which portable analysis devices are proving decisive for their effective prevention.
1
Analyte refers to the chemical entity that we wish to identify and/or quantify.