Developing efficient sensor materials with superior performance for selective, fast and sensitive detection of gases and volatile organic compounds (VOCs) is essential for human health and environmental protection, through monitoring indoor and outdoor air pollutions, managing industrial processes, controlling food quality and assisting early diagnosis of diseases. Metal–organic frameworks (MOFs) are a unique type of crystalline and porous solid material constructed from metal nodes (metal ions or clusters) and functional organic ligands. They have been investigated extensively for possible use as high performance sensors for the detection of many different gases and VOCs in recent years, due to their large surface area, tunable pore size, functionalizable sites and intriguing properties, such as electrical conductivity, magnetism, ferroelectricity, luminescence and chromism. The high porosity of MOFs allows them to interact strongly with various analytes, including gases and VOCs, thus resulting in easily measurable responses to different physicochemical parameters. Although much of the recent work on MOF-based luminescent sensors have been summarized in several excellent reviews (up to 2018), a comprehensive overview of these materials for sensing gases and VOCs based on chemiresistive, magnetic, ferroelectric, and colorimertic mechanisms is missing. In this review, we highlight the most recent progress in developing MOF sensing and switching materials with an emphasis on sensing mechanisms based on electricity, magnetism, ferroelectricity and chromism. We provide a comprehensive analysis on the MOF–analyte interactions in these processes, which play a key role in the sensing performance of the MOF-based sensors and switches. We discuss in detail possible applications of MOF-based sensing and switching materials in detecting oxygen, water vapor, toxic industrial gases (such as hydrogen sulfide, ammonia, sulfur dioxide, nitrous oxide, carbon oxides and carbon disulfide) and VOCs (such as aromatic and aliphatic hydrocarbons, ketones, alcohols, aldehydes, chlorinated hydrocarbons and N,N′-dimethylformamide). Overall, this review serves as a timely source of information and provides insight for the future development of advanced MOF materials as next-generation gas and VOC sensors.

Functional metal–organic frameworks as effective sensors of gases and volatile compounds

Xu-dong Wang*,† and Otto S. Wolfbeis*,‡ †Department of Chemistry, Fudan University, 200433 Shanghai, P. R. China ‡Institute of Analytical Chemistry, Chemoand Biosensors, University of Regensburg, D-93040 Regensburg, Germany ■ CONTENTS Books, Reviews, and Articles of General Interest 204 Sensors for (Dissolved) Gases and Vapors 204 Hydrogen 204 Hydrocarbons 206 Oxygen 206 Carbon Dioxide 208 Nitrogen Oxides 208 Other Gases 208 Ammonia 209 Ethanol 209 Other Volatile Organic Compounds (VOC)s 210 Sensors for Humidity, Water Fractions, Hydrogen Peroxide, and Hydrazine 211 Humidity 211 Water Fractions in Organic Solvents 212 Hydrogen Peroxide 213 Sensors for pH Values, Ions, and Salinity 213 pH Values 213 Ions 214 Salinity and Ionic Strength 215 Sensors for Organic Species 216 Glucose Sensing 216 Sucrose 217 Oils 217 Other Organics 217 Biosensors 218 Nucleic Acid-Based Biosensors (DNAand Aptamer-Based) 218 Immunosensors 218 Enzymatic Biosensors 219 Other Biosensors 220 New Schemes and Materials 220 New Sensing Schemes 220 Molecularly Imprinted Polymer (MIP)-Based Sensors 221 Photonic Crystals 223 Author Information 223 Corresponding Authors 223 Notes 223 Biographies 223 Acknowledgments 223 References 223

Fiber-Optic Chemical Sensors and Biosensors (2013-2015).

Optical biosensors have exhibited worthwhile performance in detecting biological systems and promoting significant advances in clinical diagnostics, drug discovery, food process control, and environmental monitoring. Without complexity in their pretreatment and probable influence on the nature of target molecules, these biosensors have additional advantages such as high sensitivity, robustness, reliability, and potential to be integrated on a single chip. In this review, the state of the art optical biosensor technologies, including those based on surface plasmon resonance (SPR), optical waveguides, optical resonators, photonic crystals, and optical fibers, are presented. The principles for each type of biosensor are concisely introduced and particular emphasis has been placed on recent achievements. The strengths and weaknesses of each type of biosensor have been outlined as well. Concluding remarks regarding the perspectives of future developments are discussed.

Optical biosensors: an exhaustive and comprehensive review.

Food safety is a prevalent concern around the world. As such, detection, removal, and control of risks and hazardous substances present from harvest to consumption will always be necessary. Metal-organic frameworks (MOFs), a class of functional materials, possess unique physical and chemical properties, demonstrating promise in food safety applications. In this review, the synthesis and porosity of MOFs are first introduced by some representative examples that pertain to the field of food safety. Following that, the application of MOFs and MOF-based materials in food safety monitoring, food processing, covering preservation, sanitation, and packaging is overviewed. Future perspectives, as well as potential opportunities and challenges faced by MOFs in this field will also be discussed. This review aims to promote the development and progress of MOF chemistry and application research in the field of food safety, potentially leading to novel solutions.

Metal-Organic Frameworks for Food Safety.

There is an ever-growing demand for measuring respiratory variables during a variety of applications, including monitoring in clinical and occupational settings, and during sporting activities and exercise. Special attention is devoted to the monitoring of respiratory rate because it is a vital sign, which responds to a variety of stressors. There are different methods for measuring respiratory rate, which can be classed as contact-based or contactless. The present paper provides an overview of the currently available contact-based methods for measuring respiratory rate. For these methods, the sensing element (or part of the instrument containing it) is attached to the subject’s body. Methods based upon the recording of respiratory airflow, sounds, air temperature, air humidity, air components, chest wall movements, and modulation of the cardiac activity are presented. Working principles, metrological characteristics, and applications in the respiratory monitoring field are presented to explore potential development and applicability for each method.

Contact-Based Methods for Measuring Respiratory Rate

https://iopscience.iop.org/article/10.1088/2040-8986/aac68d/pdf

Biomedical application of optical fibre sensors

An optical fibre long period grating (LPG) based volatile organic compound (VOC) sensor coated with ZIF-8, a material from the zeolite imidazolate framework (ZIF) family, functional coating is presented. ZIF-8 film was deposited onto the surface of the LPG using an in-situ crystallization technique by mixing freshly prepared 12.5 mM zinc nitrate hexahydrate and 25 mM 2-metyl-imidazole solutions in methanol. A concentration specific response to acetone, ethanol and methanol vapour was obtained over the high concentration range up to tens thousands ppm. The LPG based sensor works at phase-matching turning point (PMTP) and such operates at the highest sensitivity. A novel approach for the data analysis based on the measurement of the bandwidth of the U-shaped attenuation band of the LPG is introduced. The optimized sensor shows a sensitivity of 0.015 ± 0.001 and 0.018 ± 0.0015 nm/ppm and limit of detection (LOD) of 6.67 and 5.56 ppm for acetone and ethanol respectively.

Highly sensitive volatile organic compounds vapour measurements using a long period grating optical fibre sensor coated with metal organic framework ZIF-8

An optical fibre long period grating (LPG) biosensor is appealing in the detection of biomolecules because of the high sensitivity, label-free and real-time measurement. The miniaturized size, ability of remote sensing and immunity to electromagnetic interference of the LPG biosensor provide various possibility of single-point sensing in situations such as point of care diagnostics and in vivo measurement. Two optical fibre LPG based biosensors are reported for detection of streptavidin (SV) and immunoglobulin M (IgM) respectively. The LPG is coated with a film containing three layers of Poly(allylamine hydrochloride)/gold coated silica nanoparticles via the layer-by-layer method. Biotin is covalently bonded to the surface of the gold shell by means of the formation of an amide bonds for detection of streptavidin. The concentration of SV in water for detection varied from 1.25 nM to 2.7 μM. The LPG sensor, operating close to the phase matching condition shows a high sensitivity of 3.88 (ng/mm2)−1 and a detection limit of 0.86 pg/mm2 for the detection of SV. The limit of detection is 22 times lower than previously demonstrated with this type of sensor. The developed IgM sensor has the same configuration of film but has anti-IgM embedded on the LPG instead of biotin, demonstrating versatility of the sensing platform. This was used for the detection of human IgM with concentrations from 15.6 μg/ml to 1 mg/ml. The LPG sensor exhibits a sensitivity of 11 nm (ng/mm2)−1 for the detection of IgM with a detection limit of 15 pg/mm2. The developed highly sensitive IgM sensor shows the potential application of clinical point of care for detection of lower concentration of IgM in vitro. The proposed biosensor exhibits high sensitivity and rapid detection of low concentrations biomolecules from the small size of SV to the large size of IgM.

Highly sensitive label-free antibody detection using a long period fibre grating sensor

An optical fibre long period grating (LPG) based carbon dioxide (CO2) sensor coated with HKUST-1, a material from the metal organic framework family, functional coating is presented. In-situ crystallization and layer by layer (LbL) techniques of HKUST-1 thin film synthesis are compared in terms of the feasibility of the deposition procedure (time and cost efficiency) and the sensitivity of the film to carbon dioxide. The sensing mechanism is based on the measurement of the change of the refractive index (RI) of the coating that is induced by the penetration of CO2 molecules into the HKUST-1 pores. The HKUST-1 film was characterized by scanning electron microscopy (SEM). The thickness and refractive index (RI) of the 10, 20 and 40 layers thick films were determined using ellipsoetry. The crystallinity of the films was examined by X-ray diffraction pattern (XRD). While no response to CO2 was observed for the sensor coated using the in-situ crystallization technique, an LPG modified with 10, 20 and 40 layers of HKUST-1 films using LbL method upon exposure to CO2 in the range of 500 ppm to 40,000 ppm showed good sensitivity. The film containing 40 layers exhibited the highest sensitivity to CO2 with an obtained detection limit of 401 ppm.

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Carbon dioxide measurements using long period grating optical fibre sensor coated with metal organic framework HKUST-1

Fibre optic based sensors are becoming increasingly viable as replacements for traditional flight test sensors. Here we present laboratory, wind tunnel and flight test results of fibre Bragg gratings (FBG) used to measure surface strain and an extrinsic fibre Fabry–Perot interferometric (EFFPI) sensor used to measure unsteady pressure. The calibrated full scale resolution and bandwidth of the FBG and EFFPI sensors were shown to be 0.29% at 2.5 kHz up to 600 μe and 0.15% at up to 10 kHz respectively up to 400 Pa. The wind tunnel tests, completed on a 30% scale model, allowed the EFFPI sensor to be developed before incorporation with the FBG system into a Bulldog aerobatic light aircraft. The aircraft was modified and certified based on Certification Standards 23 (CS-23) and flight tested with steady and dynamic manoeuvres. Aerobatic dynamic manoeuvres were performed in flight including a spin over a g-range −1g to +4g and demonstrated both the FBG and the EFFPI instruments to have sufficient resolution to analyse the wing strain and fuselage unsteady pressure characteristics. The steady manoeuvres from the EFFPI sensor matched the wind tunnel data to within experimental error while comparisons of the flight test and wind tunnel EFFPI results with a Kulite pressure sensor showed significant discrepancies between the two sets of data, greater than experimental error. This issue is discussed further in the paper.

http://iopscience.iop.org/article/10.1088/0957-0233/27/10/104001/pdf

Ricardo Correia

Papers

Biomedical application of optical fibre sensors

Highly sensitive volatile organic compounds vapour measurements using a long period grating optical fibre sensor coated with metal organic framework ZIF-8

Highly sensitive label-free antibody detection using a long period fibre grating sensor

Carbon dioxide measurements using long period grating optical fibre sensor coated with metal organic framework HKUST-1

Development and application of optical fibre strain and pressure sensors for in-flight measurements