Two-Orders-of-Magnitude Enhancement of SERS Activity via a Simple Surface Engineering of Quasi-Metal Single-Crystal Frameworks.

Beyond noble metals and semiconductors, quasi-metals have recently been shown to be noteworthy substrates for surface enhanced Raman spectroscopy, and their excellent quasi-metal surface-enhanced Raman spectroscopy (SERS) sensing has demonstrated a wider range of application scenarios. However, the underlying mechanism behind the enhanced Raman activity is still unclear. Here, we demonstrate that surface hydroxyls play a crucial role in the enhancement of the SERS activity of quasi-metal nanostructures. As a demonstration material, quasi-metallic MoO2 single-crystal frameworks rich in surface hydroxyls have been shown to have 100 times higher SERS activity than MoO2 single-crystal frameworks without hydroxyl functionalization, with a Raman enhancement factor of up to 7.6 × 107. Experimental and first-principles density-functional theory calculation results show that the enhanced Raman activity can be attributed to an effective interfacial charge transfer within the MoO2/OH/molecule system.

A disposable fiber-optic plasmonic sensor for chemical sensing.

The integration of fiber optics and plasmonic sensors is promising to improve the practical usability over conventional bulky sensors and systems. To achieve high sensitivity, it typically requires fabrication of well-defined plasmonic nanostructures on optical fibers, which greatly increases the cost and complexity of the sensors. Here, we present a fiber-optic sensor system by using chemical absorption of gold nanoparticles and a replaceable configuration. By functioning gold nanoparticles with aptamers or antibodies, we demonstrate the applications in chemical sensing using two different modes. Measuring shift in resonance wavelength enables the Pb2+ detection with a high linearity and a limit of detection of 0.097 nM, and measuring absorption peak amplitude enables the detection of E. coli in urinary tract infection with a dynamic range between 103 to 108 CFU/mL. The high sensitivity, simple fabrication and disposability of this sensing approach could pave the way for point-of-care testing with fiber-optic plasmonic sensors.

Hydrogels for Chemical Sensing and Biosensing.

The development and synthesis of hydrogels for chemical and biosensing are of great value. Hydrogels can be tailored to its own physical structure, chemical properties, biocompatibility, and sensitivity to external stimuli when being used in a specific environment. Herein, hydrogels and their applications in chemical and biosensing are mainly covered. In particular, it is focused on the manner in which hydrogels serve as sensing materials to a specific analyte. Different types of responsive hydrogels are hence introduced and summarized. Researchers can modify different chemical groups on the skeleton of the hydrogels, which make them as good chemical and biosensing materials. Hydrogels have great application potential for chemical and biosensing in the biomedical field and some emerging fields, such as wearable devices.

Selective and Sensitive Detection of Fe3+ Ions Using a Red-Emissive Fluorescent Probe Based on Triphenylamine and Perylene-Linked Conjugated Microporous Polymer.

The Expansion of modern industry underscores the urgent need to address heavy metal pollution, which is a threat to human-health and environment. Efforts are underwent to develop precise technologies for detecting heavy metal ions (M+-ion). One promising approach involves the use of Conjugated Microporous Polymers (CMPs) modified with Triphenylamine (TPA) anderylene (Peryl), known as TPA-Peryl-CMP, which emits strong refluorescence. Various analytical techniques, such as Brunauer-Emmett-Teller analysis, Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, and thermogravimetric analysis (TGA), are utilized to characterize the synthesized TPA-Peryl-CMP and understand its functional properties. In addition to its remarkable fluorescence behavior, TPA-Peryl-CMP shows promise as a sensor for Fe3+ ions using a turn-off strategy. Due to its exceptional stability and robust π-electron system, this platform demonstrates remarkable sensitivity and selectivity, significantly improving detection capabilities for specific analytes. Detailed procedures related to the mechanism for detecting Fe3+ ions are outlined for sensing Fe3+ ions, revealing a notably strong linear correlation within the concentration range of 0-3 µM, with a correlation coefficient of 0.9936 and the Limit of detection (LOD) 20 nM. It is anticipated that development of such a kind of TPA-Peryl-CMP will observe broader applications in detecting various analytes related to environmental and biological systems.

Powders to Thin Films: Advances in Conjugated Microporous Polymer Chemical Sensors.

Chemical sensing of harmful species released either from natural or anthropogenic activities is critical to ensuring human safety and health. Over the last decade, conjugated microporous polymers (CMPs) have been proven to be potential sensor materials with the possibility of realizing sensing devices for practical applications. CMPs found to be unique among other porous materials such as metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) due to their high chemical/thermal stability, high surface area, microporosity, efficient host-guest interactions with the analyte, efficient exciton migration along the π-conjugated chains, and tailorable structure to target specific analytes. Several CMP-based optical, electrochemical, colorimetric, and ratiometric sensors with excellent selectivity and sensing performance were reported. This review comprehensively discusses the advances in CMP chemical sensors (powders and thin films) in the detection of nitroaromatic explosives, chemical warfare agents, anions, metal ions, biomolecules, iodine, and volatile organic compounds (VOCs), with simultaneous delineation of design strategy principles guiding the selectivity and sensitivity of CMP. Preceding this, various photophysical mechanisms responsible for chemical sensing are discussed in detail for convenience. Finally, future challenges to be addressed in the field of CMP chemical sensors are discussed.

Real-time, specific, and label-free transistor-based sensing of organophosphates in liquid.

Organophosphates (OP), commonly used in agriculture and as chemical warfare agents, pose significant environmental risks, necessitating real-time, low-cost OP detection methods. In particular, liquid-phase OP sensing with minimal sample volumes is crucial. While several methods allow rapid detection of low concentrations of OP vapors, they are effective only in the short term, while vapors are still being produced. Many OP compounds are semi-volatile, leading to the contamination of water, soil, and surfaces, posing a risk of secondary, long-term exposure. Detecting this contamination requires methods that can be directly applied to droplets of the affected medium. Currently, no method provides the desired combination of ultra-sensitivity, quantitative detection, rapid response, and low-cost for detecting OPs in liquid samples. This study aims to demonstrate quantitative, low-cost, real-time, specific, and label-free OP sensing in ultra-small samples using a transistor-based approach. The current work employs the 2-(4-Aminophenyl)-1,1,1,3,3,3-hexafluoro-2-propanol (aminophenyl-HFIP) functionalized meta-nano-channel field-effect chemical sensor (MNChem sensor) to monitor the organophosphate, diethyl cyanophosphonate (DCNP), in liquid samples. The silicon component of the MNChem is fabricated using a complementary metal-oxide semiconductor (CMOS) process, and the amine-based chemical functionalization of the sensing area is performed post-fabrication. The MNChem sensor provides electrostatic control over the source-drain current (IDS), allowing an optimized channel configuration that efficiently transduces localized OP recognition events into significant IDS variations. Sensing is performed using 0.5 µL buffer solution to simulate a miniature field-deployable sensor for on-site liquid analysis. We report the sensing of DCNP with a limit-of-detection of 100 fg/mL, a dynamic range of 9 orders of magnitude, and excellent linearity (≥0.97) and sensitivity. Control measurements confirm the specificity and reliability of the sensor's response, validating its applicability. This study introduces a novel method for OP detection in contaminated droplets using a low-cost disposable transistor technology.

Reconstruction of the Chemical Gas Concentration Distribution Using Partial Convolution-Based Image Inpainting.

An interpolation method, which estimates unknown values with constrained information, is based on mathematical calculations. In this study, we addressed interpolation from an image-based perspective and expanded the use of image inpainting to estimate values at unknown points. When chemical gas is dispersed through a chemical attack or terrorism, it is possible to determine the concentration of the gas at each location by utilizing the deployed sensors. By interpolating the concentrations, we can obtain the contours of gas concentration. Accurately distinguishing the contours of a contaminated region from a map enables the optimal response to minimize damage. However, areas with an insufficient number of sensors have less accurate contours than other areas. In order to achieve more accurate contour data, an image inpainting-based method is proposed to enhance reliability by erasing and reconstructing low-accuracy areas in the contour. Partial convolution is used as the machine learning approach for image-inpainting, with the modified loss function for optimization. In order to train the model, we developed a gas diffusion simulation model and generated a gas concentration contour dataset comprising 100,000 contour images. The results of the model were compared to those of Kriging interpolation, one of the conventional spatial interpolation methods, finally demonstrating 13.21% higher accuracy. This suggests that interpolation from an image-based perspective can achieve higher accuracy than numerical interpolation on well-trained data. The proposed method was validated using gas concentration contour data from the verified gas dispersion modeling software Nuclear Biological Chemical Reporting And Modeling System (NBC_RAMS), which was developed by the Agency for Defense Development, South Korea.

Monolithic MOF-Based Metal-Insulator-Metal Resonator for Filtering and Sensing.

Metal-insulator-metal (MIM) configurations based on Fabry-Pérot resonators have advanced the development of color filtering through interactions between light and matter. However, dynamic color changes without breaking the structure of the MIM resonator upon environmental stimuli are still challenging. Here, we report monolithic metal-organic framework (MOF)-based MIM resonators with tunable bandwidth that can boost both dynamic optical filtering and active chemical sensing by laser-processing microwell arrays on the top metal layer. Programmable tuning of the reflection color of the MOF-based MIM resonator is achieved by controlling the MOF layer thicknesses, which is demonstrated by simulation of light-matter interactions on subwavelength scales. Laser-processed microwell arrays are used to boost sensing performance by extending the pathway for diffusion of external chemicals into nanopores of the MOFs. Both experiments and molecular dynamics simulations demonstrate that tailoring the period and height of the microwell array on the MIM resonator can advance the high detection sensitivity of chemicals.

A Ratiometric Fluorescent Probe Dye-Functionalized MOFs Integrated with Logic Gate Operation for Efficient Detection of Acetaldehyde.

Volatile organic compounds (VOCs) are a class of hazardous gases that are widely present in the atmosphere and cause great harm to human health. In this paper, a ratiometric fluorescent probe (Dye@Eu-MOFs) based on a dye-functionalized metal-organic framework was designed to detect VOCs, which showed high sensitivity and specificity for acetaldehyde solution and vapor. A linear correlation between the integrated fluorescence intensity (I510/I616) and the concentration of acetaldehyde was investigated, enabling a quantitative analysis of acetaldehyde in the ranges of 1 × 10-4~10-5 µL/mL, with a low detection limit of 8.12 × 10-4 mg/L. The selective recognition of acetaldehyde could be clearly distinguished by the naked eye under the excitation of UV light. The potential sensing mechanism was also discussed. Significantly, a molecular logic gate was constructed based on the whole system, and finally, a molecular logic network system for acetaldehyde detection connecting basic and integrated logic operations was realized. This strategy provided an effective guiding method for constructing a molecular-level logic gate for acetaldehyde detection on a simple platform.

Exploring the Fate of Copper Ions in the Synthesis of Graphdiyne.

Copper is a crucial catalyst in the synthesis of graphdiyne (GDY). However, as catalysts, the final fate of the copper ions has hardly been concerned, which are usually treated as impurities. Here, it is observed that after simple washing with water and ethanol, GDY still contains a certain amount of copper ions, and demonstrated that the copper ions are adsorbed at the atomic layers of GDY. Furthermore, we transformed in situ the copper ions into ultrathin Cu nanocrystals, and the obtained Cu/GDY hybrids can be generally converted into a series of metal/GDY hybrid materials, such as Ag/GDY, Au/GDY, Pt/GDY, Pd/GDY, and Rh/GDY. The Cu/GDY hybrids exhibit extraordinary surface enhanced Raman scattering effect and can be applied in pollutant efficient enrichment and detection.

Emission Library and Applications of 2,1,3-Benzothiadiazole and Its Derivative-Based Luminescent Metal-Organic Frameworks.

Organic linker-based luminescent metal-organic frameworks (LMOFs) have received extensive attention due to their promising applications in chemical sensing, energy transfer, solid-state-lighting and heterogeneous catalysis. Benefiting from the virtually unlimited emissive organic linkers and the intrinsic advantages of MOFs, significant progress has been made in constructing LMOFs with specific emission behaviors and outstanding performances. Among these reported organic linkers, 2,1,3-benzothiadiazole and its derivatives, as unique building units with tunable electron-withdrawing abilities, can be used to synthesize numerous emissive linkers with a donor-bridge-acceptor-bridge-donor type structure. These linkers were utilized to coordinate with different metal nodes, forming LMOFs with diverse underlying nets and optical properties. In this Minireview, 2,1,3-benzothiadiazole and its derivative-based organic linkers and their corresponding LMOFs are summarized with which an emission library is built between the linker structures and the emission behaviors of constructed LMOFs. In particular, the preparation of LMOFs with customized emission properties ranging from deep-blue to near-infrared and sizes from dozens to hundreds of nanometers is discussed in detail. The applications of these LMOFs, including chemical sensing, energy harvesting and transfer, and catalysis, are then highlighted. Key perspectives and challenges for the future development of LMOFs are also addressed.

Gas-Induced Electrical and Magnetic Modulation of Two-Dimensional Conductive Metal-Organic Framework.

Controlled modulation of electronic and magnetic properties in stimuli-responsive materials provides valuable insights for the design of magnetoelectric or multiferroic devices. This paper demonstrates the modulation of electrical and magnetic properties of a semiconductive, paramagnetic metal-organic framework (MOF) Cu3(C6O6)2 with small gaseous molecules, NH3, H2S, and NO. This study merges chemiresistive and magnetic tests to reveal that the MOF undergoes simultaneous changes in electrical conductance and magnetization that are uniquely modulated by each gas. The features of response, including direction, magnitude, and kinetics, are modulated by the physicochemical properties of the gaseous molecules. This study advances the design of multifunctional materials capable of undergoing simultaneous changes in electrical and magnetic properties in response to chemical stimuli.

Lanthanide Functionalized Covalent Organic Frameworks Hybrid Materials for Luminescence Responsive Chemical Sensing.

Covalent organic frameworks (COFs) possess several unique features of structural and functional chemistry, together with other modular photophysical performance, which make them candidates for luminescence responsive chemical sensing. Lanthanide (Ln3+ ) functionalized COFs hybrid materials still keep the parent COFs' virtues and also embody the abundant multiple luminescence response with both COFs and Ln3+ ions or other guest species. In this review, the summary is highlighted on the lanthanide functionalized COFs hybrid materials and their relevant systems for luminescence responsive chemical sensing. It is subdivided into five sections involving the three main topics. Firstly, the basic knowledges of COFs materials related to the luminescence responsive chemical sensing are introduced (including three sections), involving the chemistry, application and post-synthetic modification (PSM) of COFs, the luminescence and luminescence responsive chemical sensing, and the luminescence responsive chemical sensing of non-lanthanide functionalized COFs hybrids materials. Secondly, the systematic progresses are outlined on the lanthanide functionalized COFs hybrid materials in luminescence responsive chemical sensing, which is the emphasis for this review. Finally, the conclusion and prospect are given.

Developments in food neonicotinoids detection: novel recognition strategies, advanced chemical sensing techniques, and recent applications.

Neonicotinoid insecticides (NEOs) are a new class of neurotoxic pesticides primarily used for pest control on fruits and vegetables, cereals, and other crops after organophosphorus pesticides (OPPs), carbamate pesticides (CBPs), and pyrethroid pesticides. However, chronic abuse and illegal use have led to the contamination of food and water sources as well as damage to ecological and environmental systems. Long-term exposure to NEOs may pose potential risks to animals (especially bees) and even human health. Consequently, it is necessary to develop effective, robust, and rapid methods for NEOs detection. Specific recognition-based chemical sensing has been regarded as one of the most promising detection tools for NEOs due to their excellent selectivity, sensitivity, and robust interference resistance. In this review, we introduce the novel recognition strategies-enabled chemical sensing in food neonicotinoids detection in the past years (2017-2023). The properties and advantages of molecular imprinting recognition (MIR), host-guest recognition (HGR), electron-catalyzed recognition (ECR), immune recognition (IR), aptamer recognition (AR), and enzyme inhibition recognition (EIR) in the development of NEOs sensing platforms are discussed in detail. Recent applications of chemical sensing platforms in various food products, including fruits and vegetables, cereals, teas, honey, aquatic products, and others are highlighted. In addition, the future trends of applying chemical sensing with specific recognition strategies for NEOs analysis are discussed.

Transitioning from Supramolecular Chemistry to Molecularly Imprinted Polymers in Chemical Sensing.

This perspective article focuses on the overwhelming significance of molecular recognition in biological processes and its emulation in synthetic molecules and polymers for chemical sensing. The historical journey, from early investigations into enzyme catalysis and antibody-antigen interactions to Nobel Prize-winning breakthroughs in supramolecular chemistry, emphasizes the development of tailored molecular recognition materials. The discovery of supramolecular chemistry and molecular imprinting, as a versatile method for mimicking biological recognition, is discussed. The ability of supramolecular structures to develop selective host-guest interactions and the flexible design of molecularly imprinted polymers (MIPs) are highlighted, discussing their applications in chemical sensing. MIPs, mimicking the selectivity of natural receptors, offer advantages like rapid synthesis and cost-effectiveness. Finally, addressing major challenges in the field, this article summarizes the advancement of molecular recognition-based systems for chemical sensing and their transformative potential.

Synthesis of TiO2-(B) Nanobelts for Acetone Sensing.

Titanium dioxide nanobelts were prepared via the alkali-hydrothermal method for application in chemical gas sensing. The formation process of TiO2-(B) nanobelts and their sensing properties were investigated in detail. FE-SEM was used to study the surface of the obtained structures. The TEM and XRD analyses show that the prepared TiO2 nanobelts are in the monoclinic phase. Furthermore, TEM shows the formation of porous-like morphology due to crystal defects in the TiO2-(B) nanobelts. The gas-sensing performance of the structure toward various concentrations of hydrogen, ethanol, acetone, nitrogen dioxide, and methane gases was studied at a temperature range between 100 and 500 °C. The fabricated sensor shows a high response toward acetone at a relatively low working temperature (150 °C), which is important for the development of low-power-consumption functional devices. Moreover, the obtained results indicate that monoclinic TiO2-B is a promising material for applications in chemo-resistive gas detectors.

Green IoT Event Detection for Carbon-Emission Monitoring in Sensor Networks.

This research addresses the intersection of low-power microcontroller technology and binary classification of events in the context of carbon-emission reduction. The study introduces an innovative approach leveraging microcontrollers for real-time event detection in a homogeneous hardware/firmware manner and faced with limited resources. This showcases their efficiency in processing sensor data and reducing power consumption without the need for extensive training sets. Two case studies focusing on landfill CO2 emissions and home energy usage demonstrate the feasibility and effectiveness of this approach. The findings highlight significant power savings achieved by minimizing data transmission during non-event periods (94.8-99.8%), in addition to presenting a sustainable alternative to traditional resource-intensive AI/ML platforms that comparatively draw and produce 20,000 times the amount of power and carbon emissions, respectively.

Redox-Active Mixed-Linker Metal-Organic Frameworks with Switchable Semiconductive Characteristics for Tailorable Chemiresistive Sensing.

Metal-organic frameworks (MOFs), with diverse metal nodes and designable organic linkers, offer unique opportunities for the rational engineering of semiconducting properties. In this work, we report a mixed-linker conductive MOF system with both tetrathiafulvalene and Ni-bis(dithiolene) moieties, which allows the fine-tuning of electronic structures and semiconductive characteristics. By continuously increasing the molar ratio between tetrathiafulvalene and Ni-bis(dithiolene), the switching of the semiconducting behaviors from n-type to p-type was observed along with an increase in electrical conductivity by 3 orders of magnitude (from 2.88×10-7  S m-1 to 9.26×10-5  S m-1 ). Furthermore, mixed-linker MOFs were applied for the chemiresistive detection of volatile organic compounds (VOCs), where the sensing performance was modulated by the corresponding linker ratios, showing synergistic and nonlinear modulation effects.

New tricks and emerging applications from contemporary azobenzene research.

Azobenzenes have many faces. They are well-known as dyes, but most of all, azobenzenes are versatile photoswitchable molecules with powerful photochemical properties. Azobenzene photochemistry has been extensively studied for decades, but only relatively recently research has taken a steer towards applications, ranging from photonics and robotics to photobiology. In this perspective, after an overview of the recent trends in the molecular design of azobenzenes, we highlight three research areas where the azobenzene photoswitches may bring about promising technological innovations: chemical sensing, organic transistors, and cell signaling. Ingenious molecular designs have enabled versatile control of azobenzene photochemical properties, which has in turn facilitated the development of chemical sensors and photoswitchable organic transistors. Finally, the power of azobenzenes in biology is exemplified by vision restoration and photactivation of neural signaling. Although the selected examples reveal only some of the faces of azobenzenes, we expect the fields presented to develop rapidly in the near future, and that azobenzenes will play a central role in this development.

A dual-channel optical chemical sensing system for selective detection of nerve agent simulant DFP.

This paper reports a novel optical chemical sensing system for selective detection of diisopropylfluorophosphate (DFP), a simulant of fluorine-containing nerve agents (Sarin and Soman). Contrary to the reported methods involving only single sensing probe, this sensing system is comprised of two molecular sensing probes (1 and 2) having intrinsic affinities for reactive subunits of DFP (electrophilic phosphorus and fluoride ion). On exposure to DFP, two molecular probes react in tandem with electrophilic phosphorus and fluoride ion (by-product of the initial phosphorylation reaction) to induce a unique modulation in the optical properties of the sensing system which leads to selective detection of DFP in solution as interferents like phosphorus-containing compounds, acids, and anions were unable to induce similar optical modulation due to lack of both electrophilic phosphorus and fluorine in the same molecule. Calibration curve between the amount of DFP added and the absorption intensity revealed the colorimetric detection limit of the system to be 4.50 µM which was further lowered to 2.22 µM by making use of a self-immolative fluoride sensing probe 5.