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1. Understanding of Förster Resonance Energy Transfer (FRET) in Ionic Materials

   https://doi.org/10.3390/suschem2040031  

   Jalihal, Amanda; Le, Thuy; Macchi, Samantha; Krehbiel, Hannah; Bashiru, Mujeebat; Forson, Mavis; Siraj, Noureen (December 2021, Sustainable Chemistry)

   Herein, an ionic material (IM) with Förster Resonance Energy Transfer (FRET) characteristics is reported for the first time. The IM is designed by pairing a Nile Blue A cation (NBA+) with an anionic near-infrared (NIR) dye, IR820−, using a facile ion exchange reaction. These two dyes absorb at different wavelength regions. In addition, NBA+ fluorescence emission spectrum overlaps with IR820− absorption spectrum, which is one requirement for the occurrence of the FRET phenomenon. Therefore, the photophysical properties of the IM were studied in detail to investigate the FRET mechanism in IM for potential dye sensitized solar cell (DSSCs) application. Detailed examination of photophysical properties of parent compounds, a mixture of the parent compounds, and the IM revealed that the IM exhibits FRET characteristics, but not the mixture of two dyes. The presence of spectator counterion in the mixture hindered the FRET mechanism while in the IM, both dyes are in close proximity as an ion pair, thus exhibiting FRET. All FRET parameters such as spectral overlap integral, Förster distance, and FRET energy confirm the FRET characteristics of the IM. This article presents a simple synthesis of a compound with FRET properties which can be further used for a variety of applications. 

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2. Single-Frequency Impedance Studies on an Ionic Liquid-Based Miniaturized Electrochemical Sensor toward Continuous Low-Temperature CO ₂ Monitoring

   https://doi.org/10.1021/acssensors.2c02040  

   Sridhar, Arun Siddarth; Chen, Xiaoyu; Glossmann, Tobias; Yang, Ziming; Xu, Yong; Lai, Wei; Zeng, Xiangqun (January 2023, ACS Sensors)

   Continuous greenhouse gas monitoring at sub-zero temperatures is needed for monitoring greenhouse gas emission in cold environments such as the Arctic tundra. This work reports a single-frequency electrochemical impedance sensing (SF-EIS) method for real-time continuous monitoring of carbon dioxide (CO2) at a wide range of temperatures (−15 to 40 °C) by using robust ionic liquid (IL) sensing materials and noninvasive, low-power, and low-cost impedance readout mechanisms since they cause minimal changes in the sensing interface, avoiding the baseline change for long-term continuous sensing. In addition, a miniaturized planar electrochemical sensor was fabricated that incorporates a hydrophobic 1-butyl-1-methylpyrrolidinium bis(trifluromethylsulfonyl)imide ([Bmpy][NTf2]) IL electrolyte and Pt black electrode materials. The high viscosity of the ILs facilitates the formation of thin, ordered, and concentrated layers of ionic charges, and the inverse relationship of IL viscosity with temperature makes them especially suited for impedance sensing at low temperatures. The unique low-temperature properties of ILs together with EIS transduction mechanisms are shown to be sensitive and selective for continuously monitoring CO2 at a −15 to 40 °C temperature range via impedance changes at a specifically selected frequency at the open circuit potential (OCP). Molecular dynamics simulations revealed insights into the structure and dynamics of the IL at varying temperatures in the presence of methane and CO2 and provided potential explanations for the observed sensing results. The miniaturized and flexible planar electrochemical sensor with the [Bmpy][NTf2] electrolyte was tested repeatedly at subzero temperatures over a 58-day period, during which good stability and repeatability were obtained. The CO2 impedance sensor was further tested for sensing CO2 from soil samples and shows promising results for their use in real-time monitoring of greenhouse gas emissions in cold temperatures such as permafrost soils. 

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3. Friction and Wear of Pd-Rich Amorphous Alloy (Pd43Cu27Ni10P20) with Ionic Liquid (IL) as Lubricant at High Temperatures

   https://doi.org/10.3390/met9111180  

   Lee, Jaeho; Yeo, Chang-Dong; Hu, Zhonglue; Thalangama-Arachchige, Vidura D.; Kaur, Jagdeep; Quitevis, Edward L.; Kumar, Golden; Koh, Yung P.; Simon, Sindee (November 2019, Metals)

   The friction and wear behavior of palladium (Pd)-rich amorphous alloy (Pd43Cu27Ni10P20) against 440C stainless steel under ionic liquids as lubricants, i.e., 1-nonyl-3-methylimidazolium bis[(trifluoromethane)sulfonyl]amide ([C9C1im][NTf2]), were investigated using a ball-on-disc reciprocating tribometer at ambient, 100 and 200 °C with different sliding speeds of 3 and 7 mm/s, whose results were compared to those from crystalline Pd samples. The measured coefficient of friction (COF) and wear were affected by both temperature and sliding speed. The COF of crystalline Pd samples dramatically increased when the temperature increased, whereas the COF of the amorphous Pd alloy samples remained low. As the sliding speed increased, the COF of both Pd samples showed decreasing trends. From the analysis of a 3D surface profilometer and scanning electron microscopy (SEM) with electron dispersive spectroscopy (EDS) data, three types of wear (i.e., delamination, adhesive, and abrasive wear) were observed on the crystalline Pd surfaces, whereas the amorphous Pd alloy surfaces produced abrasive wear only. In addition, X-ray photoelectron spectroscopy (XPS) measurements were performed to study the formation of tribofilm. It was found that the chemical reactivity at the contacting interface increased with temperature and sliding contact speed. The ionic liquids (ILs) were effective as lubricants when the applied temperature and sliding speed were 200 °C and 7 mm/s, respectively. 

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4. Self-Assembled Plasmonic Structural Color Colorimetric Sensor for Smartphone-Based Point-Of-Care Ammonia Detection in Water

   https://doi.org/10.1021/acsami.4c06615  

   Soudi, Mahdi; Cencillo-Abad, Pablo; Patel, Jay; Ghimire, Suvash; Dillon, Joseph; Biswas, Aritra; Mukhopadhyay, Kausik; Chanda, Debashis (August 2024, ACS Applied Materials & Interfaces)

   Monitoring chemical levels is crucial for safeguarding both the environment and public health. Elevated levels of ammonia, for instance, can harm both humans and aquatic ecosystems, often indicating contamination from agriculture, industry, or sewage. Developing portable, high-resolution, and affordable methods for in situ monitoring of ammonia is thus imperative. Plasmonic sensors offer a promising solution, detecting ammonia by correlating changes in their optical response to the target analyte’s concentration. While they are highly sensitive and can be fabricated in a variety of portable and user-friendly formats, some still require reagents or expensive optical equipment, which hinder their widespread adoption. Here, we present a self-assembled nanoplasmonic colorimetric sensor capable of directly detecting ammonia concentrations in aqueous matrices. The proposed sensor exploits the plasmonic resonance of the nanostructures to transduce changes in the chemical environment into alterations in color, offering a label-free method for real-time analysis. The sensor is fabricated using a self-assembling technique compatible with low-cost mass production based on aluminum and aluminum oxide, ensuring affordability and avoiding the use of other toxic chemicals. We developed a model to predict ammonia concentrations based on visible color change of the sensor, achieving a detection limit of 8.5 ppm. Furthermore, to address the need for on-site detection, we integrated smartphone technology for real-time color change analysis, eliminating the need for expensive, bulky optical instruments. Indeed, our approach offers a cost-effective, portable, and user-friendly solution for ammonia detection in water without the need for chemical reagents or spectrometers, making it ideal for field applications. Interestingly, this platform extends its applicability beyond ammonia detection, enabling the monitoring of various chemicals using a smartphone, without the need for any additional costly equipment. 

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5. Recent Advances in Electrochemical Sensors for Detecting Toxic Gases: NO2, SO2 and H2S

   https://doi.org/10.3390/s19040905  

   Khan, Md; Rao, Mulpuri; Li, Qiliang (February 2019, Sensors)

   null (Ed.)

   Toxic gases, such as NOx, SOx, H2S and other S-containing gases, cause numerous harmful effects on human health even at very low gas concentrations. Reliable detection of various gases in low concentration is mandatory in the fields such as industrial plants, environmental monitoring, air quality assurance, automotive technologies and so on. In this paper, the recent advances in electrochemical sensors for toxic gas detections were reviewed and summarized with a focus on NO2, SO2 and H2S gas sensors. The recent progress of the detection of each of these toxic gases was categorized by the highly explored sensing materials over the past few decades. The important sensing performance parameters like sensitivity/response, response and recovery times at certain gas concentration and operating temperature for different sensor materials and structures have been summarized and tabulated to provide a thorough performance comparison. A novel metric, sensitivity per ppm/response time ratio has been calculated for each sensor in order to compare the overall sensing performance on the same reference. It is found that hybrid materials-based sensors exhibit the highest average ratio for NO2 gas sensing, whereas GaN and metal-oxide based sensors possess the highest ratio for SO2 and H2S gas sensing, respectively. Recently, significant research efforts have been made exploring new sensor materials, such as graphene and its derivatives, transition metal dichalcogenides (TMDs), GaN, metal-metal oxide nanostructures, solid electrolytes and organic materials to detect the above-mentioned toxic gases. In addition, the contemporary progress in SO2 gas sensors based on zeolite and paper and H2S gas sensors based on colorimetric and metal-organic framework (MOF) structures have also been reviewed. Finally, this work reviewed the recent first principle studies on the interaction between gas molecules and novel promising materials like arsenene, borophene, blue phosphorene, GeSe monolayer and germanene. The goal is to understand the surface interaction mechanism. 

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