bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Combining the 5d→4f and 4f→4f Luminescence of Lanthanides for High-Quality Broad-Range Luminescence Thermometry
Authors: Zych Eugeniusz , Bolek Paulina , Sójka Małgorzata , Kulesza Dagmara , Zeler Justyna , Jedoń Joanna , Carlos Luis D. , Runowski Marcin , Trojan-Piegza Joanna , Shyichuk Andrii , Zheng Teng , Lis Stefan 
Published: November 2022

Accurate and sensitive remote temperature measurement is required in a growing number of existing and emerging applications. As the technology advances and nanotechnology enters still new fields, the size of objects whose temperature needs to be controlled gets smaller and the non-contact temperature reading is the only reasonable approach. Luminescence thermometry is believed to become the technology of choice for such purposes, as it is resistant to disturbances by an electromagnetic field and the sensitivity and accuracy of measurements may be tuned for the specific requirements. Thus, whether it comes to reading temperature at cryo-range, around the room, or at high temperatures, one may design a luminescent thermometer offering high-quality measurements. This is not to say that such designing is easy to do. Even under laboratory conditions, highly-sensitive and accurate luminescent thermometers are not that frequent.
Additional problems appear when it comes to measurements over a broad range of temperatures. At first, the basic physics of luminescence processes are not conducive to the design of a luminescence thermometer offering very sensitive and accurate measurements over a broad range of temperature (a few hundred degrees, for example). On the other hand, wide-range luminescence thermometers are of interest for such important fields as aviation and space industries. Fast, accurate, and credible measurements of quickly changing temperatures are of special importance in these areas.
In this presentation, we shall report a new approach toward wide-range high-quality luminescence thermometry. Phosphors activated with either Pr3+ or Eu2+ will be examined for that purpose. Both these ions are capable of generating two types of emissions: (i) intra-configurational 5f→4f and inter-configurational 4f→4f ones. We shall prove that such phosphors may offer both broad-range and high-accuracy and high-sensitivity temperature measurements. Furthermore, we will demonstrate that the sensitivity of such sensors may be deliberately tuned to reach its maximum at temperatures where it is most needed. A few examples of such phosphors will be discussed and possible expectations for further development using this approach will be discussed.
This research was supported by the Polish National Science Center (NCN) under the grant #UMO-2018/29/B/ST5/00420.

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(Digital Presentation) Electrochemical Single Impact Method for Electroactive Bacterial Detection Onto Carbon Ultramicroelectrode
Authors: Smida Hassiba , Thobie-Gautier Christine , Boujtita Mohammed , Lebegue Estelle 
Published: November 2022

This work aims to design a high sensitivity and selectivity biosensor based on the electrochemistry of single impacts onto ultramicroelectrode (UME) to detect and identify various bacterial strains. The main objective is to establish a unique electrochemical signature for each bacterial cell through the individual impact event signal on the surface of the UME [1, 2]. First, we focus on the detection of well-known electroactive Gram-negative bacteria such as Shewanella oneidensis in order to be able to selectively detect these different single cells. In this case, the strategy currently used is to record a chronoamperometric curve in an aqueous potassium phosphate buffer (pH = 7.4) solution containing a redox probe at an UME polarized at the oxidation or reduction potential of the electrochemical active aqueous species and to observe a “current step” when one bacterium impacts the UME, corresponding to a “blocking effect” [3] (Figure A). The response signal expected from single bacterium collision may also be a “current spike” corresponding to either the own electrochemical activity of the bacterium toward the redox probe and the UME applied potential or a “bouncing effect” of the bacterium which does not stick onto UME surface (Figure B).
In order to be able to identify the type of bacterial cell striking the UME surface, an adapted functionalization (covalent grafting via reduction of diazonium aryl salts) with appropriate affinity (bio)chemical species such as antibodies or aptamers could be performed. This strategy could confer to the UME surface a selectivity of the signal generated during single impacts. For example, the electro-grafting of diazo-pyridinium cations for microbial fuel cell electrodes showed to promote and improve the development of bacterial electroactive films [4].
[1] E. Lebègue, N. L. Costa, R. O. Louro, F. Barrière, J. Electrochem. Soc. 16 (2020) 105501
[2] A. T. Ronspees, S. N.Thorgaard, Electrochimica Acta. 278 (2018) 412-420
[3] G. Guanyue, W. Dengchao, B. Ricardo, Z. Jinfang, M. Michael V. Anal. Chem. 90 (2018) 12123−12130
[4] H. Smida, E. Lebègue, J-F. Bergamini, F. Barrière, C. Lagrost, Bioelectrochemistry. 120 (2018) 157-165

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Electrolyte Induced Solvent Cage Effects for Enantioselective Electrosynthesis
Authors: Nguyen Zachary A , Boucher Dylan , Minteer Shelley D. 
Published: November 2022

Electrochemistry provides a tunable, regioselective, and green alternative to traditional synthetic organic methods, and access to reactive intermediates. Problematically, electrochemical redox events often go through planar radical intermediates, thus destroying enantioselectivity. As such, researchers have sought the “chiral electron”, a general methodology to impart enantioselectivity to electroorganic reactions. One strategy has been asymmetric transition metal catalysis while replacing the typical stochiometric redox reagent needed with electricity, thus providing a chiral pathway for elecoorganic reactions. However, the general physical parameters that govern enantioselectivity at electrochemical interfaces, remains poorly understood.
Here, we focus on the effects of supporting electrolyte in synthetic organic electrochemistry, specifically its role in enantioselective reactions. Cyclic voltammetry provides a tool to investigate the mechanistic consequences of changes in electrolyte. Using the model reaction of enantioselective carboxylation with a cobalt catalyst, we observe changes in mechanism as the electrolyte size is varied. Specifically, electrolyte identity effects the lifetime of the chiral Co-alkyl intermediate. These fundamental electroanalytical studies provide a sound mechanistic basis for the origin of enantioselectivity in electroorganic reactions. In summary, these results of a general interest as a strategy to tune and improve enantioselectivity in electrochemical transformations.
Peroxynitrite Reactivity with Capsaicin: A Potential for Capsaicin-Based Sensing Devices
Authors: Kalil Haitham , Crichlow Cynthia , Bayachou Mekki 
Published: November 2022

Peroxynitrite and other reactive oxygen species (ROS) have been linked to illnesses caused by oxidative stress, such as atherosclerosis. Accurate detection of these species in biological systems is crucial not only for understanding the etiology and course of the disease but also for creating and evaluating viable therapies. In the last 30 years, there has been an exponential increase in research into capsaicin's biological relevance. Capsaicin has analgesic, antioxidant, anti-inflammatory, anti-cancer, and anti-obesity properties. Most of these investigations have focused on the analgesic, antioxidant, and anticancer properties of this chemical compound throughout the last three decades. Capsaicin has been shown to increase the production of peroxynitrite by boosting the formation of superoxide anions in combination with nitric oxide.
Preliminary UV-Vis results suggested a potential interaction at micromolar levels between capsaicin and peroxynitrite. A hyperchromic shift has been shown at a wavelength of ~ 300 nm, indicating an interaction between capsaicin and peroxynitrite, which resulted in a 2x increase in absorbance. The interaction of capsaicin and peroxynitrite was further studied using cyclic voltammetry and differential pulse voltammetry.
Design and Fabrication of Electrochemical Protein Sensors for a Fetal Membrane-on-a-Chip
Authors: Buckey Grace , Owens Olivia , Cliffel David E 
Published: November 2022

Preterm birth (PTB) is the top cause of death in newborns and the second leading cause of death in children under the age of five. Certain cytokines, like interleukin-6 (IL-6), and matrix metalloproteinases (MMPs) are known to facilitate the degradation of the fetal membrane, but the mechanisms that result in fetal membrane rupture under both normal and pathological conditions are largely unknown. Our fetal membrane-on-a-chip model will allow us to investigate the conditions and mechanisms that precede fetal membrane rupture. Our enzymatic electrochemical detection platform allows us to detect biosignatures from the fetal membrane by measuring analyte concentration changes such as glucose utilization, lactate production, and oxygen consumption. Addition of electrochemical sensors for cytokine and MMPs to the detection platform will provide further insight into the mechanisms underlying PTB by offering low-level protein biomarker quantification.
We are currently fabricating and optimizing electrochemical immunoassays for the detection of IL-6 and MMP-3 to leverage the advantages of electrochemical techniques in studying preterm births. The current protein assay design utilizes the enzyme alkaline phosphatase attached to the target protein. When introducing the substrate p-aminophenyl phosphate (PAPP) to the system, it is enzymatically converted to p-aminophenol (PAP). Upon oxidation, PAP is converted to p-quinone (PQI). We are currently studying the electrochemical behavior of PAP/PQI for application in immunoassays. We are investigating the use of different electrochemical techniques for PAP oxidation to PQI including cyclic voltammetry, square wave voltammetry, differential pulse voltammetry, and normal pulse voltammetry to see how the technique affects the reproducibility of assay measurements.
Enhanced Performance of Microbial Fuel Cells Using PVDF Activated Carbon Air Cathode and Electrochemically and Chemically Treated Carbon Felt Anode
Authors: Poureshghi Oskouei Fatemeh , Dong Nga Phuong , Das Subhashis , Petrich Chris , Calay Rajnish Kaur 
Published: November 2022

Microbial fuel cells (MFCs) harness the metabolism of microorganisms, converting chemical energy into electrical energy. Improving both Anode and Cathode design is thus of great significance to enhance the MFC performance and its commercial application. For the performance improvement of MFCs, the anode becomes a breakthrough point due to its influence on bacterial attachment and extracellular electron transfer (EET). On the other hand, air cathodes have considerable influence on the maximum power of air-driven MFCs. The cathodes used in MFCs need to have high catalytic activity for oxygen reduction, but they should be inexpensive watertight,and easy to manufacture.
As the first part of this work, carbon felt was electrochemically and chemically treated by electrolyzing in nitric acid and phosphate buffer followed by soaking in aqueous ammonia. The treated and untreated carbon felts were utilized as anodes in MFCs, and current production was compared while the cathode was stainless steel mesh (SS-316L) in both cases. The treated carbon felt displays strong interaction with the microbial biofilm of Shewanella baltica 20 facilitating electron transfer from exoelectrogens to the anode. An MFC equipped with a treated carbon felt as anode has significantly lower charge-transfer resistance and achieves considerably better performance than one equipped with an untreated carbon felt anode. The enhanced electron transfer is attributed to newly generated carboxyl containing functional groups on the treated carbon felt.
In the second part of the present study, SS-316L as a cathode was modified using phase inversion process to construct a poly vinylidenefluoride (PVDF) binder and an activated carbon catalyst according to the procedure reported previously.
Finally, the MFC with treated carbon felt anode and PVDF air cathode was tested. The MFC with both modified anode and cathode achieves considerably better performance than one with a traditional carbon felt anode and SS-316L cathode. The maximum current density, power density, and energy recovery, and sensitivity of the biofilm to the heavy metals are significantly improved.
Exploring Sub-Detection Limit Electrochemistry with Luminogenic Reporting Reactions
Authors: Linfield Steven , Gawinkowski Sylwester , Nogala Wojciech 
Published: November 2022

Electrochemistry has a limit of detection imposed by the inherent shot-noise present in electrical currents [1]. As a result, the direct measurement of single-electron charge transfer processes is not feasible using electrochemical methods. However, luminescence can be measured with single photon resolution and the development of a method to efficiently convert an electrochemical signal to an optical one is expected to be a key step in overcoming the detection limit of electrochemistry [2].
An optical conversion technique based on closed bipolar electrochemistry has recently been demonstrated using large glassy carbon electrodes [3,4]. In this technique, which is illustrated in Fig. 1, any electrochemical process of interest occurring in one cell (the detection cell) can be used to induce either fluorescence or chemiluminescence in another cell (the reporting cell). Fluorogenic reporting reactions have the advantage that several photons can be emitted during the lifetime of each fluorophore, leading to signals with a greater intensity. However, the facile photooxidation of some fluorophores introduces the need for chemical reductants, which complicates the electrochemistry [5]. Conversely, the constant electron-to-photon relationship of chemiluminescence makes it an easier process for calculating the number of electrons passed in the detection cell, but also leads to a reduced signal intensity [6]. There is still much work needed to understand which reporting mechanism is more suited to sub-detection limit electrochemistry and how to reach the maximum sensitivity of single-electron charge transfer processes.
In this work, we present our recent progress towards the measurement of sub-detection limit electrochemical processes via luminogenic reporting reactions. We compare the conversion mechanisms of reporting reactions which use either fluorescence or chemiluminescence, and we study the factors which can affect the sensitivity of the conversion, such as the presence of chemical reductants. Finally, we test the temporal resolution and sensitivity of optical conversion techniques in the measurement of single entity electrochemical processes. The results shown herein are of importance to electrochemists wishing to use optical conversion to probe below the detection limit of electrochemistry.
Literature
[1] R. Gao, M. A. Edwards, J. M. Harris and H. S. White, Curr. Opin. Electrochem., 2020, 22, 170–177.
[2] Y. Wu, S. Jamali, R. D. Tilley and J. J. Gooding, Faraday Discuss., 2022, 233, 10–32.
[3] J. P. Guerrette, S. J. Percival and B. Zhang, J. Am. Chem. Soc., 2013, 135, 855–861.
[4] J. S. Stefano, F. Conzuelo, J. Masa, R. A. A. Munoz and W. Schuhmann, J. Electroanal. Chem., 2020, 872, 113921.
[5] S. M. Oja, J. P. Guerrette, M. R. David and B. Zhang, Anal. Chem., 2014, 86, 6040–6048.
[6] P. A. Defnet and B. Zhang, ChemElectroChem, 2020, 7, 252–259.

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Investigating Nafion Responsiveness Via Coupled Transport-Mechanical Network Modelling
Authors: Goyal Priyamvada , Kusoglu Ahmet , Weber Adam Z. 
Published: November 2022

Perfluorosulfonated (PFSA) ionomer membranes owe their high conductivity and durability, which make them popular as proton-exchange membranes for fuel cells and electrolyzers, to their characteristic phase-separated morphology. The hydrophilic domains connecting the ionic moieties form the transport network for ions and water, while the hydrophobic polymeric backbone affords them the much-needed mechanical stability. Interactions between these domains constitute the structure-property relationship. PFSAs such as Nafion can be reimagined as responsive materials by leveraging this structure-property relationship, integral to their functionality, as a stimuli-response dynamic.
Modelling, in tandem with morphological, mechanical, and transport experimental evidence, can be a powerful tool to deconstruct how different stimuli can be designed to elicit a desired response from an ionomer. A large majority of relevant models have dealt with transport in and mechanics of Nafion membranes as isolated behaviors. Transport models, which are usually continuum scale, use dilute solution (Nernst–Planck) or concentrated solution (Onsager–Stefan–Maxwell) theory depending on the scale and complexity of the phenomena in focus. Mechanical models range from statistical-mechanics-led molecular scale formulations to macroscopic phenomenological approaches. Whereas the continuum models lose out on details regarding morphological changes, molecular models are simply too expensive to scale up. Mesoscale models can offer an elegant solution for this problem by incorporating phenomenon inseparable from structural details of the material while remaining computationally tenable.
In this work, the hydrophilic and hydrophobic domains in the ionomer will be modelled as two-way coupled mesoscale networks. Whereas the transport network will share characteristics with a pore-network-like configuration, the polymeric backbone will be visualized as a network of non-Hookean springs. The interspersed networks will be configured using the dual-cubic as well as the Delaunay–Voronoi conformations. The mathematical frameworks for each phase will also be modified to include mass-momentum coupling, as implemented by a few continuum models. The network nature of the topology will allow for local flux and deformation changes to organically propagate beyond the nearest neighbors, capturing the core of the ionomer’s responsiveness. Deeper insights into the stimuli-response behavior will allow for more nuanced control of operating conditions for fuel cells and electrolyzers to obtain a tailored performance from existing ionomers as well as enable development of better customized materials for the future.
The Impact of Phase Changes of Imidazolium Based Ionic Liquids on the Solubility of Hydrofluorocarbons
Authors: Baca Kalin , Olsen Greta , Haggard Dorothy , Bennett Madelyn , Matamoros Valenciano Lucia , Shiflett Mark 
Published: November 2022

Project EARTH (Environmentally Applied Research Toward Hydrofluorocarbons) is focused on developing sustainable processes for selectively separating refrigerant mixtures with high global warming potentials. The initial focus of the project is R-410A which is widely used in both commercial refrigeration systems and residential air conditioning. It is an azeotropic mixture containing 50 wt.% HFC-32 (CH2F2) and 50 wt.% HFC-125 (CHF2CF3). The separation approaches being investigated include membranes, porous media, and the use of ionic liquids as entrainers for extractive distillation.
This poster will describe the work being conducted using ionic liquids and will specifically focus on the impact of phase changes of imidazolium based ionic liquids that are solid at room temperature on the solubility of HFC-32 and HFC-125. The poster will include an overview of how we use specialized equipment including a High-Pressure View Cell and Hiden Isochema IGA gravimetric microbalance to build a comprehensive understanding of these solubility differences.
Electrodeposited from Ion-Organic Melt Ti-B Protective Coatings on Al-Foil
Authors: Devyatkin Sergei Vladimirovich , Kuksenko Sergei , Pisanenko Alexandr , Kochetova Svetlana 
Published: November 2022

The great demand for advanced batteries in applications such as mobile devices, the transportation sector, and stationary storage has spurred intensive research and development on rechargeable lithium batteries. The corrosion behavior of Al-foil, as material for theirs current collectors, has long been a concern due to uniform or localized pitting corrosion occurs in contact with an organic electrolyte. Pitting corrosion is attributed to inhomogeneous current flow through the aluminum / electrode interface and results in local breakdown of the passive film on Al-foil. Particular attention among different protective coatings of Al-foil excites Ti-B coatings as conductive and electrochemically inactive protective layers.
The main objectives of the present work are investigation of regimes for electrodeposition of Ti-B protective coatings onto Al-foil and examination of the corrosion behavior of Al-foil with such electrodeposited Ti-B protective coatings in contact with an organic electrolyte under various electrodes charging conditions.
Low melting point of aluminium (tm = 6600C) made impossible electrodeposition of Ti-B coatings from chloride-fluoride melts (tel = 7000C). But it is possible from ion-organic melts at 70−2000C. In this work was investigated electrodeposition of Ti-B coatings from carbamide melt contains titanium and boron oxides. Cyclic voltammetry has shown the limit current density and potential of electrochemical synthesis. Ultra fine Ti-B coatings were electrodeposited onto Al-foil at 1300C. Figure shows the surface morphologies of an obtained Ti-B coating. Such cost-effective method of obtaining Ti-B protective coatings on Al-foils gives excellent results under theirs using as current collectors in rechargeable lithium batteries.

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