bluuebunny/crossref_metadata_2025_split huggingface dataset:
Impact of Composition, Pressure and Local Symmetry of Impurity Site on the Optical Properties of Phosphor Materials
Authors: Piasecki Michal , Brik Mikhail G. , Srivastava Alok M. , Khyzhun Oleg Y , Beers Wiliam W , Cohen William Erwin , Novita Mega , Stef Marius , Umar Zafari , Yamamoto Tomoyuki 
Published: December 2024

The understanding of complex relationships between luminescent properties, local symmetry of an emitting center and type of chemical bonding on the host crystal structure provides a better insight into optical properties of materials. Moreover, tunability of the phosphors’ emission spectra by changing local environment around impurity center is attractive from the point of view of pressure sensors or lighting applications. We will discuss from the theoretical and experimental points of view some examples (semiconductors or insulators matrices with multivalent ions, either rare-earth (RE) or transition-metal (TM) chemical elements with unfilled 4f or 3d electron shells, as activators: respectively). The presentation also shows that the knowledge gained from the systematic study of the host-activator interaction can serve as a guide to practical improvement and tuning to desired values the key parameters of phosphors [1-9].
References:
[1] Alok M Srivastava, Mikhail G Brik, William W Beers, Chong-Geng Ma, Michal Piasecki, William E Cohen , J. Lumin. 257 (2023) 119709
[2] Andrei V Racu, Zoran Ristić, Aleksandar Ćirić, V Đorđević, G Bușe, Maria Poienar, Michael J Gutmann, Oleh Ivashko, M Ștef, Daniel Vizman, MD Dramićanin, Michal Piasecki, Mikhail G Brik, Opt. Mat.136, (2023) 113337
[3] M. G. Brik, W. W Beers, W. Cohen, S. A. Payne, N. J. Cherepy, M. Piasecki, A. M. Srivastava, Opt. Mat. 91 (2019) 338
[4] AM Srivastava, MG Brik, WW Beers, B Lou, C-G Ma, M Piasecki, W E Cohen, ECS J. Solid State Sci. Technol., 12 (2023) 066001
[5] Umar Zafari, Musashi Sagayama, Mekhrdod Subhoni, Alok M Srivastava, William W Beers, William E Cohen, Chong-Geng Ma, Michal Piasecki, Mikhail G Brik, Tomoyuki Yamamoto, Opt. Mat.: X, 16 (2022) 100197
[6] Zafari Umar, Mekhrdod S Kurboniyon, Oleg Khyzhun, Tomoyuki Yamamoto, Chong-Geng Ma, Mikhail G Brik, Michal Piasecki, J. Lumin. 266 (2024) 120278
[7] Mega Novita, Alok Singh Chauhan, Rizky Muliani Dwi Ujianti, Dian Marlina, Haryo Kusumo, Muchamad Taufiq Anwar, Michał Piasecki, Mikhail G Brik, J. Lumin. 269 (2024) 120476
[8] J Jedoń, Agata Lazarowska, Tadeusz Leśniewski, Sebastian Mahlik, MG Brik, M Piasecki, AM Srivastava, WW Beers, E Zych, Journal of Alloys and Compounds, 930 (2023) 167435
[9] Alok M. Srivastava, Mikhail G. Brik, Chong-Geng Ma, William W. Beers, William E. Cohen and Michal Piasecki, J. Phys. Chem. Lett. 15, XXX (2024) 4175–4184
Charge Transfer Luminescence of LiCa3MgV3O12 and LiCa3ZnV3O12 Under Ionizing Radiation Excitation
Authors: Kawaguchi Noriaki , Okazaki Kai , Kato Takumi , Nakauchi Daisuke , Yanagida Takayuki 
Published: December 2024

A scintillator is a material that generates a large number of excited electrons and holes under ionizing radiation excitation and immediately emits light with recombination of electrons and holes. When a scintillator combined with a photodetector, it is used as a radiation detector. Radiation detectors equipped with scintillators are applied in various fields such as medical care, security, and radiation protection. Researches are still being conducted to find novel materials with higher performance. In particular, we are attracted to compounds containing lithium (Li). This is because the Li isotope 6Li causes a nuclear reaction with neutrons, so Li-containing materials could be used as neutron scintillators. The Ce-doped lithium silicate glass (lithium glass) and the Eu-doped LiI single crystal are known as conventional Li-containing scintillators; however, the segregation of dopants in these materials can be a problem. For example, the lithium glass can be divided into areas with high and low emission intensity by the dopant segregation. It causes a double-peak in the pulse height spectra under neutron irradiation, and measurement accuracy will deteriorate.
In this study, we focused on LiCa3MgV3O12 and LiCa3ZnV3O12 as candidates for scintillators that contain Li and do not require dopants. The photoluminescence properties of powder samples of LiCa3MgV3O12 and LiCa3ZnV3O12 have already been reported; however, scintillation properties have not yet been investigated. We prepared the sintered ceramics of LiCa3MgV3O12 and LiCa3ZnV3O12 and evaluated their scintillation properties. High-purity powders of Li2CO3, CaO, MgO, ZnO, and V2O5 were used as raw materials. They were weighed in stoichiometric proportions and ground using aluminum mortar and pestle, and then calcined at 750℃ for 6 hours in aluminum crucibles. The obtained powders were ground again, pressed into pellets, and then sintered at 850℃ for 6 hours. The X-ray diffraction (XRD) patterns of the samples were measured and compared with those in the previous literature, and we confirmed that each of them had a single phase. In the X-ray induced scintillation spectra, broad luminescence peaking at around 500 nm was observed in each sample. Both emissions can be explained by the charge transfer transition between V5+–O2-.
Constructing Point-of-Care Diagnostics: Developing New Chemistry for the Functionalization and Use of High-Density Microelectrode Arrays
Authors: Moeller Kevin D 
Published: December 2024

The detection of infectious pathogens at the point-of-care remains a challenging task due to the need to detect a series of at times closely related metabolites in locations that are often remote from a major medical center. High density microelectrode arrays have the potential to serve as an effective tool to address these issues because they contain thousands of individually addressable electrodes that can each be selectively functionalized with a specific molecular recognition element. New surfaces for the arrays have lifetimes of over a year, allow for the multiplex detection of small molecules, and are compatible with urine-based samples.
However, the systems developed to date are not yet ideal. While the surfaces are stable, they are not always uniform. The mediators used for the analytical experiments are themselves not always compatible with a point-of-care application, and while the experiments are fundamentally compatible with urine, urine samples vary greatly and it is not clear exactly how general those experiments are. At the same time, arrays for this specific application are functionalize using Cu(II)-mediated cross coupling reactions. But, how good are those reactions? We know that they allow for selective placement exclusively at a targeted electrode or set of electrodes in an array, but what is the yield of such a process? Can the reactions be used to build a molecular library directly on a microelectrode array?
In this presentation, we will present answers to these questions along with a look at the general strategies being used to acquire those answers. In so doing, we hope to illustrate how a synthetic/ physical organic chemistry approach to the problem can present new solutions that are helping to bridge the gap between the idea of a point-of-care device and an actual working prototype.
Electrochemical Oxidation of Xylitol on Ag to Valuable Organic Acids: Mechanistic Study and Product Analysis
Authors: Tran David , Meng Zhe , Kristoffersen Henrik Høgh , Rossmeisl Jan , Hjelm Johan 
Published: December 2024

Switching from a non-renewable fossil-based economy to a bioeconomy relying on biomass utilisation is one of the key challenges to achieving a change towards sustainable chemical production. Biomass offers a wide variety of valuable components such as lignin, (hemi)celluloses, other (poly)saccharides, and proteins that could be used to produce biobased bulk, fine and speciality chemicals, polymers and transportation fuels. Xylitol is one of the high-value-added biomass-derived compounds that is used in the food and pharmaceutical industries and can act as a platform for the chemical synthesis of other high-value compounds like ethylene- and propylene glycol.1

The electrochemical oxidation of polyols such as glycerol, sorbitol and xylitol in alkaline media has been studied mechanistically and to determine their suitability for applications in alcohol fuel cells.2,3 Investigations with glycerol have revealed two main reaction pathways: The full oxidation to glyceric acid with subsequent C-C cleavage to glycolic and formic acid or the alkaline-driven elimination and rearrangement of glyceraldehyde to lactic acid. However, mechanistic investigation and product analysis are under-explored for the electrochemical xylitol conversion.
Here, we investigate the potential-controlled bulk electrolysis of xylitol in alkaline media on Ag in a divided cell setup to analyze the product outcome at various constant potentials and xylitol concentrations. The reaction progress is monitored with NMR spectroscopy, followed by HPLC analysis. Glycolic (GCA) and formic acid (FA) are the main products, showing the cleavage of xylitol upon oxidation and the same selectivity as glycerol. We hypothesize the formation of either xylose or xylulose as an intermediate, and both exhibit a different cleavage behaviour upon further oxidation as displayed in figure 1. Erythrose and glyceraldehyde further react to GCA and FA. Moreover, the variation of electrolysis potential and concentration shows only minor changes in the product distribution, and no signs of poisoning are visible at prolonged reaction time. This makes Ag-based electrodes a promising material for the complete conversion of xylitol to obtain biomass-derived small organic acids.
1. J. Sun, H. Liu, Green Chem., 2011, 13, 135.
2. Y. Kwon, K. J. P. Schouten, M.T.M. Koper, ChemCatChem.,
2011, 3, 1176.
3. L.J. Torres-Pacheco, A. De Leon-Rodriguez, L. Álvarez-Contreras, M. Guerra Balcázar, N. Arjona,
Electrochim. Acta, 2020, 353, 136593.
4. Z. Meng, D. Tran, J. Hjelm, H. H. Kristofferson, J. Rossmeisl, ACS Catal., 2024, 14, 4, 2455.

Figure 1
Visible-Light Induced C-H Oxygenation of Hydrocarbons Using Chlorine Dioxide as a Photoredox Catalyst
Authors: Ohkubo Kei 
Published: December 2024

Photocatalytic oxygenation of benzene occurs in an oxygen-saturated acetonitrile solution containing acridnium ion or quinolinium ion derivatives as a photoredox catalyst, benzene and water under light irradiation to yield phenol and hydrogen peroxide selectively. The benzene radical cation, which is formed by photoinduced one-electron oxidation of benzene with the excited state of catalyst, reacts with H2O to yield phenol.
Photocatalytic oxygenation of benzene with oxygen occurs under photoirradiation of an acetonitrile solution of 3-cyano-1-methylquinolinium perchlorate (QuCN+ClO4
–) in an oxygen-saturated acetonitrile (MeCN) containing benzene and H2O with a xenon lamp (500 W) attached with a color-cut glass filter. The selectivity of formation of phenol was 98% with 16% quantum yield after 1 h irradiation, and then 51% of phenol yield after 5 h irradiation. The photocatalytic turnover number (TON) was 7.5. This is the first example of photocatalytic oxygenation of benzene to phenol in a homogeneous system. A preparative gram-scale photocatalytic reaction with benzene (2.3 g, 29 mmol) and QuCN+ (210 mg, 0.8 mmol) in MeCN (200 mL) for 48 h was also examined to afford phenol (1.1 g, 12 mmol) as 41% yield.
Non-Native Bioelectrocatalytic C-C and C-N Bond Formation via Cobalamin Dependent Enzymes
Authors: Kays Luke , Boucher Dylan G. , Kumar Amardeep , Gupta Paras , Lewis Jared , Minteer Shelley D. 
Published: December 2024

Bioelectrocatalysis involves the use of biomaterials to catalyze redox reactions at an electrode. Biocatalysis offers improved selectivity and typically involves milder reaction conditions, while electrocatalysis can involve the use of renewable energy as an electron source. Cobalamin (B12) dependent enzymes catalyze C-C and C-N bond forming reactions via radical mechanisms through the formation of a Co(III)-alkyl intermediate. Homolysis of the Co(III)-C bond leads to radical coupling with various substrates to form the product. However, these alkyl radicals can react through a variety of mechanistic pathways, leading to a mixture of products. Controlling the alkyl radical intermediate would lead to improved reaction selectivity.
Here, we report on CarH*, an engineered variant of a B12 dependent photoreceptor protein, which catalyzes styrene C-H alkylation by trapping an alkyl radical intermediate in its protein scaffold. The reversible Co-alkyl bond homolysis protects the radical, allowing for selective olefin addition. However, to initiate this reactivity, the cobalt center of CarH* must be reduced through stoichiometric addition of the reducing agent titanium (III) citrate. Thus, we are developing a mediated electrochemical system to achieve this transformation without the use of a stoichiometric reductant and to investigate new reactivity in CarH* and similar variants. A diffusive redox mediator was found to deliver electrons to CarH* and drive alkyl radical formation. This methodology offers a more sustainable and general approach to electrochemical non-native biocatalysis and can be applied to discover new reactivity in B12 dependent enzymes.
(Invited) Integrated Electrochemical Devices for Microphysiological Systems
Authors: Ino Kosuke 
Published: December 2024

Animal testing has been used for drug screening applications. However, the accuracy of this testing is low due to the difference in metabolization activities between animals and humans. To challenge this issue, there is a growing interest in employing in-vitro assays using human culture cells. These assays involve three-dimensional cell cultures or stimulation within microfluidic devices to replicate in-vivo functions, known as microphysiological systems (MPSs). Also, porous membranes are used to prepare biological interfaces for MPSs, such as gut, lungs, skin, and vasculature, by culturing cells on these membranes.
MPSs have been widely evaluated using qPCR and immunostaining methods. However, these methods damage cells, making them unsuitable for real-time or time-course analysis. To challenge this issue, electrochemical (bio)sensors are being explored, as they enable real-time and time-course evaluations of metabolization without cell damage [1].
In this study, integrated electrochemical devices have been developed for MPSs. As one example, porous membrane electrodes were fabricated to cultivate cell monolayers and measure cellular activities in situ for MPS applications. Human umbilical vein endothelial cells (HUVECs) were cultured on the membrane as a vascular model and measured the release of nitric oxide (NO) from HUVECs (Fig.: Reprinted with permission from Ref. 2. Copyright 2023 American Chemical Society) [2]. This method allows for the monitoring of short-lifetime molecules like NO because the cells are attached to the electrode.
As another example, electrochemiluminescence (ECL) devices were developed for cell analysis [3]. In ECL measurements, electrochemical reactions are converted to optical signals, resulting in successful electrochemical imaging for cell analysis using only a single working electrode. In this study, the ECL devices were applied to visualize cellular respiration activity and cell adhesion.
Moving forward, these electrochemical MPS devices hold promise for drug screening and biomedical research, serving as an alternative to animal testing.
References
[1] Curr. Opin. Electrochem., 39, 101270, 2023; Electrochem. Sci. Adv., e2300026, 2024
[2] Anal Chem., 95, 49, 18158, 2023
[3] Biosens. Bioelectron., 181, 113123, 2021; Electrochim. Acta, 415, 140240, 2022; Electrochim. Acta, 458, 142507, 2023; Electrochemistry, 92, 022009, 2024

Figure 1
(Invited) Electrochemical Biosensor Using Direct Electron Transfer and an Antibody–Aptamer Hybrid Sandwich
Authors: Kim Gyeongho , Yang Haesik 
Published: December 2024

Direct electron transfer (DET) between an electrode and redox labels is feasible in electrochemical biosensors using small aptamer–aptamer sandwiches; however, its application is limited in biosensors that rely on larger antibody–antibody sandwiches. The development of sandwich-type biosensors utilizing DET is challenged by the scarcity of aptamer–aptamer sandwich pairs with high affinity in complex biological samples. In this presentation, we introduce an electrochemical biosensor using an antibody–aptamer hybrid sandwich for detecting thrombin in human serum. The biosensor enables rapid DET through an antibody–aptamer hybrid configuration comprising (i) an antibody capture probe that provides high and specific affinity to the target in human serum, (ii) the target thrombin, and (iii) an aptamer detection probe that facilitates convenient terminal conjugation with long flexible spacer DNA and polylinker peptide containing multiple amine-reactive phenazine ethosulfate (arPES) redox labels, allowing the conjugated labels to easily approach the electrode. Rapid repeated DET using arPES-catalyzed NADH oxidation strongly enhanced the electrochemical signals. Properly sized spacer and polylinker provided low nonspecific adsorption of the aptamer probe conjugated with multiple arPESs and low interference with the binding of the aptamer probe. Methods for immobilizing thiol-terminated antibodies on Au electrodes were compared and optimized. The developed biosensor using the antibody–aptamer hybrid sandwich exhibited high sensitivity and selectivity in detecting thrombin, surpassing the limitations of an aptamer–aptamer sandwich owing to the low affinity of thrombin aptamers in human serum. The calculated detection limit of the biosensor was ∼1.5 pM in buffer and ∼2.7 nM in human serum.
References
1. G. Kim, H. Yang, Biosens. Bioelectron. 253, 116184 (2024)
2. G. Kim, H. Cho, P. Nandhakumar, J. K. Park, K. Kim, H. Yang, Anal. Chem. 94, 2163 (2022)
3. S. Park, J.-E. Jeong, V. S. Le, J. Seo, B. Yu, D.-Y. Kim, S.-H. Kwon, S. Jon, H. Y. Woo, H. Yang, J. Am. Chem. Soc. 140, 2409 (2018)
Direct Contact Prelithiation of Silicon-Dominant Anodes Using Ultra-Thin Lithium Foils
Authors: Diller Felix , Wittmann Oskar , Daub Rüdiger 
Published: December 2024

With the steady growth of the electric vehicle market, the development of high-energy-density lithium-ion batteries is increasingly coming into focus. Silicon has a nearly ten times higher specific capacity for lithium storage than conventionally used graphite, making silicon a promising anode material for high-performance lithium-ion battery applications[1]. However, silicon shows a high volume expansion upon lithiation, leading to a rapid capacity fade due to the loss of active lithium associated with continuous solid electrolyte interphase formation[2]. Direct contact prelithiation is a method to compensate for the loss of active lithium by incorporating additional lithium metal during battery cell production. The use of lithium foil is a facile approach but depends on the availability of ultra-thin lithium foils[3].
In this study, silicon-dominant anodes with a silicon content of ca. 70 % were prelithiated by lithium foils with a thickness of 5 and 10 µm using a calendering process. A glove box integrated calender under an argon atmosphere was used to transfer the ultra-thin lithium foils from a carrier foil on the entire anode surface. This facilitates a homogenous prelithiation of the anode and equal compression force over the entire anode surface. A process study was conducted to find suitable process parameters for the full-surface lithium foil application on the anodes. The formed anode-lithium-composite was investigated with and without the presence of an electrolyte. Pouch cells with nickel-rich cathodes were built to show the performance improvement through the presented prelithiation technique in the full cell setup.
An increase of 16 % in full cell capacity shows the potential of direct contact prelithiation to boost the energy density of already high-energy lithium-ion battery material systems. The incorporated lithium metal compensates for the loss of active lithium and thereby enhances the cycle life of the battery cells, making the proposed prelithiation method an enabler for the use of silicon-dominant anodes for high-performance applications.

References

[1] M. N. Obrovac and L. Christensen, Electrochem. Solid-State Lett., 7, A93–A96 (2004).
[2] A. J. Louli, L. D. Ellis and J. R. Dahn, Joule, 3(3), 745-761 (2019).
[3] B. Stumper, A. Mayr and G. Reinhart, Procedia CIRP, 93, 156-161 (2020).

Acknowledgements

The authors gratefully acknowledge funding from the German Federal Ministry of Economic Affairs and Climate Action through the project CAESAR (grant number 03EI3046F). We thank the project partners from Wacker Chemie AG, BASF SE, and E-Lyte Innovations GmbH for the collaboration within the CAESAR project and for providing us with the used silicon, the cathode active material, and the electrolyte.
Effect of Electrode Curvature on Cell Behavior in Cylindrical Lithium-Ion Batteries
Authors: Jeon Byeong-jin , Lee Yeong-Hyeon , Jeong Kyeong-Min 
Published: December 2024

Lithium-ion batteries come in various form factors, with cylindrical lithium-ion batteries featuring electrodes wound in a jellyroll shape. This winding process introduces curvature to the electrodes, resulting in varying curvatures depending on the radius of the jellyroll.
In this study, we investigated the influence of electrode curvature within cylindrical lithium-ion batteries on battery performance. We fabricated single-coated electrode pouch cells using an NCM622 cathode and graphite-silicon composite anode. We developed devices to simulate various curvatures based on the radius of the jellyroll and applied these devices to the pouch cells to analyze the effect of curvature on the cell’s charging and discharging behavior.
The results revealed that changes in electrode curvature, depending on the radius of the jellyroll, alter the area available for reaction at the anode. As a result, the potential of the anode changed, leading to a corresponding change in the potential of the cathode at the same full cell's cut-off charging voltage. Additionally, we observed differences in cathode/anode utilization depending on whether they were on the inner or outer coated surface, even with the same curvature. Particularly, we found an increased risk of lithium deposition when the curvature is large with the anode on the outer coated surface. Furthermore, these effects influence changes in silicon utilization in the anode, affecting the thickness expansion and degradation differences in the anode. Consequently, the non-uniformity of cell reactions due to electrode curvature increases. Therefore, we propose methods for designing cylindrical lithium-ion batteries to minimize such non-uniformity in reactions.
Our research emphasizes the importance of curvature within cylindrical lithium-ion batteries and its impact on battery performance by elucidating the mechanism of battery performance changes due to electrode curvature. These findings are expected to contribute to the design and development of cylindrical lithium-ion batteries.

Figure 1