bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synthesis of Degradable Polymers Containing Phenylpropanoid Skeleton Via [2+2] Cycloaddition Polymerization Triggered By Electrochemical Oxidation and Photocatalysis
Authors: Nagaya Ryo , Seko Tatsuya , Ueno Kazuhide , Shida Naoki , Atobe Mahito 
Published: December 2024

Due to the increasing concern about climate change in human society, research on the use of biomass as a renewable carbon resource has become more active. Phenylpropanoids, which are obtained from the degradation of lignin, are expected as renewable aromatic monomers for plastic materials due to their availability. Various strategies have been proposed for polymerization of phenylpropanoids, including homopolymerization [1] or copolymerization [2]. However, the former strategies face challenges due to their limited scope of applicable phenylpropanoid. Furthermore, since conventional methods have mostly focused on polymerization of vinyl moiety, there remains the challenge in the chemical recycling of polymers.
In this work, we demonstrate the synthesis of degradable polymers containing phenylpropanoid by [2+2] cycloaddition polymerization. Bifunctional monomers containing two-phenylpropanoid moieties were synthesized by introducing siloxy- and (thio)phosphonate-linkage, respectively. Various phenylpropanoids are applicable to this strategy and we successfully synthesized various bifunctional monomers. Monomers were then polymerized by cycloaddition reactions triggered by electrochemical oxidation or photocatalysis. Siloxy- and (thio)phosphonate-linkage are cleavable by the reaction with specific reagents, enabling facile and chemoselective polymer degradation. The degradation reaction afforded a dimeric compound with a bisphenol skeleton, which could be used for further chemical recycling and upcycling.
[1] K. Ute et al., Polymer
2022, 246, 124780.
[2] K. Sato, Polymer Journal
2015, 47, 527-536.

Figure 1
Electrochemical Synthesis of Diarylsultones and Dibenzothiophene Dioxide Via C–O/C–S Bond Formation
Authors: Okumura Yasuyuki , Mitsudo Koichi , Suga Seiji 
Published: December 2024

Sultones and dibenzothiophene dioxides are widely used in the fields of pharmaceuticals, biologically active molecules, and material sciences [1][2]. While many synthetic methods have been reported, the synthesis of sultones and dibenzothiophene dioxides usually require stoichiometric amounts of oxidants, expensive transition metals, and harsh conditions. Therefore, the development of efficient and environmentally friendly methods for the synthesis of these compounds is in highly demand.
Meanwhile, electrochemical reactions have received considerable attention as an environmentally benign method in organic synthesis. In particular, electrochemical C–O and C–S bond formations have been a point of focus for the synthesis of useful compounds. However, there have been no reports on the electrochemical synthesis of sultones and dibenzothiophene dioxides.
Herein, we report the electrochemical synthesis of diaryl-fused sultones and dibenzothiophene dioxides through dehydrogenative C–O and C–S bond formations [3][4]. A variety of diaryl-fused sultones were obtained in moderate to good yields through hydrolysis of sulfonyl chlorides and constant current electrolysis. Control experiments suggested that the electrochemical oxidation of the sulfonates generated in situ would afford sulfo radical intermediates, and subsequent radical cyclization gave the products. For synthesizing dibenzothiophene dioxides, using Bu4NOTf as an electrolyte in HFIP/CH3NO2 was essential. On the other hand, biaryl sulfonyl hydrazides were applied to constant current electrolysis to afford the corresponding dibenzothiophene dioxides efficiently. Control experiments suggested that the electrooxidation of biaryl sulfonyl hydrazides would proceed via sulfonyl radical and cation intermediates.
References
[1] Mondal, S. Chem. Rev.
2012, 112, 5339.
[2] Dias, F. B.; Bourdakos, K. N.; Jankus, V.; Moss. K. C.; Kamtekar, K. Y.; Bhalla, V.; Santos, J.; Bryce, M. R.; Monkman, A. P. Adv. Mater.
2013, 25, 3707.
[3] Mitsudo, K.; Okumura, Y.; Yohena, K.; Kurimoto, Y.; Sato, E.; Suga, S. Org. Lett.
2023, 25, 3476.
[4] Okumura, Y.; Sato, E.; Mitsudo, K.; Suga, S. Electrochemistry
2023, 91, 112007.

Figure 1
Evaluation of Porcine Sperm Activity Using an Electrochemical Device
Authors: Terui Yuma , Kumagai Ryoma , Frubayashi Yoko , Sakuranaka Yuta , Matsuzawa Tamio , Matsuzawa Ryusuke , Kasai Shigenobu 
Published: December 2024

[Introduction] In recent years, in vitro fertilization has become an important method in the field of infertility treatment. Research is progressing in the livestock industry to improve fertility and pregnancy rates. The motility of sperm can be evaluated through time-lapse microscopy. This method is cost-effective and requires little space for activity evaluation. In addition, methods for selecting motile sperm include those that utilize centrifugation, such as density gradient centrifugation. However, there is a concern that centrifugation may physically damage sperm due to the large gravitational force it receives. We previously measured the respiratory activity levels of sperm and somatic cells in raw cow milk using amperometry; however, we did not evaluate sperm motility [1]. Therefore, in this study, we developed an electrochemical device that collects motile spermatozoa using moving gravity sedimentation without adding centrifugation, and we reported the examined changes in the oxygen reduction current before and after sperm movement.

[Experiment] Porcine (Duroc) sperm (approximately 108 sperm/mL) was purchased from the Miyagi Prefecture Livestock Experiment Station for use. The device was filled with 5.7 mL of 11.4 mM glucose-containing phosphate buffer solution (pH = 7.4), and a three-electrode system was constructed. A platinum electrode (diameter = 1.6 mm) was installed in the middle tube and a platinum electrode was installed in the counter electrode (Fig. 1). The applied voltage was maintained at -0.5 V vs. Ag/AgCl, and the sampling time was 0.1 s. After the start of measurement, 300 µL of the sperm sample was dropped onto the bottom of the outer tube, and amperometry was performed for approximately 60 minutes.

[Results and discussion] Fig. 2 shows the amperogram from 40 to 55 minutes after dropping the sperm sample. After approximately 42 minutes, the oxygen reduction current started to decrease. After approximately 10 minutes, the current became constant, and a decrease of approximately 100 nA was observed. This result suggested that the pig sperm potentially consumed oxygen during movement from the bottom of the outer ring to the center of the well. The number of sperm that swam upward and moved to the center was approximately 4.4 × 106 sperm/mL in 60 minutes, and the recovery rate was approximately 15.0%. Compared to the literature value for human sperm (approximately 13.8%), the experimental results were considered reasonable, suggesting the possibility of capturing the real-time respiratory activity of moving sperm [2]. In this paper, we thoroughly discussed the relationship between the initiation of porcine sperm migration and the oxygen reduction current.

[References]

[1]S.Kasai, A.Prasad, R.Kumagai, K.Takanohashi, Biology,2022,11,549.https://doi.org/10.3390/biology11040549.
[2] K.Tatsumi, T.Tatsumi, T.Uchida, K.Saito, H.Saito, F&S Reports, 2020,1(2), 106-112.

Figure 1
(Invited) Protein Film Electrochemistry and Surface-Enhanced Infrared Absorption Spectroscopy of Transmembrane Metalloenzymes
Authors: Kato Masaru 
Published: December 2024

Transmembrane metalloenzymes encapsulating transition metal complexes are involved in electron transfer and in material transformation in living organisms. Understanding their operating principles is not only important for identifying the origin of highly efficient enzymatic reactions but also for developing sensors and catalysts inspired by metalloenzymes [1]. Protein film electrochemistry (PFE) is a powerful technique to investigate the redox behavior and enzymatic activity of transmembrane metalloenzymes even with a submonolayer amount of the target protein (~10 pmol cm–2). The challenge of PFE of metalloenzymes is the interpretation of the results obtained in PFE: PFE provides current–potential curves like cyclic voltammograms and relatively large transmembrane metalloenzymes tend to have multiple redox active cofactors inside the protein, which makes the interpretation of cyclic voltammograms difficult.
We are using PFE coupled with surface-enhanced infrared absorption (SEIRA) spectroscopy, which is a surface-sensitive vibrational spectroscopy, to understand enzymatic mechanisms and protein–lipid or protein–protein interactions of transmembrane metalloenzymes at the electrode surface. In this talk, we will discuss PFE–SEIRA spectroscopy results about the determination of redox potential using a vibrational probe of carbon monoxide for heme proteins [2], the mechanistic insights into nitric oxide reduction to nitrous oxide at cytochrome c-dependent nitric oxide reductase (cNOR) using in situ PFE-SEIRA spectroscopy, and protein–lipid and protein–protein interactions with cNOR [3] and cytochrome c oxidase (CcO) [4].
References.
[1] M. Kato, N. Fujibayashi, D. Abe, N. Matsubara, S. Yasuda, I. Yagi, ACS Catal., 11, 2356–2365 (2021).
[2] M. Kato, S. Nakagawa, T. Tosha, Y. Shiro, Y. Masuda, K. Nakata, I. Yagi, J. Phys. Chem. Lett., 9, 5196 (2018).
[3] M. Kato, Y. Masuda, N. Yoshida, T. Tosha, Y. Shiro, I. Yagi, Electrochim. Acta, 373, 137888 (2021).
[4] M. Kato, R. Sano, N. Yoshida, M. Iwafuji, Y. Nishiyama, S. Oka, K. Shinzawa-Itoh, Y. Nishida, Y. Shintani, I. Yagi, J. Phys. Chem. Lett., 13, 9165-9170 (2022).
Voltage Hysteresis without Cation Migration in Li-Rich Layered Oxides: A Discrepancy in the Intermediate Crystal Phases
Authors: Calpa Marcela , Kubota Kei , Matsuda Shoichi , Takada Kazunori 
Published: December 2024

Li-rich layered oxides are promising as next-generation cathode materials for Li-ion batteries because of their potential to provide high voltage and large capacities. However, these materials suffer from significant voltage hysteresis between charge and discharge, and the causes are not yet well understood.
In this work, a comprehensive in-situ X-ray diffraction analysis, conducted in Li2RuO3 as a model of Li-rich cathode materials, reveals that a discrepancy in the intermediate crystal phases formed during Li extraction and re-insertion gives rise to different electrochemical potentials between charge and discharge, which causes the undesired voltage hysteresis [1]. These findings enrich the understanding of voltage hysteresis in Li-rich materials.
Reference
[1] Calpa, M., et al. Energy Storage Materials 63 (2023) 103051
Improving the Thermal Stability of Lithium-Ion Batteries Using a Separator Protective Film Made By Novel Materials
Authors: Uto Daiki , Imai Masato , Yasui Shintaro , Yoshino Kenji 
Published: December 2024

Lithium-ion batteries (LIBs) are widely used in the portable electronics, power tools, and electric vehicle power markets. As the demand for higher battery density and energy density increases, improving the safety of LIBs has become an important issue. The separator in a LIB maintains physical isolation between the cathode and anode and allows the movement of lithium ions through the electrolyte through the porous separator structure during cycling. Therefore, cycle life and energy density are important components for achieving high battery performance.
Generally, most separators are porous polyolefin films made of polyethylene or polypropylene. Polyolefin separators have excellent mechanical strength and chemical stability, but they shrink significantly at high temperatures, and internal short circuits occur under conditions such as abnormal heating. In order to improve the thermal stability of the separator, many methods have been reported for coating the surface of the separator with inorganic powder, and most of them use dip coating or simple bar coating. The coating layer formed on the surface of the separator has a porous structure and is several microns thick. Coated separators reduce thermal shrinkage while ensuring ion transport, but there are concerns that increased film thickness may reduce the battery's energy density.
In this study, the coating was carried out on porous membranes such as separators at 50 °C by spray pyrolysis using methylaluminoxane diluted with N-methylpyrrolidone. The solution penetrated the separator during spraying and deposited an ultrathin layer on the side walls of the internal pores. These layers were suggested to be fine polycrystalline Al2O3. In the obtained film, most of the pores were exposed on the surface, and there was almost no increase in film thickness. Furthermore, it has ionic conductivity equivalent to that of film and has improved thermal stability. This method was considered to be an effective technique for improving the functionality of separators used in LIB.
Two-Dimensional Covalent Organic Framework Photoanode for High Capacity Solar Battery
Authors: Rath Bibhuti Bhusan , Lotsch Bettina Valeska 
Published: December 2024

To mitigate our reliance on fossil fuels and facilitate energy transition, efficient conversion and storage of ubiquitous solar energy is a key strategy. Despite significant research progress in photovoltaics, energy storage in decentralized batteries requires the decoupling of energy conversion and storage, which causes major energy loss and higher cost. Seamless integration of a photoconversion system and an energy storage system in a single device can effectively store the excess energy. Materials that can demonstrate light harvesting, effective charge carrier separation for long-term charge storage, and on-demand charge retrieval as electrical energy, would be the most suitable choice. Such properties have been demonstrated in graphene-, carbon-nitride-, polyoxometalate-, and metal organic frameworks- based materials; however, the charge storage capacity remains uncompetitive. Driven by the need for earth-abundant and sustainable materials for solar energy storage, covalent organic frameworks (COFs) have emerged as a new generation of molecularly defined semiconductors with tunable optoelectronic properties. Herein, the rational integration of an electron reservoir in a polyimide two-dimensional COF unlocks the unique combination of light harvesting and electrical energy storage. When used as an aqueous solar battery anode, the COF demonstrated a capacity of ~40 mAh g-1 operating as a pseudocapacitor, which stores charge as long-lived radical anions for days. With photo-electrochemical measurements in conjunction with detailed spectroscopic studies and theoretical support, we attempt to unravel the mechanism of long-term charge stabilization. Furthermore, on-demand release of long-lived electrons with a suitable co-catalyst unlocks the prospects of dark photocatalysis, which will be investigated in the future.
References:

F. Podjaski, B. V. Lotsch, Adv. Energy Mater. 2021, 11, 2003049.

V. W. Lau, D. Klose, H. Kasap, F. Podjaski, M-C. Pignié, E. Reisner, G. Jeschke, B. V. Lotsch, Angew.
Chem. Int. Ed. 2017, 56, 510 –514.

S. Amthor, S. Knoll, M. Heiland, L. Zedler, C. Li, D. Nauroozi, W. Tobaschus, A. K. Mengele, M. Anjass, U. S. Schubert, B. Dietzek-Ivanšić, S. Rau, C. Streb, Nat.
Chem. 2022, 14, 321−327.

M. Stanley, F. Sixt, J. Warnan, Adv. Mater. 2023, 35, 2207280.
Photothermally Enhanced Urea-Assisted Hydrogen Production Using Cus/WO3 Direct Z-Scheme Electrocatalyst
Authors: Cha Yoolim , Kim Wonhyeong , Kim Dong-Joo 
Published: December 2024

Fossil fuels, such as coal and petroleum, are currently the primary energy source for the world’s needs. However, their depletion and role in the development of greenhouse gases, which contribute to global warming and climate change, necessitate the exploration of alternative green energy sources to promote a cleaner environment. Hydrogen, in particular, has emerged as a promising renewable energy fuel for the future. One promising method for producing hydrogen is urea-assisted water splitting, which has the potential to improve both hydrogen production productivity and energy conversion efficiency. However, urea oxidation reaction (UOR) is a complex six-electron transfer process with slow reaction kinetics and unclear mechanisms, which requires a high overpotential. This has led to the need to enhance electrocatalytic reactions. In general, the majority of research has been directed towards the synthesis of robust, efficient, and economically viable catalysts. In recent years, light irradiation has been introduced into an electrochemical system with the aim of enhancing the activities of the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and carbon dioxide reduction reaction. Insights into the mechanism demonstrate that external excitation effectively accelerates charge and mass transfer and thus improves the reaction kinetics and thermodynamics. In contrast to previous catalyst modifications, the external field assistance approach allows for greater flexibility in engineering an electrochemical process with facile, continuous, reversible, dynamic, and universal control. However, the utilization of photothermal-assisted urea oxidation reaction has not been reported yet.
In this research, we report a CuS/WO3 composite electrocatalyst with a direct Z-scheme system for photothermally-assisted UOR. Upon irradiation with light, the CuS/WO3 electrode exhibited a reduced overpotential of 308.2 mV, resulting in a UOR current density of 50 mA cm-2. Additionally, the CuS/WO3 electrode achieved a current density of 10 mA cm-2 at a potential of 1.38 V vs. RHE under irradiation. The catalytic activity of the CuS/WO3 electrode was found to be significantly enhanced, exhibiting a 2.5- and 2.8-fold increase compared to that of CuS and WO3, respectively. This enhancement can be attributed to the enhanced redox abilities of charge carriers in the direct Z-scheme system. Our studies demonstrate the importance of direct Z-scheme formation in light utilization and the synergistic effect of photon and photothermal on UOR.

Figure 1
Redox-Active Amine for Electrochemical CO2 Capture and Release
Authors: Liang Liang , Firschke Frederik , Strasser Peter 
Published: December 2024

The recent IPCC report highlights the importance of negative carbon dioxide emissions scenarios to achieve the 1.5°C Paris Agreement goal, emphasizing the crucial role of negative emission technologies (NETs) in complementing decarbonization efforts. Capturing CO2 from dilute sources, such as flue gas and the atmosphere, is essential for managing global emissions and advancing storage and utilization efforts downstream. Electrochemical carbon capture methods are notable for their high energy efficiency, decentralized operation, ambient reaction conditions, and compatibility with renewable electricity. [1, 2]
In this context, a robust electroDAC approach with switchable electroactive adsorption materials is urgently needed. Cu-based electrochemically mediated amine regeneration (EMAR) shows promise for controlled, reversible complexation with CO2 capture amines in aqueous solutions. However, uncertainties persist regarding Cu2+/Cu interfacial chemistry mechanisms, dynamic competitive interactions at the surface and in bulk, and potential degradation routes or parasitic faradaic currents. [3]
To address these uncertainties, we propose a reversible system using an electrostatic charge transfer mechanism at the electrode interface for energy-efficient CO2 capture and release. Our study focuses on investigating the stability and reactivity of various Cu-based catalysts under different conditions, employing spectroelectrochemical analysis to elucidate changes and interactions between adsorbed species and CO2 at the electrode interface.
Literature:
[1] S. Voskian, T. A. Hatton, Energy Environ. Sci., 2019,12, 3530-3547.
[2] M. Massen-Hane, K. M. Diederichsen, T. A. Hatton, Nat Chem Eng., 2024, 1, 35–44.
[3] S. E. Renfrew, D. E. Starr, P. Strasser, P. ACS Catal. 2020, 10, 21, 13058–13074.
Cathodic Decomposition Reference Electrodes As a Generalized Approach for Thermodynamic Calculations in Complex Molten Salts
Authors: Lichtenstein Timothy , Hawthorne Krista 
Published: December 2024

The rise of molten salt use in green energy applications has led to increased efforts to model and understand the underlying thermochemical properties of active species within molten salts. Molten salts can become increasingly complex during the operational lifetime through corrosion or generation of new species, resulting in changes to the thermophysical and thermodynamic properties. For example, next-generation molten salt nuclear reactors start with a binary or ternary fuel salt, but generation of fission products during operation can significantly change the behavior of active species in the salt and interactions with container materials. While processes in established molten salt electrolytes such as LiCl-KCl eutectic can use well-characterized reference electrodes such as Ag/AgCl to quantify thermochemical properties1, emerging salt systems do not have well-established reference electrode systems. Using standard reference electrodes based upon anodic electrolyte decomposition (e.g., chlorine or fluorine gas-based electrodes) introduces additional engineering and safety challenges during construction and measurement of thermochemical properties. These experimental barriers have previously limited investigation of the thermodynamics of novel molten salt systems.
Here, we use cathodic decomposition electrodes (CDEs) to measure the thermochemical properties of molten salt systems. The CDE defines 0 V as the cathodic decomposition of the pure solvent electrolyte at all temperatures. A CDE was used to make activity measurements in chloride and fluoride salts. Both steady-state emf measurements in concentration cells and transient measurements were made in an electrolyte containing active species such as GdCl3 or NiF2. The universal nature of a CDE reference can improve accuracy and repeatability of activity measurements in molten salt systems and fill the knowledge gaps that prevent prediction of thermochemical and thermophysical properties in molten salt systems.

L. YANG and R. G. HUDSON, “Some Investigations of the Ag∕AgCl in LiCl-KCl Eutectic Reference Electrode,” J. Electrochem. Soc. 106 11, 986 (1959); https://doi.org/10.1149/1.2427195.