bluuebunny/crossref_metadata_2025_split huggingface dataset:
Transition Metal and Photocatalyst Free Arylation via Photoexcitable Electron Donor Acceptor Complexes:Mediation and Catalysis
Authors: Volkov Alexey A. , Bugaenko Dmitry I. , Karchava Alexander V. 
Published: January 2024

AbstractVisible‐light‐activated organic reactions unlock novel avenues for complex molecular transformations, impossible under standard “thermal” conditions, which makes them powerful tools in the arsenal of synthetic chemistry. However, transition metal‐based or organic photoredox catalysts are often used to ensure productive absorption of visible light, which might be not desirable to medicinal chemistry and industry due to toxicity, low sustainability, and high cost of most photocatalysts. A more environmentally and economically benign approach is based on the formation of transient electron donor‐acceptor (EDA) complexes between two reagents or a reagent and an additive, that readily absorb visible light, acting as internal photosensitizers. Within the EDA complex‐based arylation strategies, chemical transformations are mediated by noncovalent interaction between two molecules, namely between electron‐poor aryl halides or their synthetic equivalents and electron‐rich nucleophilic reagents or additives. Moreover, besides stoichiometric EDA complexes between two molecules, EDA complex based organocatalysis can be achieved in certain cases through regeneration of the donor molecules in the course of the reaction. Photoexcitation of the EDA complexes induces a single electron transfer (SET) process to generate aryl radical species for the arylation step. This Review will focus on the state‐of‐the‐art EDA complex‐based arylation strategies utilizing aryl halides, aryldiazonium, diaryliodonium, arylsulfonium and arylphosphonium salts as reactants, published mainly in the last five years.
Photo‐electrochemical O2 Reduction to H2O2 Using a Co‐Porphyrin Based Metal‐Organic Framework
Authors: Ifraemov Raya , Binyamin Shahar , Pearlmutter Yanai , Liberman Itamar , Shimoni Ran , Hod Idan 
Published: January 2024

AbstractMetal‐Organic Frameworks (MOFs) hold great potential to be used as porous (photo)‐electrocatalytic platforms containing large concentration of immobilized molecular catalysts. Indeed, the use of MOFs in a photo‐electrochemical devices was recently demonstrated. However, so far there are no reports of MOFs used for photo‐electrochemical O2 reduction to H2O2. Herein, we utilize a Co‐porphyrin based MOF (Co‐MOF‐525), that produces H2O2 at high faradaic efficiency (95 %), both electrochemically and photo‐electrochemically. Electrochemical characterization show that the active catalytic site is a MOF‐tethered Co(I)‐porphyrin. Additionally, under light illumination, the MOF's intrinsic catalytic rate is significantly accelerated compared to dark electrolysis conditions. Thus, this work could open a path for future implementation of photoactive MOFs in solar fuel schemes.
Enhanced Oxygen Reduction Activity of Platinum Micropore
Authors: Nakahara Kota , Ikezawa Atsunori , Okajima Takeyoshi , Arai Hajime 
Published: January 2024

AbstractThe high overpotential of oxygen reduction reaction (ORR) prevents the wide commercialization of fuel cells and metal‐air batteries. To accelerate the reaction rate, porous electrocatalysts draw attention to obtain a higher specific surface area. However, the effect of micropores on ORR kinetics has not been understood because of the non‐uniform pore sizes, length, and tortuosity of practical electrocatalysts. In this study, we evaluate ORR activity in a micropore using platinum model electrodes with arrays of cylindrical pores with a uniform pore diameter of 1.8 nm. The model electrodes having pore lengths of 45, 100, and 380 nm are fabricated, and their ORR performances are examined by electrochemical measurements and numerical simulations in 0.1 mol dm−3 KOH aqueous solution. The intrinsic ORR activity of the micropore is successfully obtained with the electrode having a pore length of 45 nm, where oxygen transport resistance in the micropore has little effect on ORR. It is found that the intrinsic ORR activity of the micropore is higher than that of a planar Pt surface. X‐ray photoelectron spectroscopy and CO stripping voltammetry indicate a downshift of the d‐band center, which can be the origin of the high intrinsic ORR activity.
Proton transfer and regulation across chemical interfaces by small‐molecule assemblies
Authors: Nguyen Lynn , Aquino Joseline , Mao Cindy , Tavassol Hadi 
Published: January 2024

AbstractWe report on measurements and control of proton gradient across interfaces of water and dichloroethane. Such interfaces are interesting as mimics of biological membranes. We use impedance spectroscopy to quantify interfacial proton gradient and identify proton transfer modes. We quantify proton movement using reciprocal of time constant (τ−1) acquired from electrochemical impedance modeling. We show that proton gradient across interfaces of water/dichloroethane and τ−1 correlate with the aqueous phase pH, changing from ca. 1 s−1 at pH 1 to 0.2 s−1 at pH 7. τ−1 changes in the presence of proton shuttling fat‐soluble molecules. Dinitrophenol acts as a pH activated proton coupler which is active at around neutral pH and inert at pH <4. However, quinone type cofactors change the interfacial proton transport when activated by redox reactions with ferrocene type molecules, such as decamethyl ferrocence (DMFc). Quinone type cofactors show distinct features in their impedance response assigned to a proton coupled electron transfer (PCET) process, different from the uncoupled proton transfer activity of dinitrophenol. The observed PCET reaction significantly changes τ−1. We use τ−1 as a proton transport descriptor. In particular, CoQ10‐DMFc shows a τ−1 of 3.5 s−1 at pH 7, indicating how small‐molecule assemblies change proton availability.
Electrocatalytic Reduction of CO2 and H2O with Zn(II) Complexes Through Metal‐Ligand Cooperation
Authors: Norouziyanlakvan Somayeh , Berro Patrick , Rao Gyandshwar Kumar , Gabidullin Bulat , Richeson Darrin 
Published: January 2024

AbstractAir and water‐stable zinc (II) complexes of neutral pincer bis(diphenylphosphino)‐2,6‐di(amino)pyridine (“PN3P”) ligands are reported. These compounds, [Zn(κ2‐2,6‐{Ph2PNR}2(NC5H3))Br2] (R=Me, 1; R=H, 2), were shown to be capable of electrocatalytic reduction of CO2 at −2.3 V vs. Fc+/0 to selectively yield CO in mixed water/acetonitrile solutions. These complexes also electrocatalytically generate H2 from water in acetonitrile solutions, at the same potential, with Faradaic efficiencies of up to 90 %. DFT computations support a proposed mechanism involving the first reduction of 1 or 2 occurring at the PN3P ligand. Furthermore, computational analysis suggested a mechanism involving metal‐ligand cooperation of a Lewis acidic Zn(II) and a basic ligand.
Application of quasi solid electrolytes in organic based electrochromic devices: A mini review
Authors: Orimolade Benjamin O. , Draper Emily R. 
Published: January 2024

AbstractThe interest in all solid organic based electrochromic devices (ECDs) is on the increase. This is because these devices offer the applicability of electrochromic materials in products such as smart sensors, smart windows, flexible wearables and energy storage devices. The use of quasi‐solid electrolytes for the construction of these ECDs is attractive because of their ease of preparation, availability, low cost, improve electrochromic performance, good ionic conductivity and prevention of leakages in ECDs. Hence, in this review, a detailed discussion is presented on the progress in the development of semi‐solid electrolytes for ECDs fabrication. The preparation of the most common electrolytes that have been applied for organic based ECDs are summarized. Particular attention is given to efforts and strategies that have been adopted to improve the efficiency of quasi‐solid electrolytes. Importantly, knowledge gaps that warrant further research are clearly identified and recommendations for future works are suggested. This review will be very beneficial for both established and new researchers in the field of electrochromic devices and material science.
Modeling Amine Methylation in Methyl Ester Cavitand
Authors: Norjmaa Gantulga , Rebek Julius , Himo Fahmi 
Published: January 2024

AbstractMethylation of amines inside an introverted resorcinarene‐based deep methyl ester cavitand is investigated by means of molecular dynamics simulations and quantum chemical calculations. Experimentally, the cavitand has been shown to bind a number of amines and accelerate the methylation reaction by more than four orders of magnitude for some of them. Eight different amines are considered in the present study, and the geometries and energies of their binding to the cavitand are first characterized and analyzed. Next, the methyl transfer reactions are investigated and the calculated barriers are found to be in generally good agreement with experimental results. In particular, the experimentally‐observed rate acceleration in the cavitand as compared to the solution reaction is well reproduced by the calculations. The origins of this rate acceleration are analyzed by computational modifications made to the structure of the cavitand, and the role of the solvent is discussed.
Metal Influence on Cyaphide‐Azide 1,3‐Dipolar Cycloaddition Reactions: Aromaticity and Activation Strain
Authors: González‐Pinardo Daniel , Goicoechea Jose M. , Fernández Israel 
Published: January 2024

AbstractThe factors governing 1,3‐dipolar cycloaddition reactions involving C≡P‐containing compounds are computationally explored in detail using quantum chemical tools. To this end, the parent process involving tBuN3 and tBuCP is analyzed and compared to the analogous reaction involving organometallic cyaphide complexes (metal=Au, Pt, Ge, Mg), in order to understand the role of the metal fragment in such transformations. It is found that while the metal fragment does not significantly influence the aromaticity of the corresponding concerted transition states or the regioselectivity of the transformation, it may modify the reactivity of the cyaphide complexes (i. e. Ge and Mg cyaphide complexes are comparatively more reactive). The computed reactivity trends and the factors behind the regioselectivity of the cycloaddition reaction are quantitatively analyzed with the help of the activation strain model in combination with the energy decomposition analysis method.
Starfruit‐Shaped Zirconium Metal–Organic Frameworks: From 3D Intermediates to 2D Nanosheet Petals with Enhanced Catalytic Activity
Authors: Tao Cheng‐an , Wang Beibei , Zhao He , Yang Xuheng , Huang Jian , Wang Jianfang 
Published: January 2024

AbstractInvited for the cover of this issue is the group of Cheng‐an Tao, Jianfang Wang and co‐workers at the University of Defense Technology. The image depicts a novel starfruit‐shaped metal–organic framework composed of zirconium and tetra(4‐carboxyphenyl)porphine linkers and characterized by 2D nanosheet petals grown through edge‐sharing that showcases superior catalytic activity. Read the full text of the article at 10.1002/chem.202302835.
A review of just‐in‐time learning‐based soft sensor in industrial process
Authors: Sheng Weiwei , Qian Jinchuan , Song Zhihuan , Zhang Xinmin 
Published: January 2024

AbstractData‐driven soft sensing approaches have been a hot research field for decades and are increasingly used in industrial processes due to their advantages of easy implementation and high efficiency. However, nonlinear and time‐varying problems widely exist in practical industrial processes. Just‐in‐time learning (JITL) was proposed to solve these problems and has attracted great attention in practical applications. To present a comprehensive review of JITL‐based soft sensor studies and provide detailed technical guidance for new researchers, this paper introduces the recent research on JITL‐based soft sensor modelling methods in the industrial process from three aspects: similarity criterion, sample subset, and local model, which include the whole process of establishing a JITL‐based soft sensor. Moreover, the future research and innovation directions of JITL‐based soft sensors in industrial processes are also prospected.
Assembly of FAP93 at the proximal axoneme in Chlamydomonas cilia
Authors: Hwang Juyeon , Yanagisawa Haruaki , Davis Keira C. , Hunter Emily L. , Fox Laura A. , Jimenez Ariana R. , Goodwin Reagan E. , Gordon Sarah A. , Stuart Courtney D. E. , Bower Raqual , Porter Mary E. , Dutcher Susan K. , Sale Winfield S. , Lechtreck Karl F. , Alford Lea M. 
Published: January 2024

AbstractTo identify proteins specific to the proximal ciliary axoneme, we used iTRAQ to compare short (~2 μm) and full‐length (~11 μm) axonemes of Chlamydomonas. Known components of the proximal axoneme such as minor dynein heavy chains and LF5 kinase as well as the ciliary tip proteins FAP256 (CEP104) and EB1 were enriched in short axonemes whereas proteins present along the length of the axoneme were of similar abundance in both samples. The iTRAQ analysis revealed that FAP93, a protein of unknown function, and protein phosphatase 2A (PP2A) are enriched in the short axonemes. Consistently, immunoblots show enrichment of FAP93 and PP2A in short axonemes and immunofluorescence confirms the localization of FAP93 and enrichment of PP2A at the proximal axoneme. Ciliary regeneration reveals that FAP93 assembles continuously but more slowly than other axonemal structures and terminates at 1.03 μm in steady‐state axonemes. The length of FAP93 assembly correlates with ciliary length, demonstrating ciliary length‐dependent assembly of FAP93. Dikaryon rescue experiments show that FAP93 can assemble independently of IFT transport. In addition, FRAP analysis of GFP‐tagged FAP93 demonstrates that FAP93 is stably anchored in the axoneme. FAP93 may function as a scaffold for assembly of other specific proteins at the proximal axoneme.
Duchenne and Becker muscular dystrophy: Cellular mechanisms, image analysis, and computational models: A review
Authors: Escobar‐Huertas J. F. , Vaca‐González Juan Jairo , Guevara Johana María , Ramirez‐Martinez Angelica M. , Trabelsi Olfa , Garzón‐Alvarado D. A. 
Published: January 2024

AbstractThe muscle is the principal tissue that is capable to transform potential energy into kinetic energy. This process is due to the transformation of chemical energy into mechanical energy to enhance the movements and all the daily activities. However, muscular tissues can be affected by some pathologies associated with genetic alterations that affect the expression of proteins. As the muscle is a highly organized structure in which most of the signaling pathways and proteins are related to one another, pathologies may overlap. Duchenne muscular dystrophy (DMD) is one of the most severe muscle pathologies triggering degeneration and muscle necrosis. Several mathematical models have been developed to predict muscle response to different scenarios and pathologies. The aim of this review is to describe DMD and Becker muscular dystrophy in terms of cellular behavior and molecular disorders and to present an overview of the computational models implemented to understand muscle behavior with the aim of improving regenerative therapy.
Mechanochemical Hydrolysis of Polysaccharide Biomass: Scope and Mechanistic Insights
Authors: Kobayashi Hirokazu , Fukuoka Atsushi 
Published: January 2024

AbstractMechanical forces can affect chemical reactions in a way that thermal reactions cannot do, which may have a variety of applications. In biomass conversion, the selective conversion of cellulose and chitin is a grand challenge because they are the top two most abundant resources and recalcitrant materials that are insoluble in common solvents. However, recent works have clarified that mechanical forces enable the depolymerization of these polysaccharides, leading to the selective production of corresponding monomers and oligomers. This article reviews the mechanochemical hydrolysis of cellulose and chitin, particularly focusing on the scope and mechanisms to show a landscape of this research field and future subjects. We introduce the background of mechanochemistry and biomass conversion, followed by recent progress on the mechanochemical hydrolysis of the polysaccharides. Afterwards, a considerable space is devoted to the mechanistic consideration on the mechanochemical reactions.
Measuring Protein‐Protein Interactions and Quantifying Their Dissociation Constants with Mass Photometry
Authors: Kofinova Zornitsa , Karunanithy Gogulan , Ferreira Ana Sofia , Struwe Weston B. 
Published: January 2024

AbstractProtein‐protein interactions underlie most biological processes, and determining the affinity and abundance of binding partners for each interaction is often a challenging task because these interactions often involve multiple ligands and binding sites. Standard methods for determining the affinity of protein interactions often require a large amount of starting material in addition to potentially disruptive labeling or immobilization of the binding partners. Mass photometry is a bioanalytical technique that measures the mass of single biomolecules in solution, quickly and with minimal sample requirements. This article describes how mass photometry can be used to determine the mass distribution of binding partners, the complexes they form, the relative abundance of each species, and, accordingly, the dissociation constant (KD) of their interactions. © 2024 Refeyn Ltd. Current Protocols published by Wiley Periodicals LLC.Basic Protocol: Using mass photometry to measure protein‐protein binding and quantify the KD of this interaction
Tuning Carbon Dioxide Reduction Reaction Selectivity of Bi Single‐Atom Electrocatalysts with Controlled Coordination Environments
Authors: Santra Saswati , Streibel Verena , Wagner Laura I. , Cheng Ningyan , Ding Pan , Zhou Guanda , Sirotti Elise , Kisslinger Ryan , Rieth Tim , Zhang Siyuan , Sharp Ian D. 
Published: January 2024

AbstractControl over product selectivity of the electrocatalytic CO2 reduction reaction (CO2RR) is a crucial challenge for the sustainable production of carbon‐based chemical feedstocks. In this regard, single‐atom catalysts (SACs) are promising materials due to their tunable coordination environments, which could enable tailored catalytic activities and selectivities, as well as new insights into structure‐activity relationships. However, direct evidence for selectivity control via systematic tuning of the SAC coordination environment is scarce. In this work, we have synthesized two differently coordinated Bi SACs anchored to the same host material (carbon black) and characterized their CO2RR activities and selectivities. We find that oxophilic, oxygen‐coordinated Bi atoms produce HCOOH, while nitrogen‐coordinated Bi atoms generate CO. Importantly, use of the same support material assured that alternation of the coordination environment is the dominant factor for controlling the CO2RR product selectivity. Overall, this work demonstrates the structure‐activity relationship of Bi SACs, which can be utilized to establish control over CO2RR product distributions, and highlights the promise for engineering atomic coordination environments of SACs to tune reaction pathways.
ARID5B‐mediated LINC01128 epigenetically activated pyroptosis and apoptosis by promoting the formation of the BTF3/STAT3 complex in β2GPI/anti‐β2GPI‐treated monocytes
Authors: Tan Yuan , Qiao Jiao , Yang Shuo , Wang Qingchen , Liu Hongchao , Liu Qi , Feng Weimin , Yang Boxin , Li Zhongxin , Cui Liyan 
Published: January 2024

AbstractBackgroundAlterations of the trimethylation of histone 3 lysine 4 (H3K4me3) mark in monocytes are implicated in the development of autoimmune diseases. Therefore, the purpose of our study was to elucidate the role of H3K4me3‐mediated epigenetics in the pathogenesis of antiphospholipid syndrome (APS).MethodsH3K4me3 Cleavage Under Targets and Tagmentation and Assay for Transposase‐Accessible Chromatin were performed to determine the epigenetic profiles. Luciferase reporter assay, RNA immunoprecipitation, RNA pull‐down, co‐immunoprecipitation and chromatin immunoprecipitation were performed for mechanistic studies. Transmission electron microscopy and propidium iodide staining confirmed cell pyroptosis. Primary monocytes from patients with primary APS (PAPS) and healthy donors were utilised to test the levels of key molecules. A mouse model mimicked APS was constructed with beta2‐glycoprotein I (β2GPI) injection. Blood velocity was detected using murine Doppler ultrasound.ResultsH3K4me3 signal and open chromatin at the ARID5B promoter were increased in an in vitro model of APS. The epigenetic factor ARID5B directly activated LINC01128 transcription at its promoter. LINC01128 promoted the formation of the BTF3/STAT3 complex to enhance STAT3 phosphorylation. Activated STAT3 interacted with the NLRP3 promoter and subsequently stimulated pyroptosis and apoptosis. ARID5B or BTF3 depletion compensated for LINC01128‐induced pyroptosis and apoptosis by inhibiting STAT3 phosphorylation. In mice with APS, β2GPI exposure elevated the levels of key proteins of pyroptosis and apoptosis pathways in bone marrow‐derived monocytes, reduced the blood velocity of the ascending aorta, increased the thrombus size of the carotid artery, and promoted the release of interleukin (IL)‐18, IL‐1β and tissue factor. Patients with PAPS had the high‐expressed ARID5B and LINC01128, especially those with triple positivity for antiphospholipid antibodies. Moreover, there was a positive correlation between ARID5B and LINC01128 expression.ConclusionThis study indicated that ARID5B/LINC01128 was synergistically upregulated in APS, and they aggravated disease pathogenesis by enhancing the formation of the BTF3/STAT3 complex and boosting p‐STAT3‐mediated pyroptosis and apoptosis, thereby providing candidate therapeutic targets for APS.Highlights
The H3K4me3 mark and chromatin accessibility at the ARID5B promoter are increased in vitro model mimicked APS.
ARID5B‐mediated LINC01128 induces pyroptosis and apoptosis via p‐STAT3 by binding to BTF3.
ARID5B is high‐ expressed in patients with primary APS and positively correlated with LINC01128 expression.
OICR‐9429 treatment mitigates pyroptosis and related inflammation in vivo and in vitro models mimicked APS.