bluuebunny/crossref_metadata_2025_split huggingface dataset:
Elucidating the Rate‐Limiting Processes in High‐Temperature Sodium‐Metal Chloride Batteries
Authors: Landmann Daniel , Svaluto‐Ferro Enea , Heinz Meike V. F. , Schmutz Patrik , Battaglia Corsin 
Published: April 2022

AbstractSodium‐metal chloride batteries are considered a sustainable and safe alternative to lithium‐ion batteries for large‐scale stationary electricity storage, but exhibit disadvantages in rate capability. Several studies identify metal‐ion migration through the metal chloride conversion layer on the positive electrode as the rate‐limiting step, limiting charge and discharge rates in sodium‐metal chloride batteries. Here the authors present electrochemical nickel and iron chlorination with planar model electrodes in molten sodium tetrachloroaluminate electrolyte at 300 °C. It is discovered that, instead of metal‐ion migration through the metal chloride conversion layer, it is metal‐ion diffusion in sodium tetrachloroaluminate which limits chlorination of both the nickel and iron electrodes. Upon charge, chlorination of the nickel electrode proceeds via uniform oxidation of nickel and the formation of NiCl2 platelets on the surface of the electrode. In contrast, the oxidation of the iron electrodes proceeds via localized corrosion attacks, resulting in nonuniform iron oxidation and pulverization of the iron electrode. The transition from planar model electrodes to porous high‐capacity electrodes, where sodium‐ion migration along the tortuous path in the porous electrode can become rate limiting, is further discussed. These mechanistic insights are important for the design of competitive next‐generation sodium‐metal chloride batteries with improved rate performance.
Engineering Interfacial Band Bending over ZnIn2S4/SnS2 by Interface Chemical Bond for Efficient Solar‐Driven Photoelectrochemical Water Splitting
Authors: Li Shengnan , Meng Linxing , Tian Wei , Li Liang 
Published: April 2022

AbstractDeveloping a simple and effective strategy to modulate the energy band bending of heterojunction photoelectrodes is pivotal in terms of photoelectrochemical (PEC) water splitting. Herein, it is demonstrated that the introduction of the interfacial InOSn chemical bonds at the ZnIn2S4/SnS2 interface regulates the band bending of ZnIn2S4/SnS2 heterojunction photoanodes, reverses the charge transport direction, and reduces the oxygen evolution reaction (OER) overpotential. Detailed analysis indicates that the interfacial InOSn bond makes band adaptation to promote carrier separation and transfer through ultraviolet photoelectron spectrometry, hydroxyl radical production tests, and surface photovoltage measurements. Due to the special nanosheet morphology with exposed edges of the heterojunction interface, the InOSn bonds are partially exposed, which can reduce the OER overpotential and boost the surface injection efficiency according to the PEC impedance spectroscopy and density functional theory calculations. The synergistic modulation of InOSn bond yields a photocurrent of 4.57 mA cm−2 at 1.23 V (vs reversible hydrogen electrode, AM 1.5 G) and a low onset potential of −0.14 VRHE. This work provides a new solution for energy band regulation to improve the performance of heterojunction photoelectrodes for PEC water splitting.
Nonmetal (S or Se)‐Bridged Core Shell Electrodes for Promoting Electrochemical Performance
Authors: Wang Jiawei , Sun Mingshuai , Zhang Xubin , Wang Fumin , Song Jian , Zhang Weike , Wang Zheng , Li Mingzhao 
Published: April 2022

AbstractTo meet strategic applications, rational design of advanced electrochemical materials would solve the poor electrochemical performance of core‐shell electrodes caused by the weak interfacial interaction between core and shell. Herein, two novel core‐shell electrodes LCCH‐S@PBAs and LCCH‐Se@PBAs are fabricated with a nonmetal (S or Se) bridging the core and shell. Electrochemical tests show that the as‐synthesized electrodes, especially LCCH‐S@PBAs, present higher mass‐specific capacitance with 10.1 C cm−2 at 1 mA cm−2, which is much better than that of PBA‐based homologs. Experimental results and theoretical calculations show that the bridging S or Se in the interface, not only tune electronic nature of the d‐states of metal ions in core and shell, but also form ionic bonds (M1(LCCH)‐S‐M2(PBAs) and M1(LCCH)‐Se‐M2(PBAs)) which facilitates the transmission of electrons, thus making a substantial enhancement of electrochemical performance via a dynamically more favorable pathway. The comparison with LCCH‐C@PBAs, in which the rGO is connected with core and shell by Van der Waals’ forces, also suggests the outstanding role of ionic bonds for electrochemical performance. This work proves that nonmetal bridging structures make a great contribution for enhanced electrochemical performance and demonstrates the large space to modulate the nonmetal bridging status for core‐shell structures in electrochemical materials.
Urgent cytoreduction for newly diagnosed acute myeloid leukemia patients allows acquisition of pretreatment genomic data and enrollment on investigational clinical trials
Authors: Kim Kunhwa , Konopleva Marina , DiNardo Courtney D. , Borthakur Gautam , Loghavi Sanam , Tang Guilin , Daver Naval , Pemmaraju Naveen , Jabbour Elias , Rausch Caitlin R. , Yilmaz Musa , Sasaki Koji , Short Nicholas J. , Jain Nitin , Brandt Mark , Pierce Sherry , Garcia‐Manero Guillermo , Ravandi Farhad , Kantarjian Hagop , Kadia Tapan M. 
Published: April 2022

AbstractNewly diagnosed acute myeloid leukemia is often deemed a medical emergency, requiring urgent treatment. This is in contradiction with the need for accurate cytogenetic and molecular data, which is not immediately available, to select optimal therapy. We hypothesized that cytoreduction with hydroxyurea or cytarabine would enable urgent disease control and provide a bridge to clinical trial enrollment. We analyzed three prospective frontline clinical trials that allowed the use of cytoreduction before treatment initiation. Among 274 patients with a median age of 62 (range, 18–89), there was no significant difference in short‐ and long‐term outcome and safety among patients who did (CytoRed) or did not receive (NoCytoRed) cytoreduction. The overall response rate in CytoRed group was 91%, compared with 86% in NoCytoRed group (p = .264). The 30‐ and 60‐day mortality rates were 2% and 7% in CytoRed group, compared with 2% (p = .978) and 6% (p = .652) in NoCytoRed group, respectively. There was no significant difference in overall survival (OS) between in CytoRed group compared with NoCytoRed group (Hazard ratio 0.97, 95% CI 0.70–1.37, p = .879). Results were unchanged after stratification by age (< or ≥65 years) or after multivariate analyses for OS. Our data suggests that urgent cytoreduction using hydroxyurea or cytarabine is a feasible and safe approach to facilitate acquisition of complete diagnostic information prior to treatment initiation on a clinical trial.
Heterozygous PNPT1 Variants Cause Spinocerebellar Ataxia Type 25
Authors: Barbier Mathieu , Bahlo Melanie , Pennisi Alessandra , Jacoupy Maxime , Tankard Rick M. , Ewenczyk Claire , Davies Kayli C. , Lino‐Coulon Patricia , Colace Claire , Rafehi Haloom , Auger Nicolas , Ansell Brendan R. E. , van der Stelt Ivo , Howell Katherine B. , Coutelier Marie , Amor David J. , Mundwiller Emeline , Guillot‐Noël Lena , Storey Elsdon , Gardner R. J. McKinlay , Wallis Mathew J. , Brusco Alfredo , Corti Olga , Rötig Agnès , Leventer Richard J. , Brice Alexis , Delatycki Martin B. , Stevanin Giovanni , Lockhart Paul J. , Durr Alexandra 
Published: April 2022

ObjectiveDominant spinocerebellar ataxias (SCA) are characterized by genetic heterogeneity. Some mapped and named loci remain without a causal gene identified. Here we applied next generation sequencing (NGS) to uncover the genetic etiology of the SCA25 locus.MethodsWhole‐exome and whole‐genome sequencing were performed in families linked to SCA25, including the French family in which the SCA25 locus was originally mapped. Whole exome sequence data were interrogated in a cohort of 796 ataxia patients of unknown etiology.ResultsThe SCA25 phenotype spans a slowly evolving sensory and cerebellar ataxia, in most cases attributed to ganglionopathy. A pathogenic variant causing exon skipping was identified in the gene encoding Polyribonucleotide Nucleotidyltransferase PNPase 1 (PNPT1) located in the SCA25 linkage interval. A second splice variant in PNPT1 was detected in a large Australian family with a dominant ataxia also mapping to SCA25. An additional nonsense variant was detected in an unrelated individual with ataxia. Both nonsense and splice heterozygous variants result in premature stop codons, all located in the S1‐domain of PNPase. In addition, an elevated type I interferon response was observed in blood from all affected heterozygous carriers tested. PNPase notably prevents the abnormal accumulation of double‐stranded mtRNAs in the mitochondria and leakage into the cytoplasm, associated with triggering a type I interferon response.InterpretationThis study identifies PNPT1 as a new SCA gene, responsible for SCA25, and highlights biological links between alterations of mtRNA trafficking, interferonopathies and ataxia. ANN NEUROL 2022;92:122–137
Sterically Demanding Flexible Phosphoric Acids for Constructing Efficient and Multi‐Purpose Asymmetric Organocatalysts
Authors: Scharinger Fabian , Pálvölgyi Ádám Márk , Weisz Melanie , Weil Matthias , Stanetty Christian , Schnürch Michael , Bica‐Schröder Katharina 
Published: April 2022

AbstractHerein, we present a novel approach for various asymmetric transformations of cyclic enones. The combination of readily accessible chiral diamines and sterically demanding flexible phosphoric acids resulted in a simple and highly tunable catalyst framework. The careful optimization of the catalyst components led to the identification of a particularly powerful and multi‐purpose organocatalyst, which was successfully applied for asymmetric epoxidations, aziridinations, aza‐Michael‐initiated cyclizations, as well as for a novel Robinson‐like Michael‐initiated ring closure/aldol cyclization. High catalytic activities and excellent stereocontrol was observed for all four reaction types, indicating the excellent versatility of our catalytic system. Furthermore, a simple change in the diamine's configuration provided easy access to both product antipodes in all cases.
Promoted catalytic potential in sulfides oxidation and biological screening of green Pd (II) and Co (II) complexes of salicylidene isatin hydrazone ligand
Authors: Adam Mohamed Shaker S. , Makhlouf Mohamed M. , Mohamed Mamdouh A. , Desoky M. Mohamad Ahmed 
Published: April 2022

Mononucleating complexes of isatin hydrazone sodium sulfonate ligand (HLn) with palladium (II) and cobalt (II) ions: The complexes were synthesized within 1:1 and 2:1 molar ratio of HLn with Pd2+and Co2+ion in PdLn and Co (Ln)2, respectively. The catalytic reactivity of both complexes was examined in the oxidation of sulfides (diphenyl sulfide, dps, and methylphenyl sulfide, mps) using hydrogen peroxide under aerobic conditions. Oxoproducts, dipheylsufoxide, dpo, and methyl phenyl sulfoxide, mpo, are the chemoselective products with detection of large amounts of the unselective further oxidation products of dioxoproducts (dipheylsufone, dpn, and methylphenyl sulfone, mpn). The homogenous catalyst of Co (Ln)2revealed more efficient action compared to that of PdLn depending on the high electrochemical reversible potential of the central metal ion in the catalytic reaction within the electron and/or oxygen transfer system.Exploring the importance of the M2+ion in the coordinated ligand, the bio‐reactivity of HLn, PdLn, and Co (Ln)2was illustrated within some commonly well‐known bacteria and fungi strains. Additionally, they were involved as anticancer reagents against some human cancer cell lines in vitro. Both metal complexes presented high inhibited action versus the growth of the studied microorganism and cancer. The interaction effect of Pd2+and Co2+ions in their pincer complexes was tested with calf thymus DNA spectroscopically and via the viscosity changes.
Cardioprotective effect of silymarin nanoemulsion on 5‐fluorouracil‐induced cardiotoxicity in rats
Authors: Safarpour Soheila , Safarpour Samaneh , Moghadamnia Ali A. , Kazemi Sohrab , Ebrahimpour Anahita , Shirafkan Fatemeh , Mansoori Razieh , Golchoobian Ravieh 
Published: April 2022

Abstract5‐Fluorouracil (5‐FU)‐associated cardiotoxicity has been ranked as the second most common cause of cardiotoxicity induced by chemotherapeutic drugs after anthracyclines. In the present study, we investigated the protective impacts of silymarin (SIL) and silymarin nanoemulsion (SLN) against cardiotoxicity caused by 5‐FU in rats. Thirty male Wistar rats were divided into six groups as follows: control, SLN (5 mg/kg), SIL (5 mg/kg), 5‐FU + SLN, 5‐FU + SIL, and 5‐FU. Cardiotoxicity was induced by a single intraperitoneal injection of 5‐FU (100 mg/kg). The control group received an intraperitoneal injection (ip) of normal saline and the treatment groups received ips of SIL and SLN for 14 days. 5‐FU resulted in significant cardiotoxicity, represented by an increase in the serum levels of cardiac enzymes and malondialdehyde, as well as cyclooxygenase‐2 (COX‐2) and tumor necrosis factor‐α (TNF‐α) expression, and histopathological degeneration. 5‐FU treatment also induced a decrease in body weight, total antioxidant capacity (TAC), and catalase values. Evaluation of electrocardiographic parameters in 5‐FU‐treated rats showed increases in the ST segment, QRS duration, and RR interval. Treatment with SIL and SLN reduced oxidative stress, cardiac enzymes, histopathological degeneration, and the expression of TNF‐α and COX‐2 in cardiac tissue. Our results demonstrated that treatment with SIL and SLN significantly improved cardiotoxicity induced by 5‐FU in rats.
Unravelling Charge Carrier Mobility in d0‐Metal‐based Spinels
Authors: Dillenz Manuel , Sotoudeh Mohsen , Glaser Clarissa , Janek Jürgen , Groß Axel , Euchner Holger 
Published: April 2022

AbstractEnabling high Mg ion mobility, spinel‐type materials are promising candidates for cathode or solid electrolyte applications. To elucidate the factors governing the observed high mobility of multivalent ions, periodic DFT calculations of various charge carriers (A=Li, Na, K, Mg, Ca, Zn and Al) in the ASc2S4 and ASc2Se4 spinel compounds were performed, resulting in the identification of a Brønsted‐Evans‐Polanyi‐type scaling relation for the migration barriers of the various charge carriers. Combining this scaling relation with the derivation of a descriptor, solely based on easily accessible observables, constitutes a conceptual framework to investigate ion mobility in d0‐metal‐based spinel chalcogenides with significantly reduced computational effort. This approach was exemplarily verified for various d0‐metal‐based spinel chalcogenide compounds AB2X4 (B=Sc, Y, Ga, In, Er and Tm; X=O, S and Se) and led to the identification of d0‐metal‐based CaB2O4 spinels as promising compounds possibly enabling high Ca ion mobility.
Chemiluminescence assay for kanamycin based on target recycling strategy
Authors: Yu Liyuan , Zhang Xiaoqian , Jin Daobin , Lou Fangxu , Zhao Jikuan , Hun Xu 
Published: April 2022

AbstractA chemiluminescence (CL) sensing strategy for kanamycin residue detection in fish samples was established based on luminol‐functionalized gold nanoparticles as CL nanoprobe materials combined with DNA hairpin structure and carboxyl‐modified magnetic beads. Relying on nucleic acid amplification technology, the system can successfully realize the recycling of kanamycin, so that the biosensor can release a large number of luminol‐functionalized gold nanoparticles with excellent CL performance even at a low residual levels of kanamycin. The biosensor strategy showed a good linear relationship with kanamycin in the range 0.09–130 nM, the detection limit was as low as 0.04 nM. This method proves the excellent performance of the sensing strategy and provides a low‐cost and high‐sensitivity CL analysis strategy for the detection of kanamycin and even other antibiotics.
Development of a versatile, uniform, and stable initiator layer by the functionalization of a polydopamine/polyethyleneimine film
Authors: Jeong Jaehoon , Bisht Himani , Ryu Sanghyun , Hong Daewha 
Published: April 2022

AbstractPolymer brush surfaces have various interesting applications; however, to facilitate their formation on surfaces, an initiator ad‐layer is required in advance. In this study, we developed a versatile initiator film that simultaneously meets the standards of uniformity and stability using a simple surface coating strategy. In brief, co‐deposition of dopamine and polyethyleneimine formed a polydopamine/polyethyleneimine (pDP) film, which was then acylated with external α‐bromoisobutyryl bromide. The resultant initiator film, pDP functionalized with initiator (pDPI), showed a homogeneous surface morphology and resisted harsh solvent conditions. The subsequent surface‐initiated polymerization from the developed pDPI initiator layer also formed a thick polymer brush.
Impact of thresholding on the consistency and sensitivity of diffusion MRI‐based brain networks in patients with cerebral small vessel disease
Authors: De Brito Robalo Bruno M. , Vlegels Naomi , Leemans Alexander , Reijmer Yael D. , Biessels Geert Jan 
Published: April 2022

AbstractIntroductionThresholding of low‐weight connections of diffusion MRI‐based brain networks has been proposed to remove false‐positive connections. It has been previously established that this yields more reproducible scan–rescan network architecture in healthy subjects. In patients with brain disease, network measures are applied to assess inter‐individual variation and changes over time. Our aim was to investigate whether thresholding also achieves improved consistency in network architecture in patients, while maintaining sensitivity to disease effects for these applications.MethodsWe applied fixed‐density and absolute thresholding on brain networks in patients with cerebral small vessel disease (SVD, n = 86; ≈24 months follow‐up), as a clinically relevant exemplar condition. In parallel, we applied the same methods in healthy young subjects (n = 44; scan–rescan interval ≈4 months) as a frame of reference. Consistency of network architecture was assessed with dice similarity of edges and intraclass correlation coefficient (ICC) of edge‐weights and hub‐scores. Sensitivity to disease effects in patients was assessed by evaluating interindividual variation, changes over time, and differences between those with high and low white matter hyperintensity burden, using correlation analyses and mixed ANOVA.ResultsCompared to unthresholded networks, both thresholding methods generated more consistent architecture over time in patients (unthresholded: dice = .70; ICC: .70–.78; thresholded: dice = .77; ICC: .73–.83). However, absolute thresholding created fragmented nodes. Similar observations were made in the reference group. Regarding sensitivity to disease effects in patients, fixed‐density thresholds that were optimal in terms of consistency (densities: .10–.30) preserved interindividual variation in global efficiency and node strength as well as the sensitivity to detect effects of time and group. Absolute thresholding produced larger fluctuations of interindividual variation.ConclusionsOur results indicate that thresholding of low‐weight connections, particularly when using fixed‐density thresholding, results in more consistent network architecture in patients with longer rescan intervals, while preserving sensitivity to disease effects.
Transfer of continuous manufacturing process principles for mAb production in a GMP environment: A step in the transition from batch to continuous
Authors: Botelho Ferreira Kevin , Benlegrimet Asma , Diane Gabriel , Pasquier Victor , Guillot Raphael , De Poli Marc , Chappuis Loïc , Vishwanathan Nandita , Souquet Jonathan , Broly Hervé , Bielser Jean‐Marc 
Published: April 2022

AbstractImplementation of continuous in lieu of batch upstream processing (USP) and downstream process (DSP) for the production of recombinant therapeutic protein is a significant paradigm change. The present report describes how the first kilograms of monoclonal antibody were produced with equipment originally designed for batch operations while using continuous manufacturing processes and principles. Project timelines for the delivery of clinical material have driven this ambition and helped the transition. Nevertheless, because of equipment availability, a tradeoff between the envisaged continuous downstream process (cDSP) operations and the ones described in this article had to be taken. A total of 2.1 kg of monoclonal antibody were produced in two GMP runs for clinical trials. For USP, a 200‐L single‐use pilot scale bioreactor was upgraded to enable perfusion operation. DSP steps were designed to be easily transferable to cDSP for later clinical or commercial productions. An in‐line conditioning buffer preparation strategy was tested in a discontinuous way to prove its efficiency and the purification cascade was structured in parallel to the continuous collection of antibody‐containing cell culture supernatant. This strategy will avoid any process change when later moving to the continuous equipment that is currently under qualification. Alignment between small‐scale references runs and the GMP runs in terms of productivity and quality confirmed that the presented approach was valid. Thus, we demonstrate that existing fed‐batch infrastructure can be adapted to continuous manufacturing without significant additional investments. Such approach is useful to evaluate next‐generation manufacturing processes before making large investments.
Four‐Component Ugi Reaction for Optical Chirality Sensing and Surface Nanoengineering of Chiral Self‐Assemblies
Authors: Liu Bingyu , Gao Junjie , Hao Aiyou , Xing Pengyao 
Published: April 2022

AbstractUsing green chemistry to control chirality at hierarchical levels as well as chiroptical activities endows with new opportunities to the development of multiple functions. Here, the four‐component Ugi reaction is introduced for the general and precise optical chirality sensing of amines as well as the surface nanoengineering of chiral soft self‐assemblies. To overcome the relatively weak Cotton effects, direct synthesis of a folded peptide structure on a rotatable ferrocene core with axial chirality was accomplished from chiral amine, 1,1’‐ferrocenyl dicarboxylic acid, formaldehyde and isocyanide. Enhanced Cotton effects benefiting from the folded structure allow for the precise and quantitative sensing of natural and synthetic chiral amines covering alkyl, aromatic amines and amino acid derivatives. In addition, aqueous reaction enables the modification of amine‐bearing dye to microfibers self‐assembled from π‐conjugated amino acids. Surface dye‐modification via Ugi reaction barely changes the pristine morphology, showing non‐invasive properties in contrast to dye staining, which is applicable in soft nano/microarchitectures from self‐assembly. This work which combines the four‐component Ugi reaction to enable precise ee% detection and surface nanoengineering of soft chiral assemblies sheds light on the advanced application of green chemistry to chirality science.