bluuebunny/crossref_metadata_2025_split huggingface dataset:
Rechargeable Dual‐Carbon Batteries: A Sustainable Battery Technology
Authors: Tebyetekerwa Mike , Duignan Timothy T. , Xu Zhen , Song Zhao Xiu 
Published: September 2022

AbstractDual‐carbon batteries (DCBs) with both electrodes composed of carbon materials are currently at the forefront of industrial consideration. This is due to their low cost, safety, sustainability, fast charging, and simpler electrochemistry than lithium and other post‐lithium metal‐ion batteries. This article provides an overview of the past lessons on rechargeable DCBs and their future promises. In brief, it introduces the reader to DCBs as one of the most promising energy storage solutions for balancing sustainability, cost and performance, their history, electrochemistry and associated charge storage mechanisms. Then, the past lessons with respect to their ion intercalation are provided. These include DCB mechanisms during different anion/cation intercalation in layered carbons and their intercalation compounds and electrode structures versus electrochemical performance. This is followed by a description of the current issues affecting DCBs like capacity fading and self‐discharging, electrolyte instability, low energy densities and electrode exfoliation, together with their remedies. Finally, an insightful perspective proposing key areas requiring significant research efforts toward the success of DCBs is provided responsible for accelerating the commercialization and adoption of DCBs toward a sustainable and circular economy. This article is a simplified guide to understanding the current state and future research needed to develop sustainable DCBs.
Comparing various sulfur sources for soybean grown on an acid Oxisol in Brazil
Authors: Francisco Eros A. B. , Chien Sen H. , Ono Fabio , Gearhart Maria Mercedes , Cruz Antonio P. 
Published: September 2022

AbstractA greenhouse experiment and a 2‐yr field trial were conducted to compare various S sources for soybean [Glycine max (L.) Merr.] grown on an acid Oxisol in Brazil. In the greenhouse, the sources included ammonium sulfate (AMS), monoammonium phosphate with a S ratio = 50:50 of AMS/elemental S (ES) – (AMS + ES), and ES + bentonite containing 90% ES. All sources were surface‐applied at 0, 5, 10, 20, and 40 mg S kg–1. Separately, all S sources were incorporated into the soil at 20 mg S kg–1. Yield and S uptake by the grain followed the order AMS = MAP – (AMS + ES) > ES + bentonite. No significant differences in grain yield and S uptake were observed between surface application and incorporation, except those of surface application were greater than those of incorporation with MAP – (AMS + ES). In the field trial, single superphosphate (SSP) and phosphogypsum (PG) were also included. All sources were surface‐applied at 30 kg S ha–1 yr–1. Additionally, AMS was split‐applied in equal amounts at planting and R1 stage. In both years, grain yield and S uptake followed the order AMS = MAP – (AMS + ES) = PG = SSP > ES + bentonite = control. The highest S uptake was observed with split‐application of AMS in the first but not the second year. The benefit of a split application of AMS over a one‐time application for S uptake in the first year was probably caused by reduced SO4–S leaching.
Proyecto Titi: Teaching children that cotton‐top tamarins (Saguinus oedipus) are not appropriate pets
Authors: Savage Anne , Díaz Leysthen , Pasion Johana , Torregroza Katherine , Guillen Rosamira 
Published: September 2022

AbstractCotton‐top tamarins (Saguinus oedipus) are a critically endangered species found only in Colombia. Their survival is threatened by extensive habitat destruction and the illegal pet trade. Because many people in Colombia have a low level of awareness of cotton‐top tamarins and even less understanding of the impacts that the illegal pet trade has on the species and its long‐term survival, Proyecto Tití has developed a series of programs for children in rural elementary schools that introduce children to cotton‐top tamarins. This study examines Proyecto Titi's efforts to reduce the desire to have a cotton‐top tamarin as a pet with outcomes focused specifically on (1) creating an emotional connection between people and cotton‐top tamarins, (2) identifying the feelings and understanding the challenges that cotton‐top tamarin face when they are kept as pets, and (3) empowering students to make positive choices to help cotton‐top tamarins. Both TITI KIDS and TITIRITIANDO programs helped students to (1) increase their knowledge of cotton‐top tamarins, (2) understand the damage that the pet trade has on individual animals and the long‐term survival of cotton‐top tamarins and (3) provide practical actions that they can engage in to protect cotton‐top tamarins for the future. Our hope is that students from our programs become advocates for conservation in their communities and assist in the long‐term conservation activities to protect cotton‐top tamarins in Colombia.
The Linkage of Sulfonimidoyl Fluorides and Unactivated Alkenes via Hydrosulfonimidoylation
Authors: Zeng Daming , Ma Yinhao , Deng Wei‐Ping , Wang Ming , Jiang Xuefeng 
Published: September 2022

AbstractSulfur(VI) fluoride cleavage and exchanging linkage, a new generation of linkage chemistry, exhibits enormous potential for combining a range of functional molecules in an increasing number of fields. Herein, we established a metal‐free linkage of unactivated alkenes and sulfonimidoyl fluorides via hydrosulfonimidoylation to construct sulfoximines within minutes. An intermolecular hydride transfer process is the key step, and it occurs via overlap of the LUMO in the sulfonimidoyl cation and HOMO in the unactivated alkene, which was confirmed via control experiments with deuterated compounds. DFT calculations further demonstrated the concerted process involving formation of the S−C(sp3) bond and hydride transfer. Remarkably, abundant natural products and pharmaceuticals with multiple heteroatoms and sensitive functional groups have been subjected to the current linkage reaction to achieve various sulfoximine linkages, furnishing the basis for drug discovery and drug conjugation.
Dramatically Enhanced Reactivity of Fullerenes and Tetrazine towards the Inverse‐Electron‐Demand Diels–Alder Reaction inside a Porous Porphyrinic Cage
Authors: Dhamija Avinash , Gunnam Anilkumar , Yu Xiujun , Lee Hochan , Hwang In‐Chul , Ho Ko Young , Kim Kimoon 
Published: September 2022

AbstractInverse‐electron‐demand Diels–Alder reaction (IEDDA) between fullerenes and 1,2,4,5‐tetrazine generally requires harsh conditions and long reaction times due to their strong electron‐accepting nature. Herein, we report a dramatic enhancement in the reactivity of the fullerenes (C60/C70)‐tetrazine reaction inside a porous Zn‐porphyrinic cage (Zn‐PB) under sustainable conditions by installing a tetrazine‐based axle (LA) via metal‐ligand coordination bond, which modulates the cavity size to facilitate the encapsulation of fullerenes. Upon encapsulation, the close proximity of fullerenes and the tetrazine group of LA dramatically increase their reactivity towards the IEDDA reaction to form fullerene‐tetrazine adducts. Furthermore, the C60‐tetrazine adduct is rearranged upon hydration to a bent‐shaped C60‐pyrazoline adduct that can be released from the Zn‐PB cavity in the presence of excess LA, thus catalyzing the formation of C60‐pyrazoline adduct inside Zn‐PB without product inhibition.
Memory Effect in Thermoresponsive Proline‐based Polymers
Authors: Badreldin Mostafa , Le Scouarnec Rosanna , Lecommandoux Sebastien , Harrisson Simon , Bonduelle Colin 
Published: September 2022

AbstractWe report that synthetic polymers consisting of L‐proline monomer units exhibit temperature‐driven aggregation in water with unprecedented hysteresis. This protein‐like behavior is robust and governed by the chirality of the proline units. It paves the way to new processes, driven by either temperature or ionic strength changes, such as a simple “with memory” thermometer.
Target‐Triggered Formation of Artificial Enzymes on Filamentous Phage for Ultrasensitive Direct Detection of Circulating miRNA Biomarkers in Clinical Samples
Authors: Zeng Yan , Yue Hui , Cao Binrui , Li Yan , Yang Mingying , Mao Chuanbin 
Published: September 2022

AbstractIntegrating artificial enzymes onto nanostructures target‐ and site‐specifically is still a challenge. Here we show that target miRNAs trigger the formation of DNAzyme site‐specifically at the tip of filamentous phage for detecting miRNA biomarkers. Through an antibody‐modified oligonucleotide, the tip of the phage with magnetic nanoparticles on the sidewall captures a target miRNA, inducing the formation of DNAzyme that extends from the phage tip through a hybridization chain reaction. After magnetic separation, the resultant complex catalyzes a colorimetric reaction with the signal correlated to target concentrations, leading to the quantification of miRNAs with a detection limit of 5.0 fM, about 103 folds lower than the phage‐free approach. Our approach can differentiate miRNA mutants and quantify miRNA in human plasma, tumor cells, and tissues with high sensitivity, suggesting that the target‐triggered integration of enzymes and phages holds promise for searching for new catalysts.
Intramolecular Thiol‐ and Selenol‐Assisted Delivery of Hydrogen Sulfide
Authors: Hu Qiwei , Suarez S. Israel , Hankins Rynne A. , Lukesh John C. 
Published: September 2022

AbstractArylthioamides have been frequently employed to assess the chemical biology and pharmacology of hydrogen sulfide (H2S). From this class of donors, however, extremely low H2S releasing efficiencies have been reported and proper mechanistic studies have been omitted. Consequently, millimolar concentrations of arylthioamides are required to liberate just trace amounts of H2S, and via an unidentified mechanistic pathway, which obfuscates the interpretation of any biological activity that stems from their use. Herein, we report that H2S release from this valuable class of donors can be markedly enhanced through intramolecular nucleophilic assistance. Specifically, we demonstrate that both disulfide‐ and diselenide‐linked thioamides are responsive to biologically relevant concentrations of glutathione and release two molar equivalents of H2S via an intramolecular cyclization that significantly augments their rate and efficiency of sulfide delivery in both buffer and live human cells.
Discovery of a Thioxanthone–TfOH Complex as a Photoredox Catalyst for Hydrogenation of Alkenes Using p‐Xylene as both Electron and Hydrogen Sources
Authors: Kang Wen‐Jie , Li Bo , Duan Meng , Pan Guangxing , Sun Weiqiang , Ding Aishun , Zhang Yanbin , Houk K. N. , Guo Hao 
Published: September 2022

AbstractHydrogenation of alkenes is one of the most fundamental transformations in organic synthesis, and widely used in the petrochemical, pharmaceutical, and food industries. Although numerous hydrogenation methods have been developed, novel types of catalysis with new mechanisms and new hydrogen sources are still desirable. Thioxanthone (TX) is widely used in energy‐transfer photoreactions, but rarely in photoredox processes. Herein we show that a catalytic amount of TfOH as a co‐catalyst can tune the properties of TX to make it a photoredox catalyst with highly enhanced oxidative capability in the hydrogenation of carbonylated alkenes with the cheap petroleum industrial product p‐xylene serving as the hydrogen source. Deuterium can also be introduced by this method by using D2O as the D source. To the best of our knowledge, this is the first example of using p‐xylene as a hydrogen source.
Ag22 Nanoclusters with Thermally Activated Delayed Fluorescence Protected by Ag/Cyanurate/Phosphine Metallamacrocyclic Monolayers through In‐Situ Ligand Transesterification
Authors: Yuan Zhi‐Rui , Wang Zhi , Han Bao‐Liang , Zhang Cheng‐Kai , Zhang Shan‐Shan , Zhu Zhen‐Yu , Yu Jiu‐Hong , Li Tian‐Duo , Li Ying‐Zhou , Tung Chen‐Ho , Sun Di 
Published: September 2022

AbstractThe composition of protection monolayer exerts great influence on the molecular and electronic structures of atomically precise monolayer protected metal nanoclusters. Four isostructural Ag/cyanurate/phosphine metallamacrocyclic monolayer protected Ag22 nanoclusters are synthesized by kinetically controlled in‐situ ligand formation‐driven strategy. These eight‐electron superatomic silver nanoclusters feature an unprecedented interfacial bonding structure with diverse E‐Ag (E=O/N/P/Ag) interactions between the Ag13 core and metallamacrocyclic monolayer, and displays thermally activated delayed fluorescence (TADF), benefiting from their distinct donor‐acceptor type electronic structures. This work not only unmasks a new core‐shell interface involving cyanurate ligand but also underlines the significance of high‐electron‐affinity N‐heterocyclic ligand in synthesizing TADF metal nanoclusters. This is the first mixed valence Ag0/I nanocluster with TADF characteristic.
Spatial Well‐defined Bimetallic Two‐Dimensional Polymers with Single‐Layer Thickness for Electrocatalytic Oxygen Evolution Reaction
Authors: Fa Dejuan , Tao Yanhong , Pan Xin , Wang Dingjia , Feng Guangyuan , Yuan Jiangyan , Luo Qingqing , Song Yaru , Gao Xuejiao J. , Yang Ling , Lei Shengbin , Hu Wenping 
Published: September 2022

AbstractInnovative bimetallic materials provide more possibilities for further improving the performance of oxygen evolution reaction (OER) electrocatalysts. However, it is still a great challenge to rationally design bimetallic catalysts because there is not a practical way to decouple the factors influencing the intrinsic activity of active sites from others, thus hindering in‐depth understanding of the mechanism. Herein, we provide a rational design of bimetallic Ni, Co two‐dimensional polymer model OER catalyst. The well‐defined architecture, identical density of active sites and monolayer characteristic allow us to decouple the intrinsic activity of active sites from other factors. The results confirmed that the relative position and local coordination environment has significant effect on the synergistic effect of the bimetallic centres. The highest electrocatalytic activity with the turnover frequency value up to 26.19 s−1 was achieved at the overpotential of 500 mV.
Single‐Atom Catalysts on Covalent Triazine Frameworks: at the Crossroad between Homogeneous and Heterogeneous Catalysis
Authors: Iemhoff Andree , Vennewald Maurice , Palkovits Regina 
Published: September 2022

AbstractHeterogeneous single‐site and single‐atom catalysts potentially enable combining the high catalytic activity and selectivity of molecular catalysts with the easy continuous operation and recycling of solid catalysts. In recent years, covalent triazine frameworks (CTFs) found increasing attention as support materials for particulate and isolated metal species. Bearing a high fraction of nitrogen sites, they allow coordinating molecular metal species and stabilizing particulate metal species, respectively. Dependent on synthesis method and pretreatment of CTFs, materials resembling well‐defined highly crosslinked polymers or materials comparable to structurally ill‐defined nitrogen‐containing carbons result. Accordingly, CTFs serve as model systems elucidating the interaction of single‐site, single‐atom and particulate metal species with such supports. Factors influencing the transition between molecular and particulate systems are discussed to allow deriving tailored catalyst systems.
Ruthenium(II)/Imidazolidine Carboxylic Acid‐Catalyzed C−H Alkylation for Central and Axial Double Enantio‐Induction
Authors: Li Yanjun , Liou Yan‐Cheng , Oliveira João C. A. , Ackermann Lutz 
Published: September 2022

AbstractEnantioselective C−H activation has surfaced as a transformative toolbox for the efficient assembly of chiral molecules. However, despite of major advances in rhodium and palladium catalysis, ruthenium(II)‐catalyzed enantioselective C−H activation has thus far largely proven elusive. In contrast, we herein report on a ruthenium(II)‐catalyzed highly regio‐, diastereo‐ and enantioselective C−H alkylation. The key to success was represented by the identification of novel C2‐symmetric chiral imidazolidine carboxylic acids (CICAs), which are easily accessible in a one‐pot fashion, as highly effective chiral ligands. This ruthenium/CICA system enabled the efficient installation of central and axial chirality, and featured excellent branched to linear ratios with generally >20 : 1 dr and up to 98 : 2 er. Mechanistic studies by experiment and computation were carried out to understand the catalyst mode of action.
Strengthening low‐NOx combustion with flue gas recirculation in a 600‐MWe down‐fired furnace
Authors: Liu Sheng , Kuang Min , Qi Shengchen , Zhao Xiaojuan 
Published: September 2022

AbstractFor a down‐fired furnace using a cascade‐arch‐firing low‐NOx and high‐burnout configuration (CLHC, which includes flue gas recirculation and is taken as a strengthened low‐NOx combustion solution), the gas/particle flow, coal combustion, and NOx emissions were investigated at various flue gas recirculation (FGR) ratios of 5%, 10%, 15%, and 20% (labeled as settings of FGR = 5%, 10%, 15%, and 20%, respectively). The aim was to disclose the FGR role on the strengthened low‐NOx combustion characteristics and meanwhile obtain an available FGR ratio. With increasing FGR, although the downward flame penetration increased continuously, the large local high‐temperature zone favoring combustion in the furnace shrunk. Increasing FGR lowered gas temperatures and strengthened the reductive atmosphere in the downstream of the reburning zone to restrain combustion and meanwhile weaken the NO‐reduction effect of reburning. Trends of the final performance indexes with the FGR ratio showed that NOx production increased continuously, while burnout loss generally undergone an increase‐to‐decrease trend. In view of the above findings and the gained optimal furnace performance (i.e., NOx emissions of 530 mg/m3 at 6% O2 accompanied by carbon content in fly ash at 5.28%), low FGR levels such as FGR = 5% with a hot‐air dilution in FGR should be preferred for the CLHC furnace where FGR is used to deliver the fine pulverized‐coal particles for reburning. In comparison to an advanced in‐service low‐NOx art, the CLHC reduced further NOx production by 41.4% while remained a high burnout achievement except a limited increase in CO emission.
A likelihood ratio test for completed sampling in population size estimation studies
Authors: Farcomeni Alessio 
Published: September 2022

AbstractWe propose a likelihood ratio test to assess that sampling has been completed in closed population size estimation studies. More precisely, we assess if the expected number of subjects that have never been sampled is below a user‐specified threshold. The likelihood ratio test statistic has a nonstandard distribution under the null hypothesis. Critical values can be easily approximated and tabulated, and they do not depend on model specification. We illustrate in a simulation study and three real data examples, one of which involves ascertainment bias of amyotrophic lateral sclerosis in Gulf War veterans.
Energetically unfavorable protein angles: Exploration of a conserved dihedral angle in triosephosphate isomerase
Authors: Allen Patrick W. , Cook Jordan A. , Colquhoun Anh N. , Sorin Eric J. , Tapavicza Enrico , Schwans Jason P. 
Published: September 2022

AbstractOver the past 3.5 billion years of evolution, enzymes have adopted a myriad of conformations to suit life on earth. However, torsional angles of proteins have settled into limited zones of energetically favorable dihedrals observed in Ramachandran plots. Areas outside said zones are believed to be disallowed to all amino acids, except glycine, due to steric hindrance. Triosephosphate isomerase (TIM), a homodimer with a catalytic rate approaching the diffusion limit, contains an active site lysine residue (K13) with dihedrals within the fourth quadrant (Φ = +51/Ψ = −143). Both the amino acid and the dihedral angles are conserved across all species of TIM and known crystal structures regardless of ligand. Only crystal structures of the engineered monomeric version (1MSS) show accepted β‐sheet dihedral values of Φ = ‐135/Ψ = +170 but experiments show a 1000‐fold loss in activity. Based on these results, we hypothesized that adopting the unfavorable torsion angle for K13 contributes to catalysis. Using both, computational and experimental approaches, four residues that interact with K13 (N11, M14, E97, and Q64) were mutated to alanine. In silico molecular dynamics (MD) simulations were performed using 2JK2 unliganded human TIM as a starting structure. Ramachandran plots, containing K13 dihedral values reveal full or partial loss of disallowed zone angles. N11A showed no detectable catalytic activity and lost the unfavorable K13 dihedral angles across four separate force fields during simulation while all other mutants plus wild type retained activity and retained the conserved K13 dihedral angles.
Molecular genetic associations between a prominent serotonin transporter gene polymorphism (5‐HTTLPR/rs25531) and individual differences in tendencies toward autistic traits and generalized internet use disorder in China and Germany
Authors: Zhang YingYing , Yao Shuxia , Schmitt Helena , Becker Benjamin , Kendrick Keith M. , Montag Christian 
Published: September 2022

AbstractBackgroundThe serotonin transporter polymorphism 5‐HTTLPR is an extensively investigated genetic marker of autistic traits or autism spectrum disorder, and recently has also been studied in the realm of internet use disorder (IUD), yet the findings remain controversial. Therefore, the present study aimed to explore associations between 5‐HTTLPR (also including SNP rs25531) and autistic traits/IUD tendencies and to assess whether the relationship between autistic traits and IUD tendencies varies by this genetic marker in participants from China and Germany.MethodsA total of 540 Chinese and 563 German subjects were genotyped for 5‐HTTLPR/rs25531 and completed the Adult Autism Spectrum Quotient questionnaire and the short version of the Internet Addiction Test.ResultsCarriers of the low expressing S'S’ genotype (S, LG) showed significantly higher levels of autistic traits than the high expressing allele (e.g. LA) carriers in both samples. There was no significant effect of 5‐HTTLPR/rs25531 on IUD either in the Chinese or Germany samples, whereas positive correlations between autistic traits and IUD varied by 5‐HTTLPR/rs25531 genotypes and also differed between Chinese and German samples. In the Chinese sample, positive correlations were mainly driven by S'S’ and S'L' carriers, while they were mainly determined by S'L’ and L'L' carriers in the German sample. Further analyses revealed that the associations between autistic traits and IUD tended in parts to be more strongly pronounced in the complete German sample compared to the complete Chinese sample, and also varied depending on 5‐HTTLPR/rs25531 genotypes (in S'S’ carriers: China > Germany; in S'L’ and L'L’ carriers: China < Germany; both in terms of more positive associations).ConclusionsOur findings suggest carriers of low expressing alleles (S, LG) are more likely to show higher autistic traits in both Chinese and German samples. Furthermore, the present work shows that both 5‐HTTLPR/rs25531 and cultural differences might be of relevance to understand associations between autistic traits and IUD tendencies, but this needs to be further backed up.