bluuebunny/crossref_metadata_2025_split huggingface dataset:
High‐Performance Lithium Metal Batteries Enabled by a Fluorinated Cyclic Ether with a Low Reduction Potential
Authors: Wu Min , Wang Zeyi , Zhang Weiran , Jayawardana Chamithri , Li Yue , Chen Fu , Nan Bo , Lucht Brett L. , Wang Chunsheng 
Published: January 2023

AbstractElectrolyte engineering is crucial for developing high‐performance lithium metal batteries (LMB). Here, we synthesized two cosolvents methyl bis(fluorosulfonyl)imide (MFSI) and 3,3,4,4‐tetrafluorotetrahydrofuran (TFF) with significantly different reduction potentials and add them into LiFSI‐DME electrolytes. The LiFSI/TFF‐DME electrolyte gave an average Li Coulombic efficiency (CE) of 99.41 % over 200 cycles, while the average Li CEs for MFSI‐based electrolyte is only 98.62 %. Additionally, the TFF‐based electrolytes exhibited a more reversible performance than the state‐of‐the‐art fluorinated 1,4‐dimethoxylbutane electrolyte in both Li||Cu half‐cell and anode‐free Cu||LiNi0.8Mn0.1Co0.1O2 full cell. More importantly, the decomposition product from bis(fluorosulfonyl)imide anion could react with ether solvent, which destroyed the SEI, thus decreasing cell performance. These key discoveries provide new insights into the rational design of electrolyte solvents and cosolvents for LMB.
Lead(II) Formate in Rembrandt's Night Watch: Detection and Distribution from the Macro‐ to the Micro‐scale
Authors: Gonzalez Victor , Fazlic Ida , Cotte Marine , Vanmeert Frederik , Gestels Arthur , De Meyer Steven , Broers Fréderique , Hermans Joen , van Loon Annelies , Janssens Koen , Noble Petria , Keune Katrien 
Published: January 2023

AbstractThe Night Watch, painted in 1642 and on view in the Rijksmuseum in Amsterdam, is considered Rembrandt's most famous work. X‐ray powder diffraction (XRPD) mapping at multiple length scales revealed the unusual presence of lead(II) formate, Pb(HCOO)2, in several areas of the painting. Until now, this compound was never reported in historical oil paints. In order to get insights into this phenomenon, one possible chemical pathway was explored thanks to the preparation and micro‐analysis of model oil paint media prepared by heating linseed oil and lead(II) oxide (PbO) drier as described in 17th century recipes. Synchrotron radiation based micro‐XRPD (SR‐μ‐XRPD) and infrared microscopy were combined to identify and map at the micro‐scale various neo‐formed lead‐based compounds in these model samples. Both lead(II) formate and lead(II) formate hydroxide Pb(HCOO)(OH) were detected and mapped, providing new clues regarding the reactivity of lead driers in oil matrices in historical paintings.
A New PETase from the Human Saliva Metagenome and Its Functional Modification via Genetic Code Expansion in Bacteria
Authors: White Mirren F. M. , Wallace Stephen 
Published: January 2023

AbstractThe discovery and engineering of new plastic degrading enzymes is an important challenge in chemical biotechnology to enable transition to a more sustainable and circular plastics economy. This field has so far yielded a range of enzymes and microbial pathways for the recycling and valorization of plastic waste. New research from Uttamapinant et al. reports the discovery of a novel polyethylene terephthalate (PET) hydrolase from the human saliva metagenome that displays improved properties and catalytic performance over previously characterized PET hydrolases (PETases). The authors also demonstrate the site‐specific incorporation of a photocaged unnatural amino acid, 2,3‐diaminopropionic acid (DAP), which upon photodecaging enables covalent binding of DAP to the PET surface. Thus, this work highlights metagenomic datasets as an untapped source of new PET degrading enzymes and the chemical modification of PETases via genetic code expansion, enabling new biotechnologies for the circular plastics economy.
Active Separation of Water Isotopologues by Local Molecular Motion in Microporous Framework Materials
Authors: Krause Simon 
Published: January 2023

AbstractAround 10–15 % of the world's energy consumption is accounted for by the separation and purification of chemicals. Among them is the enrichment and separation of isotopologues which are an essential aspect of modern chemistry. In their recent work, Su et al. demonstrate the separation of water isotopologues by responsive dynamic pore windows in a microporous coordination polymer with unprecedented selectivity based on an elegant mechanism.
Promoting Surface Electric Conductivity for High‐Rate LiCoO2
Authors: Xu Shenyang , Tan Xinghua , Ding Wangyang , Ren Wenju , Zhao Qi , Huang Weiyuan , Liu Jiajie , Qi Rui , Zhang Yongxin , Yang Jiachao , Zuo Changjian , Ji Haocheng , Ren Hengyu , Cao Bo , Xue Haoyu , Gao Zhihai , Yi Haocong , Zhao Wenguang , Xiao Yinguo , Zhao Qinghe , Zhang Mingjian , Pan Feng 
Published: January 2023

AbstractThe cathode materials work as the host framework for both Li+ diffusion and electron transport in Li‐ion batteries. The Li+ diffusion property is always the research focus, while the electron transport property is less studied. Herein, we propose a unique strategy to elevate the rate performance through promoting the surface electric conductivity. Specifically, a disordered rock‐salt phase was coherently constructed at the surface of LiCoO2, promoting the surface electric conductivity by over one magnitude. It increased the effective voltage (Veff) imposed in the bulk, thus driving more Li+ extraction/insertion and making LiCoO2 exhibit superior rate capability (154 mAh g−1 at 10 C), and excellent cycling performance (93 % after 1000 cycles at 10 C). The universality of this strategy was confirmed by another surface design and a simulation. Our findings provide a new angle for developing high‐rate cathode materials by tuning the surface electron transport property.
Reduction of Sulfur Dioxide to Sulfur Monoxide by Ferrous Porphyrin**
Authors: Bhattacharya Aishik , Kumar Nath Arnab , Ghatak Arnab , Nayek Abhijit , Dinda Souvik , Saha Rajat , Ghosh Dey Somdatta , Dey Abhishek 
Published: January 2023

AbstractThe reduction of SO2 to fixed forms of sulfur can address the growing concerns regarding its detrimental effect on health and the environment as well as enable its valorization into valuable chemicals. The naturally occurring heme enzyme sulfite reductase (SiR) is known to reduce SO2 to H2S and is an integral part of the global sulfur cycle. However, its action has not yet been mimicked in artificial systems outside of the protein matrix even after several decades of structural elucidation of the enzyme. While the coordination of SO2 to transition metals is documented, its reduction using molecular catalysts has remained elusive. Herein reduction of SO2 by iron(II) tetraphenylporphyrin is demonstrated. A combination of spectroscopic data backed up by theoretical calculations indicate that FeIITPP reduces SO2 by 2e−/2H+ to form an intermediate [FeIII−SO]+ species, also proposed for SiR, which releases SO. The SO obtained from the chemical reduction of SO2 could be evidenced in the form of a cheletropic adduct of butadiene resulting in an organic sulfoxide.
Revealing the Formation Mechanism and Optimizing the Synthesis Conditions of Layered Double Hydroxides for the Oxygen Evolution Reaction
Authors: Chen Zongkun , Wang Xingkun , Han Zhongkang , Zhang Siyuan , Pollastri Simone , Fan Qiqi , Qu Zhengyao , Sarker Debalaya , Scheu Christina , Huang Minghua , Cölfen Helmut 
Published: January 2023

AbstractLayered double hydroxides (LDHs), whose formation is strongly related to OH− concentration, have attracted significant interest in various fields. However, the effect of the real‐time change of OH− concentration on LDHs’ formation has not been fully explored due to the unsuitability of the existing synthesis methods for in situ characterization. Here, the deliberately designed combination of NH3 gas diffusion and in situ pH measurement provides a solution to the above problem. The obtained results revealed the formation mechanism and also guided us to synthesize a library of LDHs with the desired attributes in water at room temperature without using any additives. After evaluating their oxygen evolution reaction performance, we found that FeNi‐LDH with a Fe/Ni ratio of 25/75 exhibits one of the best performances so far reported.
SASSY NMR: Simultaneous Solid and Solution Spectroscopy
Authors: Ghosh Biswas Rajshree , Soong Ronald , Jenne Amy , Bastawrous Monica , Simpson Myrna J. , Simpson André J. 
Published: January 2023

AbstractSynergism between different phases gives rise to chemical, biological or environmental reactivity, thus it is increasingly important to study samples intact. Here, SASSY (SimultAneous Solid and Solution spectroscopY) is introduced to simultaneously observe (and differentiate) all phases in multiphase samples using standard, solid‐state NMR equipment. When monitoring processes, the traditional approach of studying solids and liquids sequentially, can lead to information in the non‐observed phase being missed. SASSY solves this by observing the full range of materials, from crystalline solids, through gels, to pure liquids, at full sensitivity in every scan. Results are identical to running separate 13C CP‐MAS solid‐state and 13C solution‐state experiments back‐to‐back but requires only a fraction of the spectrometer time. After its introduction, SASSY is applied to process monitoring and finally to detect all phases in a living freshwater shrimp. SASSY is simple to implement and thus should find application across all areas of research.
Direct Probe of Electrochemical Pseudocapacitive pH Jump at a Graphene Electrode**
Authors: Wang Yongkang , Seki Takakazu , Liu Xuan , Yu Xiaoqing , Yu Chun‐Chieh , Domke Katrin F. , Hunger Johannes , Koper Marc T. M. , Chen Yunfei , Nagata Yuki , Bonn Mischa 
Published: January 2023

AbstractMolecular‐level insight into interfacial water at a buried electrode interface is essential in electrochemistry, but spectroscopic probing of the interface remains challenging. Here, using surface‐specific heterodyne‐detected sum‐frequency generation (HD‐SFG) spectroscopy, we directly access the interfacial water in contact with the graphene electrode supported on calcium fluoride (CaF2). We find phase transition‐like variations of the HD‐SFG spectra vs. applied potentials, which arises not from the charging/discharging of graphene but from the charging/discharging of the CaF2 substrate through the pseudocapacitive process. The potential‐dependent spectra are nearly identical to the pH‐dependent spectra, evidencing that the pseudocapacitive behavior is associated with a substantial local pH change induced by water dissociation between the CaF2 and graphene. Our work evidences the local molecular‐level effects of pseudocapacitive charging at an electrode/aqueous electrolyte interface.
Gaseous Nitrogen Oxides Catholyte for Rechargeable Redox Flow Batteries
Authors: Zhang Weiyao , Yang Xin , Zhang Shiyu 
Published: January 2023

AbstractThere is a strong interest in finding highly soluble redox compounds to improve the energy density of redox flow batteries (RFBs). However, the performance of electrolytes is often negatively influenced by high solute concentration. Herein, we designed a high‐potential (0.5 V vs. Ag/Ag+) catholyte for RFBs, where the charged and discharged species are both gaseous nitrogen oxides (NOx). These species can be liberated from the liquid electrolyte and stored in a separate gas container, allowing scale‐up of storage capacity without increasing the concentration and volume of the electrolyte. The oxidation of NO in the presence of NO3− affords N2O3, and the reduction of N2O3 regenerates NO and NO3−, together affording the electrochemical reaction: NO3−+3 NO⇌2 N2O3+e− with a low mass/charge ratio of 152 grams per mole of stored electron. A proof‐of‐concept NOx symmetric H‐cell shows 200 stable cycles over 400 hours with >97 % Coulombic efficiency and negligible capacity decay.
Split‐flow layouts of supercritical CO2 Brayton cycle for coal‐fired power plant considering the flue gas residual heat utilization
Authors: Wang Limin , Wang Chang'an , Bai Wengang , Jin Liyan , Yang Xiaohu , Che Defu 
Published: January 2023

AbstractThe utilization of residual energy of high‐temperature flue gas at the tail of coal‐fired boilers has attracted widespread attention in recent years. The thermal performances of the boiler and system in different split‐flow layouts still need to be analyzed and compared in detail. Thermodynamic models for four different splitting layouts of supercritical carbon dioxide (S‐CO2) Brayton cycles tailored for coal‐fired power plant are built and validated. By performing the process simulations, the effects of splitting ratios on the system thermal performance are comparatively analyzed when the secondary split point and the confluence point are set at different positions. The maximum system efficiency of the two‐split layout with a secondary splitting point at the inlet of the cold side of the high‐temperature recuperator (HTR) can be obtained within a range of secondary split ratio. The maximal and minimal boundaries are determined by the exhaust flue gas temperature and the heat capacity match in the recuperators, respectively. The mass flow rate of the cold stream in the low‐temperature recuperator (LTR) should be kept unchanged by constraining the sum of primary and secondary split ratios, the constant to prevent the cycle efficiency from decreasing dramatically, if the splitting layout with the split point at the outlet of the main compressor (MC) is used. The two‐splitting layout with a secondary splitting point at the inlet of the cold side of the HTR has the best performance by comparing the system efficiencies of different layouts. If there are any improved coupling approaches of the S‐CO2 Brayton cycle and boiler, this paper can provide the reference for the selections of the split ratios.
Effect of glass fiber loading and reprocessing cycles on the mechanical, thermal, and morphological properties of isotactic polypropylene composites
Authors: Achukwu Emmanuel O. , Owen Macaulay M. , Danladi Abdullahi , Dauda Benjamin M. , Romli Ahmad Z. , Ishiaku Umaru S. , Akil Hazizan Md 
Published: January 2023

AbstractIn this study, a preliminary finding is carried out to obtain the optimum E‐glass fiber content in polypropylene (PP) plastic products using loadings of 5, 10, 20, 30, and 40 wt%. The formulation with the optimum loading of 10 wt% glass fiber was reprocessed 10 times via extrusion and compression molding techniques to simulate actual recycling and impacts on service life properties such as mechanical, toughness, chemical, thermal, composition, and morphology. In the result, mechanical properties were lost after each reprocessing without effect on the chemical properties and elemental compositions. The thermal studies showed a decrease in degradation temperatures with the onset degradation temperature (TOnset) for the one‐time reprocessed PP recorded at 336.93°C with a maximum rate of weight loss (TMax) at 427.68°C which further reduced to 259.90°C (TMax of 388.47°C) after 10 extrusion run showing one‐step decomposition patterns. This work provides that glass fiber‐reinforced plastics should not be reprocessed beyond 3 times except when refreshed with the addition of virgin PP to make up for the lost property. This will be very useful for manufacturers who want to simultaneously save costs (retain profit margin) and maintain the environment.
A novel GSTe2 involved in metamorphosis by regulating 20E signal pathway in Tribolium castaneum
Authors: Kim KumChol , Song XiaoWen , Yu RunNan , Zhang YongLei , Gao Han , Wang SuiSui , Li Bin 
Published: January 2023

AbstractInsect‐specific epsilon glutathion S‐transferases (GSTs) are a class of multifunctional GST superfamily, which play important roles in detoxification of xenobiotic substances. Most research on GSTs has focused on insecticide detoxification and resistance, with little research on other physiological functions. Here, we identified and cloned the novel GSTe2 from Tribolium castaneum (TcGSTe2). Recombinant TcGSTe2 protein was successfully overexpressed in Escherichia coli and purified with affinity purification, which had high ability to catalyze the conjugation of reduced glutathione with 1‐chloro‐2,4‐dinitrobenzene (CDNB). The expression level of TcGSTe2 was significantly decreased after exposure with four insecticides, phoxim, λ‐cyhalothrin, dichlorvos, and carbofuran, in larval stage. Interestingly, RNA interference knockdown of TcGSTe2 caused metamorphosis deficiency in larval and pupal stages by inhibiting the 20E signal pathway. Furthermore, exogenous 20E injection partially rescued this metamorphosis deficiency and also increased the expression levels of 20E downstream response genes. This study illustrated TcGSTe2 plays an important role at metamorphosis beside the insecticide detoxification and resistance in T. castaneum.
Anticryptococcal activity and mechanistic studies of short amphipathic peptides
Authors: Aaghaz Shams , Sharma Komal , Maurya Indresh K. , Rudramurthy Shivaprakash M. , Singh Shreya , Kumar Vinod , Tikoo Kulbhushan , Jain Rahul 
Published: January 2023

AbstractCryptococcus neoformans, an opportunistic fungal pathogen, causes cryptococcosis in immunocompromised persons. A series of modified L‐histidines‐containing peptides are synthesized that exhibit promising activity against C. neoformans. Analog 11d [L‐His(2‐adamantyl)‐L‐Trp‐L‐His(2‐phenyl)‐OMe] produced potency with an IC50 of 3.02 µg/ml (MIC = 5.49 µg/ml). This peptide is noncytotoxic and nonhaemolytic at the MIC and displays synergistic effects with amphotericin B at subinhibitory concentration. Mechanistic investigation of 11d using microscopic tools indicates cell wall and membrane disruption of C. neoformans, while flow cytometric analysis confirms cell death by apoptosis. This study indicates that 11d exhibits antifungal potential and acts via the rapid onset of action.
A deep learning framework for analyzing cloud characteristics of aggregated convection using cloud‐resolving model simulations
Authors: Chen Yi‐Chang , Wu Chien‐Ming , Chen Wei‐Ting 
Published: January 2023

AbstractThis study introduces a framework to extract the high‐dimensional nonlinear relationships among state variables for aggregated convection. The prototype of such a framework is developed that applies the convolutional neural network models (CNN models) to retrieve the cloud characteristics from cloud‐resolving model (CRM) simulations. CNN model prediction factors are hidden in the high dimensional weighted parameters in each neural network layer. Therefore, we can dig out relevant physics processes by iterating the CNN models' training process and eliminating the features with the physics explanation we can provide at a given stage. Within a few iterations, explainable nonlinear relationships among variables can be provided. We identified that the averaged cloud water path (CWP), the maximum value of CWP in each cloud, and the cloud coverage rate are essential for identifying aggregation. Furthermore, by analyzing the encoded channels of the CNN model, we found a strong relationship between aggregation, cloud peripherals, and fractal dimensions. The results suggest that the important nonlinear cloud characteristics for identifying the aggregation can be captured with the proper adjustment and limitation of the input data to the CNN models. Our framework provides a possibility that we can explore the high dimensional relationship between the physics process with the assistance of the CNN model.
Guanidine‐Functionalized Fluorescent sp2 Carbon‐Conjugated Covalent Organic Framework for Sensing and Capture of Pd(II) and Cr(VI) Ions
Authors: Das Sribash , Hazarika Gunanka , Manna Debasis 
Published: January 2023

AbstractPalladium is a key element in fuel cells, electronic industries, and organic catalysis. At the same time, chromium is essential in leather, electroplating, and metallurgical industries. However, their unpremeditated leakage into aquatic systems has caused human health and environmental apprehensions. Herein, we reported the development of an sp2 carbon‐conjugated fluorescent covalent organic framework with a guanidine moiety (sp2c‐gCOF) that showed excellent thermal and chemical stability. The sp2c‐gCOF showed effective sensing, capture, and recovery/removal of Pd(II) and Cr(VI) ions, which could be due to the highly accessible pore walls decorated with guanidine moieties. The fluorescent sp2c‐gCOF showed higher selectivity for Pd(II) and Cr(VI) ions, with an ultra‐low detection limit of 2.7 and 3.2 nM, respectively. The analysis of the adsorption properties with a pseudo‐second‐order kinetic model showed that sp2c‐gCOF could successfully and selectively remove both Pd(II) and Cr(VI) ions from aqueous solutions. The polymer also showed excellent capture efficacy even after seven consecutive adsorption‐desorption cycles. Hence, this study reveals the potential of fluorescent sp2c‐gCOF for detecting, removing, and recovering valuable metals and hazardous ions from wastewater, which would be useful for economic benefit, environmental safety, human health, and sustainability. The post‐synthetic modification of sp2c‐COF with suitable functionalities could also be useful for sensing and extracting other water pollutants and valuable materials from an aqueous system.
A Molecular Insight into the Dehydration of a Metal–Organic Framework and its Impact on the CO2 Capture
Authors: Lian Jian Xiang , Siahrostami Samira 
Published: January 2023

AbstractMetal–organic frameworks (MOFs) are porous material formed by the self‐assembly of metallic ligands and organic linkers. They are a good candidate for CO2 gas capture because they have large surface areas and the metal or linker can be tuned to improve CO2 uptake. In the quest for water and acid stable MOFs, a phosphonate‐based organic linker has recently been designed by Glavinovic et al. (Chem. Eur. J. 2022, 28, e202200874). By combining ionic calcium nodes, water and methanol molecules, they formed a microporous network, CALF‐37. This network has been shown to be robust and can maintain its pore shape even in absence of water molecules or by the inclusion of gas molecules, such as CO2. The network can be heated to release the water and methanol molecules and form a dehydrated MOF, which retains its shape with the imprinted pore within. Herein, we perform molecular dynamics (MD) simulations in order to provide insight into the CO2 capture and sequestration ability of the CALF‐37. We model the dehydration of the inactivated MOF (HCALF‐37) in the absence and in the presence of methanol molecules by progressively withdrawing water molecules from the MOF networks. We determine the crystal structure of the intermediate states from HCALF‐37 to CALF‐37 and shed light on the critical role of water molecules in the mediation of metal‐linker bonds. Our calculations also reveal that the favorable interactions between the CO2 molecules and the aromatic core of the linkers and metallic ions are responsible for the efficient sequestration of the gas in the CALF‐37.