bluuebunny/crossref_metadata_2025_split huggingface dataset:
Vibrational Spectroscopy Insight into the Electrode|electrolyte Interface/Interphase in Lithium Batteries
Authors: Weiling Matthias , Pfeiffer Felix , Baghernejad Masoud 
Published: October 2022

AbstractLithium‐ion batteries (LIBs) have transformed the use of mobile electronics and storage technologies. Alongside advances in materials, an in‐depth understanding of the interfacial phenomena and interphase formation mechanisms in LIBs is crucial. Interphases are widely recognized as the most important and the least understood components of LIBs and play a direct role in defining cell performance, cyclability, and safety. This article presents a review of recent developments in vibrational spectroscopy techniques of Raman, infrared, and sum‐frequency generation spectroscopies to probe the fundamental aspects of interphases on the anode and cathode of LIBs. First the vibrational spectroscopy techniques and their relevant technical considerations for interphase characterization are briefly introduced. In the next step, the latest studies on the fundamental properties, composition, and structure of interphases employing vibrational spectroscopy techniques are presented. This review focuses on in situ/operando investigations; however, post‐mortem studies are also discussed briefly.
Fast Ion Conduction Nanofiber Matrix Composite Electrolyte for Dendrite‐Free Solid‐State Sodium‐Ion Batteries with Wide Temperature Operation
Authors: Wu Shuanglin , Yu Zhifeng , Nie Xiaolin , Wang Zhihui , Huang Fenglin , Wei Qufu 
Published: October 2022

AbstractSodium‐ion batteries (SIBs) based on solid‐state electrolytes (SSEs), although safe for high temperatures, are less capable of transferring ions at ambient temperatures, let alone at low temperatures. This work offers a simple and scalable technique to construct a nanofiber matrix composite electrolyte with boosting Na+ transport and interfacial compatibility for SIBs. Benefitting from the salt dissociation and selective cation conduction synergistic effect of the acylamino, carbonyl, and ester groups in the low‐cost copolymer synthesized from 2‐(methacryloyloxy)ethyl acetoacetate and N,N′‐methylenebisacrylamide, a facilitating of Na+ transport at extreme temperatures is realized. Besides, flexible flame retardance ceramic SiO2 nanofibers greatly enhance high‐temperature safety. The ultrathin functional AlF3 layer generated by binder‐free magnetron sputtering suppresses the dendrites, eliminating the interfacial issues between the electrolyte and anode, which is proved by 5500 h of ultrasteady plating/stripping. Superior ionic conductivity of 0.153 mS cm−1 at −30 °C implies fast Na+ transport, which is further evidenced by molecular dynamics simulations. Rate performance at 0.05–10 C from −30 to 130 °C further demonstrates the excellent electrochemical performance of the electrolyte. This work provides encouraging guidance for high‐safety SSEs with rapid Na+ conduction for SIBs operating at extra‐wide temperatures.
Adaptability and stability of corn hybrids for silage via genotype and genotype × environment interaction biplot
Authors: Crevelari Jocarla Ambrosim , Souza Yure Pequeno de , Santos Juliana Saltires , Ambrósio Moisés , Gonçalves Vivane Mirian Lanhellas , Pereira Messias Gonzaga 
Published: October 2022

AbstractThe occurrence of the genotype × environment (G × E) interaction is one of the main factors that hinder the selection of adapted and stable genotypes. The genotype and G × E interaction (GGE) biplot methodology is an efficient process to detect corn (Zea mays L.) hybrids for silage and, consequently, will help in the recommendation of new and more stable hybrids in different environments in breeding programs. In this sense, this study aimed to evaluate and select corn hybrids for silage that simultaneously combine high yield and stability in different environments in the state of Rio de Janeiro, Brazil, via GGE biplot. Eleven corn hybrids, eight precommercial topcrosses and three commercial controls, were evaluated at three sites (Campos dos Goytacazes, Cambuci, and Itaocara, Rio de Janeiro) during two seasons: the 2017–2018 season and 2018–2018 off‐season. The experiments were designed in completely randomized blocks with three replications. Individual and joint analyses of variance were performed and, after detecting significant interaction between genotype and environment, the adaptability and phenotypic stability of corn genotypes for silage were analyzed using the GGE biplot methodology. The GGE biplot analysis was efficient in interpreting the data and represented 83.68% of the total variation in the first two principal components. The use of the GGE biplot method allowed the recommendation of more productive, stable, and responsive hybrids for the state of Rio de Janeiro. The hybrid UENF MS2208 is indicated for cultivation in the state of Rio de Janeiro for combining high green biomass yield and stability.
Impacts of trans‐anal tube placement in patients with sigmoid colon cancer: Risk verification analysis using inverse probability weighting analysis
Authors: Tominaga Tetsuro , Nonaka Takashi , Shiraishi Toshio , Yano Hiroshi , Sato Shuntaro , Fukuda Akiko , Hisanaga Makoto , Hashimoto Shintaro , Sawai Terumitsu , Nagayasu Takeshi 
Published: October 2022

AbstractPurposeAnastomotic leakage (AL) is a serious postoperative complication that affects short‐ and long‐term outcomes. The use of a trans‐anal drainage tube (TDT) is reported to prevent AL in rectal cancer patients, but its value in sigmoid colon cancer patients is unknown.MethodsAdmitted to the study were 379 patients who underwent surgery for sigmoid colon cancer between 2016 and 2020. Patients were divided into two groups according to the placement (n = 197) or nonplacement of a TDT (n = 182). To determine the factors affecting the association between TDT placement and AL, we estimated average treatment effects by stratifying each factor using the inverse probability of treatment weighting method. The association between prognosis and AL was evaluated in each identified factor.ResultsFactors associated with postsurgical insertion of a TDT were advanced age, male sex, high body mass index (BMI), poor performance status, and presence of comorbidities. TDT placement was associated with a significantly lower AL in male patients (odds ratio [OR], 0.22; 95% confidence interval [CI], 0.07–0.73; P = .013) and for BMI ≥ 25 kg/m2 (OR, 0.13; 95% CI, 0.02–0.65; P = .013). In addition, there was a significant association of AL with poor prognosis in patients with BMI ≥ 25 kg/m2 (P = .043), age > 75 y (P = .021), and pathological node‐positive disease (P = .015).ConclusionSigmoid colon cancer patients with BMI ≥ 25 kg/m2 are the most appropriate candidates for postoperative TDT insertion, in terms of reduced incidence of AL and improved prognosis.
Enhanced compatibility and selectivity in mixed matrix membranes for propylene/propane separation
Authors: He Rongrong , Cong Shenzhen , Peng Donglai , Zhang Yatao , Shan Meixia , Zhu Junyong , Wang Jing , Gascon Jorge 
Published: October 2022

AbstractMixed matrix membranes (MMMs) based on metal–organic framework (MOF) have great promising application in separation of gas mixtures. However, achieving a good interfacial compatibility between polymer and MOF is not straightforward. In this work, focusing on one of the most challenging olefin/paraffin separations: propylene/propane (C3H6/C3H8), we demonstrate that modification of the MOF filler via dopamine polymerization using a double solvent approach strongly improves interfacial compatibility. The resulting membranes show an outstanding separation performance and long‐term stability with propylene permeability nearly 90 Barrer and propylene/propane selectivity close to 75. We anticipate that similar MOF modification strategies may help solve the problem of interface defects in the manufacture of MMMs and be extended to other porous fillers.
Dynamic densification of wet granular materials in continuous dense flows under gravity
Authors: Wang Chao , Yang Yao , Huang Zhengliang , Sun Jingyuan , Wang Jingdai , Yang Yongrong , Du Bing 
Published: October 2022

AbstractThe continuous granular flow under gravity extensively exists in chemical processes, and the dynamic behaviors of granular flow under different gas–liquid environments are investigated by synchronous slide‐type high‐speed photography. Results show that a hexagonal arrangement is observed after three‐stage densification in wet granular flow, while these structures are almost absent in the dry system. Further analysis shows that under the induction of liquid, the special cavity collapse in stage І is the pre‐condition of granular densification, and the subsequent densification in stage ІІ for the first time gives the experimental proof for the hypothesis that energy barriers exist and depend on the friction characteristics, and the cage effect in stage ІІІ provides a guarantee for the formation of a hexagonal contact network. Besides, three‐stage densification in the three‐phase system mainly occurs in the region with low gas and liquid velocities (G* < 0.716 and L* < 0.023 in this work).
Fixation of Carbon Dioxide with Functionalized Ionic Liquids
Authors: Yang Jiawen , Chen Peibo , Pan Yingming , Liang Ying 
Published: October 2022

AbstractFunctional ionic liquids are formed by introducing functional groups into traditional ionic liquids. They have both good absorption capacity and excellent catalytic activity for carbon dioxide, and therefore are widely used in the chemical conversion of carbon dioxide. This paper focuses on the application of amino‐functionalized ionic liquids, carboxyl‐functionalized ionic liquids, hydroxyl‐functionalized ionic liquids and various other functionalized ionic liquids in carbon dioxide conversion. Their possible role in chemical carbon fixation is discussed by analyzing several typical chemical carbon fixation mechanisms.
Inflammatory endotype of odontogenic sinusitis
Authors: Craig John R. , Dai Xiangguo , Bellemore Stacey , Woodcroft Kimberley J. , Wilson Carl , Keller Christian , Bobbitt Kevin R. , Ramesh Mayur 
Published: October 2022

AbstractBackgroundOdontogenic sinusitis (ODS) is distinct from non‐odontogenic rhinosinusitis with regard to clinical features as well as diagnostic and therapeutic approaches. While numerous studies have explored immune profiles of chronic rhinosinusitis, very few studies have explored the inflammatory endotype of ODS.MethodsOdontogenic sinusitis was diagnosed by confirming infectious sinusitis adjacent to infectious maxillary odontogenic pathology. Maxillary sinus cultures and mucosal biopsies were obtained during endoscopic endonasal surgery in ODS and control patients. Controls were patients undergoing endoscopic skull base surgery with no sinus disease. Specimens were snap frozen in liquid nitrogen and stored at −80°C. Analysis was performed using a multiplex assay to measure Th‐1 (TNFα, IFNγ, IL‐2,12,18), Th‐2 (IL‐4,5,9,13), Th‐17 (IL‐17A,17F,22), and innate (CCL5,CXCL9,CXCL10, IL‐6,8,10,12,23,27) immune pathways. Groups were compared via independent sample t‐tests; if assumptions were violated, nonparametric Wilcoxon ranked sum tests were performed.ResultsSpecimens from 22 ODS patients were compared to nine controls. ODS mucosal tissue was sampled in the setting of the following dental pathologies: post‐dental extraction (n = 15), untreated apical periodontitis (n = 2), apical periodontitis after root canal therapy (n = 2), and maxillary sinus bone grafting with or without dental implantation (n = 3). The following cytokines were significantly elevated in ODS compared to controls: IFNγ, TNFα, IL‐6, 8, 10, 27, and CXCL9. IL‐17 levels were similar in both ODS and controls. Therefore, ODS demonstrated heightened innate and Th1 immune activity.ConclusionODS demonstrated both innate immune and Th1 inflammatory endotypes. Further studies are needed to explore ODS immunopathobiology and its potential impact on ODS management.
High‐Performance Inverted Perovskite Solar Devices Enabled by a Polyfullerene Electron Transporting Material
Authors: Yin Junli , Shi Xiaoyu , Wang Lingyuan , Yan He , Chen Shangshang 
Published: October 2022

AbstractElectron transporting materials (ETMs) play vital roles in determining the efficiency and stability of inverted perovskite solar cells. The widely used PCBM is prone to undesirable aggregation and migration in a cell, thus impairing device stability. In this work, we develop a new type of ETMs by polymerizing C60 fullerene with an aromantic linker unit. The resultant polyfullerene (PFBS‐C12) not only maintains the good optoelectronic properties of fullerenes, but also can address the aforementioned aggregation problem of PCBM. The polyfullerene‐based blade‐coated cells exhibit a high efficiency of 23.2 % and good device stability that maintain 96 % of initial efficiency after >1300‐hour light soaking. An aperture efficiency of 18.9 % is also achieved on a 53.6‐cm2 perovskite mini‐module. This work provides a new strategy for designing ETMs that retain the key figure‐of‐merits of conventional fullerene molecules and enable more stable perovskite solar devices simultaneously.
Atom‐Economical Synthesis of Dimethyl Carbonate from CO2: Engineering Reactive Frustrated Lewis Pairs on Ceria with Vacancy Clusters
Authors: Li Lei , Liu Wenxiu , Chen Runhua , Shang Shu , Zhang Xiaodong , Wang Hui , Zhang Hongjun , Ye Bangjiao , Xie Yi 
Published: October 2022

AbstractThe chemical conversion of CO2to long‐chain chemicals is considered as a highly attractive method to produce value‐added organics, while the underlying reaction mechanism remains unclear. By constructing surface vacancy‐cluster‐mediated solid frustrated Lewis pairs (FLPs), the 100 % atom‐economical, efficient chemical conversion of CO2to dimethyl carbonate (DMC) was realized. By taking CeO2as a model system, we illustrate that FLP sites can efficiently accelerate the coupling and conversion of key intermediates. As demonstrated, CeO2with rich FLP sites shows improved reaction activity and achieves a high yield of DMC up to 15.3 mmol g−1. In addition, by means of synchrotron radiation in situ diffuse reflectance infrared Fourier‐transform spectroscopy, combined with density functional theory calculations, the reaction mechanism on the FLP site was investigated systematically and in‐depth, providing pioneering insights into the underlying pathway for CO2chemical conversion to long‐chain chemicals.
Enzymatic C4‐Epimerization of UDP‐Glucuronic Acid: Precisely Steered Rotation of a Transient 4‐Keto Intermediate for an Inverted Reaction without Decarboxylation
Authors: Borg Annika J. E. , Esquivias Oriol , Coines Joan , Rovira Carme , Nidetzky Bernd 
Published: October 2022

AbstractUDP‐glucuronic acid (UDP‐GlcA) 4‐epimerase illustrates an important problem regarding enzyme catalysis: balancing conformational flexibility with precise positioning. The enzyme coordinates the C4‐oxidation of the substrate by NAD+ and rotation of a decarboxylation‐prone β‐keto acid intermediate in the active site, enabling stereoinverting reduction of the keto group by NADH. We reveal the elusive rotational landscape of the 4‐keto intermediate. Distortion of the sugar ring into boat conformations induces torsional mobility in the enzyme's binding pocket. The rotational endpoints show that the 4‐keto sugar has an undistorted 4C1 chair conformation. The equatorially placed carboxylate group disfavors decarboxylation of the 4‐keto sugar. Epimerase variants lead to decarboxylation upon removal of the binding interactions with the carboxylate group in the opposite rotational isomer of the substrate. Substitutions R185A/D convert the epimerase into UDP‐xylose synthases that decarboxylate UDP‐GlcA in stereospecific, configuration‐retaining reactions.
Access to N−CF3 Formamides by Reduction of N−CF3 Carbamoyl Fluorides
Authors: Zivkovic Filip G. , D.‐T. Nielsen Christian , Schoenebeck Franziska 
Published: October 2022

AbstractThe departure into unknown chemical space is essential for the discovery of new properties and function. We herein report the first synthetic access to N‐trifluoromethylated formamides. The method involves the reduction of bench‐stable NCF3 carbamoyl fluorides and is characterized by operational simplicity and mildness, tolerating a broad range of functional groups as well as stereocenters. The newly made N−CF3 formamide motif proved to be highly robust and compatible with diverse chemical transformations, underscoring its potential as building block in complex functional molecules.
Darobactins Exhibiting Superior Antibiotic Activity by Cryo‐EM Structure Guided Biosynthetic Engineering**
Authors: Seyfert Carsten E. , Porten Christoph , Yuan Biao , Deckarm Selina , Panter Fabian , Bader Chantal D. , Coetzee Janetta , Deschner Felix , Tehrani Kamaleddin H. M. E. , Higgins Paul G. , Seifert Harald , Marlovits Thomas C. , Herrmann Jennifer , Müller Rolf 
Published: October 2022

AbstractOver recent decades, the pipeline of antibiotics acting against Gram‐negative bacteria is running dry, as most discovered candidate antibiotics suffer from insufficient potency, pharmacokinetic properties, or toxicity. The darobactins, a promising new small peptide class of drug candidates, bind to novel antibiotic target BamA, an outer membrane protein. Previously, we reported that biosynthetic engineering in a heterologous host generated novel darobactins with enhanced antibacterial activity. Here we utilize an optimized purification method and present cryo‐EM structures of the Bam complex with darobactin 9 (D9), which served as a blueprint for the biotechnological generation of twenty new darobactins including halogenated analogs. The newly engineered darobactin 22 binds more tightly to BamA and outperforms the favorable activity profile of D9 against clinically relevant pathogens such as carbapenem‐resistant Acinetobacter baumannii up to 32‐fold, without observing toxic effects.
Near‐Room‐Temperature Magnetoelectric Coupling via Spin Crossover in an Iron(II) Complex
Authors: Owczarek Magdalena , Lee Minseong , Liu Shuanglong , Blake Ella R. , Taylor Chloe S. , Newman Georgia A. , Eckert James C. , Leal Juan H. , Semelsberger Troy A. , Cheng Hai‐Ping , Nie Wanyi , Zapf Vivien S. 
Published: October 2022

AbstractMagnetoelectric coupling is achieved near room temperature in a spin crossover FeII molecule‐based compound, [Fe(1bpp)2](BF4)2. Large atomic displacements resulting from Jahn–Teller distortions induce a change in the molecule dipole moment when switching between high‐spin and low‐spin states leading to a step‐wise change in the electric polarization and dielectric constant. For temperatures in the region of bistability, the changes in magnetic and electrical properties are induced with a remarkably low magnetic field of 3 T. This result represents a successful expansion of magnetoelectric spin crossovers towards ambient conditions. Moreover, the observed 0.3–0.4 mC m−2 changes in the H‐induced electric polarization suggest that the high strength of the coupling obtained via this route is accessible not just at cryogenic temperatures but also near room temperature, a feature that is especially appealing in the light of practical applications.
Durable High‐Temperature Proton Exchange Membrane Fuel Cells Enabled by the Working‐Temperature‐Matching Palladium‐Hydrogen Buffer Layer
Authors: Huang Gen , Li Yingying , Tao Li , Huang Zhifeng , Kong Zhijie , Xie Chao , Du Shiqian , Wang Tehua , Wu Yujie , Liu Qie , Zhang Dongcai , Lin Jiaqi , Li Miaoyu , Wang Jun , Zhang Jin , Lu Shanfu , Cheng Yi , Wang Shuangyin 
Published: October 2022

AbstractThe durability degradation during stack‐operating conditions seriously deteriorates the lifetime and performance of the fuel cell. To alleviate the rapid potential rise and performance degradation, an anode design is proposed to match the working temperature of high‐temperature proton exchange membrane fuel cells (HT‐PEMFCs) with the release temperature of hydrogen from palladium. The result is significantly enhanced hydrogen oxidation reaction (HOR) activity of Pd and superior performance of the Pd anode. Furthermore, Pd as hydrogen buffer and oxygen absorbent layer in the anode can provide additional in situ hydrogen and absorb infiltrated oxygen during local fuel starvation to maintain HOR and suppress reverse‐current degradation. Compared with the traditional Pt/C anode, the Pd/C also greatly improved HT‐PEMFCs durability during start‐up/shut‐down and current mutation. The storage/release of hydrogen provides innovative guidance for improving the durability of PEMFCs.
An efficient interface model to develop scalable methodology of melt processing of polypropylene with graphene oxide produced by an improved and eco‐friendly electrochemical exfoliation
Authors: Dündar Gülayşe Şahin , Saner Okan Burcu 
Published: October 2022

AbstractThis study developed a scalable and straightforward adaptation methodology for melt processing of polypropylene (PP) to provide a high degree of exfoliation of multilayer graphene oxide (GO) by using a high‐shear mixer. GO was first produced by an improved and eco‐friendly electrochemical exfoliation by using an environmentally friendly aqueous methanesulfonic acid (MSA) and a sodium sulfate salt system to minimize the environmental impact. The produced GOs then were melt blended with PP and their mechanical, thermal, and morphological properties were investigated under different GO loadings to attain ideal configuration and increase interfacial interactions between polymer matrix and reinforcer. Comparisons were made by producing different PP composites using two different GO types produced in salt and acid environments. Additionally, by applying different voltages to salt system, the effect of applied voltage on the properties of both GO material and the composites were discussed. The characterization results indicated that GO obtained in MSA solution caused a 71% increase in flexural modulus and 46% in flexural strength with the addition of 1 wt% GO. The rheological characterization also showed that dispersion and viscosity improved with lower GO loadings compared to neat polymer by providing cost‐effective and scalable graphene manufacturing.
Hydrophobic deep eutectic solvent‐based ionic conductive gels with highly stretchable, fatigue‐resistant and adhesive performances for reliable flexible strain sensors
Authors: Gao Yifeng , Wu Linlin , Zhou Jiacheng , Ma Xiaofeng , Fang Ying , Fang Xianli , Dou Qiang 
Published: October 2022

AbstractOwing to the advantages of temperature resistance, low cost, and biocompatibility, deep eutectic solvent (DES)‐based ionic conductive gels have attracted increasing research interest for flexible devices in recent years. However, current DES gels are all based on hydrophilic DES, which tend to absorb a large amount of environmental moisture, resulting in gel softening and adversely affecting the durability of the device. In this work, we highlight for the first time that N,N‐dimethylacrylamide monomer, and the obtained polymer can form hydrogen‐bonding networks with hydrophobic DES, methyl trioctyl ammonium chloride/ethyl 4‐hydroxybenzoate (1:2), thereby obtaining a hydrophobic DES‐based gel through photo‐polymerization. The resultant DES gel displays high stretchability (~900%), toughness (341.14 kJ m−3), anti‐fatigue property (recovery after 500 compression cycles), desirable conductivity (0.12 mS cm−1), adhesiveness and high transparency (>90% visible light transmittance). Notably, the hydrophobic DES‐based gel absorbs only 2 wt% water but exhibits significant water‐induced stiffening after exposing in ambient air for 1 week. These properties lead to the successful realization of the DES gels as wearable sensors to precisely monitor human motion. This work may open new avenues for the development of hydrophobic DES‐based gel ionotronics with functional performance.