bluuebunny/crossref_metadata_2025_split huggingface dataset:
Pressure‐Engineered Photoluminescence Tuning in Zero‐Dimensional Lead Bromide Trimer Clusters
Authors: Li Qian , Chen Zhongwei , Li Mingze , Xu Bin , Han Jiang , Luo Zhishan , Tan Li , Xia Zhiguo , Quan Zewei 
Published: October 2020

AbstractZero‐dimensional (0D) hybrid metal halides are promising light emitters. However, it is still challenging to accurately design their structures with targeted photoluminescence properties. Herein, high pressure is used to change the self‐trapped exciton (STE) emission of 0D (bmpy)9[ZnBr4]2[Pb3Br11] (bmpy: 1‐butyl‐1‐methylpyrrolidinium). Under initial compression, the simultaneous contraction and distortion of photoactive [Pb3Br11]5− vary the equilibrium of STE emissions between different excited states, tuning the emission color from yellow green to cyan. Notably, sufficient structural distortion under continuous compression leads to the formation of more and deeper STE states, exhibiting an unprecedented broadband white‐light emission. This study reveals the structure‐dependent optical properties of 0D hybrid metal halides, providing novel insights into the mechanism of STE emission.
Spectroscopic and Electrokinetic Evidence for a Bifunctional Mechanism of the Oxygen Evolution Reaction**
Authors: Bai Lichen , Lee Seunghwa , Hu Xile 
Published: October 2020

AbstractA bifunctional oxygen evolution reaction (OER) mechanism, in which the energetically demanding step of the attack of hydroxide on a metal oxo unit is facilitated by a hydrogen atom transfer to a second site, has the potential to circumvent the scaling relationship. However, the bifunctional mechanism has hitherto only been supported by theoretical computations. Here we describe an operando Raman spectroscopic and electrokinetic study of two highly active OER catalysts, FeOOH‐NiOOH and NiFe layered double hydroxide (LDH). The data support two distinct mechanisms for the two catalysts: FeOOH‐NiOOH operates by a bifunctional mechanism where the rate‐determining O−O bond forming step is the OH− attack on a Fe=O coupled with a hydrogen atom transfer to a NiIII‐O site, whereas NiFe LDH operates by a conventional mechanism of four consecutive proton‐coupled electron transfer steps. The experimental validation of the bifunctional mechanism enhances the understanding of OER catalysts.
A Cerium Vanadate Nanozyme with Specific Superoxide Dismutase Activity Regulates Mitochondrial Function and ATP Synthesis in Neuronal Cells
Authors: Singh Namrata , NaveenKumar Somanathapura K. , Geethika Motika , Mugesh Govindasamy 
Published: October 2020

AbstractNanoparticles that functionally mimic the activity of metal‐containing enzymes (metallo‐nanozymes) are of therapeutic importance for treating various diseases. However, it is still not clear whether such nanozymes can completely substitute the function of natural enzymes in living cells. In this work, we show for the first time that a cerium vanadate (CeVO4) nanozyme can substitute the function of superoxide dismutase 1 and 2 (SOD1 and SOD2) in the neuronal cells even when the natural enzyme is down‐regulated by specific gene silencing. The nanozyme prevents the mitochondrial damage in SOD1‐ and SOD2‐depleted cells by regulating the superoxide levels and restores the physiological levels of the anti‐apoptotic Bcl‐2 family proteins. Furthermore, the nanozyme effectively prevents the mitochondrial depolarization, leading to a significant improvement in the cellular levels of ATP under oxidative stress.
Evidence of a Phenolic Pool as a Key Intermediate for Zeolite‐Catalyzed Lignin Pyrolysis
Authors: Liu Chunjiang , Chen Xiamin , Liu Xinghua , Cui Cunhao , Zhou Zhongyue , Jia Liangyuan , Qi Fei 
Published: October 2020

AbstractThe phenolic pool is considered to be an important intermediate during the catalytic conversion of biomass. However, no direct evidence has been reported on its full picture on a molecular level due to the huge challenges in probing the reactive and lowly volatile phenolic oligomers with state‐of‐the‐art technologies. Herein, we report the online detection and structural identification of a phenolic pool by utilizing in‐situ atmospheric‐pressure photoionization mass spectrometry, demonstrating that the phenolic pool is formed through repolymerization of monomers with an equidistant group pattern and acts as a key mechanistic step for both valuable aromatic products and undesired coke. The exploration of the real reactive species is also of great importance for the rational design and synthesis of advanced catalysts with high activity.
Die Natur der Tellur‐Stickstoff‐Wechselwirkungen vom Chalkogen‐Bindungs‐Typ: eine erste experimentelle Gasphasen‐Struktur
Authors: Glodde Timo , Vishnevskiy Yury V. , Zimmermann Lars , Stammler Hans‐Georg , Neumann Beate , Mitzel Norbert W. 
Published: October 2020

Abstract(C6F5)Te(CH2)3NMe2 (1) wurde synthetisiert und charakterisiert. Das Perfluorphenyltellur‐Derivat ist in der Lage, intramolekulare N⋅⋅⋅Te‐Wechselwirkungen zu bilden. Die donorfreie Referenzsubstanz (C6F5)TeMe (2) und das nicht unterstützte Addukt (C6F5)(Me)Te⋅NMe2Et (2 b) wurden ebenso untersucht. Die Molekülstrukturen von 1, 2 und 2 b wurden durch Einkristall‐Röntgenbeugung und für 1 und 2 durch Gasphasen‐Elektronenbeugung bestimmt. Die Strukturen von 1 zeigen N⋅⋅⋅Te‐Abstände von 2.639(1) Å (Festkörper) und 2.92(3) Å (Gas). Ab‐initio‐ sowie NBO‐ und QTAIM‐Rechnungen zeigen erhebliche Ladungstransfereffekte innerhalb der N⋅⋅⋅Te‐Interaktionen und weisen auf σ‐Loch‐Wechselwirkungen hin.
Rheological study of the incorporation of grape seed extract in chitosan and gelatin coatings
Authors: Romanelli Vicente Bertolo Mirella , da Conceição Amaro Martins Virginia , de Guzzi Plepis Ana Maria , Bogusz Junior Stanislau 
Published: October 2020

AbstractThis study aims to evaluate the incorporation, addition order and concentration of grape seed extract (Vitis vinifera L.) in chitosan and gelatin solutions, candidates as food coatings due to their excellent antioxidant and barrier properties. This study originally assesses how such variables can affect the rheological parameters of this particular combination of materials. Initially, 1% (w/w) solutions of chitosan (C) and gelatin (G) are mixed at a 1:1 ratio (CG). For grape seed extract addition, ethanolic solutions (50%, v/v) are prepared in different concentrations, with two incorporation orders: 1) addition to CG and 2) addition to the chitosan gel (C), followed by G mixing. The addition order reveals a direct influence on the rheological properties, and low extract concentrations leads to solutions with adequate viscosity for coating applications. The findings of this study confirm that it is essential to standardize the addition procedures during the preparation of the materials.
Highly toughened poly(lactic acid) blends prepared by reactive blending with a renewable poly(ether‐block‐amide) elastomer
Authors: Xia Yiwei , Wang Guangxin , Feng Yulin , Hu Yuexin , Zhao Guiyan , Jiang Wei 
Published: October 2020

AbstractRenewable poly(ether‐block‐amide) (PEBA) elastomer was grafted with glycidyl methacrylate (GMA) to prepare PEBA‐GMA, then it was melting blended with poly (lactic acid) (PLA) in an effort to achieve fully bio‐based super‐toughened PLA materials. The notched Izod impact strength of PLA/PEBA‐GMA blend was significantly enhanced when the content of PEBA‐GMA was higher than 20 wt%, and the tensile toughness was also improved. It was found a new copolymer was formed at the interface due to the reaction of the end groups (OH, COOH) of PLA with the epoxide group of PEBA‐GMA. This greatly improves the interfacial adhesion between PLA and PEBA‐GMA component, leading to finer dispersed particles of PEBA‐GMA which were better wetted by the PLA matrix. Therefore, the highly enhanced notched impact strength was ascribed to the effective reactive compatibilization promoted by the interfacial reaction. This provides a new idea for preparing super tough PLA materials with bio‐based elastomer, which will widely extend the application of PLA.
A Robust Coin‐Cell Design for In Situ Synchrotron‐based X‐Ray Powder Diffraction Analysis of Battery Materials
Authors: Liang Gemeng , Hao Junnan , D'Angelo Anita M. , Peterson Vanessa K. , Guo Zaiping , Pang Wei Kong 
Published: October 2020

AbstractUnderstanding structure/chemistry‐function relationships of active battery materials is crucial for designing higher‐performance batteries, with in situ synchrotron‐based X‐ray powder diffraction widely employed to gain this understanding. Such measurements cannot be performed using a conventional cell, with modifications necessary for the X‐ray diffraction measurement, which unfortunately compromises battery performance and stability. Consequently, these measurements may not be representative of the typical behaviour of active materials in unmodified cells, particularly under more extreme operating conditions, such as at high voltage. Herein, we report a low‐cost, simple, and robust coin‐cell design enabling representative and typical cell performance during in situ X‐ray powder diffraction measurements, which we demonstrate for the well‐known high‐voltage electrode material LiNi0.5Mn1.5O4. In addition to excellent cell stability at high voltage, the modified cell delivered an electrochemical response comparable to the standard 2032‐type coin cell. This work paves an efficient way for battery researchers to perform high‐quality in situ structural analysis with synchrotron X‐ray radiation and will enable further insight into complex electrochemical processes in batteries.
A rheological approach to identify efficient biopolymer producing bacteria
Authors: Malvar Sara , Cardoso Letícia O. B. , Karolski Bruno , Perpetuo Elen A. , Carmo Bruno S. , Meneghini Julio R. 
Published: October 2020

AbstractThis study investigates the relationship between collective motion and propulsion of bacterial consortia and their biopolymer production efficiency. Rheological tests were conducted for suspensions of two different methanotrophic bacterial consortia obtained after enrichment of sediment samples from mangrove sites in Brazil. We considered the linear viscoelasticity region and analyzed the values of storage and loss moduli as functions of days of cultivation, for different values of the volume fraction. The suspensions' rheological behaviors reflected the bacterial growth stage. We found that the formation of structures over time in some types of consortia can hinder the movement of bacteria in the search for nutrients. The change in complex viscosity of the two consortia followed a different and rich behavior that appears to be closely related to their capacity to capture methane. Our analysis showed a possible correlation between collective motion, viscosity reduction, and biopolymer production. The pieces of evidence from this study suggest that the efficiency of bacterial motion is directly related to biopolymer production, and this could facilitate the process of identifying the best consortium of biopolymer producing bacteria.
Comparative analyses of site‐directed mutagenesis of human melatonin MTNR1A and MTNR1B receptors using a yeast fluorescent biosensor
Authors: Nakamura Yasuyuki , Asama Ririka , Tabata Takuya , Morita Kenta , Maruyama Tatsuo , Kondo Akihiko , Ishii Jun 
Published: October 2020

AbstractMelatonin is an indoleamine neurohormone made by the pineal gland. Its receptors, MTNR1A and MTNR1B, are members of the G‐protein‐coupled receptor (GPCR) family and are involved in sleep, circadian rhythm, and mood disorders, and in the inhibition of cancer growth. These receptors, therefore, represent significant molecular targets for insomnia, circadian sleep disorders, and cancer. The yeast Saccharomyces cerevisiae is an attractive host for assaying agonistic activity for human GPCR. We previously constructed a GPCR‐based biosensor employing a high‐sensitivity yeast strain that incorporated both a chimeric yeast‐human Gα protein and a bright fluorescent reporter gene (ZsGreen). Similar approaches have been used for simple and convenient measurements of various GPCR activities. In the current study, we constructed a fluorescence‐based yeast biosensor for monitoring the signaling activation of human melatonin receptors. We used this system to analyze point mutations, including previously unreported mutations of the consensus sequences of MTNR1A and MTNR1B melatonin receptors and compared their effects. Most mutations in the consensus sequences significantly affected the signaling capacities of both receptors, but several mutations showed differences between these subtype receptors. Thus, this yeast biosensor holds promise for revealing the functions of melatonin receptors.
The effects of poverty stereotype threat on inhibition ability in individuals from different income‐level families
Authors: Wang Shanshan , Yang Dong 
Published: October 2020

AbstractIntroductionPoverty is characterized by a scarcity of resources and a threat of certain stereotypes. However, the effects of stereotype threat are largely dependent on various factors, both negative and positive. Few psychophysiological studies have studied the effects of poverty stereotype threats on inhibition ability in wealth and impoverished individuals.MethodsTo fill this gap in the literature, this study used the event‐related potential (ERP) technique to explore the brain mechanisms associated with stereotype threat in 135 participants.ResultsBehavioral results showed that the rich group (participants from higher‐income families) had better inhibition ability than the impoverished group (participants from lower‐income families), with significantly shorter reaction time and significantly greater accuracy for poverty‐related stimuli when in the nonthreat condition. Additionally, poverty stereotype threat could improve performance of the impoverished group for poverty‐related stimuli. The electrophysiological results showed significantly larger P3 mean amplitude and significantly longer P3 latency in the rich group than the impoverished group in the nonthreat condition. Although no significant between‐group differences were found in the threat condition, the results show that the effect of poverty stereotype threat varies with different income‐level persons, for both behavioral and P3 data.ConclusionThese findings suggest that impoverished people have worse inhibition abilities. Further, poverty stereotype threat has different effects on people according to their income level and could help to explain irrational consumption behaviors in people.
RAPTA‐Decorated Polyacrylamide Nanoparticles: Exploring their Synthesis, Physical Properties and Effect on Cell Viability
Authors: Sandland Jordon , Savoie Huguette , Boyle Ross W. , Murray Benjamin S. 
Published: October 2020

AbstractIn this study, we report the first successful immobilisation of a known cytoactive [Ru(η6‐arene)(C2O4)PTA] (RAPTA) complex to a biologically inert polyacrylamide nanoparticle support. The nanoparticles have been characterised by zetasizer analysis, UV/Vis, ATR‐FTIR, TGA and ICP‐MS to qualitatively and quantitatively confirm the presence of the metallodrug on the surface of the carrier. The native RAPTA complex required a concentration of 50 μM to produce a cell viability of 47.1±2.1 % when incubated with human Caucasian colorectal adenocarcinoma cells for 72 h. Under similar conditions a cell viability of 45.1±1.9 % was obtained with 0.5 μM of RAPTA complex in its immobilised form. Therefore, conjugation of the RAPTA metallodrug to our nanoparticle carriers resulted in a significant 100‐fold decrease in effective concentration of ruthenium required for a near identical biological effect on cell viability.
Myxofibrosarcoma of the leg: A diagnostic challenge
Authors: Rachdi Imène , Daoud Fatma , Khanchel Fatma , Arbaoui Ibrahim , Somai Mehdi , Zoubeidi Hana , Aydi Zohra , Ben Dhaou Besma , Debbiche Achraf , Boussema Fatma 
Published: October 2020

AbstractWe should keep in mind slowly growing malignancies when the lesion is located close to the synovial regions of the extremities. The diagnosis of certainty of myxofibrosarcoma is histological and is based on the demonstration of the myxoid matrix, fibroblastic cells with a curvilinear arrangement of the vessels.
Simultaneous H2 Production and Bleaching via Solar Photoreforming of Model Dye‐polluted Wastewaters on Metal/Titania
Authors: Puga Alberto V. , Barka Noureddine , Imizcoz Mikel 
Published: October 2020

AbstractDyestuff substances in textile wastewaters are harmful pollutants which pose serious disposal challenges. A solar photocatalytic treatment combining degradation of structurally diverse dyes (Rhodamine B, Reactive Orange 16 or Auramine O) and energetic valorisation by H2 production on systematically varied M/TiO2 (M=Au, Ag, Cu or Pt) is herein explored. Bleaching was efficient in all cases, and especially rapid for azo (>98 % after 2 h) as compared to poly‐heterocyclic chromophores. Interestingly, dye degradation rates were similar to literature results under aerobic conditions, whereby no energy recovery is possible. Due to the recalcitrant dye structures, H2 production becomes markedly sensitive to metal co‐catalyst chemistry and morphology. The occurrence of active metallic, i. e. M(0), surfaces in sufficiently large nanoparticles are key to ensurie initial H2 evolution. An increase in Au domain sizes from 101 up to 102 nm ranges resulted in 10‐fold site‐specific catalytic activity (TOF) enhancement, whereas growth of Pt nanoparticles well above the sub‐nanometric regime was essential for efficient H2 production. In quest of using affordable metallic elements, bleaching and sustained H2 evolution was proven after prolonged irradiation using Cu/TiO2, owing to the in situ reduction of the copper co‐catalyst. In summary, anaerobic photoreforming can be as efficient as the more common aerobic approach, also allowing energy recovery in the form of waste‐derived hydrogen.
Open Data in Catalysis: From Today's Big Picture to the Future of Small Data
Authors: Mendes Pedro S. F. , Siradze Sébastien , Pirro Laura , Thybaut Joris W. 
Published: October 2020

AbstractOpen science and data are yet to make a real breakthrough and research policies will have a critical role in it. The history and general context around open data is hence firstly addressed, including how researchers perceive the existing incentives, leading to recommendations on how to foster data sharing. Subsequently, the focus is on catalysis, with a particular emphasis on benchmarking the data sharing practices against other fields and surveying the type of data currently being shared. The current infrastructure, including data repositories, and standards formats is maped. The striking differences among different disciplines are discussed, serving as a basis to propose specific actions to promote data sharing in catalysis. Short‐term initiatives are needed to boost the amount of openly available data, particularly in heterogeneous catalysis, but a high degree of standardization in data formats will be needed to ensure optimal and automated data mining in the long run. Because of its unique, central role in understanding the catalytic action, kinetic catalytic data is of particular interest. As formats and mining tools are dependant on the type of data, kinetic catalytic data is firstly characterized. Guidelines for a standardized sharing format are proposed, taking into account the small, well‐structured nature of this type of data. To maximize the extraction of information, the low volume of kinetic catalytic data will be compensated by incorporating fundamental knowledge into statistics‐based tools. Whencoupled with knowledge generation tools, i. e. kinetic models, new insights at the active site and mechanism levels will be reached in an ever more automated and powerful way.
Similarities and Differences between Crystal and Enzyme Environmental Effects on the Electron Density of Drug Molecules
Authors: Kleemiss Florian , Wieduwilt Erna K. , Hupf Emanuel , Shi Ming W. , Stewart Scott G. , Jayatilaka Dylan , Turner Michael J. , Sugimoto Kunihisa , Nishibori Eiji , Schirmeister Tanja , Schmidt Thomas C. , Engels Bernd , Grabowsky Simon 
Published: October 2020

AbstractThe crystal interaction density is generally assumed to be a suitable measure of the polarization of a low‐molecular weight ligand inside an enzyme, but this approximation has seldomly been tested and has never been quantified before. In this study, we compare the crystal interaction density and the interaction electrostatic potential for a model compound of loxistatin acid (E64c) with those inside cathepsin B, in solution, and in vacuum. We apply QM/MM calculations and experimental quantum crystallography to show that the crystal interaction density is indeed very similar to the enzyme interaction density. Less than 0.1 e are shifted between these two environments in total. However, this difference has non‐negligible consequences for derived properties.
Synthesis of Asparagine Derivatives Harboring a Lewis X Type DC‐SIGN Ligand and Evaluation of their Impact on Immunomodulation in Multiple Sclerosis
Authors: Doelman Ward , Marqvorsen Mikkel H. S. , Chiodo Fabrizio , Bruijns Sven C. M. , van der Marel Gijsbert A. , van Kooyk Yvette , van Kasteren Sander I. , Araman Can 
Published: October 2020

AbstractThe protein myelin oligodendrocyte glycoprotein (MOG) is a key component of myelin and an autoantigen in the disease multiple sclerosis (MS). Post‐translational N‐glycosylation of Asn31 of MOG seems to play a key role in modulating the immune response towards myelin. This is mediated by the interaction of Lewis‐type glycan structures in the N‐glycan of MOG with the DC‐SIGN receptor on dendritic cells (DCs). Here, we report the synthesis of an unnatural Lewis X (LeX)‐containing Fmoc‐SPPS‐compatible asparagine building block (SPPS=solid‐phase peptide synthesis), as well as asparagine building blocks containing two LeX‐derived oligosaccharides: LacNAc and Fucα1‐3GlcNAc. These building blocks were used for the glycosylation of the immunodominant portion of MOG (MOG31‐55) and analyzed with respect to their ability to bind to DC‐SIGN in different biological setups, as well as their ability to inhibit the citrullination‐induced aggregation of MOG31‐55. Finally, a cytokine secretion assay was carried out on human monocyte‐derived DCs, which showed the ability of the neoglycopeptide decorated with a single LeX to alter the balance of pro‐ and anti‐inflammatory cytokines, inducing a tolerogenic response.
Aromaticity Survival in Hydrofullerenes: The Case of C66H4 with Its π‐Aromatic Circuits
Authors: Chen Dandan , Szczepanik Dariusz W. , Zhu Jun , Muñoz‐Castro Alvaro , Solà Miquel 
Published: October 2020

AbstractThe isolated‐pentagon rule (IPR) is a determining structural feature that accounts for hollow fullerene stabilization and properties related to Cn (n≥60) cages. The recent characterization of an unprecedented non‐IPR hydrofullerene, C2v C66H4, bearing two heptagons with adjacent fused‐pentagon motifs, largely dismisses this feature. Herein, employing DFT calculations, the 13C NMR spectroscopy and aromatic behavior of C2v C66H4 are explored. The results show the presence of three π‐aromatic circuits at the bottom boat section of C66H4, indicating the unique features of this hydrofullerene in comparison to those of pristine C60. In addition, under specific orientations of the external field, certain π‐aromatic circuits are enabled, resulting in a more aromatic fullerene than that of C60, but lower than that of the spherical aromatic C606− fulleride. Notably, under a field aligned with the saturated carbon atoms, nonaromatic characteristics are exposed. This reveals that spherical‐like cages can involve a complex magnetic response that heavily depends on the orientation of the applied field.