bluuebunny/crossref_metadata_2025_split huggingface dataset:
Enhanced Nonlinear Yield from Barium Titanate Metasurface Down to the Near Ultraviolet
Authors: Timpu Flavia , Reig Escalé Marc , Timofeeva Maria , Strkalj Nives , Trassin Morgan , Fiebig Manfred , Grange Rachel 
Published: September 2019

AbstractMetasurfaces are artificial nanopatterned 2D architectures that can offer a solution to the bottleneck problem of bulky optical elements. They have the ability of wavefront shaping and light sub‐wavelength manipulation because they are formed of resonantly scattering elements. Recently, the properties of metasurfaces gained interest for nonlinear optics in the efforts to miniaturize nonlinear optical devices while maintaining high photon–photon interactions. Herein, a new type of nonlinear metasurface based on the metal oxide barium titanate is developed, which demonstrates an efficient nonlinear optical response over a broad spectral range, from near‐ultraviolet to the visible range, where metals and semiconductors typically have losses. Contrary to previously demonstrated nonlinear plasmonic metasurfaces, these dielectric metasurfaces are less sensitive to surface roughness and gain their optical nonlinearity from the noncentrosymmetric crystal structure of the ferroelectric barium titanate.
Data‐Driven Materials Science: Status, Challenges, and Perspectives
Authors: Himanen Lauri , Geurts Amber , Foster Adam Stuart , Rinke Patrick 
Published: September 2019

AbstractData‐driven science is heralded as a new paradigm in materials science. In this field, data is the new resource, and knowledge is extracted from materials datasets that are too big or complex for traditional human reasoning—typically with the intent to discover new or improved materials or materials phenomena. Multiple factors, including the open science movement, national funding, and progress in information technology, have fueled its development. Such related tools as materials databases, machine learning, and high‐throughput methods are now established as parts of the materials research toolset. However, there are a variety of challenges that impede progress in data‐driven materials science: data veracity, integration of experimental and computational data, data longevity, standardization, and the gap between industrial interests and academic efforts. In this perspective article, the historical development and current state of data‐driven materials science, building from the early evolution of open science to the rapid expansion of materials data infrastructures are discussed. Key successes and challenges so far are also reviewed, providing a perspective on the future development of the field.
A rare case of Reye's syndrome induced by influenza A virus with use of ibuprofen in an adult
Authors: Hongo Takashi , Momoki Noriya , Mae Souichiro , Nozaki Satoshi , Takahashi Kenji , Fujiwara Toshifumi 
Published: September 2019

BackgroundReye's syndrome (RS) is a rare but severe acute life‐threating disease characterized by encephalopathy and fatty liver damage. Reye's syndrome is most common in children and rarely occurs in adults.Case presentationA 56‐year‐old woman was admitted to the emergency department with disturbance of consciousness and respiratory failure. She had taken ibuprofen for headache. Her Glasgow Coma Scale score was E3V3M5 on admission. The laboratory findings revealed acute liver failure with prothrombin time – international normalized ratio of 3.16, aspartate aminotransferase 12,548 IU/L, alanine aminotransferase 5,725 IU/L, and blood ammonia 102 μg/dL. Head magnetic resonance imaging showed hyperintense signals on diffusion‐weighed images of globus pallidus.We diagnosed the patient with RS induced by influenza A and use of ibuprofen. The patient received supportive care in the intensive care unit and her clinical outcome was favorable.ConclusionIbuprofen might be a risk factor for RS.
The Power of Iodane‐Guided C−H Coupling: A Group‐Transfer Strategy in Which a Halogen Works for Its Money
Authors: Chen Wei W. , Cuenca Ana B. , Shafir Alexandr 
Published: September 2019

AbstractHypervalent organoiodane reagents are ubiquitous in organic synthesis, both as oxidants and as electrophilic group‐transfer agents. In addition to these hallmark applications, a complementary strategy is gaining momentum that exploits the ability of λ3‐iodanes to undergo iodine‐to‐arene group transfer, for example, via iodonio‐Claisen‐type rearrangement processes. This Minireview discusses recent advances in the use of this method to access a variety of the C−H‐functionalized iodoarenes. While Section 2 is focused on the ortho C−H propargylation, allylation, and the more unusual para C−H benzylation, Section 3 is devoted to the C‐arylation of enol and phenol substrates. The accompanying discussion includes mechanistic considerations and goes into the synthetic applications of the final iodoarene cores. The Minireview concludes with further conceptual extensions of the method, including the use of non‐conventional coupling partners (for example, cyanoalkylation), improved access to λ3‐iodane building blocks, and the development of iterative approaches to polysubstituted iodoarenes.
Surface‐Electron Coupling for Efficient Hydrogen Evolution
Authors: Fu Weiwei , Wang Yanwei , Hu Jisong , Zhang Huijuan , Luo Ping , Sun Fang , Ma Xinguo , Huang Zhengyong , Li Jian , Guo Zaiping , Wang Yu 
Published: September 2019

AbstractMaximizing the activity of materials towards the alkaline hydrogen evolution reaction while maintaining their structural stability under realistic working conditions remains an area of active research. Herein, we report the first controllable surface modification of graphene(G)/V8C7heterostructures by nitrogen. Because the introduced N atoms couple electronically with V atoms, the V sites can reduce the energy barrier for water adsorption and dissociation. Investigation of the multi‐regional synergistic catalysis on N‐modified G/V8C7by experimental observations and density‐functional‐theory calculations reveals that the increase of electron density on the epitaxial graphene enable it to become favorable for H* adsorption and the subsequent reaction with another H2O molecule. This work extends the range of surface‐engineering approaches to optimize the intrinsic properties of materials and could be generalized to the surface modification of other transition‐metal carbides.
Nucleophile Coordination Enabled Regioselectivity in Palladium‐Catalyzed Asymmetric Allylic C−H Alkylation
Authors: Fan Lian‐Feng , Luo Shi‐Wei , Chen Shu‐Sen , Wang Tian‐Ci , Wang Pu‐Sheng , Gong Liu‐Zhu 
Published: September 2019

AbstractBranched selectivity in asymmetric allylic C−H alkylation is enabled by using 2‐acylimidazoles as nucleophiles in the presence of a chiral phosphoramidite‐palladium catalyst. A wide range of terminal alkenes, including 1,4‐dienes and allylarenes, are nicely tolerated and provide chiral 2‐acylimidazoles in moderate to high yields and with high levels of regio‐, and enantio‐, and E/Z‐selectivities. Mechanistic studies using density‐functional theory calculations suggest a nucleophile‐coordination‐enabled inner‐sphere attack mode for the enantioselective carbon–carbon bond‐forming event.
Aren‐freie Ruthenium(II/IV)‐katalysierte gegabelte Arylierungen für oxidative C‐H/C‐H‐Funktionalisierungen
Authors: Rogge Torben , Ackermann Lutz 
Published: September 2019

AbstractExperimentelle und computerchemische Studien gaben detaillierte Einblicke in selektivitäts‐ und reaktivitätsbestimmende Faktoren in verzweigten Ruthenium‐katalysierten direkten C‐H‐Arylierungen und dehydrierenden C‐H/C‐H‐Funktionalisierungen. Umfassende Untersuchungen belegten die Signifikanz von Aren‐Ligand‐freien Komplexen für die Bildung von biscyclometallierten Intermediaten innerhalb eines Ruthenium(II/IV/II)‐Mechanismus.
Water‐Mediated Synthesis of a Superionic Halide Solid Electrolyte
Authors: Li Xiaona , Liang Jianwen , Chen Ning , Luo Jing , Adair Keegan R. , Wang Changhong , Banis Mohammad Norouzi , Sham Tsun‐Kong , Zhang Li , Zhao Shangqian , Lu Shigang , Huang Huan , Li Ruying , Sun Xueliang 
Published: September 2019

AbstractTo promote the development of solid‐state batteries, polymer‐, oxide‐, and sulfide‐based solid‐state electrolytes (SSEs) have been extensively investigated. However, the disadvantages of these SSEs, such as high‐temperature sintering of oxides, air instability of sulfides, and narrow electrochemical windows of polymers electrolytes, significantly hinder their practical application. Therefore, developing SSEs that have a high ionic conductivity (>10−3 S cm−1), good air stability, wide electrochemical window, excellent electrode interface stability, low‐cost mass production is required. Herein we report a halide Li+ superionic conductor, Li3InCl6, that can be synthesized in water. Most importantly, the as‐synthesized Li3InCl6 shows a high ionic conductivity of 2.04×10−3 S cm−1 at 25 °C. Furthermore, the ionic conductivity can be recovered after dissolution in water. Combined with a LiNi0.8Co0.1Mn0.1O2 cathode, the solid‐state Li battery shows good cycling stability.
Selective CO2 Electroreduction to Ethylene and Multicarbon Alcohols via Electrolyte‐Driven Nanostructuring
Authors: Gao Dunfeng , Sinev Ilya , Scholten Fabian , Arán‐Ais Rosa M. , Divins Nuria J. , Kvashnina Kristina , Timoshenko Janis , Roldan Cuenya Beatriz 
Published: September 2019

AbstractProduction of multicarbon products (C2+) from CO2 electroreduction reaction (CO2RR) is highly desirable for storing renewable energy and reducing carbon emission. The electrochemical synthesis of CO2RR catalysts that are highly selective for C2+ products via electrolyte‐driven nanostructuring is presented. Nanostructured Cu catalysts synthesized in the presence of specific anions selectively convert CO2 into ethylene and multicarbon alcohols in aqueous 0.1 m KHCO3 solution, with the iodine‐modified catalyst displaying the highest Faradaic efficiency of 80 % and a partial geometric current density of ca. 31.2 mA cm−2 for C2+ products at −0.9 V vs. RHE. Operando X‐ray absorption spectroscopy and quasi in situ X‐ray photoelectron spectroscopy measurements revealed that the high C2+ selectivity of these nanostructured Cu catalysts can be attributed to the highly roughened surface morphology induced by the synthesis, presence of subsurface oxygen and Cu+ species, and the adsorbed halides.
Pushing the Lewis Acidity Boundaries of Boron Compounds With Non‐Planar Triarylboranes Derived from Triptycenes
Authors: Ben Saida Ali , Chardon Aurélien , Osi Arnaud , Tumanov Nikolay , Wouters Johan , Adjieufack Abel I. , Champagne Benoît , Berionni Guillaume 
Published: September 2019

AbstractBending the planar trigonal boron center of triphenylborane by connecting its aryl rings with carbon or phosphorus linkers gave access to a series of 9‐boratriptycene derivatives with unprecedented structures and reactivities. NMR spectroscopy and X‐ray diffraction of the Lewis adducts of these non‐planar boron Lewis acids with weak Lewis base revealed particularly strong covalent bond formation. The first Lewis adduct of a trivalent boron compounds with the Tf2N− anion illustrates the unrivaled Lewis acidity of these species. Increasing the pyramidalization of the boron center and using a cationic phosphonium linker resulted in an exceptional enhancement of Lewis acidity. Introduction of a phosphorus and a boron atom at each edge of a triptycene framework, allowed access to new bifunctional Lewis acid‐base 9‐phospha‐10‐boratriptycenes featuring promising reactivity for the activation of carbon‐halogen bonds.
Site‐Selective C−H Oxygenation via Aryl Sulfonium Salts
Authors: Sang Ruocheng , Korkis Stamatis E. , Su Wanqi , Ye Fei , Engl Pascal S. , Berger Florian , Ritter Tobias 
Published: September 2019

AbstractHerein, we report a two‐step process forming arene C−O bonds in excellent site‐selectivity at a late‐stage. The C−O bond formation is achieved by selective introduction of a thianthrenium group, which is then converted into C−O bonds using photoredox chemistry. Electron‐rich, ‐poor and ‐neutral arenes as well as complex drug‐like small molecules are successfully transformed into both phenols and various ethers. The sequence differs conceptually from all previous arene oxygenation reactions in that oxygen functionality can be incorporated into complex small molecules at a late stage site‐selectively, which has not been shown via aryl halides.
Potent ribonucleotide reductase inhibitors: Thiazole‐containing thiosemicarbazone derivatives
Authors: Ertas Merve , Sahin Zafer , Bulbul Emre F. , Bender Ceysu , Biltekin Sevde N. , Berk Barkin , Yurttas Leyla , Nalbur Aysu M. , Celik Hayati , Demirayak Şeref 
Published: September 2019

AbstractThe antioxidant, antimalarial, antibacterial, and antitumor activities of thiosemicarbazones have made this class of compounds important for medicinal chemists. In addition, thiosemicarbazones are among the most potent and well‐known ribonucleotide reductase inhibitors. In this study, 24 new thiosemicarbazone derivatives were synthesized, and the structures and purity of the compounds were determined by IR, 1H NMR, 13C NMR, mass spectroscopy, and elemental analysis. The IC50 values of these 24 compounds were determined with an assay for ribonucleotide reductase inhibition. Compounds 19, 20, and 24 inhibited ribonucleotide reductase enzyme activity at a higher level than metisazone as standard. The cytotoxic effects of these compounds were measured on the MCF7 (human breast adenocarcinoma) and HEK293 (human embryonic kidney) cell lines. Similarly, compounds 19, 20, and 24 had a selective effect on the MCF7 and HEK293 cell lines, killing more cancer cells than cisplatin as standard. The compounds (especially 19, 20, and 24 as the most active ones) were then subjected to docking experiments to identify the probable interactions between the ligands and the enzyme active site. The complex formation was shown qualitatively. The ADME (absorption, distribution, metabolism, and excretion) properties of the compounds were analyzed using in‐silico techniques.
Novel discoveries targeting gemcitabine‐based chemoresistance and new therapies in pancreatic cancer: How far are we from the destination?
Authors: Luo Wenhao , Yang Gang , Qiu Jiangdong , Luan Jingyang , Zhang Ying , You Lei , Feng Mengyu , Zhao Fangyu , Liu Yueze , Cao Zhe , Zheng Lianfang , Zhang Taiping , Zhao Yupei 
Published: September 2019

AbstractPancreatic cancer (PC) remains one of the deadliest malignancies worldwide. Chemoresistance is a significant clinical problem in pancreatic ductal adenocarcinoma (PDAC) and numerous potential mechanisms have been demonstrated but much remains to be understood. To overcome the existing limitations in PC treatment, newer approaches targeting intrinsic or acquired mechanisms have been found to improve drug therapeutic effectiveness in PC patients. Here, we provide an update of the most recent findings and their implications for clinicians, and attempt to summarize the various aspects of different individualized novel therapies for PC that could most benefit metastatic PDAC patients.
Compactness of Protein Folds Alters Disulfide‐Bond Reducibility by Three Orders of Magnitude: A Comprehensive Kinetic Case Study on the Reduction of Differently Sized Tryptophan Cage Model Proteins
Authors: Horváth Dániel , Taricska Nóra , Keszei Ernő , Stráner Pál , Farkas Viktor , Tóth Gábor K. , Perczel András 
Published: September 2019

AbstractA new approach to monitor disulfide‐bond reduction in the vicinity of aromatic cluster(s) has been derived by using the near‐UV range (λ=266–293 nm) of electronic circular dichroism (ECD) spectra. By combining the results from NMR and ECD spectroscopy, the 3D fold characteristics and associated reduction rate constants (k) of E19_SS, which is a highly thermostable, disulfide‐bond reinforced 39‐amino acid long exenatide mimetic, and its N‐terminally truncated derivatives have been determined under different experimental conditions. Single disulfide bond reduction of the E19_SS model (with an 18‐fold excess of tris(2‐carboxyethyl)phosphine, pH 7, 37 °C) takes hours, which is 20–30 times longer than that expected, and thus, would not reach completion by applying commonly used reduction protocols. It is found that structural, steric, and electrostatic factors influence the reduction rate, resulting in orders of magnitude differences in reduction half‐lives (900>t1/2>1 min) even for structurally similar, well‐folded derivatives of a small model protein.
Tuning Nitrogen Species in Two‐Dimensional Carbon through Pore Structure Change for High Supercapacitor Performance
Authors: Liu Hao , Tang Qian Fang , Qiu Zhi Guo , Chen Xiang Ying , Zhang Zhong Jie 
Published: September 2019

AbstractCarbonaceous materials have long been a key component of supercapacitor energy storage systems, and exploring nitrogen atom doping and its role is currently the focus of carbon‐based electrode development. However, achieving a high proportion of pyridinic N (active N) in N‐doped carbon is still a big challenge. Here, by introducing a triblock copolymer F127 into the phenolic resin, the pore structure of the two‐dimensional carbon material is successfully adjusted, thereby increasing the probability of generation of active nitrogen. We found that this two‐dimensional porous structure is beneficial to the formation of pyridinic N. Through the change of pore structure, the ratio of pyridinic N to the total N was further increased by 13.9 %. Therefore, it provides a large specific capacitance (220 F g−1), excellent cycle stability (93.6 %) and high rate performance (71.2 %) in the alkaline KOH electrolyte. To further increase the energy density, we constructed an symmetrical supercapacitor device using an ionic liquid electrolyte (equal amount of 1‐ethyl‐3‐methylimidazolium tetrafluoroborate and acetonitrile). As a result, since the electrolyte has a voltage window of up to 3 V, the energy density is as high as 37.5 Wh kg−1. This superior performance indicates that adjusting the ratio of pyridinic N provides a promising method for preparing excellent N‐doped carbon materials for energy storage systems.
Two Highly Stable Proton Conductive Cobalt(II)–Organic Frameworks as Impedance Sensors for Formic Acid
Authors: Liu Rui‐Lan , Shi Zhi‐Qiang , Wang Xin‐Yue , Li Zi‐Feng , Li Gang 
Published: September 2019

AbstractMetal–organic frameworks (MOFs) have been extensively explored as advanced chemical sensors in recent years. However, there are few studies on MOFs as acidic gas sensors, especially proton conductive MOFs. In this work, two new proton‐conducting 3D MOFs, {[Co3(p‐CPhHIDC)2(4,4′‐bipy)(H2O)]⋅2 H2O}n (1) (p‐CPhH4IDC=2‐(4‐carboxylphenyl)‐1 H‐imidazole‐4,5‐dicarboxylic acid; 4,4′‐bipy=4,4′‐bipyridine) and {[Co3(p‐CPhHIDC)2(bpe)(H2O)]⋅3 H2O}n (2) (bpe=trans‐1,2‐bis(4‐pyridyl)ethylene) have been solvothermally prepared and investigated their formic acid sensing properties. Both MOFs 1 and 2 show temperature‐ and humidity‐dependent proton conductive properties and exhibit optimized proton conductivities of 1.04×10−3 and 7.02×10−4 S cm at 98 % relative humidity (RH) and 100 °C, respectively. The large number of uncoordinated carboxylic acid sites, free and coordination water molecules, and hydrogen‐bonding networks inside the frameworks are favorable to the proton transfer. By measuring the impedance values after exposure to formic acid vapor at 98 % or 68 % RH and 25 °C, both MOFs indicate reproducibly high sensitivity to the analyte. The detection limit of formic acid vapor is as low as 35 ppm for 1 and 70 ppm for 2. Meanwhile, both MOFs also show commendable selectivity towards formic acid among interfering solutions. The proton conducting and formic acid sensing mechanisms have been suggested according to the structural analysis, Ea calculations, N2 and water vapor absorptions, PXRD and SEM measurements. This work will open a new avenue for proton‐conductive MOF‐based impedance sensors and promote the potential application of these MOFs for indirectly monitoring the concentrations of formic acid vapors.
Few‐Layer MoS2 Nanosheets Encapsulated in N‐Doped Carbon Hollow Spheres as Long‐Life Anode Materials for Lithium‐Ion Batteries
Authors: Wang Faze , Li Fanggang , Ma Li , Zheng Maojun 
Published: September 2019

AbstractTwo‐dimensional molybdenum disulfide (MoS2) has been recognized as a promising anode material for lithium‐ion batteries (LIBs) due to its high theoretical capacity, but its rapid capacity decay owing to poor conductivity, structure pulverization, and polysulfide dissolution presents significant challenges in practical applications. Herein, triple‐layered hollow spheres in which MoS2 nanosheets are fully encapsulated between inner carbon and outer nitrogen‐doped carbon (NC) were fabricated. Such an architecture provides high conductivity and efficient lithium‐ion transfer. Moreover, the NC shell prevents aggregation and exfoliation of MoS2 nanosheets and thus maintains the integrity of the nanostructure during the charge/discharge process. As anode materials for LIBs, the C@MoS2@NC hollow spheres deliver a high reversible capacity (747 mA h g−1 after 100 cycles at 100 mA g−1) and excellent long‐cycle performance (650 mA h g−1 after 1000 cycles at 1.0 A g−1), which confirm its potential for high‐performance LIBs.
Exploring Caffeine–Phenol Interactions by the Inseparable Duet of Experimental and Theoretical Data
Authors: Usabiaga Imanol , Camiruaga Ander , Calabrese Camilla , Maris Assimo , Fernández José A. 
Published: September 2019

AbstractIntermolecular interactions are difficult to model, especially in systems formed by multiple interactions. Such is the case of caffeine–phenol. Structural data has been extracted by using mass‐resolved excitation spectroscopy and double resonance techniques. Then the predictions of seven different computational methods have been explored to discover structural and energetic discrepancies between them that may even result in different assignments of the system. The results presented herein highlight the difficulty of constructing functionals to model systems with several competing interactions, and raise awareness of problems with assignments of complex systems with limited experimental information that rely exclusively on energetic data.
Understanding the barriers and factors associated with consumer adoption of wearable technology devices in managing personal health
Authors: Sergueeva Ksenia , Shaw Norman , Lee Seung Hwan (Mark) 
Published: September 2019

AbstractThis research seeks to identify the barriers and factors associated with adopting wearable technology devices (WTDs) for managing personal health. Based on a partial least square (PLS) analysis of 277 US‐based residents, the findings demonstrate that performance expectancy, social influence, facilitating conditions, hedonic motivation, habit, and personalization are significant predictors of consumers' intention to use WTDs. Interestingly, price value, privacy concerns, and health consciousness are not significant. This study will inform future research on WTDs in personal health management. Theoretical and practical implications of the study are also presented.