bluuebunny/crossref_metadata_2025_split huggingface dataset:
Tuning the Electronic Structure of LaNiO3 through Alloying with Strontium to Enhance Oxygen Evolution Activity
Authors: Liu Jishan , Jia Endong , Wang Le , Stoerzinger Kelsey A. , Zhou Hua , Tang Chi Sin , Yin Xinmao , He Xu , Bousquet Eric , Bowden Mark E. , Wee Andrew T. S. , Chambers Scott A. , Du Yingge 
Published: August 2019

AbstractThe perovskite oxide LaNiO3 is a promising oxygen electrocatalyst for renewable energy storage and conversion technologies. Here, it is shown that strontium substitution for lanthanum in coherently strained, epitaxial LaNiO3 films (La1−x
SrxNiO3) significantly enhances the oxygen evolution reaction (OER) activity, resulting in performance at x = 0.5 comparable to the state‐of‐the‐art catalyst Ba0.5Sr0.5Co0.8Fe0.2O3−δ. By combining X‐ray photoemission and X‐ray absorption spectroscopies with density functional theory, it is shown that an upward energy shift of the O 2p band relative to the Fermi level occurs with increasing x in La1−xSrxNiO3. This alloying step strengthens Ni 3d–O 2p hybridization and decreases the charge transfer energy, which in turn accounts for the enhanced OER activity.
Tuning the Photoresponse of Nano‐Heterojunction: Pressure‐Induced Inverse Photoconductance in Functionalized WO3 Nanocuboids
Authors: Rahman Saqib , Samanta Sudeshna , Kuzmin Alexei , Errandonea Daniel , Saqib Hajra , Brewe Dale L. , Kim Jaeyong , Lu Junling , Wang Lin 
Published: August 2019

AbstractInverse photoconductivity (IPC) is a unique photoresponse behavior that exists in few photoconductors in which electrical conductivity decreases with irradiation, and has great potential applications in the development of photonic devices and nonvolatile memories with low power consumption. However, it is still challenging to design and achieve IPC in most materials of interest. In this study, pressure‐driven photoconductivity is investigated in n‐type WO3 nanocuboids functionalized with p‐type CuO nanoparticles under visible illumination and an interesting pressure‐induced IPC accompanying a structural phase transition is found. Native and structural distortion induced oxygen vacancies assist the charge carrier trapping and favor the persistent positive photoconductivity beyond 6.4 GPa. The change in photoconductivity is mainly related to a phase transition and the associated changes in the bandgap, the trapping of charge carriers, the WO6 octahedral distortion, and the electron–hole pair recombination process. A unique reversible transition from positive to inverse photoconductivity is observed during compression and decompression. The origin of the IPC is intimately connected to the depletion of the conduction channels by electron trapping and the chromic property of WO3. This synergistic rationale may afford a simple and powerful method to improve the optomechanical performance of any hybrid material.
The Gravettian child mandible from El Castillo Cave (Puente Viesgo, Cantabria, Spain)
Authors: Garralda María‐Dolores , Maíllo‐Fernández José‐Manuel , Higham Thomas , Neira Ana , Bernaldo de Quirós Federico 
Published: August 2019

AbstractObjectivesThis article documents an incomplete child's mandible found in H. Obermaier's excavation campaign (in 1912) in El Castillo Cave, Spain. This fossil was assigned to what was then considered a phase of the “Aurignacian‐delta”.Materials and MethodsWe exhaustively analyzed the original Obermaier documents, with particular attention to those corresponding to the year of the discovery. We extracted a bone sample to radiocarbon date the fossil directly. We also followed established methods to measure, describe and compare the mandible with other human remains.ResultsThe analysis of Obermaier's documents and new data derived from modern excavations, show that the mandible was discovered in an interior area of the cave. Direct radiocarbon dating yielded a result of 24,720 ± 210 BP and 29,300 – 28,300 cal BP, a date similar to those known for the Gravettian technocomplex both in the El Castillo site and across Europe.The jaw corresponded to a child aged 4–5 years, with modern morphology, but with a certain robustness, especially in the symphyseal region. Comparisons were made with several modern children (Granada, Spitalfields, and Black series) and with immature fossils (European Aurignacian and Gravettian). The few differences between the modern and the fossil children are related to the symphysis and mandibular corpus thickness and height, and to the symphyseal morphology and larger teeth dimensions. Paleoisotopic data for Castillo C correspond with a varied diet. Numerous cutmarks were identified in the midline internal symphyseal region.Discussion and ConclusionsThe results agree with those published for other fossils of similar age and chronology (e.g., the mandible of the Lagar Velho child) and show clear differences from the jaws of the young Neanderthals.The interpretation of the original data on the mandible discovery may indicate the destruction of a burial and the displacement, by percolation or by a den, at least of part of the skeleton. The perimortem manipulations in the child's mandible are the first described in the Gravettian world of Western Europe.
Exogenous Galactosylceramide as Potential Treatment for CLN3 Disease
Authors: El‐Sitt Sally , Soueid Jihane , Maalouf Katia , Makhoul Nadine , Al Ali Jamal , Makoukji Joelle , Asser Bilal , Daou Daniel , Harati Hayat , Boustany Rose‐Mary 
Published: August 2019

ObjectiveCLN3 disease is the commonest of the neuronal ceroid lipofuscinoses, a group of pediatric neurodegenerative disorders. Functions of the CLN3 protein include antiapoptotic properties and facilitating anterograde transport of galactosylceramide from Golgi to lipid rafts. This study confirms the beneficial effects of long‐term exogenous galactosylceramide supplementation on longevity, neurobehavioral parameters, neuronal cell counts, astrogliosis, and diminution in brain and serum ceramide levels in Cln3
Δex7/8 knock‐in mice. Additionally, the impact of galactosylceramide on ceramide synthesis enzymes is documented.MethodsA group of 72 mice received galactosylceramide or vehicle for 40 weeks. The effect of galactosylceramide supplementation on Cln3
Δex7/8 mice was determined by performing behavioral tests, measuring ceramide in brains and serum, and assessing impact on longevity, subunit C storage, astrogliosis, and neuronal cell counts.ResultsGalactosylceramide resulted in enhanced grip strength of forelimbs in male and female mice, better balance on the accelerating rotarod in females, and improved motor coordination during pole climbing in male mice. Brain and serum ceramide levels as well as apoptosis rates were lower in galactosylceramide‐treated Cln3
Δex7/8 mice. Galactosylceramide also increased neuronal cell counts significantly in male and female mice and tended to decrease subunit C storage in specific brain regions. Astrogliosis dropped in females compared to a slight increase in males after galactosylceramide. Galactosylceramide increased the lifespan of affected mice.InterpretationGalactosylceramide improved behavioral, neuropathological, and biochemical parameters in Cln3
Δex7/8 mice, paving the way for effective therapy for CLN3 disease and use of serum ceramide as a potential biomarker to track impact of therapies. ANN NEUROL 2019;86:729–742
Supported Intermetallic PdZn Nanoparticles as Bifunctional Catalysts for the Direct Synthesis of Dimethyl Ether from CO‐Rich Synthesis Gas
Authors: Gentzen Manuel , Doronkin Dmitry E. , Sheppard Thomas L. , Zimina Anna , Li Haisheng , Jelic Jelena , Studt Felix , Grunwaldt Jan‐Dierk , Sauer Jörg , Behrens Silke 
Published: August 2019

AbstractThe single‐step syngas‐to‐dimethyl ether (STD) process entails economic and technical advantages over the current industrial two‐step process. Pd/ZnO‐based catalysts have recently emerged as interesting alternatives to currently used Cu/ZnO/Al2O3 catalysts, but the nature of the active site(s), the reaction mechanism, and the role of Pd and ZnO in the solid catalyst are not well established. Now, Zn‐stabilized Pd colloids with a size of 2 nm served as the key building blocks for the methanol active component in bifunctional Pd/ZnO‐γ‐Al2O3 catalysts. The catalysts were characterized by combining high‐pressure operando X‐ray absorption spectroscopy and DFT calculations. The enhanced stability, longevity, and high dimethyl ether selectivity observed makes Pd/ZnO‐γ‐Al2O3 an effective alternative system for the STD process compared to Cu/ZnO/γ‐Al2O3.
Dearomatization Approach Toward a Superbenzoquinone‐Based Diradicaloid, Tetraradicaloid, and Hexaradicaloid
Authors: Li Guangwu , Han Yi , Zou Ya , Lee Johnathan Joo Cheng , Ni Yong , Wu Jishan 
Published: August 2019

AbstractReported here is the step‐by‐step dearomatization of a highly aromatic polycyclic aromatic hydrocarbon (PAH), the hexa‐peri‐hexabenzocoronene (also called as “superbenzene”), to give a series of superbenzoquinones containing two, four, and six ketone groups. Different from traditional PAH‐based quinones, these superbenzoquinones show open‐shell multiradical character by rearomatization in the open‐shell forms as experimentally validated by X‐ray crystallographic analysis, NMR and ESR spectroscopy, and FT‐IR measurements, as well as theoretically supported by restricted active space spin‐flip calculations. These compounds exhibit structure‐ and molecular‐symmetry‐dependent optical, electrochemical, and magnetic properties.
Diastereo‐ and Enantioselective Synthesis of (E)‐δ‐Boryl‐Substituted anti‐Homoallylic Alcohols in Two Steps from Terminal Alkynes
Authors: Miura Tomoya , Oku Naoki , Murakami Masahiro 
Published: August 2019

AbstractWe report the highly diastereo‐ and enantioselective preparation of (E)‐δ‐boryl‐substituted anti‐homoallylic alcohols in two steps from terminal alkynes. This method consists of a cobalt(II)‐catalyzed 1,1‐diboration reaction of terminal alkynes with B2pin2 and a palladium(I)‐mediated asymmetric allylation reaction of the resulting 1,1‐di(boryl)alk‐1‐enes with aldehydes in the presence of a chiral phosphoric acid. Propyne, which is produced as the byproduct during petroleum refining, could be used as the starting material to construct homoallylic alcohols that are otherwise difficult to synthesize with high stereocontrol.
A Halogen‐Bond Donor Catalyst for Templated Macrocyclization
Authors: Guillier Kévin , Caytan Elsa , Dorcet Vincent , Mongin Florence , Dumont Élise , Chevallier Floris 
Published: August 2019

AbstractA halogen‐bond templated 1:1 macrocyclization in solution is reported. Tetra(iodoperfluorophenyl) ethers were used as halogen‐bonded exotemplates in a substoichiometric amount (5 mol %). Pyridine‐containing macrocyclic architectures were formed by ruthenium‐catalyzed tandem metathesis/transfer hydrogenation sequence using sodium borohydride and methanol as non‐dihydrogen hydrogen source. The halogen‐bonded stabilization energies were analyzed relying on density functional theory.
Regio‐ and Enantioselective Preparation of Chiral Allylic Sulfones Featuring Elusive Quaternary Stereocenters
Authors: Cai Aijie , Kleij Arjan W. 
Published: August 2019

AbstractWe describe here the first general asymmetric synthesis of sterically encumbered α,α‐disubstituted allylic sulfones via Pd‐catalyzed allylic substitution. The design and application of a new and highly efficient phosphoramidite ligand (L10) proved to be crucial, and a wide variety of challenging allylic sulfones featuring quaternary stereocenters could be obtained in good yields and with good to excellent levels of regio‐ and enantioselectivities under attractive process conditions. The developed methodology employs easily accessible chemical feedstock including racemic allylic precursors and sodium sulfinates. The utility of the method is further demonstrated by the synthesis of the sesquiterpene (−)‐Agelasidine A.
Merging Regiodivergent Catalysis with Atom‐Economical Radical Arylation
Authors: Mühlhaus Felix , Weißbarth Hendrik , Dahmen Tobias , Schnakenburg Gregor , Gansäuer Andreas 
Published: August 2019

AbstractA titanocene‐catalyzed regiodivergent radical arylation is described that allows access to either enantiomerically pure tetrahydroquinolines or indolines from a common starting material. The regioselectivity of epoxide opening that results in the high selectivity of heterocycle formation is controlled by two factors, the absolute configuration of the enantiopure ligands of the (C5H4R)2TiX2 catalyst and the inorganic ligand X (X=Cl, OTs). The overall reaction is atom‐economical and constitutes a radical Friedel–Crafts alkylation.
Direct Addition of Amides to Glycals Enabled by Solvation‐Insusceptible 2‐Haloazolium Salt Catalysis
Authors: Nakatsuji Yuya , Kobayashi Yusuke , Takemoto Yoshiji 
Published: August 2019

AbstractThe direct 2‐deoxyglycosylation of nucleophiles with glycals leads to biologically and pharmacologically important 2‐deoxysugar compounds. Although the direct addition of hydroxyl and sulfonamide groups have been well developed, the direct 2‐deoxyglycosylation of amide groups has not been reported to date. Herein, we show the first direct 2‐deoxyglycosylation of amide groups using a newly designed Brønsted acid catalyst under mild conditions. Through mechanistic investigations, we discovered that the amide group can inhibit acid catalysts, and the inhibition has made the 2‐deoxyglycosylation reaction difficult. Diffusion‐ordered two‐dimensional NMR spectroscopy analysis implied that the 2‐chloroazolium salt catalyst was less likely to form aggregates with amides in comparison to other acid catalysts. The chlorine atom and the extended π‐scaffold of the catalyst played a crucial role for this phenomenon. This relative insusceptibility to inhibition by amides is more responsible for the catalytic activity than the strength of the acidity.
Fisher accessibility and habitat complexity influence the distribution of adult Cherax cainii (Decapoda: Parastacidae) in a water supply reservoir
Authors: Beatty Stephen J. , Ryan Tom , Morgan David L. 
Published: August 2019

Abstract

Almost one third of all freshwater crayfishes are threatened with extinction. The factors influencing the distribution of freshwater crayfishes in lentic systems are poorly understood, hampering the conservation and enhancement of those populations. Cherax cainii is the third largest freshwater crayfish in the world and is endemic to south‐western Australia. The distribution of the species has declined markedly, largely attributable to secondary salinization and habitat decline. There is the potential for population enhancement through habitat restoration and the restocking of reservoirs that act as important non‐salinized refuges; however, there is limited understanding of the distribution and habitat associations of C. cainii in these systems.
Mark–recapture was undertaken to determine the population abundance and fine‐scale distribution of C. cainii in a large reservoir over a 5‐month period, with generalized linear mixed modelling used to determine those factors that explained the variation in its distribution.
Cherax cainii distribution in the reservoir was positively associated with complex habitat (large woody material) and the level of inaccessibility to humans, and negatively associated with depth. The population had a non‐uniform distribution within the reservoir with significant hot‐ and cold‐spots present and there was limited distance between recaptures during the coolest period of the year.
The findings suggest that C. cainii would benefit from the provision of additional complex habitat in such habitat depauperate reservoirs to provide increased shelter from predators. It may also be vulnerable to localized depletion through legal and illegal fishing pressure. The study highlights the importance of understanding habitat preferences and movement patterns of freshwater crayfish to underpin their conservation.
Oral supplementation with ginseng polysaccharide promotes food intake in mice
Authors: Wang Jiawen , Li Yongxiang , Luo Pei , Chen Yuhuang , Xi Qianyun , Wu Hanyu , Zhao Weijie , Shu Gang , Wang Songbo , Gao Ping , Zhu Xiaotong , Zhang Yongliang , Jiang Qingyan , Wang Lina 
Published: August 2019

AbstractIntroductionGinseng polysaccharide (GPS, same as Panax polysaccharide) is a kind of polysaccharide extracted from ginseng. It has been reported that GPS has the ability to activate innate immunity, regulates blood sugar balance, and improves antioxidant capacity, but the effect on feeding behavior and its mechanism remains unclear.MethodTo investigate the possible effect of GPS on feeding behavior of animals, mice were supplied with GPS in water, and food intake, hedonic feeding behavior, anxiety‐like behavior, expression of appetite‐regulation peptides in the central nervous system and glucose‐related hormone levels in the serum of mice were measured.ResultsGinseng polysaccharide significantly increased the average daily food intake in mice and promoted hedonic eating behavior. Meanwhile, the levels of serum glucose and glucagon were significantly reduced by GPS, and GPS promoted hypothalamic neuropeptide Y expression, inhibited proopiomelanocortin (POMC) expression, and reduced dopamine D1 receptor (DRD1) levels in the midbrain. We also found that the anxiety level of mice was significantly lower after GPS intake. In conclusion, oral supplementation with GPS promoted food intake in mice, most likely through the regulation of circulating glucose levels.
Field‐programmable gate array‐based laboratory oriented to control theory courses
Authors: Cruz‐Miguel Edson E. , Rodríguez‐Reséndiz Juvenal , García‐Martínez José R. , Camarillo‐Gómez Karla A. , Pérez‐Soto Gerardo I. 
Published: August 2019

AbstractThis article presents a methodology to improve the performance of learning of students in the major of Automation Engineering, through the development of a multidisciplinary project that involves the use of contemporary technological tools and knowledge of previous subjects. It is sought to add in their educational training, theory and practice for the student, learning, new knowledge, and skills within their training as an engineer. Despite advances in teaching methods and the inclusion of contemporary tools in the learning process, the success rate is low. A qualitative and quantitative analysis of student learning is made by integrating a multidisciplinary project based on contemporary tools compared with other reviewed works. This laboratory based on a field‐programmable gate array helps the student to acquire skills related to the implementation of reconfigurable logic and instrumentation applied to control theory. The development of the final project involves the design of a graphic user interface, hardware description, communication protocols, and implementation of motion control, it is looking for is that the student can relate theory to practice in order to motivate and increase skills and knowledge, as well as solving both didactic and industrial problems. The results obtained show that the students are satisfied with the course and that the experience with the integration of this type of multidisciplinary projects directly impacts the motivation and learning of the student, considerably increased developed based on the specific indicators that the Querétaro State University has accredited by Accreditation Board for Engineering and Technology since 2016.
Clinical outcomes of BRAF plus MEK inhibition in melanoma: A meta‐analysis and systematic review
Authors: Yu Qingliang , Xie Jiayi , Li Jiangmiao , Lu Yunxin , Liao Liang 
Published: August 2019

AbstractBackgroundMelanoma is a potentially fatal malignancy with poor prognosis. Several recent studies have demonstrated that combination therapy of BRAF and MEK inhibition achieved better curative effect and appeared less toxic effects. We conducted a meta‐analysis to evaluate the efficacy and safety between BRAF inhibition plus MEK inhibition combination therapy and BRAF inhibition monotherapy in melanoma patients.MethodsWe performed the search in PubMed, EMBASE, and the Cochrane Library from January 2010 to January 2019. Inclusion and exclusion of studies, assessment of quality, outcome measures, data extraction, and synthesis were independently accomplished by two reviewers. Revman 5.3 software was used for the meta‐analysis.ResultsTotally, seven randomized controlled trials involving 3146 patients met our inclusion criteria. Comparing the results of combination therapy and monotherapy, combination therapy significantly improved OS (RR = 1.13; 95% CI, 1.08, 1.19; P < 0.00001), ORR (RR = 1.36; 95% CI, 1.28, 1.45; P < 0.00001), PFS (RR = 0.57; 95% CI, 0.52, 0.63; P < 0.00001) and reduced deaths (RR = 0.78; 95% CI, 0.69, 0.88; P < 0.0001). Skin‐related adverse events such as hyperkeratosis, cutaneous squamous‐cell carcinoma were less compared with monotherapy. However, gastrointestinal events like nausea, diarrhea, and vomiting were at a higher frequency.ConclusionDoublet BRAF and MEK inhibition achieved better survival outcomes over single‐agent BRAF inhibition and occurred less skin‐related events, but gastrointestinal events were more in combination therapy.
Electrochemical Characterization of Isolated Nitrogenase Cofactors from Azotobacter vinelandii
Authors: Lydon Brian R. , Lee Chi Chung , Tanifuji Kazuki , Sickerman Nathaniel S. , Newcomb Megan P. , Hu Yilin , Ribbe Markus W. , Yang Jenny Y. 
Published: August 2019

AbstractThe nitrogenase cofactors are structurally and functionally unique in biological chemistry. Despite a substantial amount of spectroscopic characterization of protein‐bound and isolated nitrogenase cofactors, electrochemical characterization of these cofactors and their related species is far from complete. Herein we present voltammetric studies of three isolated nitrogenase cofactor species: the iron–molybdenum cofactor (M‐cluster), iron–vanadium cofactor (V‐cluster), and a homologue to the iron–iron cofactor (L‐cluster). We observe two reductive events in the redox profiles of all three cofactors. Of the three, the V‐cluster is the most reducing. The reduction potentials of the isolated cofactors are significantly more negative than previously measured values within the molybdenum–iron and vanadium–iron proteins. The outcome of this study provides insight into the importance of the heterometal identity, the overall ligation of the cluster, and the impact of the protein scaffolds on the overall electronic structures of the cofactors.