bluuebunny/crossref_metadata_2025_split huggingface dataset:
Rational Development of Guanidinate and Amidinate Based Cerium and Ytterbium Complexes as Atomic Layer Deposition Precursors: Synthesis, Modeling, and Application
Authors: Kaur Parmish , Mai Lukas , Muriqi Arbresha , Zanders David , Ghiyasi Ramin , Safdar Muhammad , Boysen Nils , Winter Manuela , Nolan Michael , Karppinen Maarit , Devi Anjana 
Published: January 2021

AbstractOwing to the limited availability of suitable precursors for vapor phase deposition of rare‐earth containing thin‐film materials, new or improved precursors are sought after. In this study, we explored new precursors for atomic layer deposition (ALD) of cerium (Ce) and ytterbium (Yb) containing thin films. A series of homoleptic tris‐guanidinate and tris‐amidinate complexes of cerium (Ce) and ytterbium (Yb) were synthesized and thoroughly characterized. The C‐substituents on the N‐C‐N backbone (Me, NMe2, NEt2, where Me=methyl, Et=ethyl) and the N‐substituents from symmetrical iso‐propyl (iPr) to asymmetrical tertiary‐butyl (tBu) and Et were systematically varied to study the influence of the substituents on the physicochemical properties of the resulting compounds. Single crystal structures of [Ce(dpdmg)3] 1 and [Yb(dpdmg)3] 6 (dpdmg=N,N'‐diisopropyl‐2‐dimethylamido‐guanidinate) highlight a monomeric nature in the solid‐state with a distorted trigonal prismatic geometry. The thermogravimetric analysis shows that the complexes are volatile and emphasize that increasing asymmetry in the complexes lowers their melting points while reducing their thermal stability. Density functional theory (DFT) was used to study the reactivity of amidinates and guanidinates of Ce and Yb complexes towards oxygen (O2) and water (H2O). Signified by the DFT calculations, the guanidinates show an increased reactivity toward water compared to the amidinate complexes. Furthermore, the Ce complexes are more reactive compared to the Yb complexes, indicating even a reactivity towards oxygen potentially exploitable for ALD purposes. As a representative precursor, the highly reactive [Ce(dpdmg)3] 1 was used for proof‐of‐principle ALD depositions of CeO2 thin films using water as co‐reactant. The self‐limited ALD growth process could be confirmed at 160 °C with polycrystalline cubic CeO2 films formed on Si(100) substrates. This study confirms that moving towards nitrogen‐coordinated rare‐earth complexes bearing the guanidinate and amidinate ligands can indeed be very appealing in terms of new precursors for ALD of rare earth based materials.
Experimental and Computational Studies on Quadruply Bonded Dimolybdenum Complexes with Terminal and Bridging Hydride Ligands
Authors: Pérez‐Jiménez Marina , Curado Natalia , Maya Celia , Campos Jesús , Ruiz Eliseo , Álvarez Santiago , Carmona Ernesto 
Published: January 2021

AbstractThis contribution focuses on complex [Mo2(H)2(μ‐AdDipp2)2] (1) and tetrahydrofuran and pyridine adducts [Mo2(H)2(μ‐AdDipp2)2(L)2] (1⋅thf and 1⋅py), which contain a trans‐(H)Mo≣Mo(H) core (AdDipp2=HC(NDipp2)2; Dipp=2,6‐iPr2C6H3). Computational studies provide insights into the coordination and electronic characteristics of the central trans‐Mo2H2 unit of 1, with four‐coordinate, fourteen‐electron Mo atoms and ϵ‐agostic interactions with Dipp methyl groups. Small size C‐ and N‐donors give rise to related complexes 1⋅L but only one molecule of P‐donors, for example, PMe3, can bind to 1, causing one of the hydrides to form a three‐centered, two‐electron (3c‐2e) Mo‐H→Mo bond (2⋅PMe3). A DFT analysis of the terminal and bridging hydride coordination to the Mo≣Mo bond is also reported, along with reactivity studies of the Mo−H bonds of these complexes. Reactions investigated include oxidation of 1⋅thf by silver triflimidate, AgNTf2, to afford a monohydride [Mo2(μ‐H)(μ‐NTf2)(μ‐AdDipp2)2] (4), with an O,O’‐bridging triflimidate ligand.
Separation of Xylene Isomers in the Anion‐Pillared Square Grid Material SIFSIX‐1‐Cu
Authors: Yang Liping , Liu Hanbang , Xing Jiacheng , Yuan Danhua , Xu Yunpeng , Liu Zhongmin 
Published: January 2021

AbstractXylene isomer separation is considered one of the seven separation challenges that changed the world. In addition, the high‐energy demand of xylene separation highlights the need for efficient novel adsorbents. Herein, the liquid‐phase separation potential of the anion‐pillared hybrid material SIFSIX‐1‐Cu was studied for preferential adsorption of o‐xylene and m‐xylene over p‐xylene, which was inspired by a previous complexation crystallization method for separating m‐xylene. We report detailed experimental liquid‐phase adsorption experiments, yielding selectivities of 3.0 for o‐xylene versus p‐xylene and 2.6 for m‐xylene versus p‐xylene. Our theoretical calculations thus provide a reasonable explanation that the xylene adsorption selectivity is attributed to the C−H⋅⋅⋅F interaction, and the host–guest interaction order agrees with the adsorption priority: o‐xylene > m‐xylene > p‐xylene.
Control and stability analysis of DC microgrid system including wind and solar generation sources and grid‐connected voltage source converter
Authors: Hassantaghi Hassan , Rahimi Mohsen 
Published: January 2021

SummaryThe study system in this paper is a grid‐connected DC microgrid system comprising PV and wind generation sources, resistive and constant power loads (CPLs), and grid‐connected VSC. The VSC keeps the DC link voltage constant, and the wind and PV sources operate in maximum power point tracking (MPPT) mode, and thus, the DC–DC converters related to these sources act such as controlled current sources behaving similar to negative CPLs. The study system suffers from the stability under high CPL penetration and weak AC grid conditions. Hence, this paper investigates and enhances the system stability under both high CPL penetration and weak AC grid conditions. To do this, modal and small‐signal stability analysis of the system is carried out, and then, as the main findings, impacts of the wind and PV sources output powers, CPL power, and AC grid short‐circuit power on the system stability are studied. Next, as the main contribution, VSC control structure is modified by adding stabilizing signals to enhance the system stability under high CPL penetration, reduced output powers of the wind and PV sources, and weak AC grid conditions. At the end, several simulation results verify the theoretical results at different conditions.
Nalfurafine reduces neuroinflammation and drives remyelination in models of CNS demyelinating disease
Authors: Denny Lisa , Al Abadey Afnan , Robichon Katharina , Templeton Nikki , Prisinzano Thomas E , Kivell Bronwyn M , La Flamme Anne C 
Published: January 2021

AbstractObjectivesMultiple sclerosis (MS) is a neurodegenerative disease characterised by inflammation and damage to the myelin sheath, resulting in physical and cognitive disability. There is currently no cure for MS, and finding effective treatments to prevent disease progression has been challenging. Recent evidence suggests that activating kappa opioid receptors (KOR) has a beneficial effect on the progression of MS. Although many KOR agonists like U50,488 are not suitable for clinical use because of a poor side‐effect profile, nalfurafine is a potent, clinically used KOR agonist with a favorable side‐effect profile.MethodsUsing the experimental autoimmune encephalomyelitis (EAE) model, the effect of therapeutically administered nalfurafine or U50,488 on remyelination, CNS infiltration and peripheral immune responses were compared. Additionally, the cuprizone model was used to compare the effects on non‐immune demyelination.ResultsNalfurafine enabled recovery and remyelination during EAE. Additionally, it was more effective than U50,488 and promoted disease reduction when administered after chronic demyelination. Blocking KOR with the antagonist, nor‐BNI, impaired full recovery by nalfurafine, indicating that nalfurafine mediates recovery from EAE in a KOR‐dependent fashion. Furthermore, nalfurafine treatment reduced CNS infiltration (especially CD4+ and CD8+ T cells) and promoted a more immunoregulatory environment by decreasing Th17 responses. Finally, nalfurafine was able to promote remyelination in the cuprizone demyelination model, supporting the direct effect on remyelination in the absence of peripheral immune cell invasion.ConclusionsOverall, our findings support the potential of nalfurafine to promote recovery and remyelination and highlight its promise for clinical use in MS.
Hibernacula microclimate and declines in overwintering bats during an outbreak of white‐nose syndrome near the northern range limit of infection in North America
Authors: Vanderwolf Karen J. , McAlpine Donald F. 
Published: January 2021

AbstractWe document white‐nose syndrome (WNS), a lethal disease of bats caused by the fungusPseudogymnoascus destructans(Pd), and hibernacula microclimate in New Brunswick, Canada. Our study area represents a more northern region than is common for hibernacula microclimate investigations, providing insight as to how WNS may impact bats at higher latitudes. To determine the impact of the March 2011 arrival ofPdin New Brunswick and the role of hibernacula microclimate on overwintering bat mortality, we surveyed bat numbers at hibernacula twice a year from 2009 to 2015. We also collected data from iButton temperature loggers deployed at all sites and data from HOBO temperature and humidity loggers at three sites. Bat species found in New Brunswick hibernacula includeMyotis lucifugus(Little Brown Bat) andM. septentrionalis(Northern Long‐eared Bat), with small numbers ofPerimyotis subflavus(Tricolored Bat). All known hibernacula in the province werePd‐positive with WNS‐positive bats by winter 2013. A 99% decrease in the overwintering bat population in New Brunswick was observed between 2011 and 2015. We did not observeP. subflavusduring surveys 2013–2015 and the species appears to be extirpated from these sites. Bats did not appear to choose hibernacula based on winter temperatures, but dark zone (zone where no light penetrates) winter temperatures did not differ among our study sites. Winter dark zone temperatures were warmer and less variable than entrance or above ground temperatures. We observed visiblePdgrowth on hibernating bats in New Brunswick during early winter surveys (November), even though hibernacula temperatures were colder than optimum for in vitroPdgrowth. This suggests that cold hibernacula temperatures encountered near the apparent northern range limit forPddo not sufficiently slow fungal growth to prevent the onset of WNS and associated bat mortality over the winter.
Estimating animal abundance and effort–precision relationship with camera trap distance sampling
Authors: Cappelle Noémie , Howe Eric J. , Boesch Christophe , Kühl Hjalmar S. 
Published: January 2021

AbstractEffective monitoring methods are needed for assessing the state of biodiversity and detecting population trends. The popularity of camera trapping in wildlife surveys continues to increase as they are able to detect species in remote and difficult‐to‐access areas. As a result, several statistical estimators of the abundance of unmarked animal populations have been developed, but none have been widely tested. Even where the potential for accurate estimation has been demonstrated, whether these methods estimators can yield estimates of sufficient precision to detect trends and inform conservation action remains questionable. Here, we assess the effort–precision relationship of camera trap distance sampling (CTDS) in order to help researchers design efficient surveys. A total of 200 cameras were deployed for 10 months across 200 km2in the Taï National Park, Côte d'Ivoire. We estimated abundance of Maxwell's duikers, western chimpanzees, leopards, and forest elephants that are challenging to enumerate due to rarity or semi‐arboreality. To test the effects of spatial and temporal survey effort on the precision of CTDS estimates, we calculated coefficient of variation (CV) of the encounter rate from subsets of our complete data sets. Estimated abundance of leopard and Maxwell's duiker density (20% < CV < 30% and CV = 11%, respectively) were similar to prior estimates from the same area. Abundances of chimpanzees (20% < CV < 30%) were underestimated, but the quality of inference was similar to that reported after labor‐intensive line transect surveys to nests. Estimates for the rare forest elephants were potentially unreliable since they were too imprecise (60% < CV < 200%). Generalized linear models coefficients indicated that for relatively common, ground‐dwelling species, CVs between 10% and 20% are achievable from a variety of survey designs, including long‐term (6+ months) surveys at few locations (50), or short term (2‐week to 2‐month) surveys at 100–150 locations. We conclude that CTDS can efficiently provide estimates of abundance of multiple species of sufficient quality and precision to inform conservation decisions. However, estimates for the rarest species will be imprecise even from ambitious surveys and may be biased for species that exhibit strong reactions to cameras.
Solvation Structure and Dynamics of Mg(TFSI)2 Aqueous Electrolyte
Authors: Yu Zhou , Juran Taylor R. , Liu Xinyi , Han Kee Sung , Wang Hui , Mueller Karl T. , Ma Lin , Xu Kang , Li Tao , Curtiss Larry A. , Cheng Lei 
Published: January 2021

Using ab initio molecular dynamics (AIMD) simulations, classical molecular dynamics (CMD) simulations, small‐angle X‐ray scattering (SAXS), and pulsed‐field gradient nuclear magnetic resonance (PFG‐NMR), the solvation structure and ion dynamics of magnesium bis(trifluoromethanesulfonyl)imide (Mg(TFSI)2) aqueous electrolyte at 1, 2, and 3 m concentrations are investigated. From AIMD and CMD simulations, the first solvation shell of an Mg2+ ion is found to be composed of six water molecules in an octahedral configuration and the solvation shell is rather rigid. The TFSI− ions prefer to stay in the second solvation shell and beyond. Meanwhile, the comparable diffusion coefficients of positive and negative ions in Mg(TFSI)2 aqueous electrolytes have been observed, which is mainly due to the formation of the stable [Mg(H2O)6]2+ complex, and, as a result, the increased effective Mg ion size. Finally, the calculated correlated transference numbers are lower than the uncorrelated ones even at the low concentration of 2 and 3 m, suggesting the enhanced correlations between ions in the multivalent electrolytes. This work provides a molecular‐level understanding of how the solvation structure and multivalency of the ion affect the dynamics and transport properties of the multivalent electrolyte, providing insight for rational designs of electrolytes for improved ion transport properties.
Nitrosonisoldipine is a selective inhibitor of inflammatory caspases and protects against pyroptosis and related septic shock
Authors: Chen Qianyue , Zheng Jiashuo , Wang Dingyu , Liu Qiyao , Kang Lulu , Gao Xiang , Lin Zhaoyu 
Published: January 2021

AbstractPyroptosis is a type of acute cell death that mainly occurs in immune cells. It is characterized with robust release of inflammatory cytokines and has emerged to play a critical role in the pathogenesis of sepsis‐associated immune disorders. In this study, we screened for pyroptotic inhibitors with the ultimate goal to benefit sepsis treatments. Accidentally, we identified that nitrosonisoldipine (NTS), a photodegradation product of calcium channel inhibitor nisoldipine, inhibits noncanonical pyroptosis. Using murine immortalized BM‐derived macrophage and human THP‐1 cell line, we further discovered that NTS not only inhibits noncanonical pyroptosis mediated by caspase‐11 or caspase‐4 but also canonical pyroptosis mediated by caspase‐1. Mechanistically, NTS directly inhibits the enzyme activities of these inflammatory caspases, and these inhibitory effects persist despite extensive washout of the drug. By contrast, apoptosis mediated by caspase‐3/‐7 was not affected by NTS. Mice pretreated with NTS intraperitoneally displayed improved survival rate and extended survival time in LPS‐ and polymicrobe‐induced septic models, respectively. In conclusion, NTS is a selective inhibitor of inflammatory caspases that blocks both the noncanonical and canonical pyroptotic pathways. It is safe for intraperitoneal administration and might be used as a prototype to develop drugs for sepsis treatments.
Redox Induced Tunable Functionalization of Picolylamines on Selective Ru‐Platform
Authors: Singh Aditi , Dey Sanchaita , Panda Sanjib , Lahiri Goutam Kumar 
Published: January 2021

AbstractRedox induced ligand centered reactivity has garnered significant attention in recent times. In this context, the present article described intermolecular oxygenation, dehydrogenation and C−N bond cleavage processes of structurally robust picolylamine derivatives (HL) on selective {Ru(acac)2} metal platform encompassing electron rich acac (=acetylacetonate) co‐ligand. The diverse functionalization of {Ru(acac)2} coordinated β‐ketoiminate embedded picolylamines under basic condition included (i) oxygenation of methylene (Cα) position of picolyl fragment (−CH2−NH−→−CO−NH−), (ii) dehydrogenation of phenyl substituted Cα (−CH−NH−→−C=N−) and (iii) C−N bond cleavage of the picolinoyl moiety to yield picolinate (−CO−N−−→−CO−O−). Besides structural, spectroscopic (mass, 1H/13C−NMR, EPR, UV‐vis.) and electrochemical authentication of the products, correlation of the reactivity pattern was addressed via transition state (TS) calculations. Theoretical results supported the consideration of a common dianionic intermediate to address the aforementioned reactivities. The pertinent question of intramolecular cyclization versus intermolecular oxygenation of picolylamine on simple switching from {Ru(Cl)(H)(CO)(PPh3)3} (earlier work[4a]) metal fragment to {Ru(acac)2} (present report) was also elaborated by TS calculation.
P2X7‐induced nociception in the temporomandibular joint of rats depends on inflammatory mechanisms and C‐fibres sensitization
Authors: Teixeira Juliana M. , Pimentel Rafael M. , Abdalla Henrique B. , de Sousa Hortência M. X. , Macedo Cristina G. , Napimoga Marcelo H. , Tambeli Cláudia H. , Oliveira‐Fusaro Maria C. G. , Clemente‐Napimoga Juliana T. 
Published: January 2021

AbstractBackgroundP2X7 receptors are responsible for triggering inflammatory responses contributing to processes of pain in articular tissues. This study aimed to investigate whether the activation of the P2X7 receptor located in the temporomandibular joint (TMJ) tissues induces nociception through an inflammatory mechanisms and/or the activation of C‐fibres (small‐diameter primary afferents) of rats’ TMJ.MethodsThe TMJ hypernociception induced by the activation of P2X7 receptor was assessed by measuring the behavioural nociceptive responses. After behavioural experiments, the animals were terminally anaesthetized and periarticular tissues were removed and homogenate for enzyme‐linked immunosorbent assay, leukocyte infiltration and western blotting analysis.ResultsThe nonselective P2X7 receptor agonist BzATP induced a dose‐dependent TMJ nociception, which was blocked by the selective P2X7 receptor antagonist A‐438079. The co‐administration of the selective β2‐adrenoceptor antagonist (ICI‐118,551) and the pre‐treatment with cyclooxygenase inhibitor indomethacin or with the nonspecific selectin inhibitor Fucoidan significantly reduced BzATP‐induced TMJ nociception. BzATP also induced an increase of pro‐inflammatory cytokines TNFα, IL‐1β and CINC‐1 levels, as well as leukocyte recruitment in TMJ tissue, effects that were reduced by A‐438079. Moreover BzATP‐induced TMJ nociception was inhibited in rats neonatal‐treated with Capsaicin (depleting C‐fibers). Finally, BzATP‐induced an increase in TRPV1 expression in TMJ tissue.ConclusionsThese findings suggest that P2X7 receptor activation in TMJ of rats induces nociceptive responses mediated by sympathomimetic amines, prostaglandins, leukocyte migration and increased levels of pro‐inflammatory cytokines. Furthermore, the P2X7 receptor activation induces nociceptive responses dependent on the activation of the primary afferent nociceptors of rats’ TMJ.SignificanceThe activation of P2X7 receptors has an essential role in TMJ nociception and could be an interesting target to control the inflammatory pain in temporomandibular disorders.
Rehabilitation effects on gully sediment yields and vegetation in a savanna rangeland
Authors: Koci Jack , Wilkinson Scott N. , Hawdon Aaron A. , Kinsey‐Henderson Anne E. , Bartley Rebecca , Goodwin Nicholas R. 
Published: January 2021

AbstractGully rehabilitation can contribute to catchment management by stabilizing erosion and reducing downstream sediment yields, yet the globally observed responses are variable. Developing the technical basis for gully rehabilitation and establishing guidelines for application requires studies that evaluate individual rehabilitation measures in specific environments. An eight‐year field experiment was undertaken to evaluate sediment yield and vegetation responses to several gully rehabilitation measures. The rehabilitation measures aimed to reduce surface runoff into gully head cuts, trap sediment on gully floors and increase vegetation cover on gully walls and floors. The study occurred in a savanna rangeland in northeast Australia. Two gullies were subject to treatments while four gullies were monitored as untreated controls. A runoff diversion structure reduced headcut erosion from 4.3 to 1.2 m2 yr−1. Small porous check dams and cattle exclusion reduced gully total sediment yields by more than 80%, equivalent to a reduction of 0.3 to 2.4 t ha−1 yr−1, but only at catchment areas less than 10 ha. Fine sediment yields (silt and clay) were reduced by 7 and 19% from the two treated gullies, respectively. The porous check dam deposits contained a lower percentage of the fine fraction than the parent soil. Significant regeneration of gully floor vegetation occurred, associated with trapping of organic litter and fine sediment. Increases in vegetation cover and biomass were comprised of native perennial grasses, trees and shrubs. In variable climates, long‐term gully rehabilitation will progress during wetter periods, and regress during droughts. Understanding linkages between rehabilitation measures, their hydrologic, hydraulic and vegetation effects and gully sediment yields is important to defining the conditions for their success.
Hyalinizing epithelioid tumors with OGT‐FOXO fusions. A case report of a non‐acral soft tissue mass harboring a novel FOXO4 gene rearrangement
Authors: Torrence Dianne , Zhang Lei , Sung Yun‐Shao , Dickson Brendan C. , Antonescu Cristina R. 
Published: January 2021

AbstractRecurrent fusions between OGT and members of the Forkhead box (FOXO) family of genes have been recently described in three cases of hyalinizing epithelioid acral soft tissue tumors in young adults showing co‐expression for EMA and CD34. Despite the lack of an established myoepithelial lineage by immunohistochemistry, these lesions have been labeled as myoepithelioma‐like due to their epithelioid phenotype and sclerotic background. In this study, we report a novel FOXO4‐OGT fusion identified by targeted RNA sequencing in an unclassified shoulder soft tissue mass in a 40‐year‐old male. The tumor showed nodular foci of increased cellularity in a uniformly hyalinized background. The neoplastic cells were mainly epithelioid and focally spindled, with eosinophilic cytoplasm and indented nuclei with mild atypia. The tumor lacked significant mitotic activity and necrosis. Immunohistochemically, the tumor showed variable positivity for EMA, pan‐CK, CD34, ERG and FLI1, while it was negative for CD31, S100, SOX10, desmin, and MUC4. INI1 expression was retained. Due to its unusual histology and conflicting immunoprofile, TruSight RNA fusion panel sequencing was performed which revealed a fusion between FOXO4 exon 2 to OGT exon 2. This is the first example of a soft tissue lesion harboring OGT‐related fusions occurring in a non‐acral location and associated with FOXO4 gene. Its line of differentiation and biologic potential remain uncertain.